Exploration Geochemistry: Short Course Manual

EXPLORATION GEOCHEMISTRY
SHORT COURSE MANUAL
Newmont Exploration Limited

NEWMONT EXPLORATION LIMITED
EXPLORATION GEOCHEMISTRY
SHORT COURSE MANUAL
'bibliotec *
CFtSO^L. PALACIOS CÎLl-C
Prepared by
J. Alan Coope
Owen P. Lavin
Erick F. Weiland
Newmont Exploration Limited’

Geochemistry Department
and
Lloyd D. James
Geochemical Consultant
July 1991
2nd Printing March 1993
'COPYRIGHT ©Newmont Exploration Limited 1991

TABLE OF CONTENTS
TABLE OF CONTENTS........................................................................ j
LIST OF FIGURES........................................................................ v
LIST OF TABLES........................................................................ XIV
1. INTRODUCTION........................................................................
2. DEFINITIONS................................. t..................................... 2
3. BRIEF HISTORY........................................................................ 4
4. INFORMATION SOURCES................................................................. 5
5. BASIC PRINCIPLES................................................................... 7
5.1. Geochemical Environment..................................................... 7

5.2. Characteristic Element Abundancesand Associations......................... 8
5.3. Element Associations of MineralDeposits.................................... 14
6. DISPERSION PROCESSES.............................................................. 18
6.1. General....................................................................... 13
6.2. Primary....................................................................... 18
6.3. Surficial Environment.......................................................
6.3.1. Chemical Dispersion....................................................... 19
6.3.2. Mechanical Dispersion . . . ,.................... 25
6.3.3. Biological Dispersion..................................................... 26
7. WEATHERING AND SOIL DEVELOPMENT.................................................. 27
7.1. General....................................................................... 27
7.2. Factors and Processes....................................................... 27
7.3. Examples of Surface Environments............................................ 33
7.3.1. Arid and Semi-Arid.......................................................... 33
7.3.2. Humid Tropics.............................................................. 35
7.3.3. Temperate Maritime.......................................................... 3g
7.3.4. Continental Middle Latitudes.............................................. 38
7.3.5. Higher Latitudes............................................................ 40
ii
8. PRIMARY GEOCHEMICAL HALOES AND PATTERNS ASSOCIATED WITH

MINERAL DEPOSITS.................................................................... 41
8.1. General......................................................................... 41
8.2. Plutonic Association.......................................................... 42
8.3. Volcanogenic MassiveSulfide Deposits....................................... 45
8.4. Sedimentary Exhalitive Deposits............................................. 48

8.5. Gold Deposits.................................................................. 50
9. SECONDARY GEOCHEMICAL PATTERNS ASSOCIATED WITH MINERAL

DEPOSITS............................................................................. 54
10. ROLE OF GEOCHEMISTRY IN THE MINERAL EXPLORATION

SEQUENCE............................................................................. 60
10.1 Mineral Exploration Sequence................................................. 60

10.2 Role of Geochemistry.......................................................... 60
10.3 Integrated Exploration ..................................................... 64
11. PROGRAM DESIGN AND PLANNING OF GEOCHEMICAL EXPLORATION

PROGRAMS............................................................................. 66
11.1. General........................................................................ 66
11.2. Conceptual Models............................................................ 68
11.2.1. Principles................................................................... 68
11.2.2. Objectives................................................................... 69
11.2.3. Procedures................................................................... 69
11.2.4. Examples..................................................................... 69
11.3. Orientation..................................................................... 75
11.3.1. Principles............................ •..................................... 75
11.3.2. Objectives................................................................... 75
11.3.3. Procedures................................................................... 76
11.3.4. Examples.................. 82
12. FIELD SURVEY PROCEDURES............................................................ 89
12.1. General........................................................................ 89
12.2. Sample Media................................................................... 90
12.2.1. Rocks........................................................................ ‘90
12.2.2. Soils........................................................................ 98
12.2.3. Stream Sediments........................................................ 106
12.2.4. Lake Sediments.......................................................... 117
12.2.5. Glacial Sediments........................................................ 119
iii
12.2.6. Vegetation.................................................................. 129
12.2.7. Water...................................................................... 146
12.2.8. Gases...................................................................... 151
12.2.9. Particulates............................................................... 159
12.2.10. Microorganisms............................................................. 160
12.2.11. Animal Tissues............................................................... 161
13. FIELD/LABORATORY LIAISON........................................................ 162
14. LABORATORY PROCEDURES............................................................. 163
14.1. Sample Preparation.......................................................... 163

14.1.1. Drying...................................................................... 164
14.1.2. Crushing and Grinding......... '........................................ 164
14.1.3. Sieving................................................. ;................ 170
14.1.4. Mineral Separation........................................................ 171
14.2. Sample Analysis............................................................. 175
14.2.1. Decomposition............................................................. 175
14.2.1.1. Strong Acid Decomposition.......................................... 179
14.2.1.2. Phase Selective Leaches (Partial and Sequential Extraction). . . 183
14.2.2. Separation................................................................. 186
14.2.3. Measurement............................................................... 187
14.2.3.1. Colorimetry............................................................ 189
14.2.3.2. Fluorimetry............................................................ 191
14.2.3.3. Atomic Absorption Spectrophotometry.............................. 193
14.2.3.4. Emission Spectroscopy - DC Arc (DC-ES) and
Inductively Coupled Plasma (ICP-ES)................................ 201
14.2.3.5. X-Ray Fluorescence Spectrometry (XRF).............................. 206
14.2.3.6. Instrumental Neutron Activation Analysis.......................... 211
14.2.3.7. Electroanalytical Methods (pH, Eh, and Specific Ion
Electrodes,and Jerome Hg Analyser).................................. 212
14.3. Data Reporting............................................................... 214
14.4. General Conclusions........................................................ 214
15. QUALITY CONTROL..........;....................................................... 217
15.1. General..................................................................... 217

15.2. Principles................................................................... 218
15.3. Procedures................................................................... 219
15.3.1. Systematic Duplicate Analysis......................................... 219
15.3.2. Standard Reference Samples.............................................. 219
15.3.3. Duplicate Field Sample Analysis....................................... 219
15.4. Recommended Procedure..................................................... 222
iv
16. INTERPRETATION.................................................................... 224
16.1. Definition and General Procedure.......................................... 224

16.2. Data Compilation.......................................................... 226
16.3 Geochemical Pattern Delineation........................................... 226
16.3.1. Data Display Maps........................................................ 228
16.3.1.1. Posting Geochemical Values.......................................... 230
16.3.1.2. Symbol Maps............................................................. 231
16.3.1.3. Contour Maps.......................................................... 241
16.1.1.4. Image Analysis........................................................ 250
16.3.1.5. Catchment Basin Maps.................................................. 258
16.3.2. Class Selection........................................................... 258
16.3.2.1. Data Specific..................... f.................................. 260
16.3.2.2. Serial................................. *.............................. 260
16.4. Geochemical Anomalies..................................................... 262
16.5. Statistical Analysis........................................................ 264
16.5.1. Univariate................................................................. 266
16.5.2. Multivariate............................................................. 276
16.6. Data Management............................................................. 277
16.7. Data Assessment and Integration.......................................... 282
17. FOLLOW-UP.......................................................................... 283
18. REPORT WRITING................................................................... 285
19. LONG TERM STORAGE OF DATA ANDSAMPLES............................. 286
20. CONCLUSIONS AND RECOMMENDATIONS..................................... 287
21. LIST OF REFERENCES.............................................................. 289

V
LIST OF FIGURES
FIG 2.1 The stages of exploration geochemistry related to a "House of

Cards"....................................................................................................... 3
FIG 5.1 Geochemical Cycle.................................................................................... 7
FIG 5.2a Location map............................................................................... . ... . 11
FIG 5.2b Nickel content............................................................................................ 12
FIG 5.3 Relationship between geology and the pattern of
nickel in residual soil, Nguge region, Tanzania..................................... 13
FIG 5.4 Element associations of some mineral deposits..................................... 16
FIG 5.4 continued ................................................................................................ 17
FIG 6.1 Approximate position of some natural environments as characterized
by Eh and pH....................... t.................................................................. 21
FIG 6.2 Eh and pH values of mine waters, (x) oxidized ore zone; (•) primary
ore zone........................................................................... 21
FIG 6.3 Eh-pH for the system Zn-O-H-S-C....................................................... 22
FIG 6.4 Fields of stability of solids and dissolved zinc
species ........................................................................... 22
FIG 6.5 Eh-pH for system Au-CI-O-H ................................................................ 23
FIG 6.6 Eh-pH for system Au-CI-O-H ............................................................... 23
FIG 6.7 Fractional adsorption of metals............................................................. 24
FIG 6.8 Absorption-desorption results with changing pH for
Mn-oxide exposed to solutions of 10'3M Co.......................................... 25
FIG 7.1 Distribution and extent of main types of weathering of silicate
rocks.................................................................................. 29
FIG 7.2 Hypothetical soil profile showing the principal horizons........................ 31
FIG 7.3 Map of the main zonal and intrazonal soils................... 34
FIG 7.4 Fersiallitic profile (see general key) ...................................................... 36
FIG 7.5 Profiles of ferruginous and ferrallitic soils (see general key)............... 36
FIG 7.6 Profile of brown soil (see general key)................................................. 38
FIG 7.7 Isohumic profiles (see general key)...................................................... 39
FIG 7.8 Podzolic soil profile (see general key) ................................................. 40
FIG 7.9 Ranker profile (see general key)............................................................. 40
FIG 8.1 Some typical examples of general geologic settings of ore
deposits..................... 41
FIG 8.2 Diffusion aureoles around an orebody and a small vein, Wisconsin-
Illinois Zn district............................................................... 42
FIG 8.3 Variation of K and Rb in barren and mineralized granitoids................. 43
FIG 8.4 Variation of Rb:Sr and K:Rb in granitoids............................................ 43
FIG 8.5 Relation between Sn content of granites and tin mineralization,
eastern Australia............................................................... 44
FIG 8.6 Schematic diagram illustrating form of geochemical anomalies in
rocks around massive sulfide deposits in New Brunswick, Canada. . 47
FIG 8.7 Range and average of Cu, Hg, Zn, and Mn ....................................... 48
vi
FIG 8.8 Distribution of O and Mn in limestone ............................................... 49

FIG 8.9 Distribution of total Mn in limestone................................... 49
FIG 8.10 Geochemistry of the Jason Deposit................................... .. 50
FIG 8.11 Alteration patterns, distribution of Au, Ag, Tl, W, Sb, As, and Hg in
bedrock at Round Mountain, Nevada, U.S.A........................................ 53
FIG 8.12 Distribution of Au, As, and Sb in rock chips and fracture coatings
around the Pinson Mine, Nevada, U.S.A.................... 53
FIG 9.1 Classification and general characteristics of the principal types of
surficial dispersion patterns............................................ 54
FIG 9.2 Syngenetic (clastic) patterns in residual overburden. .... . . . . 55
FIG 9.3 Syngenetic (clastic) patterns in transported overburden.............. .. 53
FIG 9.4 Principal types of dispersion patterns in surface drainage. ...... . . 57
FIG 9.5 Syngenetic (clastic) pattern in, outwash fan and piedmont sheetwash
alluvium................................................................. 57
FIG 9.6 Epigenetic patterns in transported overburden. Similar dispersion
may also contribute to patterns in residual overburden. 59
FIG 10.1. Decision and activity stages from commodity selection to finding an
ore deposit.................................................................... 61
FIG 10.2 Optimum relationships between geology and some associated
disciplines, including exploration geochemistry, in an integrated
mineral exploration program................................... 55
FIG 11.1 The stages of exploration geochemistry related to a "House of
Cards"................................................................ 67
FIG 11.2 Simplified conceptual geochemical dispersion model showing
formation of geochemical anomalies................................ 68
FIG 11.3 Idealized model for rock type change ................................ 70
FIG 11.4 Model B1 (Cordillera). Idealized models for geochemical dispersion
of mobile elements in well-drained and poorly drained ground -
residual soils (see Fig 11.3. for legend).......................... 71
FIG 11.5 Model E2 (Cordillera). Idealized models of the effect of chemical
mobility of elements on th'eir dispersion pattern in till-covered areas
(see Fig 11.3 for legend).................................................. 72
FIG 11.6 Idealized models for geochemical dispersion of
mobile elements in areas of stratified drift............................................ 73
FIG 11.7 Landform situation B. Complete deep weathered profile, moderate
relief........................................................................ 74
FIG 11.8 Hypothetical frequency distributions .......................................... 76
FIG 11.9 Profile distribution of Pb, Zn, and Sb ................................... 83
FIG 11.10 Graphical representation of lead, zinc, and antimony over mineralized
vein at 18 to 24-in. depth, Trench A................................ 83
FIG 11.11 Horizontal distribution of perchloric acid-extractable zinc as a function
of size fraction in soils over lead-zinc mineralization, Ar Ridaniyak,
Kingdom of Saudi Arabia.............................................. ’ 84
vii
FIG 11.12 Summary of maximum gold dispersion trend obtained in the minus
80 m fraction of wadi sediments for 8 gold prospects. 86
FIG 11.13 Grain-size distribution of some eolian materials from the Central
pediplain (Kingdom of Saudi Arabia)............................... 87
FIG 11.14 Stream sediment survey of River Sende, Sierra Leone. Data on -80
mesh fraction............................. 88
FIG 12.1 Cretaceous granitoids in the Canadian Cordillera ................................ 93
FIG 12.2 Distribution of mean Zn content in granitoids ...................................... 93 .
FIG 12.3 Simplified geology in the Goosley-Owen lake area ............................. 94
FIG 12.4 Distribution of As and Cu around the Bradina and
Goosley deposits ................................................................................ 94
FIG 12.5 Carlin District, Nevada. Locations of samples collected for analysis.
See Figure 12.5c for explanation of geologic symbols......................... 96
FIG 12.5c Carlin District. Geological Legend........................................................ 97
FIG 12.6 Example of ridge-and-spur soil-sampling pattern, Cebu Project,
Republic of Philippines. Data on -80-mesh fraction............................. 99
FIG 12.7 Example of base-of-slope sampling pattern, Lemieux District,
Quebec. Data on -1cm fraction....................................... 99
FIG 12.8 Spatial variation of anomalous soil samples ..................................... 100
FIG 12.9 Outlines of areas that contain anomalous values.............................. 101
FIG 12.11 Detailed geochemistry (Zn) in the vicinity of the Perkoa Deposit,
Burkino Faso. Values in ppm.............................................................. 102
FIG 12.10 Regional soil geochemistry (Zn) in the area around the Perkoa
Deposit, Burkino Faso. Values in ppm................................................. 102
FIG 12.12 Reconnaissance laterite geochemistry over the
Saddleback Greenstone Belt........................... 104
FIG 12.13 Diagrammatic cross-section in lateritic duricrust. 104
FIG 12.14 Comparison of Au anomalies in -6 + 2 mm lags and
-6 mm soils, Eastern Goldfields Province,
Western Australia................................................................................... 105
FIG 12.15 Zinc anomalies in soils, Buchans District............................................. 105
FIG 12.16 Empire Mining District, Colorado. Gold distribution in mull ash. Light
stipple, ash contains 0.2-0.59 ppm gold; heavy stipple, ash contains
at least 0.6 ppm gold. Heavy lines are veins.............. 107
FIG 12.17 Empire Mining District, Colorado. Gold distribution in soil (6-to 12-
inch depth). Light stipple, soil contains 0.2-0.59 ppm gold; heavy
stipple, soil contains at least 0.6 ppm gold. Heavy lines are veins. 107
FIG 12.18 Hemlo Gold District, Ontario. Williams Option - gold in humus. ... 108
FIG 12.19 Hemlo Gold District, Ontario. Williams Option - gold in basal till, -250
mesh fraction........................ 108
FIG 12.20a Water discharge of a river under ordinary conditions with normal
amounts of water............................................................ 110
FIG 12.20b Water discharge of a river during a major flood. Overbank
sedimentation takes place on the river plain................. 110
viii
FIG 12.21 A diagrammatic depiction of how geochemical dispersal patterns

for active stream sediment and overbank sediment may be
influenced by mineralization and sediment sources... 111
FIG 12.22 Hot nitric acid soluble Mo in overbank sediment, Norway. An
anomalous sample down stream from the Nordli deposit is indicated
with an arrow................................................................... 112
FIG 12.23 Geochemical results for the 1970-71 stream sediment survey. Que
River Prospect, Tasmania............................................... 114 -
FIG 12.24a Sample location map for Magruder Mine area,
Georgia............................................................................. 115
FIG 12.24b Downstream dispersion from zinc, copper, and lead in
minus 80-mesh stream sediments and oxide coatings,
Magruder Mine area....................................................... 115
FIG 12.25 Copper content of organic stream sediments in the Vehkavaara area,
Pajala district.................................................................... 116
FIG 12.26 Cut-away section of sample bailer for lake-sediment sampling. ... 117
FIG 12.27 Distribution of U in lake sediments in the vicinity of the Key Lake U-Ni
deposit, Saskatchewan................................................. 118
FIG 12.28 Uranium (ppm) in lake sediments near the Rabbit Lake uranium
deposit, Saskatchewan. Location of deposit shown by solid
triangle............................................................................. 118
FIG 12.29 Distribution of Zn (ppm) in nearshore lake bottom materials, Agricola
Lake area, N.W.T............................................................ 119
FIG 12.30 Gold in lake sediment, Cape Ray Fault area, Newfoundland............. 120
FIG 12.31 Gold in lake sediment, White Bay area, Newfoundland...................... 120
FIG 12.32 Simplified sketch of the reverse circulation drilling system............... 121
FIG 12.33 Idealized geochemical dispersion model for lodgement till................ 122
FIG 12.34 Diagrammatic overburden profiles in the Abitibi clay belt, Ontario. . 123
FIG 12.35a Results of reverse circulation drilling from Golden
Pond, Quebec.. 125
FIG 12.35b Results of the initial and follow up phases of reverse
circulation drilling at Golden Pond East, Quebec......... 125
FIG 12.36 Owl Creek Gold Mine, Timmins, Ontario. Gold values for "Older"
ti».......... 126
FIG 12.37 Owl Creek Gold Mine, Timmins, Ontario. Gold values for Matheson
till...................................................................................... 126
FIG 12.38 Murphy-Hoyle J. V., Timmins area, Ontario, Canada. Gold in till
anomaly plotted in relation to induced polarization/resistivity and
horizontal loop electromagnetic survey results............ 127
FIG 12.39 Gold distribution in the -63 m and nonmagnetic heavy-mineral
fraction of till associated with mineralization at Hemlo, Ontario. ... 128
FIG 12.40 Comparison of the Au distribution in the heavy-mineral concentrate
and the -63 m fraction of tills from Owl Creek, Ontario. 128
ix
FIG 12.41a Species distribution, geology along a transect across several zones
of Helichrysum leptolepis (DC) occurrences in Witvlei area, Namibia. 133
FIG 12.41b Species distribution, geology along a transect across several zones
of Helichrysum leptolepis (DC) occurrences in Witvlei area, Namibia. 132
FIG 12.42 Vegetation associations and Helicbrysum leptolepis (DC)
occurrences over one area near Witvlei, Namibia....... 131
FIG 12.43 Copper values in surface soil in area shown in Fig. 12.42........ 134
FIG 12.44 Sample sites and contoured Au values for the Standard Hillarea,
California. Gold in plants determined by INAA................................... 138
FIG 12.45 Base map showing site locations............................................... 139
FIG 12.46 Gold levels along traverse A .............................................................. 139
FIG 12.47 Variations in the gold content of a variety of organs in a balsam fir
growing over mineralization, sampled at varying heights................... 140
FIG 12.48 Comparison for poorly drained ground for spruce,
fir and B horizon soils.................................................... 141
FIG 12.49 Comparison for birch, alder, and B horizon soils ............................ 141
FIG 12.50 Comparison for freely drained ground for spruce,
fir, and B horizon soils................................................... 142
FIG 12.51 Comparison for alder and B horizon soils.......... 142
FIG 12.52 Elements in ash of outer scales of spruce bark, Nova Scotia: (a)
(above) gold, (b) (above) arsenic, (c) (next page) antimony, (d) (next
page) selenium ........................................................................... 144/145
FIG 12.53 Regional uranium concentration levels in lake waters -(a) with and (b)
without contaminated samples...................................... 149
FIG 12.54 (a) Radon and (b) uranium concentration levels in stream water
without contaminated samples .......................................................... 150
FIG 12.55 Map showing distribution of molybdenum in ground water, Pima
Mining District, Arizona................................................... 152
FIG 12.56 Correlation plots for groundwaters in Arizona. . . 153
FIG 12.57 The Track Etch Process. ;.................................................................. 155
FIG 12.58 Track Etch Sample Cup. .................................................................. 155
FIG 12.59 Radon contour map of the Lone Gull U discovery.............................. 156
FIG 12.60 Components of the Aurex Hg-vapor integrative detector.................... 157
FIG 12.61 Schematic representation of Hg-vapor measurement utilizing the
Aurex detector...................................................................................... 157
FIG 12.62 Plan of simplified geology and COS dispersion pattern in surface
microlayer at Johnson Camp, Arizona.......................... 158
FIG 12.63 CO2 content of soil air over mineralized breccia pipe, Arizona........... 159
FIG 12.64 Plot of log B. cereus................................ 160
FIG 14.1 Sample preparation safety curves for gold bearing materials............. 166
FIG 14.2 Size of sample required to contain an expected
20 particles of Au................................................................................. 167
FIG 14.3 Relation of Au grain size and grade for analysis............................... 168
X
FIG 14.4 A Heavy-mineral concentration procedure using a shaking table

followed-up by heavy liquid separation.......................... 173
FIG 14.5 Flow sheet from separation of sediment samples into magnetic (M)
and nonmagnetic (NM) fractions.................................... 174
FIG 14.6 Schematic representation of the ability to release metals .............. 177
FIG 14.7a Distribution of copper, molybdenum, and cold-extractable heavy
metals in soils, Sheslay area, British Columbia............ 178
FIG 14.7b Distribution of copper, molybdenum, and cold-extractable heavy
metals in soils, Sheslay area.......................................... 178
FIG 14.8 Schematic diagram of the classic Pb fire assay
procedure......................................................................... 184
FIG 14.9 Linear working range........................................................................... 190
FIG 14.10 Determination of As by generation of arsine...................................... 191
FIG 14.11 Schematic diagram of atomic absorption
spectrophotometers............................................................................. 193
FIG 14.12 Errors in uncorrected and background corrected
measurements of Pb............................................................................. 195
FIG 14.13 Apparatus for AAS determination of elements................................. 197
FIG 14.14 Cold vapor generation and determination of Hg
by AAS.................................................................................................. 200
FIG 14.15 A double beam mercury vapor meter................................................ 200
FIG 14.16 Analysis by AAS. Sensitivities with respect tocrustal abundances 201
FIG 14.17a Direct reading spectrograph with grating andD.C. arc source. . . . 202
FIG 14.17b Photographic spectrograph with prism............................................... 202
FIG 14.17c Inductively coupled plasma.................................................................. 203
FIG 14.17d Direct current plasma........................................................................... 203
FIG 14.18 Analysis of samples by DC-ES............................................................ 204
FIG 14.19 Analysis by ICP-AES. Sensitivities withrespect to crustal
abundances ........................................................................................ 205
FIG 14.20a X-ray spectrometer. Wavelength dispersive........................................ 208
FIG 14.20b X-ray spectrometer. Energy dispersive................................................ 208
FIG 14.20c X-ray spectrometer. Portable unit with isotope
source............................ 208
FIG 14.21 Analysis by XRF. Sensitivities with respect to crustal abundances 210
FIG 14.22 Detection limits by XRF at 95% confidence level. . 210
FIG 14.23 Analysis by INAA. Sensitivities with respect to crustal abundances. 211
FIG 14.24 A pH electrode and silver/silver chloride reference electrode............ 213
FIG 14.25 Some of the pathways for preparation, dissolution and analysis of
exploration samples.............................................................................. 215
FIG 15.1 Random and systematic errors............................................................. 217
FIG 15.2 Precision and accuracy.......................................................................... 218
FIG 15.3 Graphical plot of duplicate analytical data............................................ 220
FIG 15.4 Graphical plot of SRS analytical data.................................................... 221
xi
FIG 15.5 Model for insertion of control samples to determine analytical
accuracy and precision ............................................... 222
FIG 16.1 The stages of exploration geochemistry related to a
"House of Cards"........................................................... 225
FIG 16.2 Diagrammatic representation of the data integration process in
geochemical interpretation ..................................... 227
FIG 16.3 Map showing relation of Cu in dambos and outlet-stream sediments
to location of ore horizon, Baluba area, Zambia. Data on -80-mesh
fraction............................................................................. 229
FIG 16.4 Cu data obtained from the organic soil horizon samples at the end
of the second field season (25 x 100 m grid).............. 230
FIG 16.5 Examples of sets of symbols used in point symbol
geochemical maps........................................................ 231
FIG 16.6 Examples of point system and worm diagram
representations ............................................................. 232
FIG 16.7 Sn content of -28 + 65 mesh soils.................................................... 234
FIG 16.8 Sn content of -80 mesh drainage sediments................................. 235
FIG 16.9 Nordkallott Project. Ni content of heavy mineralfraction of Tills . . 236
FIG 16.10 Distributions of Nb in stream sediments....................................... 238
FIG 16.11 Distribution of Be in stream sediment, Ishashaarea, south-western
Uganda. (A) Indicates position of undisturbed pegmatite discovered
by sediment sampling........................................................................... 238
FIG 16.12 Variation in nickel content of stream sediments derived from different
areas of basic rocks...................................................... 239
FIG 16.13 Example of point symbol usage in a regional map.............................. 240
FIG 16.14 Gold in Till (-63 fraction) Geochemical Atlas of Finland.................... 242
FIG 16.15 Multivariate point-symbol maps: (a) pie diagram; (b) pseudo
histogram; and (c) windrose representation................ 243
FIG 16.16 Stream sediment data displayed spatially in the form of Kleiner-
Hartigan trees................................................................. 243
FIG 16.17 Molybdenum distribution in soils as shown by
sampling at a constant depth (mainly A horizon) and uniformly
from the B horizon.......................................................... 244
FIG 16.18 Rectilinear soil sampling grid, Petolahti, Finland .............................. 244
FIG 16.19 Contour map for zinc (ppm) in 2156 B-horizon soil samples, Key
Anacon, New Brunswick, Canada. Sample stations at 100 ft (30 m)
along lines 400 ft (122 m) apart........................................................... 245
FIG 16.20 Example of moving window in two successive
patterns ........................................................................ 246
FIG 16.21 Contour map for zinc (ppm) in B-horizon soil samples, Key Anacon,
New Brunswick, Canada, averaged over 602 non-overlapping 400 x
400 ft (122 x 122 m) blocks........................................... 247
xii
New Brunswick, Canada averaged over 300 non-overlapping 600 x
600 ft (183 x 183m) blocks............................................ 248
New Brunswick, Canada, averaged over 186 non-overlapping 800 x
800 ft (244 x 244m) blocks............................................ 248
FIG 16.24 Examples of 8 nearest neighbors to a central grid
node................................................................................ 249
FIG 16.25 920 lake sediment samples in a portion of NTS sheet
64N, Kasmere Lake Sheet.................................................................... 249
FIG 16.26 Contours of uranium in lake sediments............................................... 250
FIG 16.27 Distribution of cell averaged Zn in stream
sediments........................................................................ 251
FIG 16.28 Distribution of gap filled unsmoothed Zn in stream
sediments........................................................................ 251
FIG 16.29 Geochemical Atlas of Finland Ba contents in -62 m fraction
of till................................................................................ 254
FIG 16.30 Geochemical Atlas of Finland Ni and Cu in -62 m fraction of till. . . . 254
FIG 16.31 Geochemical Atlas of Finland Alignment of geochemical patterns
and significant mineral deposits........................................................... 255
FIG 16.32 Distribution of gold and pathfinder elements in southwest Scotland:
(a) gold in pan concentrates; (b) arsenic; (c) antimony; (d)
bismuth................................................................................................... 256
FIG 16.33 Plate 2. Image analysis of geochemical data for south west
Scotland............................................................................................... 257
FIG 16.34 Samples localities, streams and catchment basins for a study area. 258
FIG 16.35 Maps showing (a) observed and (b) residual zinc values................... 259
FIG 16.36 Maps showing (a) Location of sample sites and (b) Spatial
distribution of radon in lake bottom waters of "Dop" Lake............... 261
FIG 16.37 Hypothetical soil profile across a mineralized zone............................ 264
FIG 16.38 Hypothetical soil profile illustrating spurious anomalies related to
geological and geomorphological complexities........... 265
FIG 16.39 Development of a break of slope anomaly, etc. in mountainous
areas. Anomaly may have hydromorphic and clastic components. 265
FIG 16.40 Overlap of values in background and ore populations (derived as
random samples from two log-normally distributed populations). . . 267
FIG 16.41 Definition of box-plot as a graphical display ..................................... 268
FIG 16.42 Empiracial distribution of Al and Mn displayed by EDA techniques . 268
FIG 16.43 Log probability plot of (a) a single background population and (b) of
two combined populations .......................................... 269
FIG 16.44 Probability graphs (cumulative curves) for Zn and Cu in B horizon
soil samples over the Daisy Creek strata-bound copper prospect,
western Montana. Cumulated from high to low values . 270
FIG 16.45 Probability graph of Cu in soils......................................................... 271
xiii
FIG 16.46 Frequency curves for (a) normal, (b) lognormal, (c) normal with
outliers and (d) multipopulation distributions................ 272
FIG 16.47 Distribution of (x ± 1s)(x ± 2s), (x ± 3s) data for a normal
population......................................................................... 274
FIG 16.48 Relationship of mean, median and mode as determined by direction
of skewness................................................................ • • 275
FIG 16.49 Kurtosis nomenclature for peaked, normal and flat (bell-shaped) data
distribution............................................................................................... 275
FIG 16.50 Log10 transformed (a) vs untransformed (b) Mo data from a granite
body .................................................................................................... 276
FIG 16.51 Northern Fennoscandia Mineral Resource Assessment Map .......... 278
FIG 16.51 Legend (continued) .................................................................. 279
FIG 16.52 A diagrammatic representation of some typical factors which
influence the selection and rating of significant geochemical
patterns................................................................................................... 281
xiv
LIST OF TABLES
TABLE 5.1 Geochemical characteristics of selected elements. • • • • ................... 9

TABLE 5.2 Average abundances (ppm - except where otherwise indicated) of
selected elements in some common rock types..... 10
TABLE 5.3 Associated elements (pathfinders) useful in
ore-typing..................................................................................................
TABLE 6.1 Relative mobilities of elements in the surficial environment.................. 20
TABLE 7.1 Types of climatic weathering................................................................... 30
TABLE 7.2 Plant associations.............................. 32
TABLE 8.1 Characteristic zoning patterns around some copper and molybdenum
porphyry deposits. Zoning given is from the deposit outward. ..... 44
TABLE 8.2 Summary of change to lower case Local-scale geochemical
responses in bedrock around some volcanic-and sediment-hosted
massive sulfide deposits from recent literature.............. 46
TABLE 8.3 Summary of local and mine scale geochemical response from some
elements in host rocks around massive sulfide deposits in
Australasia, Europe and North America.................................. 47
TABLE 8.4 Characteristic geochemical responses for some gold deposits. .... 51
TABLE 10.1 Possible roles of some common geochemical survey sample media
at various stages of mineral exploration......... 62
TABLE 11.1 Parameters to be derived from a properly planned orientation
survey............................• • • •................ : ' ' ’;............. ' 78
TABLE 11.2 Major factors to be evaluated by an orientation survey in residual soil
of transported overburden................... • • • •................... 79
TABLE 11.3 Check list of factors to be optimized by an orientation survey
preparatory to rock sampling.......................... 80
TABLE 11.4 Check list of factors to be optimized and evaluated by an orientation
survey preparatory to drainage sampling...... 81
TABLE 11.5 Check list of factors to be optimized and evaluated by an orientation
survey preparatory to biogeochemical sampling............ 82
TABLE 12.1 Summary of elements................................. .••••;.............................. 92
TABLE 12.2 Checklist for the organization of a geochemical soil survey.............. 109
TABLE 12.3 Seasonal changes in the gold content of ashed
alder twigs and leaves.......................... ••••••........................... :'' 135
TABLE 12.4 Basic rules to be applied at each sampling station when conducting
a biogeochemical survey................. 137
TABLE 12.5 A summary for the application of hydrogeochemical
prospecting in different environments............ .............. 147
TABLE 14.1 Potential contaminants from laboratory materials............................... 170
TABLE 14.2 Comparison table of U.S.A., Tyler, Canadian, British, French, and
German standard sieve series............. ........................ 172
TABLE 14.3 Classification of some dissolution techniques useful in
exploration geochemistry............................................... 176
XV
TABLE 14.4 Variation of Cr from different lithologies with five digestion

procedures....................................................................... 180
TABLE 14.5 Accuracy of acid digestions ............................................................... 181
TABLE 14.6 Comparison of six stream-sediment analyses for Ni........................... 182
TABLE 14.7 Decomposition techniques for some resistantminerals.................. 182
TABLE 14.8 Hypothetical examples of metal extracted (ppm) by "Total" and
"Partial" methods from background and anomalous samples........... 185
TABLE 14.9 Preferred analytical methods and analytical detection limits (ppm) for
solid state geological materials at a typical major commercial
geochemical laboratory (Chemex)................................. 188
TABLE 14.10 Some colorimetric reagents used in analysis of
geochemical samples..................................................... 192
TABLE 14.11 Correction for background absorption in lead analysis
of a synthetic rock solution............................................ 195
TABLE 14.12 Some interferences in the determination of trace elements in
geological matrices by flame atomic absorption spectrophotometry. 196
TABLE 14.13 Application of hydride generation to analysis of geochemical
samples by atomic absorption spectrophotometry...... 198
TABLE 14.14 Characteristics of some specific ion electrodes (based on Orion
Research literature) ..................................................... 213
TABLE 14.15 Evaluation of performance of analytical methods commonly used
in exploration geochemistry........................................... 216
TABLE 17.1 Common failings encountered in follow-up of geochemical soil
surveys............................................................................ 284
BIBI IOTEO
CELSQ L. PALACIOS CAPft/LLQ
1. INTRODUCTION
Although geochemistry is being used appropriately within many company

exploration projects, more efficient and cost effective application could probably be often
achieved if closer attention were given to certain critical fundamental principles. To assist
attainment of this objective, the Geochemical Department will be organizing periodic
geochemical workshops. It is intended that these will enable review of the fundamentals
of exploration geochemistry as well as provide forums within which Newmont’s current
geochemical practices can be objectively assessed, and possible improvements
suggested and discussed.
This manual is designed to provide background material for the workshops and will
be distributed to all participants. Obviously it is neither possible nor even desirable to
cover the entire field of exploration geochemistry in this context, but basic principles and
potential problem areas are briefly reviewed. The more rarely used methods, such as
stable and radioisotope analysis, fluid inclusion analysis, laser induced luminescence, etc.,
are not discussed. Details of these, together with additional information on the more
common methods can be found in specialist publications.
This manual begins with a brief discussion of the history, basic principles and role
of geochemical exploration. Subsequent sections provide more detailed discussions of
the primary components of successful programs, including conceptual models, program
design, technique selection, quality control, field and laboratory procedures, interpretation,
follow-up, and last, but by no means least, report writing. A fairly extensive list of up-to-
date and useful references is provided in the final chapter.
Geochemical Department personnel are always available to assist in the planning

and budgeting of exploration programs, and the selection and/or development of
appropriate geochemical techniques. Consultation at an early stage could sometimes
help prevent crises developing down the foad.
2
2. DEFINITIONS
The objective of exploration geochemistry, or geochemical prospecting, is to apply

the principles governing the distribution and migration of elements in the natural
environment to the search for mineral deposits. Success is based on a fundamental
premise, which is substantiated by extensive empirical data, that the chemical composition
of certain constituents of the natural environment in the vicinity of a mineral deposit differ
from those of similar constituents where there is no mineral deposit. Detection of these
differences requires systematic measurement of one or more chemical or chemically
influenced properties of a naturally occurring material. The property measured is most
commonly the trace concentration of some chemical element or group of elements;
however, it may sometimes also include molecular and isotopic compositions and
bacterial counts. The naturally occurring material may be rock, soil, stream sediment,
glacial sediment, surface water, groundwater, vegetation, microorganisms, animal tissues,
particulates, or gases including air.
Although exploration geochemistry involves many of the basic principles of the

science of geochemistry, it encompasses a far wider range of practical concerns. A
geochemical exploration program comprises a number of critical phases (including design
and planning, sampling, sample preparation, analysis, and interpretation), the relative
importance and interdependence of which are clearly illustrated by the "house of cards"
(Fig. 2.1). Each successive independent function is wholely dependent on those
preceding so that errors or inadequacies in one will negatively effect all those that follow.
For example, no matter how accurate and precise the techniques used for analysis or
how advanced the statistical treatments and computer programs used for data handling
and interpretation, problems resulting from inadequate or improper sampling and/or
sample processing cannot be overcome.
Exploration geochemistry is of course only one of a cost effective number of

techniques available to the exploration geologist which can assist in the location of
concealed ore deposits, and also provide efficient coverage of large areas. It does,
however, possess certain potential advantages over many others in that it generally
depends on direct measurement of target or closely associated elements, rather than
indirectly related phenomena. It must be emphasized that geochemical prospecting, like
other mineral exploration techniques, is primarily a geological activity and must always be
applied and interpreted within a sound geological framework. To do otherwise is to invite
failure!
3
FIG 2.1 The stages of exploration geochemistry related to a 'House of Cards'.

(Modified after Lavin. Grant, and Nichol, 1987)
4
3. BRIEF HISTORY
It is clear from historical records that the principles of geochemical exploration have
been applied in prospecting over several thousands of years. The prospector who
panned for gold and traced the colors upstream to a bedrock source used mineralogical
observations in a similar way to the modern geochemist, who utilizes careful sampling and
sensitive chemical analyses to outline patterns of dispersion in the surficial environment.
Geobotanical indicators were recognized as early as the eighth and ninth centuries (Boyle,
1967). The mid-sixteenth century writings of Biringuccio and Agricola describe the
analysis of natural waters, springs, and their residues (Hawkes, 1957; Boyle, 1967).
Levinson (1974) records that modern methods of exploration geochemistry were

first used in the early 1930's in the Soviet Union. Shortly thereafter the methods were
applied in the Scandinavian countries, particularly Sweden.
In North America, the earliest geochemical surveys were carried out between 1938
and 1940 by Lundberg in Newfoundland and in 1944 by Warren in British Columbia
(Brummer et al., 1987). The first comprehensive geochemical exploration studies
commenced at the US Geological Survey under the leadership of H. E. Hawkes in 1947
and at the Geological Survey of Canada with R. W. Boyle in the early 1950's. The
Geochemical Prospecting Research Center was established at the Imperial College of
Science and Technology in London in 1954 under the direction of J. S. Webb. In France,
research related to exploration geochemistry began in 1955.
The successful application and adaptation of geochemical exploration techniques

in all parts of the world, the rapid development of analytical and computer technology,
and improvements in field transportation have made geochemistry one of the more cost
effective and widely applied exploration disciplines. Analytical capability is such that
relatively rapid, sensitive analysis can be achieved for virtually all metals of economic
interest. Continuing research is expanding our established capability to cost-effectively
detect and interpret dispersion patterns related to mineral deposits in a wide variety of
often complex environments.
Through multi-element analysis, geochemical data can reveal multi-parameter

signatures related to distinct geological units and processes. This capability, when
applied to rock samples, permits geological correlation as well as the more precise
delineation of otherwise invisible alteration features related to mineralization. When
applied to soil and other types of samples, multi-element data can help outline major
geological units and, in some cases, identify the presence of mineralization buried under
extensive cover (Hoffman, 1987).
5
4. INFORMATION SOURCES
The body of technical literature in the English language dealing with exploration
geochemistry has grown dramatically over the years, particularly since the founding in
1970 of the Association of Exploration Geochemists (AEG). This Association’s official
technical publication (the Journal of Geochemical Exploration - JGE), and newsletter
(EXPLORE), are excellent sources of useful information, especially when used in
conjunction with the AEG Bibliography volumes (Hawkes, 1982, 1985, and 1988). The
proceedings of various international (generally biennial) and regional symposia organized
since 1970 by the AEG, are also useful references. Initially these were published as
individual volumes by the local sponsoring organizations, but more recently have been
presented in special volumes of the JGE:
1966 - Ottawa, Canada (Cameron, 1967)

1968 - Golden, U.S.A. (Canney, Bloom, and Hansuld, 1969)
1970 - Toronto, Canada (Boyle, 1971)
1972 - London, England (Jones, 1973a)
1974 - Vancouver, Canada (Elliot and Fletcher, 1975)
1975 - Fredericton, Canada (Govett, 1976)
1976 - Sydney, Australia (Butt and Wilding, 1977)
1978 - Denver, U.S.A. (Watterson and Theobald, 1979)
1980 - Hannover, Germany (Rose and Gundlach, 1981)
1982 - Saskatoon, Canada (Parslow, 1983)
1983 - Espoo, Finland (Bjorklund, 1984)
1985 - Toronto, Canada (Garrett, 1987)
1987 - Orleans, France (Jenness, 1989)
1989 - Rio de Janeiro, Brazil (Rose and Taufen, 1991)
For many years the Institution of Mining and Metallurgy (London), and also occasionally
the Canadian Institute of Mining and Metallurgy, have organized symposia on prospecting
techniques. The main emphasis has generally been on geochemical exploration in
glaciated terrain:
1973 - Trondheim, Norway (Jones, 1973b)

1975 - Edinburgh, Scotland (Jones, 1975)
1977 - Helsinki, Finland (IMM, 1977)
1979 - Dublin, Ireland (IMM, 1980)
1982 - St. John’s, Newfoundland (Davenport, 1982a)
1984 - Glasgow, Scotland (IMM, 1984)
1986 - Kupio, Finland (IMM, 1986).
1988 - Halifax, Nova Scotia (MacDonald, 1988)
6
Some attention has recently also been given to arid terrain:
1984 - Rabat, Morocco (IMM, 1985)

1988 - Perth, Australia (AIMM, 1988).
Over the years the Journal of Exploration Geochemistry has included a number of
extremely useful volumes dealing with conceptual geochemical exploration models for a
variety of weathering environments. These discuss:
(i) The Canadian Cordillera and Canadian Shield - (Bradshaw, 1975);

(ii) Norden (Scandinavia and Greenland) - (Kauranne, 1976a);
(iii) The Basin and Range Province of the Western United States and Northern
Mexico - (Lovering and MacCarthy, 1978);
(iv) Australia - (Butt and Smith, 1980).
The JGE has also produced a number of other useful special volumes, including:
(i) Exploration Geochemistry in the Appalachians (Govett, 1976);

(ii) Geochemical Exploration in Arid and Deeply Weathered Terrain - (Davy and
Mazzucchelli, 1984).
Thorough English language treatments of the basic principles of exploration

geochemistry have been produced, amongst others, by Rose, Hawkes and Webb (1979)
and Levinson, McCammon and Hitchon, (1980).
Anyone involved in exploration geochemistry would be well advised to consider

becoming a member of the Association of Exploration Geochemists. The annual dues
are low and the publications received are of a generally high standard. They contain
numerous useful case histories, review articles, descriptions of new techniques, etc., and
should, in any case, be a prominent component of any mineral exploration library.
7
5. BASIC PRINCIPLES
5.1. Geochemical Environment
Geologically and geochemically the earth constitutes a dynamic system in which

matter is moved from one place to another, and changed in form and composition by a
variety of processes, including melting, crystallization, erosion, dissolution, precipitation,
vaporization and radioactive decay. The geochemical cvde (Fig. 5.1) diagrammatically
illustrates these complex physicochemical changes and the variety of pathways that earth
material and their contained
elements follow in response to
these processes. It conven
iently defines the major deep-
seated and surficial geo
chemical environments which
are distinguished by gross
differences in pressure,
temperature and chemistry.
The deep-seated environ

ment extends downward from
the lowest levels reached by
circulating surface waters to the
deepest levels at which normal
rocks can be formed. It is
characterized by high tempera
ture and pressures, restricted
circulation of fluids, and
relatively low free-oxygen
content (Rose, Hawkes and
Webb, 1979). Magmatic and
metamorphic processes pre
dominate. In contrast, the
surficial environment o f
weathering, erosion and
sedimentation at (or near) the
surface of the earth is generally
characterized by low tempera
FIG 5.1 Geochemical Cycle.
tures, nearly constant low (Rose, Hawkes, and Webb, 1979)
pressure, free movement of
aqueous solutions, and
abundant free oxygen, water
and carbon dioxide.
8
The great majority of geochemical prospecting programs have been concerned
with the surficial environment as this is the most readily accessible. However, improved
exploration technology and the exhaustion of near surface exploration potential,
particularly in some of the more developed mineral districts, is now resulting in greater
attention being given to the deep-seated environment.
Geochemists have long recognized systematic behavior amongst certain element

groups and established classification schemes based on observed natural groupings
(Goldschmidt, 1923 and 1954, and Table 5.1). These are:
(i) siderophile, affinity for iron, concentrated in the Earth’s core;

(ii) chalcophile, affinity for sulfur, concentrated in sulfides;
(iii) lithophile, affinity for silicates, concentrated in the Earth’s crust;
(iv) atmophile, present as gas in the atmosphere;
(v) biophile, occurring as biological material.
In the recent past, modified versions of Goldschmidt’s classification have been

developed which cover more of the observed complexities (e.g. Table 5.1). In practice
these can assist the recognition of geochemical environments with which specific mineral
deposit types might be associated.
5.2. Characteristic Element Abundances and Associations
Individual rock types display characteristic average element abundance levels and
associations (Table 5.2). For example ultrabasic rocks generally contain relatively high
Co, Cr and Ni and low Ba, F, Ga, Pb, Ti, TI compared to other common rock types. On
the other hand basic rocks are characterized by relatively high Ag, Cu, Ti, V. The
contrast between the element abundance levels in adjacent major rock units is sometimes
so pronounced that regional geochemical concentration patterns related to bedrock, or
even derived surficial material (e.g. soils, and stream sediments), closely reflect local and
regional geology (Figs. 5.2a, 5.2b, and 5.3). The fact that some rock types contain
relatively high concentrations of certain elements which are significant in geologic, but not
economic terms, obviously needs to be taken into account when interpreting data from
geochemical exploration programs.
In exploration geochemistry the normal element abundance level in an

unmineralized earth material is commonly referred to as the geochemical background for
that particular material. However, as element distribution in specific earth material (e.g.
rock, soil, stream sediment, etc.) is rarely uniform, even when it is derived from an
apparently homogeneous source, it is more realistic to visualize background as a range
rather than an absolute value. Any departures from normal ranges, be they positive or,
more rarely, negative, are viewed as anomalous. The upper and lower limits, above or
below which, respectively, values are considered to be anomalous, are defined as
thresholds.
9
GEOCHEMICAL CHARACTERISTICS OF THE ELEMENTS
Goldschmidt's clasS'f'Cahon $zade<??kY-K?'d?5s Cla??iliC;il.Qn (1.972)
Siderophile Au Siderophile Au
Ge Sn (Pb)
C P (As)
Mo (W)
Re
Fe Co Ni Fe Co Ni
Ru Rh Pd Ru Rh Pd
Os Ir Pt Os Ir Pt
Chalcophile Cu Ag Sulpho- Cu Ag
Zn Cd Hg chalcophile (Zn) (Cd) Hg
Ga In T1
(Ge) (Sn) Pb
As Sb Bi As Sb S Se Te (P)
(Mo)
S Se Te Oxy - Ge Sn Pb
Fe (Co) (Ni) chalcophile Ga In T1
(Ru) (Pd) (Pt) (Zn) (Cd) (P)
Lithophile U Na K Rb Cs Lithophile - (Li) Na K Rb Cs

in a
Be Mg Ca Sr Ba narrow (Be) Mg Ca Sr Ba
Ra sense
(Zn) (Cd)
B Al Sc Y Al Si
La Cs Pr Nd Sm
Eu Gd Tb Dy Ho Pegmatophile B V Zr Mn transition
Er Tm Yb Lu elements
Ac Th Pa U Np
Pu Am Cm
Ga (In) (Tl) Sc Y
C Si Ti Zr Hf La- Lu
(Ge) (Sn) (Pb) Th U (Hf)
V Nb Ta Nb Ta W Mo
P As Sedimentophile B
0 Cr W Mn C
(Fe) (Co) (Ni) (N)
H F O Br 1 FO (Br) (1)
Atmophile H C N> Atmophile H N

0 1 Hg He Ne Ar
He Ne Ar Kr Xe Rn
Kr Xe Rn
Biophile H C N OP
(Na) (Mg) S a
(K) (Ca) (Fe)
(B) (F) (Si)
(Mn) (Cu) (1)
TABLE 5.1 Geochemical characteristics of selected elements. (Smith & Hallberg, 1982)
10
AVERAGE ABUNDANCES
OF SELECTED ELEMENTS IN SOME COMMON ROCK TYPES
Crustal Ultra- Basic Intermed. Acid Slates Sand- Carbonates

Abundance basic & stone &
Shales Limestones
Au .004 .006 .004 OCX .004 oox OOX OOX

Pt' .005 .12 .02 ? .008
Fe 5.6% 9.4% 9.8% 3.6-58% 2.7% 4.7% .98% .38%
Cu 55 10 87 5 20 45 X 4
Pb 13 1 6 12 20 20 7 9
Zn 70 50 105 130 60 95 15 20
Ni 75 2000 130 4 8 68 2 20
Co 25 150 48 1 5 19 .3 .1
As 1.8 1 2 1.4 1.5 13 1 1
Sb .2 .1 .2 .X .26 1.5 OX .2
Bi .17 ?.001 .15 .1 .18 ? ?
Mo 1.5 .3 1.5 .6 1 2.6 .2 .4
Ag .07 .06 .11 OX .05 .07 OX •OX
Se .05 .05 .05 .05 .05 .6 .05 .08
S 260 300 300 300 400 2400 240 1200
n .45 .06 .21 1.4 1.5 1.4 .8 OX
Sn 2 .5 1.5 X 3 4 X .X
Ge 1.5 1.5 1.3 1 .4 1.6 .8 .2
Ga 15 1.5 17 20 20 19 12 ?<1
U 20 X 17 28 30 66 15 ?5
Be 2.8 X 1 1 5.5 3 X X
Ba 425 .4 330 600 830 580 XO 10
Ti 5700 .03% 1.0% .35% .23% .46% .15% .04%
Cr 100 1600 170 20 4 90 35 11
V 135 40 250 30 40 130 20 20
Zr 165 45 140 500 200 160 220 19
Mn 950 1620 1500 850 600 850 XO 1100
Th 10 .004 2 13 17 12 1.7 1.7
U 2.7 .001 1 3 3.5 3.7 .45 2.2
Nb 20 16 19 35 20 11 .OX .3
Ta 2 1 1.1 2.1 . 35 .8 OX OX
w 1.5 .8 .7 1.3 1.5 1.8 1.6 .6
B 10 3 5 9 15 100 35 20
F 625 100 400 1200 800 740 270 330
*4
XO believed to be in the range 10 to 90
\O ■Vq X 1 to 9
W ■’ .1 to .9
OX ,ot to .09
1 elements in the platinoid group.

Values are in ppm except where shown as percent (%)
except where otherwise indicated) of selected elements

in some common rock types. (Smith & Hallberg, 1982)
11
FIG. 5.2a Location map showing geology, selected mineral occurrences and study areas. Geology
after Geological Survey of Sierra Leone. (Nichol, James & Viewing, 1966)
12
FIG. 5.2b Nickel content, ppm, in -80 mesh fraction of stream sediments. (Nichol, James &
Viewing, 1966)
13
FIG 5.3 Relationship between geology and the pattern of nickel in residual soil, Nguge region,
Tanzania. (Colluvial and alluvial overburden occur flanking the main rivers.) (Rose,
Hawkes & Webb, 1979)
14
5.3. Element Associations of Mineral Deposits
Mineral deposits, like other more common geological units, frequently display
characteristic multi-element associations (Tables 5.3 and 5.4). These are sufficiently
consistent to enable prediction of the element suites to be expected in different types of
mineralization, and conversely, to assist in the interpretation of geochemical exploration
data.
In exploration geochemistry, use is frequently made of target (i.e. potentially

exploitable) elements as indicators of the presence of possibly significant mineralization.
However, in some situations this either is not possible or not particularly effective. Instead
attention is given to associated (i.e. pathfinder) elements of little or no economic
significance, which may have useful features (e.g. mobility, immobility, easier analysis,
particularly low detection limits, low analytical costs, etc.). In gold exploration, despite
fairly recent improvements in the cost, sensitivity and reliability of gold analytical methods,
considerable emphasis is still given to commonly associated elements such as As, Hg,
Sb, etc., which behave very differently to gold in the supergene environment.
15
Associated elements (pathfinders) useful in ore-typing
Type of deposit Major components Associated elements
Magmatic deposits
Chromite ores (Bushveld) Cr Ni, Fe, Mg
Layered magnetite (Bushveld) Fe V, Ti, P
Immiscible Cu-Ni-sulfide Cu, Ni, S Pt, Co, As, Au
(Sudbury)
Pt-Ni-Cu in layered
intrusion (Bushveld) Pt, Ni, Cu Cr, Co, S
Immiscible Fe-Ti-oxide
(Allard Lake) Fe, Ti P
Nb-Ta carbonatite (Oka) Nb, Ta Na, Zr, P
Rare-metal pegmatite Be, Li, Cs, Rb B, U, Th, rare earths
Hydrothermal deposits
Porphyry copper (Bingham) Cu, S Mo, Au, Ag, Re, As, Pb,
Zn, K
Porphyry molybdenum
(Climax) Mo, S W, Sn, F, Cu
Skam-magnetite (Iron Springs) Fe Cu, Co, S
Skarn-Cu (Yerington) Cu, Fe, S Au, Ag
Skarn-Pb-Zn (Hanover) Pb, Zn, S Cu, Co
Skarn-W-Mo-Sn (Bishop) W, Mo, Sn F, S, Cu, Be, Bi
Base-metal veins Pb, Zn, Cu, S Ag, Au, As, Sb, Mn
Sn-W greisens Sn, W Cu, Mo, Bi, Li, Rb, Si, Cs,
Re, F, B
Sn-sulfide vein Sn, S Cu, Pb, Zn, Ag, Sb
Co-Ni-Ag vein (Cobalt) Co, Ni, Ag, S As, Sb, Bi, U
“Epithermal” precious metal Au, Ag Sb, As, Hg, Te, Se, S, U
Mercury Hg, S Sb, As
Uranium vein U Mo, Pb, F
Copper in basalt (L. Superior
type) Cu Ag, As, S
Volcanogenic massive-sulfide
Cu Cu, S Zn, Au
Volcanogenic massive-sulfide
Zn-Cu-Pb Zn, Pb, Cu, S Ag, Ba, Au, As
Au-As-rich Fe formation Au, As, S Sb
Mississippi Valley Pb-Zn Zn, Pb, S Ba, F, Cd, Cu, Ni, Co, Hg
Mississippi Valley fluorite F Ba, Pb, Zn
Sandstone-type U U Se, Mo, V, Cu, Pb
Red-bed Cu Cu, S Ag, Pb
Calcrete U u V
Sedimentary types
Copper shale (Kupferschiefer) Cu, S Ag, Zn, Pb, Co, Ni, Cd, Hg
Copper sandstone Cu, S Ag, Co, Ni
TABLE 5.3 Associated elements (pathfinders) useful in ore-typing. (Rose, Hawkes & Webb, 1979
16
ELEMENT ASSOCIATIONS OF SOME MINERAL DEPOSITS.
Siderapfule Choice*bile
Suipne-choicophlto Oiy-chaleophie
- i"*”!
I" st. < » ] cr i i- j -o ' ; s. 1 t. Ual«( s TI 1 $n • Co to(c)
Coid dopotlis Illi 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1

1 Ouom-pebble cong<om.'Ole 1 1 1
2 Ouarti voire, i.KtOi vo<ns. (lock ~o«k>
J 5«orn typ. • 1 1 t 1 1 1 A • A • 1
4 CNsseminoled Au deposits •l*l*l*l*l*l*l*l*l |A|*|A|A|A|* 1*1 1
Illi lllllllllllllll 1 1 1
Ptolinvm deposits
5 In Ml-Cu ores • 1 • 1 1 1 • « 1 • 1 • • A 1 A 1 1 1 • A > A 1 A 1 « 1 A '
4 ■ogmeWiC pyrotonile • 1 A 1 j • j • • 1 1 A 1 1 1 1 • 1 A ' A 1 A ' • 1 1 1
Ml-Cu swipMde deposiit 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

7 Mosstvo 4 4nMmi"o<td • 1 • 1 1 1 • • |O|O|*|«|«|O|A| I 1 1 • 1 • 1 • 1 1 • 1 O 1 I
Illi lllllllllllllll 1 1 1
Cr deposits
8 Cbrom*l« ' A ' 1 1 ******* ' * ‘ 1 1 1 1 * 1
Coop*' depon's •«€. lllllllllllllll 1 I 1

9 Moil"! Cu-Zn. Pb-Zn
10 Porphyry Cu A | • • A A | a | 1 1*1*1 | 1 1*1*1 1*1^1
1 i Moll.. Cu Ir botott *1*1*1 1 I * 1 1 1 I 1 1*1 1 1*
12 Cu-shale (Whit, Pino) 1 A * 1 A ' 1 1 1 1
15 Cu-sbOl. (KupforscNot.r) 1 1 • 1 1 • 1 • 1 • 1 1 • 1 • 1 • 1 1 • 1 1 1 1
14 Cu. '*d beds 1 1 • 1 1 •l*<*l*l*l*l*l 1*1 1 • 1 • 1 • 1 ' • ' 1 1 1
AIAIAIaIaIAIaIAIAI Isbldtl 1*1 i
14 Zn in corbo not. «<<• (Mmiis.ppi volley) i i i i • * | • I • 1 O | 0 | IQ) I • | I | A | | |OI
1’ Vein * fspiacemenl Zn deposits i i • *1*1*1 1 1 1 1 I I 1 |*l I I I
19 T-ankllhi'.-willorr l.-jlncil. deposits AAA A
19 Sm3t'son>*o. calamine. elll.m.le deposits
20 *t> depos.lt. »•• above depot.ft. generally • A i A 1 A * • 1 A A 1 A A A A A A • 1 • 1 • 1 •
21 Matteo Ag dopOtNS t 1 I
1 1 1 1 1 I 1 1 1 1 1 1 1 ' 1 1
Tim deposits eic i i i i 1 1 1
22 Sn —bearing pegmatites iiii 1 1 1 1 1 • 1 1*1 1 1*1 1 1 1 1 1*1 1
23 Mo n quart! votni. pegmatites a *
24 Sn-skoms .< i• i . i 2 ! i! i! i i < i i. . 1 J 1 A 1 *
• i i i i 7 i i i i i i i i i i •
2* CassHeriio pipet
27 Aloes' $r depos.U 1 1 1 1 1*1 1
t i i i i i i ! i i i ! i ! i
Otho- depee.it
28 ueneeol p.gmcli*. dapot.lt 1 1*1 1 • • •
29 W in pegmol l*t A Oplilet *i i i * i i*i i i*i
50 ■ r tkorn. • • ! ! • 1 • A A A A • I « 1 1 1 - 1 _ ' 1 1 1^
Ji W reins «.»h auom gangue • • 1 • 1 ' '• 1 1 « A ' A 1 A 1 *
32 Mb m granite A syenif.c pegmatites 1 1 1 1 1 1 • 1 « 1 1 1 1 1 1
33 Mb -» olb.’e g'an les 1 1 • 1 1 llllllllll|l| 1 • 1 1
34 Mb m co'bono'Hst • 1 • • * | • | | | | | | | O | . , •
33 Mb M eluvial * Ollvvi.1 dtMlill
38 Oroninlle tn .eni, pipes, lodes (Type 11 ■ * 1 1*1 1*1 I*
37 Uraninite m veins. p.pos, lodes (Typo 2) ■
38 Sarditone 0 depaslis • A e e e . e n a h a r. n a 1 A ' A
39 U In pyrit.c a-om pebb1* conglomerates a 1 i l • 1 a 1 1 1 1 1 • 1 * 1 ’A 1 1 1
40 Ahosponfe deposits of U A ■Ct iiii • • 1 • 1 • 1 1 • 1 1 1 1 1 • 1 • 1 • 1 1 1 1 1 1
(o) ■Io IIn urn g>Oup elements.

(t>) AIM SldorophWe
<c) Also pog'vto'opni'o.
(aj Alto etmophile.
(•> oorfh elomenfs.
FIG 5.4 Element associations of some mineral deposits. (Smith and Hallberg, 1982)
17
SUMMARIZED LARGELY FROM BOYLE (1974)
Ulhophii*
PagmoiopAHa $«4lrran'opMifl
li ' »b c« Sr ** s< n C* V I. <•>

Th 1 U Mb 1 Tfl w a Ma 1 Un
1 1 _____'_____
1 Go kJ aapoal'a
l • • • Ouortj-pabbla cor.g«oanaro<a
A A 2
J Shorn typ«
I A A A A A | 4 Oiaaaminolad Av dopoain
l 1
rio’W'sXT' dapoaila
A s m Ml-Cu araa
• • ’•gmallllc p»»o«an«*a
i Ml Cm aviphlda dapoiHa
1 | 1 Moasrva A •laaam-oiad
1 Cr Aapoaila
• a CNromila
Copp«e dapoula a*c.

* • * I » Uan<v. Cu-Zn.
□ 1 rOrr>r>r-r Cu
• 1 ko'lva Cu In (x .-x
12 Cx-ahoU (Wh,i. »-.)
1 1 I Cu-ahota (Kup'a»»c*.alar)
• •
1 • a
• A • la Cm. rod b.ia
1 A * IS C«-*b-Z" ikon. dapoa.li
• •
1 □ • l< bi .a corbopola k«i (Uiaaiaxpp. n>ii«)
| * rapioc anaoni Zn
• I FronklinWa-vlllflma’a -linci’a daooi4a
A I SfUlhaontta. rolo-<r« ..Ham”. dapon'a
■ • • • • • A o o 2 <5apoa<l. im oto-i dapoa.'i gaoa'Mla
* 2 Mo'Na Ag dapoHN
| r.A dapoa.la Me
• l • • • • * • • • • • • 1 2 Sf-BaorVig pogmoklai
• | • A A • 2 5 M In quorN •»"«, pagmot.laa
• • • Sr.-ikonis
• 1 • • • • • 2 1 Sn. W ar Mo V. grvraan A aarolUW lanot
• • 2 Caatl’ari’a plpaa
* * • 1 2 Koear Sr. dapoaâ
1
O’* a' dopoam

• ' • • • A • • • • 28 Choral pagmolha dapo.il.
• •
Q fl • • • • • • 2 1 » io pogmol.'fla A oplliaa
• • • 549 V in akoma
• ’ • • • • ' • A • • A A J W raina al»h quor'l Qongtra
• ' • • • • • • A • • • • • • 1 s ? kb la g-orrHe A rraavl.C pog-no'.'aa
A • A • A A A • X. “b in aiblia g.cn.<aa
* | • • • • • • • o • 1 Mb in eoitaonotlaa
• • •
1
•
• 1 s
Mb m A rMh j imi dannaita
Ureniitftfl k» rfl.na, p<p«a. Iodo* (’»P« l)
J Uron.niia k» •a.ai, p«paa. iodaa I’ypfl 2)
• ’ • A A • A • A • J Sondala na U dapo.ita
• • A 1 , 5 U in prrtlle qvo«*A^flbbia conga<Mnam**a
• • • 1 • • • 44 rhoapodia dapoa/S al U A Kt
FIG 5.4 continued

18
6. DISPERSION PROCESSES
6.1. General
The chemical, mechanical and biochemical processes involved in the movement
of material between different locations in the natural environment result in geochemical
dispersion. Purely mechanical processes, apart from alluvial sorting, usually involve
mixing but not differentiation. In contrast, chemical and biochemical processes
commonly create fractions of widely differing chemical composition due to the enhanced
mobility of specific elements. In both primary and secondary (i.e. surficial) environments
geochemical dispersion is often reflected by distinct geochemical patterns. The fact that
the dispersion patterns associated with mineral deposits are commonly far more extensive
than the actual deposits provides the justification for most geochemical exploration
techniques.
The response of an element to geochemical dispersion processes is governed by
its mobility in the prevailing environment. This in turn is influenced by the physical and
chemical characteristics of the element in question. In geochemical exploration,
environments are normally categorized as primary (i.e. deep-seated) or surficial. The
majority of geochemical exploration programs are concerned with the collection and
analysis of samples from the surficial environment. Therefore the processes controlling
geochemical dispersion in the surficial environment will be discussed in some detail.
6.2. Primary Environment
In deep-seated magmatic environments geochemical dispersion may result from

exclusively mechanical agencies such as magma injection. More often dispersion results
from a combination of chemical and mechanical processes as for example as a result of
partitioning during crystallization and the separation of mobile aqueous solutions. The
mobility of components (H2O. CO2, H2S,-SO2, F, Cl, B, and sometimes also Cu, Pb, Zn,
Au, etc.), which enter the aqueous solutions, are significantly enhanced and are more
likely to undergo significant dispersion.
Metamorphic environments differ from magmatic in that most reactions occur in the
solid state. No actual melting is involved in metamorphism except at the very highest
temperatures. However, pore fluids rich in water furnish mobile phases into which some
rock constituents may be extracted and dispersed by mineral solution or exchange.
Again both chemical and mechanical processes are important factors in the development
of geochemical dispersion patterns.
A wide range of chemical and physical changes occur in sediments during and
after burial; changes which alter solid mineral phases and interstitial fluids by a complex
series of so-called diagenetic processes. Some of these processes may occur over
extended periods of time, but the diagenetic history of a sedimentary mass may by
BlBUOTFCa
CfLSR L. PALACIOS CARRILLO
19
punctuated by episodic events, such as loss of fluid and dissolved material that may
occur during tectonism. In conjunction with normal basinal fluid migration these
processes obviously have a major influence on geochemical dispersion in sedimentary
rocks.
It is also of course necessary to emphasize that faults, fractures, and intergranular

Openings provide channelways for dispersion of materials in aqueous solution in a wide
variety of bedrock environments, especially at shallow to moderate depths.
6.3. Surficial Environment
On exposure to the surficial environment as a result of uplift and erosion,

dispersion patterns created at depth are modified and new patterns formed by surficial
processes. The surficial environment is characterized by low temperature and pressure,
and high concentrations of water, free oxygen and carbon dioxide. Most of the minerals
formed under deep-seated conditions are not stable in this environment (Rose, et al.,
1979).
In surficial environments chemical, mechanical, and biological processes all play

major roles in geochemical dispersion. Although these processes often operate
simultaneously, their relative importance depends on the local environment. Thus in arid,
arctic and mountainous terrain mechanical processes tend to dominate, whilst in the
humid tropics chemical processes generally become more important.
6.3.1. Chemical Dispersion
Chemical dispersion in the surficial environment is dominated by aqueous solution

geochemistry. The behavior of trace metals in natural aqueous systems is highly complex
due to the large numbers of possible interactions with ill-defined dissolved and particulate
compounds, and non-equilibrium conditions (Salomons and Forstner, 1984). However,
extensive observations of element mobility in the surficial aqueous environment have
permitted development of certain generalizations. (Table 6.1). These demonstrate the
strong influence of pH (hydrogen ion concentration) and Eh (oxidation-reduction (redox)
potential) on chemical dispersion in the secondary environment.
As the Eh and pH conditions in natural surficial environments can be estimated

(Figs. 6.1 and 6.2) or, better still, measured, published Eh-pH diagrams (Figs. 6.3. and
6.4) permit some prediction of solution chemistry. However, these predictions must be
treated with extreme caution. Natural conditions are generally far more complex and
influenced by 5 far greater number pf factors than the controlled laboratory experiments
and theoretical calculations used to construct the Eh-pH diagrams. This is well illustrated
in the case of gold, where practical experience suggests greater mobility than might be
expected from published theoretical solution chemistry studies (Figs. 6.5 and 6.6). The
phase diagrams indicate some gold transport is possible under very acidic oxidizing
20
Relative Environmental conditions

Mobilities
Oxidizing Neutral Io alkaline Reducing
Very high CI.I.Br CI.I.Br
S.B
Mo.V.U.Se.Re
High Mo.V.U.Se.Re Mo.V.U.Se.Re
Co, Na. Mg. F. Sr. Ro Ca.Na.Mg.F.Sr.Ra Co.Na.Mg.F.Sr,Ro Co.Na.Mg.F.Sr.Ra

Zn Zn
Cu.Co.Ni.Hg.Ag.Au
Cu.Co.Ni.Hg.Ag.Au
As.Cd
Si.P.K Si.P.K Si.P.K Si.P.K

Pb.Li.Rb.Bo.Be Pb.Li.Rb.Bo.Be Pb.Li.Rb.Bo.Be
Bi.Sb.Ge.Cs.TI Bi.Sb.Ge.Cs.TI Bi.Sb.Ge.Cs.TI
F e.Mn Fe.Mn Fe.Mn
Very Fe.Mn
low to
immobile
Al.Ti.Sn.Te.W Al.Ti.Sn.Te.W Al.Ti.Sn.Te.W Al.Ti.Sn.Te.W
Nb.To.Pt.Cr.Zr Nb.To.Pt.Cr.Zr Nb.To.Pt.Cr.Zr Nb.To.Pt.Cr.Zr
Th,Rare Earths Th.Rare Earths Th,Rare Earths Th,Rare Earths
S.B
Mo.V.U.Se.Re
Zn Zn
Cu.Co.Ni.Hg.Ag.Au Cu.Co.Ni.Hg.Ag.Au
As.Cd
Pb.Li.Rb.Bo.Be
Bi.Sb.Ge.Cs.TI
in the surficial environment.

(Modified after Andrew-Jones, 1968)
21
and pH. (Rose, Hawkes, & Webb,

1979)
FIG 6.2 Eh and pH values of mine waters, (x

oxidized ore zone; (•) primary ore
zone. (Rose, Hawkes & Webb, 1979)
22
activities for dissolved species are: species in system Zn + CO? + S

Zn=10<'*, C=1ff3, S = 10‘3. + H? 0 at 2f? C and 1 atm pressure
(Brookins, 1988) in relation to Eh and pH.
Dissolved zinc activity, 10‘5
moles/l; dissolved carbon dioxide
and sulfer species, 103 moles/l.
(Hem, 1972)
conditions in the presence of dissolved chlorine. At Summitville, Colorado observations

suggest that gold can in fact also be locally mobilized in acidic, low-chloride environments
(Stoffregen, 1986) as a result of the transient formation of gold-thiosulfate complexes.
Mobile gold-thiosulfate complexes can also form under the neutral to basic, moderately
oxidizing conditions found in the vicinity of weathering carbonate veins (Webster and
Mann, 1984). Baker (1978) showed that humic acids can play an important role in the
dissolution of gold in the supergene environment, whilst Ong and Swanson (1969)
provided experimental evidence that these acids can stabilize gold colloids in solutions
and thereby enhance their mobility.
23
FIG. 6.5 Eh-pH diagram for part of the system FIG 6.6 Eh-pH diagram for part of the system
Au-CI-O-H. The assumed activities for Au-CI-O-H. The assumed activities for
dissolved species are: Au = 10M ’10,CI dissolved species are: Au = 10‘10 ’12,
= 10'35. (Brookins, 1988) Cl = 10'1. (Brookins, 1988)
Mercury is another element whose behavior in the surficial environment differs

substantially from that indicated by theoretical solution chemistry calculations (and in this
case also vapor phase chemistry). Theoretical solution chemistry takes no account of
adsorption by iron and manganese oxides and chemical bonding which can restrict
mercury mobility in many situations (Carr, et al., 1986). The mobility of many trace
elements in the surficial environment is in fact strongly influenced by adsorption by and
ion exchange onto colloidal particles, especially those of iron and manganese oxides and
hydroxides, organic matter, clays and silica. Typically, adsorption onto metal oxides and
organic substances increases dramatically with fairly small increases in pH (Fig. 6.7).
Initially, ions adsorbed on surfaces are in active equilibrium with the host solutions and
therefore readily desorp if pH conditions decrease. However, with time they may move
into crystal lattice sites and become less effected by changes in local environmental
conditions. Experiments have shown that when an absorbent material (i.e. manganese
24
______________________________________________________________
FIG. 6.7 Fractional adsorption of metals of various oxide substrates (Fig. a: amorphous Fe(OH) 3;
Fig b: -T-AljOji Fig. c: a-SiC^) and effects of adsorbate concentrations.
(Salomon & Forstner, 1984)
25
FIG 6.8 Absorption-desorption results with changing

pH for Mn-oxide exposed to solutions of
103M Co. (Rose, Hawkes & Webb, 1979)
oxide) is exposed to a more dilute solution, only a proportion of the expected amount of
adsorped ions are in fact released (Fig. 6.8).
6.3.2. Mechanical Dispersion
Mechanical processes play a major role in the dispersion of solid weathering

products in geochemical exploration. The principal force responsible for mechanical
dispersion is of course gravity, acting directly or indirectly (i.e. through water or ice
movement) on solid surficial materials. .Even on gentle slopes, rock debris and soil
continually move downhill under the influence of gravity. The presence of moisture acts
as a lubricant and helps accelerate this movement, sometimes with catastrophic results.
Surface water runoff in the form of sheetwash and stream flow is also responsible for the
dispersion of large amounts of solid material. Sheetwash mainly involves the selective
erosion and transport of soil fines, especially clay size materials. Streams, depending on
flow and source materials, can transport a far wider range of material from boulders on
down. Groundwater movement, under the influence of gravity or hydrostatic head,
generally involves dissolved ions rather than the solid particulate products of
weathering.
Large areas, especially at the higher latitudes, have been subject to periods of
intensive glaciation in recent geologic time. The resulting erosion and deposition has
involved a variety of processes which are reflected by extensive glacially derived surficial
cover obscuring bedrock. A proportion of this cover is lodgement till formed at the base
26
of continental ice sheets from crushed and pulverized transported material plucked from
bedrock by the ice. Ablation tiH, deposited by surficial melting of the ice, commonly
overlies the lodgement till. A variety of water-deposited sediments form within (e.g.
eskers) and along the margins (e.g. kames) of glaciers. The large streams flowing out
of glaciers often cover extensive areas with glaciofluvial deposits (outwash). The glaciers
themselves can disrupt local drainage systems. Fine stratified sediments are often
deposited in the resultant lakes.
Erosion and transport by wind action is most important in arid and semi-arid areas
where there is little or no protective vegetation cover. In desert terrain this can result in
sand cover over large areas, whilst in the vicinity of some arid desert and glaciated areas,
loess deposits are common. Wind is also responsible for the dispersion of man made
contaminants from industrial sites.
Substantial amounts of sub-surface weathered material are transported to surface

by many burrowing animal species, especially worms and termites. This is particularly
important in deeply leached areas where transport of mineralized fragments to surface
can significantly enhance surface geochemical response.
6.3.3. Biological Dispersion
Uptake of inorganic matter by plant root systems results in the redistribution of this
matter throughout the remainder of the plant (which is the basis of the biogeochemical
exploration method). During subsequent plant decay the more insoluble components are
concentrated in the upper part of the soil profile, whilst the more mobile tend to be
removed by ground and surface waters (bioqeo-chemical cycle).
Microorganisms (bacteria, algae, fungi, etc.) are also important factors in metal
dispersion as they are intimately involved in many redox reactions. (The influence of redox
conditions on element mobility has been-discussed above.) Microorganisms also often
appear to capable of assimilating and concentrating certain metals.
27
7. WEATHERING AND SOIL DEVELOPMENT
7.1. General
From the preceding discussion it is apparent that a wide variety of interacting

factors, including climate, geology, mineralogy, vegetation, geomorphology and
topography have a significant influence on geochemical mobility and dispersion in the
surface (and near surface) environment. More detailed attention will now be given to
weathering and soil development. These processes are of critical importance in
exploration geochemistry as they have such a major influence on the size and nature of
the surface and near surface geochemical patterns which are the subject of the majority
of geochemical sampling programs.
It should be noted, especially when planning or conducting geochemical

exploration programs based on samples of surficial material, that widespread major
climate changes have occurred since the mid-Tertiary. In some regions, existing surface
environments have developed under conditions very different to those currently prevailing.
Thus large areas in temperate and higher latitudes (e.g. much of northern Canada) still
reflect the effects of Pleistocene glaciation, whilst the lower latitudes locally possess thick
lateritic soils which were originally developed under seasonal tropical conditions in the
Cretaceous, or earlier, until the mid-Tertiary. Remarkable examples of the latter are to be
found in Western Australia, which now has an arid climate.
Following a review of some of the more significant factors and processes involved
in weathering and soil development, a number of the major soil environments will be
briefly described. In geochemical exploration, recognition of the precise nature of the soil
cover is particularly important as this provides a useful indication of the potential
effectiveness of the constituent horizons as geochemical sampling media.
7.2. Factors and Processes
Weathering can be defined as the change of rocks from the massive to the clastic
state in response to local surficial conditions (Rose, Hawkes and Webb, 1979). It involves
a twofold process:
(i) physical and mechanical disaggregation without chemical modification of the

minerals;
(ii) chemical weathering resulting in the transformation of primary, and the

formation of secondary minerals.
Physical and mechanical disaggregation of rocks is particularly characteristic of

cold or desert climates as it is dominated by the effects of temperature variations, freezing
and thawing of water, and erosion agents (e.g. ice, brief periods of heavy rainfall and
<77/¥*fro soiSDM *» •$’» I
28 t <f33AXMW J
turbulent water flow, strong winds, etc.). However, various combinations of a number of
these processes are also active in most other climatic zones. The process of rock
disaggregation is generally initiated by the fundamental geological processes of uplift and
erosion. Unloading of rocks allows expansion towards the surface and the resulting
differential stresses produce a network of cracks and joints (Rose, Hawkes and Webb,
1979). These provide access to surface waters which initiate the chemical weathering
processes, and in colder climates produce additional stresses related to freeze-thaw
cycles. Plant roots contribute to the physical weathering of rocks by widening any cracks
they might penetrate. Various burrowing insects and animals contribute indirectly to
physical weathering by facilitating the access of active weathering agents.
Chemical weathering of rocks is most active in humid equatorial climates, and

becomes less important in cold boreal or alpine climates, as it is, to a large degree,
temperature dependent (i.e. more aggressive at higher temperatures), and requires the
presence of water carrying active agents such as oxygen, organic acids, and carbon
dioxide. It is generally dominated by hydrolysis (i.e. the effect of water containing active
constituents such as hydrogen ions (H*)), which will therefore be examined in some
detail.
The most extreme form of hydrolysis (i.e. total hydrolysis) occurs in tropical soils
under neutral, well drained conditions, in the absence of organic acid anions (Duchaufour,
1982). Primary minerals are totally destroyed and their constituents (particularly silica and
alumina) are freed. This total hydrolysis favors the elimination not only of basic cations
(Ca2+, Mg2+, K*. Na+), but also silica, which is almost as mobile. In contrast the oxides
of iron and aluminum are only slightly mobile and accumulate in situ. When the
elimination of silica is impeded by poor drainage, clay formation by recombination of silica
and alumina (i.e. neoformation) becomes possible. In temperate climates, hydrolysis is
generally more gradual than in tropical climates and clays are in most cases derived from
phyllitic minerals by transformation processes. This type of hydrolysis is controlled by the
nature and quantity of soluble organic ions present. It can take place under non-acid,
base-rich (e.g. carbonate) environments (i.e. neutral hydrolysis) or, more commonly, in
the presence of organic acids (i.e. acid hydrolysis).
Primary rock minerals have a very variable resistance to hydrolysis (Duchaufour,

1982). Quartz is generally only slightly affected, but in hot and humid climates it suffers
from surface corrosion, and fine granular varieties can be almost entirely dissolved.
Feldspar weathering is influenced by silica content; the lower the silica content the faster
the weathering. Biotite weathers rapidly, often to vermiculite, whilst muscovite is very
resistant and forms sericite by physical subdivision. The various ferromagnesium minerals
are subject to a simultaneous hydrolysis and oxidation which removes iron in the ferric
state (Fe3*). The subsequent clays are almost always magnesium rich (e.g. chlorite,
serpentine, etc.).
■* • • "«i •
• .,• .... .
29
Apart from hydrolysis, certain other chemical rock weathering processes can be
locally significant. These include:
(i) dissolution of saline rocks;

(ii) hydration which results in water molecules combining with certain slightly
hydrated rock minerals, such as ferric oxides, thus aiding the process of
rock decomposition and disaggregation;
(iii) oxidation, which causes the release of ferrous ions (Fe2*) contained ih
certain primary minerals, and thereby disrupts their crystal lattices;
(iv) reduction occurs more rarely, but under hydromorphic and badly aerated
conditions it can cause the solution of some ferruginous sandstone
cements.
Chemical weathering produces:
(i) soluble materials such as carbonates or bicarbonates, the cations of which

are either leached or enter into exchange reactions;
FIG 7.1 Distribution and extent of main types of weathering of silicate rocks. (Duchaufour
1982)
30
Type of clay formation

Climate Soil Weathering type Transformations Neoformation
boreal podzolic complexolysis degradation and solution nil
temperate podzolic (mor) complexolysis degradation and solution nil

brown (mull) acid hydrolysis transformation (and weak (kaolinite)
(gradual) moderate degradation)
subtropical fersiallitic neutral hydrolysis (inheritance, moderate moderate

transformation) (montmorillonite)
tropical (with a well drained tropical total hydrolysis limited inheritance and moderate kaolinite
dry season) ferriginous (neutral) transformation
poorly drained total hydrolysis limited inheritance and strong

vertisols (neutral) transformation montmorillonite
humid equatorial ferrallitic total hydrolysis no inheritance and strong

(neutral) transformation kaolinite (gibbsite)
TABLE 7.1 Types of climatic weathering. (Duchaufour 1982)
(ii) silica with a maximum solubility of 100 ppm in agueous solutions;

(iii) colloidal .gels by hydration and polymerization of free heavy cations of Al
and Fe. However, the immobilization of these cations, which is rapid in
most soils, decreases in acid environments rich in soluble organic matter
which favors complex formation;
(iv) clays which attract iron and aluminum to their surfaces.
Although a variety of factors influence the weathering process, general climate

plays a pre-eminent role, presumably due to importance of water and temperature
(Duchaufour, 1982). On a global scale it is in fact possible to differentiate three
fundamentally different major types of climatically controlled weathering (Fig. 7.1 and
Table 7.1), one being strongly influenced by temperature (geochemical weathering) and
the others primarily by organic matter (biochemical weathering). In the tropics,
geochemical weathering predominates. This is reflected by extreme hydrolysis which, as
discussed previously, results in the complete liberation of the chemical constituents of the
primary minerals and the formation of some clays (i.e. neoformation). In contrast,
biochemical weathering predominates in more temperate climates. This is a gradual and
gentle process, and is often incomplete. The original crystalline rock structure is
31
Organic debris lodged on th* toil

0 Organic debris only partially decomposed
Horizons of maximum Dork-colored horizon, organic (humus)
At
biological activity, of rich, mixed with mineral matter
The Solum eluviation (removal of -ight — colored horizon of maximum
materials suspended eluviation Prominent in some soils, faint
(the generic or dissolved in water), or absent in others. Generally loose
soil developed or both.
by soil-forming
processes)
Horizons of illuviation Brown to orange - brown horizons.
(accumulation of Accumulation of clay minerals or of iron
material by deposition and organic matter; compact blocky,
or precipitation from prismatic (sometimes concretionary)
percolating water). stucture.
Some tolls show intensely gleyed layers

(Horizon G of hydromorphic soils; G may
appear directly beneath A ), or layers of
Parent material derived by weathering
calcium carbonate (Horizon Cq0 of
calcareous soils).
Bedrock
FIG 7.2 Hypothetical soil profile showing the principal horizons.

(Rose, Hawkes & Webb, 1979)
frequently preserved end cleys generally result from a greduel transformation of primery
minerals. Biochemical weathering is also important in colder climates as certain soluble
organic compounds are active in both hydrolysis and complex formation (complexolysis).
Over time soils which develop as a result of climatically influenced surface and near
surface weathering processes, pass through successive stages of youth and then
maturity, towards a state of stable equilibrium. Distinctive profiles develop as a result of
generally vertical (downward and, to a far lesser extent, upward) movement of material
in aqueous solution and suspension, and complex series of chemical reactions. Individual
layers within these profiles can be differentiated on the basis of color, texture and
structure.
Most well developed soil profiles display four principal horizons which are
designated from the surface on down as A, B, C, and R. A and B constitute the actual
soil, whilst C and R are partly weathered parent material and subjacent indurated
bedrock, respectively (Fig. 7.2). A zone of organic debris (O or AO) may lie on the A
horizon. However, the entire sequence is not always present, as for example in the case
32
TABLE 7.2 I. cold climate sequence with decreasing aridity; II, hot climate sequence with
decreasing aridity; III, humid climate sequence with mean temperature increasing.
Intrazonal soils shown in bold type also.
Plant associations: (1) cold semi-desert, (2) sparsely vegetated steppe, (3) densely
vegetated and forested steppe, (4) forest-steppe, (5) boreal continental deciduous
forest, (6) prairie. (7) garrique or maquis, (8) Sclerophyll forest, (9) hot semi-desert,
(10) sparsely vegetated savanna, cacti and grasses, (11) thornbush savanna, (12)
tropical savanna with sparse trees, (13) humid tropical forest, (14) boreal coniferous
forest and ericacae, (15) mixed boreal forest, (16) atlantic deciduous forest, (17)
humid subtropical forest, (18) very humid equatorial forest. (Duchaufour, 1982)
of soil profiles truncated by erosion, or immature soils which often lack a B horizon. It
should be noted that parent materials are not always necessarily directly related to the
subjacent indurated bedrock, as soil profiles can develop on transported surficial materials
such as alluvium, glacial tills, etc. In addition, soil profiles can also develop on the
remnants of earlier soil profiles.
The water that circulates in the soil pores carries with it both dissolved and fine
particulate matter and is responsible for their general downward movement (Duchaufour,
1982). A significant proportion of the mobilized material is removed from the soil profile,
but some is deposited at lower levels. The process of impoverishment resulting from this
mobilization and transport is known as eluviation, and is generally confined to the A
horizon. The process of enrichment at lower levels (generally in the B horizon) is termed
illuviation.
Not surprisingly, in view of global, regional, and local variations in climate (Table
7.2), vegetation and parent material, a wide variety of soil types occur (Fig. 7.3.). Each
has its own unique profile development, mineralogy, chemistry, and relationship to
underlying source material. This must obviously be taken into account when soils or
33
derivative products (e.g. stream sediments) are used as geochemical exploration sample
media.
Major developments in soil classification over the past 15-20 years are generally not
reflected in the geochemical exploration literature. Most geochemists still tend to rely on
the older classifications which were based on inferred genesis as controlled by
environmental factors. The newer systems (e.g. Duchaufour, 1982) are mainly descriptive
and emphasize measurable chemical and physical properties that reflect genesis and
agricultural potential. They could be of considerable value in exploration geochemistry
as they assist understanding of the nature and extent of chemical dispersion in soils.
Greatest potential advantages appear to be provided by the French classification system
(Duchaufour, 1982) in view of its consistent concern with genesis, and comprehensive
treatment of sub-tropical and tropical soils.
7.3. Examples of Surface Environments
Some major soil types are briefly described in the following discussion of some
commonly encountered surface environments. It must be emphasized that this is only
a selection and many other soil types occur as a result of local variations in climate,
vegetation, surface geology, altitude, aspect, past weathering history, etc., etc. Each soil
type possesses distinct physical and chemical characteristics which have a significant
influence on geochemical dispersion. It is therefore necessary to develop a clear
understanding of the soil cover in all geochemical exploration survey areas.
7.3.1. Arid and Semi-Arid
Although thin forest cover may occur in the wetter parts of arid or semi-arid areas,
vegetation, if present, more generally comprises shrubs, grasses and desert plants.
Limited water availability restricts chemical weathering and leaching at surface. In extreme
situations there may be little or no chemical breakdown of the primary rock forming
minerals (or even sulfides in mineral deposits), but abrupt variations in temperature and
humidity result in physical mechanical disaggregation. Evaporation after rare rains can
result in the deposition of iron-manganese oxides on rock fragments as well as the
formation of gypsiferous-calcareous crusts. Soil profiles are normally shallow and
indistinct and of a juvenile or immature nature (i.e aridisols). Geochemical dispersion in
the surface environment tends to be primarily physical. Intermittent, but torrential
rainstorms produce rapid surface run-off and turbulent water flow along the drainage
channels. Surface material is subject to sheet wash and abrasion, with fine fragments
tending to disperse further than coarse. Windblown dusts of distal origin, and eolian
sands of both distal and proximal origin sometimes constitute a significant or even
dominant component of the surficial cover in the more arid regions. These can diminish
or even completely mask any surface expression in the constituent fine fractions of the
surficial cover of geochemical patterns related to local bedrock (Zeegers et al, 1985).
34
mounttint — venous types boreal rone, coniferous

of aftrtudinsl toquenews forests (podrots'
detent tundn and boreal

peaty sorts
serm-detent; co*d (srero/em). hot subtropical and mediterranean

Ignry end brown sub end sorts, rone with a dry season
reddish chestnut so*7s, troptcei IfersitthtfC sorts dominant)
isohurrvc sorts. ate. I
humid subtropical rone
M»r»e*v vegetated steppe iutfrsotsl and tropical rone
(chestnut sorts. burotems) with dry season [ferruginous
sorts •nd femsots)
densefy vegetated steppe
(chernozems) humid equitonal rone dense
forest \ferratlitic and fernsots
prairies (brunrrerm) dominant)
hydromorphic intraronal soils

temperate deciduous forest [alluvium, gleys, planosols'
{brunrhed SOfts}
vernc. mtraronai wit
deciduous and rmsed forest
of the boreal transition rone
seiodic. mtraronai soils
(pottohe and bores/ tessnred
softs, grey tonst sorts'
FIG 7.3 Map of the main zonal and intrazonal soils. (Duchaufour, 1982)
35
Groundwater can promote a certain amount of subsurface chemical weathering
and dispersion in arid environments. The geochemistry of deep rooted plants which tap
this groundwater sometimes reflect the resultant geochemical patterns, and therefore
provide useful geochemical exploration sample media.
As has been mentioned previously, some arid areas (e.g. Western Australia)
possess soil profiles which were initially developed under past humid tropical conditions.
The resultant laterites have been modified to varying degrees by subsequent erosion and
changed chemical environments.
7.3.2. Humid Tropics
In strong contrast to arid areas, those with tropical climates and much greater
water availability are subject to extreme chemical weathering and leaching down to depths
as great as 100 m. Organic matter remains in the near surface zone and is generally
subject to rapid biodegradation. The zone of active weathering is generally at some
depth and outside the influence of the acid organic compounds produced at surface.
Consequently weathering is dominantly geochemical (i.e. neutral or slightly acid
hydrolysis) and is characterized by the presence of relatively high concentrations of free
oxides, especially those of iron, but in some cases also aluminum. The resultant soils fall
into several broad categories which reflect progressive climatically controlled phases of
the weathering process:
(i) fersiallitic - sub-tropics with a relatively cold wet season and a hot
dry summer;
(ii) ferruginous - seasonal humid tropics;
(iii) ferrallitic - hot and humid tropics.
This progression is distinguished by an increasing degree of weathering of the primary

minerals (including sulfides in mineral deposits), an increasing loss of combined silica and
finally, an increasing dominance of clays derived from materials previously in solution (i.e.
neoformation clays). The end member (ferrallite - i.e. laterite) mainly comprises kaolinite,
quartz, ferric oxides, gibbsite, and resistate minerals.
Modal red soils are the most characteristic and widespread of the fersiallitic group.
They are generally of only moderate thickness (i.e. < 1 m), include A, B and C horizons,
and are developed over a wide range of rock types (Fig. 7.4). The Bt horizon is generally
enriched in clay as a result of pervection from the A1 and A2. The distinctive red
coloration, which is most pronounced in the Bt horizon, results from a process known as
rubification. In the dry season iron oxides released in the normal process of weathering
and subsequently bound to clay surfaces, crystallize to form hematite as a result of
dehydration. While the profile is normally decarbonated, it remains rich in bases,
particularly Ca2+ and Mg2+, and base saturation is normally about 100%. Silica "rich" (i.e.
2:1) clays dominate and are of inherited, transformation and neoformation types. They
36
Fersiallitic
red soil
(terra rossa) Tropical Ferrallitic soil
ferruginous soil (with kaolinite)
FIG. 7.4 Fersiallitic profile (see general key FIG. 7.5 Profiles of ferruginous and
(Duchaufour, 1982) ferrallitic soils (see general key)
(Duchaufour, 1982)
accumulation of dehydrated
ferric iron (red)
localised precipitation of
ferric iron
ifon - manganese concretions
gley : ferrous iron dominant

(greenish greyl
free alumina
weathering parent rock
unweathered siliceous parent rock
unweathered calcareous parent rock
Non:
the abundance o< these different
matenals « indicated by the
spacing of the fines or the
densrry of the aymboia utflhed
37
tend to occur in higher concentrations than in temperate brown soils over equivalent
parent materials.
The weathered profile of ferruginous soil is deeper than of fersiallitic types and
reaches and often exceeds 2 m (Fig. 7.5a). The humus rich A1 horizon is typically 15-20
cm thick whilst a pervected A2 horizon extends down to a depth of 60-80 cm. The clay
rich Bt horizon is strongly colored (i.e. red, brown or ochreous), but the degree of
rubification is generally less than in fersiallitic soils. The elimination of silica is greater than
in the latter and although some 2 : 1 clays persist, 1 : 1 clays (i.e. kaolinite) formed by
neoformation dominate. Surface accumulation of organic matter and the formation of very
stable humic compounds tends to increase as the dry season becomes more intense.
These humic compounds can retain bases and hence raise the pH and percentage base
saturation. Hence the pH of the Bt horizon might be less than 5 where the dry season
is not particularly intense, but be around 6 elsewhere. This could have important
implications in base metal mobility.
The ferrallitic class of soils represent the final phase of development and
weathering of soils in hot and humid climates with profiles being at least several meters
thick (Fig. 7.5b). Neutral or near neutral pH conditions again generally prevail in the
active weathering zone at the base of the soil profile over most rock types due to the
abundance of cations. In the middle part of the profile (C) known as saprolite (or mottled
zone), pH stabilizes at around 5 due to the removal of bases in the kaolinite neoformation
process. Even more acid conditions (i.e. pH 4) are found in the upper parts (A and B
horizons) due to organic acids produced by decay of organic litter. These acid
environments permit mobilization, redistribution, and subsequent local concentration of
sesquioxides (mainly iron) as goethite at or near the water table and/or at the base of
slopes where oxygen is more available. The iron oxides may become indurated when
exposed to less humid conditions after forest clearing or climate change, to form so-called
hard pan or duricrust. As might be expected the A horizons are highly depleted in clay
and iron whilst the B horizon is generally enriched in iron (and consequently, strongly
colored).
The prevailing environmental conditions in the humid tropics encourage chemical

dissolution of sulfides in mineral deposits in the weathering zone and depletion of the
constituent elements. However, a proportion of the elements (e.g. As, Cu, Pb, Zn, etc.)
are retained, especially by the sesquioxides.
Although water plays an obviously important role in geochemical dispersion in the

tropics, physical erosion is also locally significant. Not surprisingly, erosion rates of
lowland basement areas (e.g. Amazon and Orinoco) are very slow and extreme
weathering is possible (Stallard, 1988). In tectonically active areas erosion rates are often
as much as three four orders of magnitude greater than in the lowlands, being similar or
slightly less than uplift rates.
38
Consequently, extreme weathering has far
less opportunity to develop. Easily
weathered lithologies are exposed on
steep slopes and weathering rates are
lithology dependent. Aluminosilicate
minerals do not necessarily weather
completely, and some unweathered
primary minerals (locally even sulfides)
remain exposed at surface.
7.3.3. Temperate Maritime
In northwestern Europe and the

northeastern U.S.A., temperate humid
climates (i.e. atlantic or semi-continental)
prevail, and the natural vegetation cover is
deciduous or mixed forest. The humus is
biologically active and decomposition is so
rapid that there is practically no distinct
humus (AO) horizon and almost all the
humus is incorporated in the mineral soil
to form mull. Under these conditions so-
called brunified soils (Fig. 7.6) develop
over many well drained parent materials
(e.g. granites, gabbros, mica schists,
sandstones, various glacial deposits, etc.)
that can provide sufficient quantities of iron oxides and fine clays. The latter are
responsible for the rapid insolubilization of organic complexing agents produced by
humus decomposition. Weathering consists of a gentle and gradual acid hydrolysis, and
clays are generally either inherited (illites)-or moderately transformed (vermiculites). The
soil profile comprises the above mentioned A1 (i.e. mull) horizon, and a brown colored
(mainly due to poorly crystalline ferric oxide around clay particles) B horizon over the C.
Heavy metal mobility in this environment is fairly limited, and concentration in typical soil
profiles over mineralization show a progressive increase with depth.
7.3.4. Continental Middle Latitudes
Continental regions at middle latitudes experience major seasonal changes in

climate and this is reflected by the characteristics of the soils. In Dakota, Manitoba and
the steppes of the U.S.S.R. (Ukraine) the natural vegetation is grass with sparse or patchy
forest, rainfall is moderate (400-500 mm/yr), and winters tend to be cold. Spring thaw
of frozen soil profiles causes waterlogging and relatively anaerobic conditions. However,
early summer heating, when biological activity is at a maximum, followed by marked
desiccation, promotes rapid humus maturation and development of a porous black
39
organic rich A1 horizon with immobilized
free iron and base saturated clays (illite
and montmorillonites). As there is minimal
eluviation and illuviation, significant B
horizons are not normally developed (Fig. 'Z/Z/ZZZZZZJ
IIIHIIM/MII.
•ntim/wiim
7.7a). A poorly developed B horizon only r/ZZZZZZZZZz
rzzzzzzzzzzz tirmiiiiiiun
occurs in areas where natural forest cover zzzzzzzzzza
Z////Z////Z
'Z//ZZ///ZZZ///ZZ,
IW/MH/IINh
is (or was) present (Fig. 7.7b). These A1 zzzzzzzz/zz •HiMliilliiin

VZZZZZZ/ZZJ •M/tmmwfi.
rzzzzzz/rzzi Al ZZZ7ZZZ7ZZZ//ZZZ.
steppe soils are known as chernozems. ZZZZZZZZZZZz lUllllllllllllli
iiiiiiiiiii. wwiinm/n
The mobility of heavy metals in this 7/Z//////Z/////Z
ZZZZZZ//ZZZZZZZZ.
environment tends to be low as a result of Z//ZZ//ZZZ/ZZZZZZ
zzzzzzzzzzzzzzzzi
A1Cca
the alkaline conditions. FZJ
Further north, over the southern Cea (8)

portion of the Canadian Shield, northern
Appalachian region, portions of northern
Steppe Humic
Europe, etc., the mean temperatures are
chernozem chernozem
somewhat lower and the natural forest
cover better developed with conifers
dominant. Lower temperatures result in
slow decomposition of the organic
material in the forest litter (AO) and FIG 7.7 Isohumic profiles (see general key)
massive production of active organic (Duchaufour, 1982)
compounds. These produce acid
conditions and cause biochemical weathering (complexolysis) of silicates and certain clay
minerals. In well drained areas, low concentrations of "major" cations and anions in
surface waters resulting from low water/rock contact times further increase soil acidity
(Plant, Hale and Ridgway, 1989). Consequently, eluviation of the upper part of the soil
profile leaves behind a fine quartz residue (A2 horizon), whilst illuviation produces distinct
humus-rich and sesquioxide-rich layers in the B horizon. These soils are classified as
Podzols (Fig. 7.8). In general, over sulfide’mineralization the metal content of these soils
tends to increase progressively with depth, however, well developed A2 horizons are
normally strongly impoverished.
Accumulation of organic detritus, due to low oxidation rates for organic matter in
the prevailing climatic conditions, promotes reducing conditions. Although iron and
manganese are extremely soluble in this environment, precipitation occurs at the surface
due to oxidation. The ability of the oxides of iron and manganese and organic matter to
absorb large concentrations of certain trace elements (e.g. Ba, Zn, Cu, etc.) has a
significant influence on the mobility of these elements in the surficial environment.
40
7.3.5. Higher Latitudes
At higher latitudes, in the tundra

regions (e.g. Northern Scandinavia,
Canada and the U.S.S.R.), low oxidation
rates, related to low temperatures,
seriously impede biochemical processes.
Humus is modified at a very slow rate and
therefore large accumulations are
common (e.g. muskeg swamps). The soil
profiles are of the AC or AR type (i.e have
no B horizon) and are known as rankers
in the French terminology (Fig. 7.9). The
resultant reducing conditions again have a
very restrictive effect on heavy metal
mobility. Due to the relatively small period
of time which has elapsed since the most Modal
recent glaciation, weathering of both podzolic soil
exposed and suboutcropping (i.e. beneath
the muskeg, etc.) bedrock and recent
surficial deposits is often limited to minor
oxidation. FIG. 7.8 Podzolic soil profile (see general key).
(Duchaufour, 1982)
Weathering and surficial transport in

the more arid arctic/sub-arctic regions
(e.g. North Greenland), where vegetation
is at best only very sparse, is mainly
mechanical.
Past and present glaciation has a

major influence on geochemical dispersion
in many areas at higher latitude. The
degree to which the geochemistry of
glacial deposits reflect local geology
depends of course on their nature.
Ranker
FIG 7.9 Ranker profile (see general key).

(Duchaufour, 1982)
41
8. PRIMARY GEOCHEMICAL HALOES AND PATTERNS ASSOCIATED WITH

MINERAL DEPOSITS
8.1. General
Many types of mineral deposit are enveloped in distinct patterns (i.e. haloes) of
geochemical enrichment. These vary in strength from the strong but sub-economic, down
to the weak but detectable trace concentration. They may include target as well as
associated elements. In some instances haloes of depletion also occur. Haloes often
provide excellent exploration guides, especially in the case of buried deposits, as they
tend to be far more extensive then the associated mineralization.
Haloes may be of epigenetic or syngenetic origin and sometimes a combination

of both. Two broad categories of epigenetic halo are recognized; one, resulting from the
diffusion of dissolved metals into wall rock adjacent to a vein or other zone of high metal
content, is known as a diffusion halo; whilst the other, which results from precipitation or
adsorption of metals from "ore" related fluid in veins, fractures and pore spaces through
which they are flowing, is known as a leakage halo. Haloes can greatly assist
geochemical exploration as they often significantly increase the target size and sometimes
provide surface indications of blind occurrences (Fig. 8.1). Leakage haloes can extend
for hundreds or even thousands of feet from a mineral deposit, whilst diffusion haloes
rarely exceed 100 ft (33 m) as illustrated by data from the Wisconsin-Illinois Zinc District
FIG 8.1 Some typical examples of general geologic settings of ore deposits.
42
FIG 8.2 Diffusion aureoles around an orebody and a small vein,

Wisconsin-Illinois Zn district. (Rose, Hawkes & Webb,
1979)
(Fig. 8.2). It should also be noted that the ratios of the different elements introduced into
haloes during the mineralizing phase vary with distance from the principal deposit in
accordance with the properties of these elements and the host rocks, and the
physicochemical conditions at the time of deposit formation. The resultant zoning
patterns sometimes also constitute useful exploration guides.
Many of the following examples of geochemical haloes are drawn from an excellent
recent review of bedrock geochemistry by Govett (1989). They are mostly presented in
accordance with their general geological environment (i.e. plutonic association, stratiform
deposits of volcanic association, and stratiform deposits of volcanic association). Gold is
treated separately in view of the current high interest level.
8.2. Plutonic Association
On a regional scale geochemical sampling of plutonic rocks has met with varied
success. Attempts to characterize mineralized granitoids by total and H2O-soluble
halogens in whole rock and biotite, and by base metals and other elements in micas (Sn)
and feldspars (Pb) has produced, at best, equivocal results (Govett, 1983). In contrast,
other whole rock geochemistry studies suggest that granitoids hosting Sn, U, W and rare
metals tend to be siliceous and peraluminous, and are characteristically enriched in such
elements as Sn, U, Th, Rb, F, Li, W, Ta, Be, B, Mo, Nb, REE, Y, and Zr, and are generally
low in CaO, MgO, Ba, Sr, Co, and V (Govett, 1989). In addition, specialized granitoids,
genetically related to Sn and U mineralization, are clearly defined by Rb-K and, especially,
Rb:Sr-K:Rb plots (Figs. 8.3 and 8.4). The whole rock content of Sn has been used, with
mixed success, as a predictor for tin mineralized granitoids (Fig. 8.5 and Govett, 1983).
Most of the published geochemical case histories on local and mine scale sampling
of plutonic rocks are for porphyry copper/molybdenum deposits. The main features of
the deposits include anomalous haloes of Cu and S extending for up to 1 km from the
ore zones, and alteration zones with enhanced K and Rb, and depleted Ca and Sr
43
Rb
ppm • Porphyry
Rb.Sr
1000 1000 - Sn-U
Minor Sn
Other
minerolizotion
100 Barren
Crustal
averages
10 :•
100 -
Porphyry
Sn-U 1
J • \
Minor Sn 8 I - \ Porphyry
\
Other
minerolizotion '0 ''
Barren 0.1 - - X
Crustal
overages
0.01 4- -------- 1—1 ‘ ““‘H

10 100 1000
10
1 K %
K:Rb
FIG 8.3. Variation of K and Rb in barren and FIG 8.4. Variation of Rb:Sr and K:Rb in barren
mineralized granitoids. (Govett, 1989) and mineralized granitoids. Granitoids
are: 1. Sardinia, mineralized: 2.
Sardinia, barren: 3. Arabian Shield: 4.
Cairngorm (U.K.): 5. Seagull (Canada):
6. Mareeba (Australia); 7. Esmeralda
(Australia): 8. Ylojarvi (Finland): 9.
Rautio (Finland): 10. Kuukhdanaari
(Finland): W. New Zealand W-bearing
granitoids. Note that the main
production from the Mareeba and
Esmeralda “tin" granites has been W
and Au, respectively. (Govett, 1989)
44
and tin mineralization, eastern Australia.

(Govett. 1983)
CHARACTERISTIC ZONING PATTERNS AROUND SOME COPPER AND MOLYBDENUM PORPHYRY

DEPOSITS. ZONING IS GIVEN FROM THE DEPOSIT OUTWARDS.______
Deposit Geochemical Zoning Comments Source
Hall (Nevada. U.S.) Mo-Cu. Sn(W), F-As, 2x background Shaver (1986)

Mo, Cretaceous Pb-Zn-Ag-Mn-Au • F <1 Km;
Rautio (Finland) Mo-As-K, Cu-Au 1 km2 Nurmi and

Mo-Cu-Au, Proterozoic Isohanni (1984)
Kuukhdanaari (Finland) Mo, Cu. K-Au Mo 2km, K-Au Nurmi (1985)

Mo-Cu, Proterozoic 2 km
Dexing (Jiangxi, China) Mo-Cu, Ag-K, Rb, F depletion of Na and Yu (1981)

Mo-Cu, Jurassic Sr in K-Rb-F zone
Shanfang (Henan, China) Mo-W-Sn-F, Cu-Zn haloes <700 m Zhang et al. (1984)
Mo-W, Proterozoic Pb-Ag
Berg (B.C., Canada) Cu-Mo-Ag. F, Pb-Zn Heberlein et al.

Cu-Mo, Tertiary (1983)
______________________________________________________________________________________
TABLE 8.1 Charateristic zoning patterns around some copper and molybdenum porphyry deposits.
Zoning given is from the deposit outwards. .(Govett, 1989)
45
(Govett, 1989). The pronounced large scale geochemical zoning involving various
elements, including As, Sb, Te, Au, Ag, Zn, Mn, etc., exhibited by many deposits, could
provide potentially useful guides in the search for deeply buried occurrences (Table 8.1).
8.3. Vplcanogenlc Massive Sulfide Deposits
Despite the close genetic association between volcanoqenic massive sulfide (VMS)
deposits and their host rocks, attempts to define associations between these deposits
and specific volcanic associations have not been particularly successful (Govett, 1989).
In contrast, at the local and mine scale, consistent geochemical patterns have been
recognized around numerous occurrences, irrespective of age and location. Main
features include (Tables 8.2 and 8.3):
(i) Extensive aureoles (500 m or more stratigraphically vertically and up to 1

to 2 km laterally).
(ii) Foot wall anomalies, especially around proximal deposits, are more intense
than hanging wall anomalies; significant hanging wall anomalies seem to be
absent in Archean deposits.
(iii) Cu may be enriched in the foot wall and depleted in the hanging wall; Mn
tends to show the reverse behavior.
(iv) Both K and Mn may be relatively depleted close to the ore zone and
enriched further away.
(v) Fe and Mg are enriched, and Na and Ca are depleted in nearly all cases.
Exceptions are mostly due to differences in ore composition and to
variation in lava fractionation, texture of rock, whether deposits are proximal
or distal.
(vi) The ore elements, especially Zn, are commonly enriched. In some cases
Cu is depleted, except in the immediately adjacent wall rocks.
The range of geochemical anomalies found in one specific district (i.e. New
Brunswick, Canada) is illustrated in Figure 8.6. The nature of the anomalous geochemical
patterns found in the vicinity of VMS deposits tend to be primarily epigenetic in the foot
wall, but a combination of epigenetic and syngenetic in the hanging wall.
46
SUMMARY OF LOCAL-SCALE GEOCHEMICAL. RESPONSES IN BEDROCK AROUND SOME VOLCANIC-

AND SEDIMENT-HOSTED MASSIVE SULPHIDE DEPOSITS FROM RECENT LITERATURE
Deposit Anomalous elements Comments Source
Volcanic hosted
Jones Hill (New * Mg, Fe. Mn. Cu. Pb. 300 m around deposit Peterson (1983)
Mexico. U.S.), Zn, As, -Na. Ca. Sr
Proterozoic
Condor (Yellowknife. ♦ Mg. Bubar and Heslop

Canada). Archean -Na (1985)
Lyon Lake (Ontario, ♦ Cu, Zn. Fe, Mn. Ca, Harvey and Hinzer
Canada, Archean Mg. -Na. K (1981)
23 deposits, Abitibi ♦ Mg < 1 km diameter Marcone and David

Beit (Quebec, -Na. Ca (1981)
Canada). Archean
Stirling Hill-Pinnacles ♦ Cu. Zn. Fe. K. Rb, - Rugless and Govett

(N.S.W., Australia). Ba. Na. Sr, Pb (1984)
Archean
Joutel, Poirier, E. ♦ Fe. Mg (Zn, Ag) typically proximal Amor and Nichol
Waite, Mattabl -Na, Ca (1983)
(Superior Prcarince,
Canada). Archean
South Bay, Sturgeon +K Amor and Nichol

Lake, Mobrun. Mattabl, -Na. Fe. P. Mg (1983)
E. Waite (Superior
Province. Canada),
Archean
Crandon (Wisconsin, ♦ SIO, Lavery (1985)

U.S.) Precambrian -Na
Sediment hosted
Lady Loretta ♦ Zn (Hg. Pb. Ag. Ba) 50 m HW. 100 m Carr (1984)
(Queensland, FW, 1.5 km lateral
Australia), Proterozoic
Green Mountain (Calif. ♦ Mg FW Mattinen and Bennett

U.S.), Jurassic -Na (1986)
Howard’s Pass ♦ Zn. Pb. Hg, Ca in Same elements Goodfellow et al.

(Yukon. Canada), FW. ♦ Cu. Ni. Co. anomalous in (1983)
Silurian Mo. Sb. Devonian due to
As. Fe lateral reactivation of
hydrothermal activity
Tom (Yukon. Canada). ♦ Zn, Ba Zn, 3.5 km Large (1981)

Siurian
Jason (Yukon. Cu, As. Mn • Smee and Baies

Canada) Siurian (1986)
TABLE 8.2 Summary of change to lower case Local-scale geochemical responses in bedrock
around some volcanic-and sediment-hosted massive sulfide deposits from recent
literature. (Govett, 1989)
47
SUMMARY OF LOCAL AND MINE SCALE GEOCHEMICAL RESPONSE FOR SOME ELEMENTS IN HOST
ROCKS AROUND MASSIVE SULPHIDE DEPOSITS IN AUSTRALASIA, EUROPE AND NORTH AMERICA
Number of % of cases
cases ______
Enrichment Depletion Variable
Cu 18 61 28 11
Pb 13 92 8
Zn 29 93 7
Ni 7 100
Co 10 80 20
Fe 27 96 4
Mn 20 85 - 15
Na 33 6 94
K 16 44 38 18
Ca 25 4 92 4
Mg 32 88 12
TABLE 8.3 Summary of local and mine scale geochemical response from some elements in host
rocks around massive sulfide deposits in Australasia, Europe and North America. (Govett,
FIG 8.6 Schematic diagram illustrating form of geochemical anomalies

in rocks around massive sulfide deposits in New Brunswick,
Canada. (Govett, 1983)
48
8.4. Sedimentary Exhaiitive Deposits
Extremely large (kms) anomalous syngenetic haloes are often found in the vicinity
of sediment-hosted stratiform exhaiitive sulfide (SEDEX) deposits (Table 8.2). The extent
of the anomalous Cu, Zn, Hg and Mn haloes around recent relatively undisturbed
mineralized exhalites in the Red Sea is shown in Figure 8.7. Comparable dimensions are
displayed by the manganese haloes surrounding limestone hosted massive sulfide
mineralizations in Ireland and Germany (Figs. 8.8 and 8.9). More recently Smee and
Bailes (1986) found a weak negative Mn anomaly in hanging wall rocks in the immediate
vicinity of the Jason Pb-Zn-Ag deposit, which occurs in a shale/ turbidite sequence in the
Yukon Territory of Canada (Fig. 8.10). This feature parallels a foot wall Cu anomaly and
is thought to reflect acid and reducing conditions in the immediate sulfide deposition
source area. Ba shows a typical diffusion-type epigenetic decay pattern into the hanging
wall rocks.
FIG 8.7 Range (vertical bars) and average (horizontal bars of Cu, Hg, Mn, and Zn in sediment
cores from around Atlantis II Deep with distance from major metalliferous sediments.
Broken lines represent background values in sediments from axial valley sides. (Govett,
1983)
49
FIG 8.9 Distribution of total Mn in limestone around the Meggan Pb-Zn-BaSO4 deposit, Germany.
(Govett, 1983)
50
FIG 8.10 Geochemistry of South Zone of the Jason Pb-Zn-Ag deposit. Yukon, Canada. Top right:
longitudinal section showing main mineral facies. Top left: distribution of Mn in hanging
wall (HW), and As and Cu (first 20 m) in footwall (FW). Bottom right: variation of Ba
concentration with distance In hanging wall. Bottom left: distribution of Ba and rate of
change in Ba concentration in first 10 m of hanging wall. (Govett. 1989)
8.5. Gold Deposits
Characteristic geochemical response for a number of Archean and Post

Precambrian gold deposits are listed in Table 8.4. District-deposit scale major element
responses to Archean gold deposits in metavolcanic (dominantly mafic) rocks are typically
gains in Si and K, and losses of Na and Ca. Trace element haloes include the elements
characteristic of more recent epithermal deposits (i.e. As, Sb, Bi, W), as well as base
metals and S in some cases. Where Au has been determined it provides district scale
ppb anomalous haloes. Anomalies around stratiform exhalitive deposits (e.g. Madsen and
Starrett-Olsen mines, Ontario) are generally the most extensive (i.e. _<9 km). Deposit
scale responses involve the same elements as those for district scale (Govett, 1989 and
Fyon and Crocket, 1982). Extensive studies of the metavolcanics in the Timmins area of
Ontario suggest that large areas (several km2) with CO2:CaO ratios close to 1 and As
concentrations >1 ppm can be identified as targets for follow-up. On a local scale
anomalous targets can be defined by various combinations of the following anomalies:
CO2:CaO ratios >1, As >10 ppm and K2O >0.75% (Davies, et al., 1982 and Govett,
1989).
51
Deposit Anomalous elements Comments Source

ARCHEAN
Eastern Red Lake area ♦SiO2. CO2. K. As, Sb pervasive alteration Pine (1982)
(Ontario. Canada) -Fe. Mg, Ca, Na. Sr several km1
Campbell Red Lake, ♦SiO2. Au, As anomaly 1x2 km MacGeehan er al.

Dickenson -Na, Ca. (Mg. Fe, K) (1982)
(Ontario, Canada) peraluminosity index:
(mole % Al2O3/CaO+Na2O+K2O)>2
dolomite-ferrodolomite veinlets
Madsen, Starrett-Olsen ♦K 9 km in tuff. 600 m FW Durocher (1983)
(Ontario. Canada) -Na, low CO2 200 m HW
Madsen ore zone ♦Au. As. S. Sb. Bi Au (1 km). As and S (2 km),
a few 10s m in HW and FW
Sb and B 3 km. 500 m FW.
200 m HW
Timmins area ♦Au, Sb. (As, Bi. Li. Cu, Pb) deposit-scale Fyon and
(Ontario. Canada), Crocket (1982)
cherty dolomitic deposits
Bousquet ♦K, Si. -Na, Ca FW tuff Valliant er al.
(Quebec, Canada) ♦K. Si. Rb. -Na. Ca. Sr 70 perpendicular to deposit (1982)
Doyan +K. -Na. Ca 300-500 m Guha er al.
(Quebec, Canada) ♦S >3400 m X 150-300 m (1982)

Big Bell ♦ K. -Na 120 m FW. 10-30 m HW Chown er al.
(W.A., Australia) (♦S. Bi. Ba, Mo. Ag, Sb. (1984)
As. W. base metals)
POST-PRECAMBRIAN
Round Mountain ♦Au. As. Ti. Sb. Ag, Mo, W, Hg Au largest.
(Nevada. U.S.A.) -Ca. Mn >1 km; Berger and
Silberman (1985)
Cinola ♦Au. W 1 x 3 km for Au >500 ppb. Champigny
(B.C., Canada) W >23 ppm and Sinclair
♦ Hg. Sb 0.8 x 2.25 km 1982
♦Ag 0.4 x 1.1 km (limit of deposit)
TABLE 8.4 Characteristic geochemical responses for some gold deposits. (Govett, 1989)
52
As mentioned above the trace element suites found in anomalous haloes

associated with epithermal gold occurrences in Post-Precambrian rocks are often similar
to those associated with the Archean deposits (Table 8.4). At the Round Mountain hot
spring-type gold deposit in Nevada, extensive anomalous haloes have been reported in
the rhyolitic ash flow tuff host rocks (Berger and Silberman, 1985). The pervasively
altered area around the mineralization displays anomalous Au, As, Sb, Tl, Ag, Mo, W and
Hg (Fig. 8.11). The largest anomaly is provided by Au (>50 ppb). At the Pinson
sediment hosted fine disseminated gold deposit in Nevada, Crone et al. (1984) sampled
whole rock and Fe-oxide coatings from joints and fractures in the expectation that the
latter represented part of the plumbing system for the mineralizing solutions. Anomalous
haloes of Au, Hg, As, and Sb were found to occur in both fracture coatings and whole
rocks (Fig. 8.12). Relative anomaly sizes were found to be Au<Sb<Hg<As for both
sample media, but the fracture coating provide the largest anomalies.
53
q sopmtr91 p,t
FIG 8.11 Alteration patterns, distribution of Au, Ag, Tl, W, Sb, As, and Hg in bedrock at Round
Mountain, Nevada, U.S.A. (Govett, 1989)
the Pinson Mine, Nevada, U.S.A.

(Govett, 1989)
54
9. SECONDARY GEOCHEMICAL PATTERNS ASSOCIATED WITH

MINERAL DEPOSITS
In the preceding chapter the nature and form of primary geochemical haloes
associated with a selection of major mineral deposit types were illustrated by means of
examples from specific deposits. In the following discussion of some typical surficial
dispersion patterns encountered in the vicinity of mineral deposits, the emphasis is more
on generalized description and diagrammatic representation. This relates, at least in part,
to the greater availability of information on surficial geochemical dispersion processes and
patterns than on primary. The great majority of past geochemical exploration programs
have in fact been concerned with the surficial environment. The use of diagrammatic
representations will also help prepare the way for the discussion of conceptual
geochemical models in the chapter following. Attention is drawn to Figure 9.1 which both
classifies and lists the general characteristics of many of the more important types of
surficial dispersion patterns.
Principal Mode of Form of

Genet* Dispersion tramporting Macris occurrence of diapers ion
dinificitio" process d.«o«r~d ekments pattens
agent
Weathered rock Superjacent

Weathering ws mu Residual overburden patterns
Gossan
Residual overburden Fans and asymmetrical

Gravity Gossan superjacent patterns
Colluvium
.St Resistant primary and secondary
minerals, minor constituents of clay
! d Moraine minerals and secondary hydrous oxides Fans
Movement of Ice
E •olid panicles Glaciofluvial deposits Trains and irregular patterns
a by:
Sheetwash deposits Fans
1
Water Stream sediment Trains
E
V)
Lake sediment Delta fans
Aeolian deposits Fans

Wind
Ground water Ground-water solution Fam

Soluble salt complexes and sob
M Movement of
solutions Surface
water
Surface-water solution
Precipitates and
evaporite deposits Precipitated salts
Trains
Lateral patterns
Living-plant tissue Superjacent and

Plant Uptake by Metallo-organic compounds
metabolism living plants lateral patterns
Organic debris
Any clastic overburden Superjacent patterns; fam
I Ground
<1
Movement of
water Soils of seepage areas Ions sorbed on clay minerals. hydrous Lateral patterns
s solutions followed
1 by precipitation oxides and organ* mailer; ions
Surface water Stream sediments coprodpitated and occluded in hydrous Train
1 oxides; metalJo-organic compounds;
precipitated salts
Plant metabolism followed Any clastic Superjacent and
by redistribution of organ* Nutrient solutions;
soil moisture overburden lateral patterns
<3 decomposition products
FIG 9.1 Classification and general characteristics of the principal types of surficial dispersion
patterns. (Rose, Hawkes, and Webb, 1979)
55
It is readily apparent from earlier discussion that the nature and form of secondary
geochemical patterns associated with mineral deposits will be strongly influenced by the
local geological, geochemical, geomorphological, and climatic environment. Obviously
the effects of oxidation, weathering, erosion, transportation, and sedimentation on
mineralization in the surficial environment are likely to be complex. However, broadly
speaking, local physiochemical conditions will determine the relative extent to which
weathering products will disperse in hydromorphic (i.e. aqueous solution), or clastig (i.e.
solid) forms. For example, the low pH and high Eh conditions found in and around
oxidizing massive sulfides will promote the solubilization of many base metal and other
elements and their more widespread hydromorphic dispersion in surface and ground
waters. On the other hand, alkaline conditions developed, for example, over weathering
carbonate rocks or in a semi-arid environment, will impede or even prevent this
hydromorphic dispersion. Under these conditions, clastic patterns related to the
mechanical dispersion of insoluble metal bearing particles are more likely to predominate.
Biogenic dispersion patterns will often reflect patterns of readily available clastic and/or
hydromorphic metals in the underlying soils. These patterns can be found in both live
and associated partially decomposed plant material.
When interpreting geochemical surficial patterns, the time of formation relative to

the host matrix is just as important as the mode of formation. Patterns introduced or
deposited at the same time as the host matrix are classified as $yngenetjp whilst those
introduced into the matrix after its formation are known as epigenetic. The former may
be of clastic, hydromorphic or biogenic origin whilst the later can be hydromorphic or
biogenic. (Fig. 9.1).
Surficial dispersion patterns developed more or less directly over mineralization are
defined as superjacent, as distinct from lateral patterns that are displaced to one side and
entirely underlain by barren bedrock. Superjacent patterns more or less symmetrically
arranged around mineralization are defined as haloes. Directional movement during
dispersion results in asymmetry, the pattern then taking the form of a fan or a train.
(Rose, et al., 1979).
The forms of syngenetic clastic dispersion patterns related to mineralization will be

influenced by the nature of the dispersion medium. With residual overburden (i.e. soil)
superjacent syngenetic patterns may result (Fig. 9.2a), but compaction (Fig. 9.2b), soil
mixing by frost action, biological activity, etc. (Fig. 9.2c), or gravity creep can often cause
some distortion. In extreme cases of gravity creep in soils, distinct fans may develop (Fig.
9.2d). Dispersion fans are also found in transported overburden such as glacial tills and
eolian deposits (Fig. 9.3). The apex of these clastic syngenetic patterns commonly lies
near the source. Generally, streams develop linear clastic dispersion trains along their
courses (Fig. 9.4). However, alluvial outwash fans can occur where streams become
suddenly unconfined as for example on entering pediment areas (Fig. 9.5), whilst clastic
deltaic fans may develop where streams enter a lake (Fig. 9.4e) or the ocean.
56
(c ) Weothermg with soil (d ) Weathering with soil creep

miung by frost ocflon, Fan pattern
biologicol activity, etc
Holo pattern
FIG 9.2 Syngenetic (clastic) patterns in residua

overburden. (Rose, Hawkes and Webb, 1979)
FIG 9.3 Syngenetic (clastic) patterns in transported overburden.

(Rose, Hawkes and Webb, 1979)
57
Stream water only-, Stream woter and sed

no precipitation iments, with precipitation only, by erosion of
soil anomaly
Dispersion pattern
in water
Dispersion pattern
in sediments
sediments
FIG 9.4 Principal types of dispersion patterns in surface drainage. (Rose, Hawkes and Webb, 1979
FIG 9.5 Syngenetic (clastic) pattern in outwash fan and piedmont

sheetwash alluvium. (Rose, Hawkes and Webb, 1979)
58
The forms of hydromorphic .dispersion patterns are influenced by both the flow
patterns of aqueous solutions and local chemical environments which might favor loss of
the constituent of interest from solution by precipitation, absorption, etc. Unear trains are
again characteristic of most surface drainage channels (Fig. 9.4) and also some
groundwater flow systems. However, groundwater patterns more commonly tend toward
fan shapes (Fig. 9.6), except where modified by local geological features. These patterns
may display syngenetic and/or epigenetic forms. The latter can occur when changes in
physicochemical conditions along the flow path promote precipitation or absorption of
elements of interest by clastic matrix materials. Epigenetic hydromorphic haloes
sometimes form as a result of the upward movement of metal bearing soil moisture (Fig.
9.6a).
The form of biogenic dispersion patterns in plants and partly decomposed plant
material is determined by the pattern of available metal in the root zone (Fig. 9.6).
Biogenic patterns may therefore range from superjacent to lateral, from haloes to fans,
and even trains. They may also be either syngenetic or epigenetic. The latter type can
form as the result of the incorporation of leached constituents from plant materials into
adjacent soils. It should be noted that as a result of the complexity of the biogeochemical
cycle, biogenic patterns are often less well defined than the parent clastic or
hydromorphic patterns.
In view of the increasing level of interest in certain types of soil gas as exploration
geochemistry sample media, brief mention should also be made of gaseous dispersiQO
patterns. The relatively limited amount and often unsubstantiated nature of available
relevant data discourages development of generalizations regarding these patterns.
However, both syngenetic and epigenetic forms have been recognized.
59
Hydromorphic patterns
Plan Plan
( a ) Halo from upward ( b ) Subsurface fan from lateral ground-wafer

movement of soil flow; lateral surface pattern developed In
moisture seepage area
FIG 9.6 Epigenetic patterns in transported overburden. Similar dispersion may also contribute to
patterns in residual overburden. (Rose, Hawkes and Webb, 1979)
60
10. ROLE OF GEOCHEMISTRY IN THE MINERAL EXPLORATION SEQUENCE
10.1. Mineral Exploration Sequence
Mineral exploration programs generally aim to define drill targets within large areas
of potentially favorable geologic terrain. This often requires increasingly more detailed
and more expensive techniques as the search area is progressively decreased. An
operational objective throughout the program is to achieve the maximum probability of
discovery at the lowest possible cost. Given the enormous variation in geological
conditions it is not possible to design an exploration program that will be applicable to all
situations However, it is possible to define a generalized sequence of exploration stages
as shown for example by Govett (1983). (Fig. 10.1). Obviously, not all components will
be necessary in every exploration program as essential information will sometimes already
be available as a result of previous studies.
Govett also provided useful definitions of the sequential pre-drilling exploration

phases based on the general order of magnitude of the areas covered. These are:
(i) region - >5000 km2 (>2000 sq. miles)

(ii) district - 50-5000 km2 (20-2000 sq. miles)
(iii) area - 5-50 km2 (2-20 sq. miles)
(iv) target - <5 km2 (<2 sq. miles).
Obviously, these are very generalized definitions, and most exploration programs do not
involve all of these stages.
10.2 Role of Geochemistry
Geochemistry can play a useful role in many (Table 10.1), if not all phases of
mineral exploration, so long as it is applied within a well defined geological framework,
and effectively integrated with the other selected techniques. It must never be forgotten
that whatever exploration techniques are used in a program the ultimate aim is the
location of a mineral deposit. As discussed in more detail elsewhere in this manual
(Chapter 11 - Design and Planning of Geochemical Exploration Programs), the selection
of specific geochemical exploration techniques will be influenced by the nature of the
target, terrain and available sample material, and the relative cost and efficiency of
alternative methods.
Selection of a region in which exploration is to be concentrated is generally made

on the basis of broad geological, economic and political factors. When available,
geochemical survey data from large scale geochemical programs (e.g. stream sediment,
lake sediment, glacial till sampling, etc.) which have been previously undertaken for
national mineral potential and/or environmental assessment purposes, can sometimes
assist this process.
61
POLITICAL FACTORS
i.i«aiion, fiscal and resource
policies of governments
GEOGRAPHICAL FACTORS
transportation, labour, energy
markets, working, conditions
GEOLOGICAL FACTORS
favourability for particular
minerals
SELECTION OF REGION
acquisition of
regional scale
geological data
reconnaissance
exploration
follow Up
exploration
1
—
detailed ' J
exploration
— .1 .... — --------- 1 IDENTIFICATION OF TARGET 1

_____|
exploration
drilling
1
1 IDENTIFICATION OF
assessment
drilling
____________ 1
1 IDENTIFICATION OF
__
1 MINERAL UEPOSI 1
development I
work
IDENTIFICATION OF
ORE DEPOSIT
Stop work due to unfavourable results Possible revision of commodity targets
FIG 10.1. Decision and activity stages an ore

1983)
62
Scale Of Mineral Exploration Program
Region District Area Target

Sample Medium
X XX XX
Rock X
X XX XX
Soil X
XX XX X
Steam Sediment
And/Or Water
XX XX X
Lake Sediment
And/Or Water
XX X
Groundwater XX
XX XX X
Glacial Deposits XX
X XX X
Biogeochemistry
X X X
Geobotany
X X
Gas
NOTE: xx - Commonly used in suitable environments.

x - Occasionally used in suitable environments.
TABLE 10.1. Possible roles of some common geochemical survey sample media at various stages of
mineral exploration.
63
Reconnaissance geochemical exploration techniques often play a critical role in the

definition of areas of potential interest in regional and district surveys as they permit rapid
delineation of localities with potentially significant metal concentration within extensive
background areas. Depending on the local environment, the methods used might include
one or more of the following (also see Table 10.1):
(i) drainage surveys: sampling stream or lake sediment, stream or lake water,
groundwater, etc.;
(ii) glacial deposit surveys: sampling of till, etc.;
(iii) rock surveys: sampling and analysis of rocks to discriminate ore-bearing
and barren plutons, favorable stratigraphic horizons, etc.;
(iv) soil surveys: sampling of surface and deep soil, residual soil, and
transported soil. This approach is generally only used for regional
reconnaissance in certain restricted circumstances, as for example in arid
areas with minimal surface drainage, residual soils, and fairly large targets
(e.g. VMS exploration in Burkina Faso, Sub-Saharan region). Other
examples are provided by glaciated areas where anomalous dispersion
trains provide large reconnaissance targets (e.g. carbonate hosted SEDEX
exploration in Ireland);
(v) geobotanical surveys: studies of vegetation by visual observation from the
air or from the ground, as well as by interpretation of aerial photographs
and satellite images have been occasionally used to locate potentially
significant geobotanical patterns.
Follow-up studies of promising leads detected in reconnaissance geochemical

programs, as well as initial geochemical studies of smaller areas selected by other means,
are designed to detect and delineate targets for progressively more detailed study. They
might involve (also see Table 10.1):
(i) soil surveys: this is probably among the most, if not the most, commonly
used follow-up procedure due to its effectiveness, relative simplicity and
fairly low cost in many commonly encountered environments.
(ii) rocks surveys: can be especially effective when there is good exposure,
(iii) glacial deposit surveys: these are sometimes necessary in glaciated areas
with little or no outcrop and/or where soils are ineffective sample media;
(vi) stream sediment surveys: close interval stream sediment sampling is often
used as the preliminary follow-up procedure for favorable areas delineated
in reconnaissance stream sediment surveys;
(v) stream bank surveys: sampling base-of-slope colluvium is sometimes used,
often in conjunction with close interval stream sediment sampling, in the
initial follow-up of reconnaissance stream sediment sampling programs;
(vi) biogeochemical surveys: sometimes used in areas with transported
overburden;
(vii) geobotanical surveys: rarely used;
64
(viii) soil gas surveys: these are being increasingly used in arid or semi-arid
areas with transported overburden (e.g. parts of Nevada).
Geochemical procedures, in particular sampling of rock (weathered and

unweathered) exposed in the course of trenching and exploration drilling, can often also
play a significant role in mineral deposit location and definition.
Although geochemistry techniques can generally contribute significantly to most

exploration programs it must be stressed that there are some situations where they are
inappropriate due to insurmountable technical difficulties and/or the availability of other
more cost effective approaches.
10.3. Integrated Exploration
Whereas in the past successful mineral exploration could often be undertaken with
the assistance of single contributory techniques (e.g. geophysical or geochemical),
deposits are now becoming increasingly difficult to locate and integrated multi-technique
approaches are becoming necessary. The response of commonly sought blind ore
deposits to individual exploration techniques is sometimes, at best, subdued, but by
integrating the responses from several suitable techniques potential targets can be
delineated with far greater efficiency and confidence. When mineral exploration requires
a multidisciplined approach it is essential that the sequence of application and areal
coverage avoids or at least minimizes acquisition of redundant data, and is cost effective.
This requires effective communication and cooperation between the representatives of the
relevant disciplines throughout an exploration program from the planning stage onward
(Fig. 10.2).
An early review of certain critical aspects of integrated exploration, in particular the

need for integration from the very earliest stages of every program, was provided by
Coope and Davidson (1979). They noted the fact that geophysics and geochemistry can
detect certain important aspects of the geological environment that the geologist cannot
directly observe. They then proceeded to emphasize that the conversion of geophysical
and geochemical data into geological information must always be carried within a strict
geological regime, otherwise the results can be unacceptably ambiguous and imprecise.
Some progress has been achieved in the field of integrated exploration over the
intervening ten years, but there still remains much room for improvement.
65
Optimum relationships between geology and some associated disciplines, including

exploration geochemistry, In an integrated mineral exploration program.
66
11. PROGRAM DESIGN AND PLANNING
11.1. General
As has been previously mentioned in Chapter 2, the relative importance and

interdependence of the various components of a geochemical exploration program are
clearly illustrated by the "house of cards" (Fig. 11.1). Each successive independent
function is wholely dependent on those preceding so that errors or inadequacies in one
will negatively effect those that follow. Careful design and planning (including conceptual
model development and orientation studies), and well-conducted sampling and sample
processing constitute the basic foundation of all effective programs. No matter how
accurate and precise the techniques used for analysis or how advanced the statistical
treatments and computer programs used for data handling and interpretation, problems
resulting from inadequate or improper sampling and/or sample processing cannot be
overcome. Any errors introduced in these phases will destroy the value of all those
succeeding.
Although a simplification, the "house of cards" presents a convenient perspective

of the geochemical exploration process. In practice the phases often overlap to varying
degrees and despite the fact that interpretation is the last phase to be completed, its
implementation is not simply confined to the concluding stages. Interpretation occurs
throughout a program, from planning and design onward, in fact wherever conclusions
need be drawn from available data. The interpretation phase shown in the illustration
would probably be better designated "final interpretation £f gepch^miga.l data and
integration with data from other sources".
Initiation of the design phase of a geochemical exploration program requires clear

understanding of the exploration objectives as well as the economic parameters. The
actual design process then entails careful analysis and synthesis of available relevant
information on the type of mineralization sought, as well as local geology, pedology,
geomorphology, dispersion characteristics of target elements, access, etc. As the
available data base increases, conceptual models of geochemical dispersion mechanisms
and processes can be developed and progressively refined. In new areas, accumulation
of adequate information will almost certainly require a series of preliminary field and
laboratory investigations, known as orientation studies, of the general area of interest.
These enable determination of the local character of geochemical dispersion related to
mineralization as well as other relevant information. On completion of these preparatory
investigations there should be sufficient information to enable informed decisions to be
made as to optimum survey procedures, under the prevailing conditions.
Once the design stage has been successfully completed attention can be given to
program planning. The practical details of survey procedures and the order in which they
are to be applied can now be decided. In the past, a variety of factors including time and
budget restrictions, lack of requisite expertise, etc., have frequently prevented sufficient
67
FIG 11.1 The stages of exploration geochemistry related to a "House of Cards".

(Modified after Lavin, Grant, and Nichol, 1987)
68
attention being given to program design, planning and, in particular orientation. This, as
others have previously emphasized (eg. Thomson, 1987), is not an acceptable situation
in today’s competitive exploration environment!
A detailed review of the design and planning of geochemical exploration programs

is beyond the scope of this manual, but fortunately, an extensive discussion of the subject
by Closs and Nichol (1989) has been recently published. The following section’s attention
is concentrated on conceptual model development and the orientation study, which are
probably the most critical components of effective program design and planning.
11.2. Conceptual Models
11.2.1. Principles
Cumulative experience gained from numerous orientation surveys and case

histories covering a broad spectrum of environments has provided considerable
information on the dispersion processes and mechanisms responsible for the formation
of geochemical patterns in the vicinity of many types of mineralization. This has enabled
exploration geochemists to develop conceptual interpretation models that pictorially
represent dispersion behavior in a wide variety of landscape configurations. A simplified
example is shown in Figure 11.2.
FIG 11.2 Simplified conceptual geochemical dispersion model showing formation o

geochemical anomalies. (Hoffman and Thomson, 1987)
69
The initial framework for the conceptual models came from the portrayal of
landscape geochemistry by the Soviets as early as the 1930’s and was adapted to
synthesize geochemical data by Fortescue (1975, 1980). All conceptual models display
certain common features (Hoffman and Thomson, 1987):
(i) a body of mineralization or another source that may mimic mineralization;

(ii) the relative distribution of bedrock, overburden, soil, groundwater, surface
water, vegetation, and other factors;
(iii) highlighted dispersion pathways related to mineralization and anomaly
formation.
Each model portrays dispersion as a series of patterns related to and controlled by a

variety of identifiable natural factors.
11.2.2. Objectives
Well constructed conceptual models permit accurate prediction of the factors

influencing geochemical dispersion, and help ensure clear definition of the parameters
which need be considered in the design, planning and interpretation phases of
geochemical exploration programs for specific areas. Early consideration of these factors
enables orientation studies to be concentrated on areas where essential knowledge is
obviously lacking.
It is necessary to stress the fact that conceptual models can only indicate the
mechanisms (i.e. mechanical or hydromorphic dispersion, etc.) responsible for
geochemical pattern formation. The dimensions and relief of patterns are generally
influenced by a variety of local factors which defy summary.
11.2.3. Procedures
Preliminary conceptual models for proposed study areas need to be constructed

at an early stage of every program. In order to be effective these models must be based
on knowledge of the factors influencing geochemical dispersion in the areas of interest.
The requisite information is obtained through examination of relevant published reports,
company files, etc., field visits, and where preliminary conceptual models show essential
knowledge is lacking, on comprehensive field and/or laboratory orientation studies.
Models must be subject to continuous critical review throughout the life of a project.
Modification and refinement will be required as project data provide progressively
increasing knowledge of the local environment.
11.2.4. Examples
The simplified example in Figure 11.2 illustrates the influence of some common
natural landscape factors on anomalous geochemical pattern development. It depicts
70
geochemical dispersion of mobile elements from mineralization in a landscape
characterized by residual soils which are freely drained, except in seepage areas and
bogs, and moderate youthful topography. In this situation a rpsidugl geochemical
anomaly is formed directly over mineralization as a result of the normal mechanical and
chemical processes associated with soil formation. The anomaly may possess
dimensions roughly similar to that of the mineralized sub-outcrop, but more commonly will
be significantly larger, primarily as a result of down slope mechanical soil creep. A
biogeochemical anomaly is also developed over the mineralization, whilst epigenetic
hydromorphic anomalies occur in seepage areas at the break of slope and in streams
below the mineral occurrence. The latter result from metals which entered groundwater
in the acid environment of the weathering sulfide mineralization, being deposited when
groundwater reaches the oxidizing and less acid surface environment. Mechanipa.1
transport of material from these residual and hydromorphic anomalies can produce
anomalous stream sediment dispersion trains.
The example in Figure 11.3 represents a commonly encountered situation in which

a specific rock type possesses high background concentrations of an element of
FIG 1173 Model F2 (Cordillera). Idealized model for the effect of rock type change on the
geochemistry of the overlying soils and sediments.
Anomaly types: SL(R) = residual soil anomaly, SL(M) = mechanically

smeared soil anomaly (by glacial action), SS = stream sediment anomaly, LS = lake
sediment anomaly, SP = seepage anomaly. BG = bog anomaly.
Overburden types: 1 = bedrock, 2 = residual soil, 3 = recent alluvium,
4 = till, 5 = overburden of remote origin.
Others: OB = orebody,::: = the density of dots indicates anomaly strength.
(Bradshaw, 1975)
71
exploration interest. Residual

soils and stream sediments
display patterns which could be
mistaken for anomalous in
routine geochemical surveys, if
orientation studies had not been
previously undertaken.
More realistic empirical

models have been developed
for a wide variety of natural
environments, including those in
the Canadian Cordillera and the
Canadian Shield (Bradshaw,
1975), in Northern Europe
(Kauranne, 1976), in the Basin
and Range (Lovering and
McCarthy, 1978) and in
Australia (Butt and Smith, 1980).
One of the least compli

cated situations ordinarily met
with in geochemical exploration
is illustrated in Figure 11.4. This
is similar to the simplified model
described above (Fig. 11.2) and
represents dispersion of mobile FIG 11.4 Model B1 (Cordillera). Idealized models for
geochemical dispersion of mobile elements in
elements from mineralization in
well-drained and poorly drained ground - residual
an area with moderate topo soils (see Fig 11.3. for legend). (Bradshaw, 1975)
graphy, and residual soils which
are freely drained, except in
seepage areas and bogs. Pronounced anomalous patterns are commonly found in
residual soils over and a little downslope of mineralization as a result of normal weathering
processes and soil creep, respectively. Metal taken into solution in the acid environment
of the weathering sulfide mineralization is transported in groundwater until a change of
chemical environment (e.g. less acid and/or more oxidizing) is encountered in seepage
areas at the break of slopes or in lakes and streams.
Naturally, the presence of transported overburden complicates conceptual model

construction. Much depends on the nature of the overburden and the mobility of the
mineral deposit elements in the prevailing environment. In glaciated areas with till cover
and partially mobile elements, residual soils might be expected to reflect the glacial clastic
dispersion train (Fig. 11.5a). In addition, hydromorphic dispersion in surface and/or
72
ground water can often produce
anomalous patterns in the waters
and/or sediments of adjacent lakes
and streams. Where the elements
of interest are immobile only clastic
patterns will likely develop (Fig.
11.5b). Conversely, where the
cover comprises stratified drift of
distal provenance the only possible
dispersion from suboutcropping
mineralization will likely be
hydromorphic (Fig. 11.6). Anoma
lous patterns might occur in the
water and/or sediments of seepage
areas and streams, where migra
ting groundwater, which has been
in contact with the mineralization,
reaches the surface.
A variety of geochemical
environments are found in many
parts of Australia which have been
(i.e. Cretaceous or earlier to mid
Tertiary), and in some areas
continue to be, subjected to deep
weathering, usually lateritic. Most FIG 11.5 Model E2 (Cordillera). Idealized models of
the effect of chemical mobility of elements on
of the weathering is relict and their dispersion pattern in till-covered areas
frequently only partially preserved (see Fig 11.3 for legend). (Bradshaw, 1975)
(Butt and Smith, 1980). Figure 11.7
illustrates typical situations in an
area with moderate relief and completely weathered profiles. At location B1 long term
topographic prominence of exposed bedrock has resulted in intensive leaching of certain
mobile target elements (e.g. Cu, Pb, Zn, etc.) and enrichment of immobile pathfinders (Bi,
Sn, Sb, As, etc.). Anomalies might also be found in the residual soil at B2. These will be
weak except where elements are held in resistate minerals or retained in Fe oxides. Also
stream sediment anomalies may be present in weakly incised stream channels as a result
of the erosion of gossan, oxidized mineralization and/or soil anomalies. Lateral
dispersion of gossan fragments by soil creep or sheetwash could also produce anomalies
in adjacent transported overburden (see location B3).
73
FIG 11.6 Model A5 (Shield). Idealized models for geochemical dispersion of mobile elements
in areas of stratified drift.
•
Anomaly types: soil anomaly derived by mechanical means, SL(H) = soil
anomaly derived by hydromorphic means, SS(M) = steam sediment anolmaly derived
by mechanical means, SS(H) = stream sediment anomaly derived by hydromorphic
means, LS = lake sediment anomaly, SP = seepage anomaly, BG = bog anomaly.
Overburden types: 1 = bedrock, 2 = residual soil, 3 = recent alluvium,
4 = till, 7 = transported overburden of remote rigin.
Others: OB = orebody, ::: = the density of dots is proportional to anomaly
strength. (Bradshaw, 1975)
74
Sample media Nature of bedrock and overburden

M,M(S) mineralization; mineralization at aurface
Transported
G(S) gossan, surface
8 glacial
G(SSJ gossan, subsurface
7 aeolian (e.g., sandplain)
OM(S) oxidized mineralization, surface
6 alluvium or colluvium
OM(SS) oxidized mineralization, subsurface
5 pisolitic ironstones
PG pseudogossan
4 slumped soil and colluvium
P fault ironstone
Residual
WB weathered bedrock
3 soil
SL residual soil
2 weathered bedrock
TO transported overburden
1 fresh bedrock
SS stream sediments
Anomaly types
R ” residual; M ■ mechanical; H • hydromorphic.

Contours show general nature of anomaly; broken contours show subsurface anomaly.
FIG 11.7 Landform situation B. Complete deep weathered profile, moderate relief.
(Butt and Smith, 1980)
glBLIOTECA
| GELSQ L. PAL' "'°S cMLO- 75
11.3. Orientation
11.3.1. Principles
Decisions regarding optimum geochemical field, laboratory and interpretational

procedures for new exploration programs are too often made on the basis of previous
experience gained elsewhere. Despite the common availability of extensive case history
data from apparently comparable areas, such extrapolations can prove extremely
dangerous as no two areas are generally identical in every respect, and even subtle
variations can result in significant differences in geochemical dispersion behavior. It is
therefore essential that information gained from case histories be augmented by careful
orientation (i.e. pilot) field, laboratory and interpretational studies designed to determine
the precise geochemical characteristics of the actual area of interest.
11.3.2. Objectives
Orientation surveys should be designed to determine the nature and extent of

dispersion patterns (i.e. primary and secondary) associated with, preferably undisturbed,
mineralization of the type sought. An important secondary objective should be to
determine the distribution and behavior of elements of potential interest in unmineralized
background areas, with otherwise similar environmental conditions to those found in the
mineralized areas. An orientation study should enable optimum field, laboratory and
interpretation procedures to be determined. Ideally, these will permit clear resolution of
significant anomalous patterns (Fig. 11.8c), with as little uncertainty, related to overlap
between anomalous and background populations (Figs. 11.8a and 11.8b), as possible.
Factors which need be considered in the course of an orientation study include

(modified from Closs & Nichol, 1989):
(i) nature of surficial environment;

(ii) sample types available;
(iii) optimum sample type(s);
(iv) sample collection procedures;
(v) sample size requirements;
(vi) optimum sampling interval;
(vii) field observations required;
(viii) sample preparation procedures;
(ix) sample fraction for analysis;
(x) geochemical suite for analysis;
(xi) analytical method(s) required;
(xii) data presentation formats, and
(xiii) fundamental interpretational procedures.
76
FIG 11.8 Hypothetical frequency distributions for populations of

background and anomalous values for three methods or
types of samples. Despite the high absolute values of
method (a), and the equal contrast of (b) and (c), method
(c) gives the best resolution.
(Rose, Hawkes & Webb, 1979)
As has been previously discussed the nature of the surficial environment will be
very much influenced by past and present climatic conditions. The available sample types
might include one or more of the following: soils, stream sediments, surface waters,
ground waters, glacial sediments, lake sediments, rocks, vegetation, mull, or more rarely,
soil gas, air, particulates, animal tissues, or microorganisms.
Although imagination is a useful • attribute in program design and technique

selection, realism is also essential. Published case histories on some of the more exotic
techniques are often based on fairly restricted studies and sometimes for a variety of
reasons, including commercial and academic pressures, tend to be unduly optimistic. No
technique should be employed in a geochemical exploration program unless its
effectiveness can be unequivocally demonstrated in preliminary orientation test studies.
It is necessary to accept the fact there are in fact some exploration objectives which
cannot be achieved with currently available geochemical exploration technology.
11.3.3. Procedures
The required information can be obtained through a combination of:
(i) traditional orientation survey based on field, laboratory and interpretation

studies;
77
(ii) case histories of geochemical programs in general area of interest or other

areas with similar geological and surficial environment.
Except in cases where the local geochemical environment is already well

understood through previous studies, effective orientation generally requires some effort
along traditional lines. The accompanying table (Table 11.1) is a synthesis of the
important parameters that should be derived from such a survey. Based on this
information, the optimum physical parameters (e.g. sample depth, sample interval,
analytical technique, etc.) for routine surveying can be chosen that necessarily take into
account the defined dispersion characteristics of the elements of interest (i.e. target
and/pathfmder) as well as the physical, logistical, and economic conditions pertaining to
the project.
Field areas selected for orientation studies should contain the full range of
geological and surficial conditions (including geochemical background) and types of
mineralization anticipated in the proposed project area (Closs and Nichol, 1989). To
ensure effective definition of optimum survey parameters, samples of the various sample
media should be collected at sufficiently close intervals. These should be significantly less
then those considered likely to be selected, on the basis of previous experience and
knowledge of the area, for the subsequent survey. The samples should be of sufficient
size to permit the full evaluation of the parameters of potential interest (Table 11.1).
Further information on recommended procedures for orientation sampling, sample

preparation and analysis are outlined in a number of publications including Rose, Hawkes
and Webb (1979), Bradshaw (1975 - Section D), and Closs and Nichol (1989). Useful
individual check lists for orientation surveys involving rocks, residual soil or transported
overburden, drainage media, and plant material have been developed by Coker (pers.
comm. 1983) (Tables 11.2, 11.3, 11.4, and 11.5).
79
Major factors to be evaluated by an orientation survey in residual soil

or transported overburden
Optimum contrast between samples at a mineralized zone, representative of that being

sought, as compared to a range of background conditions in the survey area, considering
the factors below:
Determination of the most suitable indicator element or elements, either ore elements or
pathfinder elements or both.
Nature of overburden:
(a) Residual vs. transported, and transport mechanism and direction;
(b) Soil profile development;
(c) Depth variation of indicator elements;
(d) Effects of topography, drainage, vegetation, rock types.
Optimum depth of sampling.
Optimum size or density fraction (clays, silts, heavy minerals, etc.).

Most suitable analytical procedure:
(a) Extraction method (total, hot-acid extractable, cold-extractable, etc.);

(b) Determination method (detection limit, interferences, cost);
Range of background and intensity of anomaly near mineralization.
Shape, extent and homogeneity of anomaly, using preferred method and one or two
traverses across mineralization.
Reproducibility of sampling and analysis.
Possibility of contamination.
TABLE 11.2. Major factors to be evaluated by an orientation survey in residual soil of transported
overburden. (Coker, pers. comm, 1983)
80
Check list ot factors to be optimized by an orientation survey

preparatory to rock sampling
Type of sample (rock, vein material; comparison with soil or drainage samples).
Size and character of sample (size large chunk, many small chips, channel sample, length
of drill core).
Best indicator elements (ore element, pathfinder elements, major elements, rare earth
elements, element ratios-equations, plots).
Applicability of separated minerals (sulphides, limonite, biotite, calcite, etc.).
Effects of weathering, rock type, hydrothermal alteration and other geological variables
on background and contrast of anomalies.
Shape, extent and homogeneity of anomalies and reproducibility of anomalies from a

single site.
Method of sample decomposition and analysis (total analysis, sulphide-or oxide-selective

leach, acid digestion).
Sources of contamination (metal from collecting and crushing equipment, dust, drill steel,
drill grease or muds, circulating waters, smelter fumes).
TABLE 11.3. Check list of factors to be optimized by an orientation survey preparatory to rock sampling.
(Coker, pers. comm., 1983)
81
Check list of factors to be optimized and evaluated by an orientation

survey preparatory to drainage sampling
Sediment I Water
Best indicator elements, including both major and minor constituents of ore
Optimum material (sediment from Optimum material (ground water vs

seepages, stream channels, flood surface water)
plain, center-lake, near-shore lake).
Optimum fraction (size, heavy For ground water, the relation to

minerals, organic fraction). recharge areas, difference between
aquifers, controls on water flow and
Most effective extractant or method availability of points where ground
of anomaly enhancement. water can be sampled. For lake
waters, possible variations with depth
Magnitude of contrast of anomaly and type of lake
at source.
Length of downstream decay pattern; controls on decay pattern:

Metal content of bank material. I ph, Eh, precipitants, absorbents
Background values of indicator elements, range, relation to rock types:

Correlation with Fe-Mn-oxides, I Relation to total dissolved solids and
organic matter. I major elements.
Analytical methods (detection limits, precision, accuracy, form of element).
Seasonal or temporal variations.
Cost of sampling and analytical procedures, and elapsed time for reporting results.
TABLE 11.4 Check list of factors to be optimized and evaluated by an orientation survey preparatory to
drainage sampling. (Coker, pers. comm., 1983)
82
Check list of factors to be determined during biogeochemical

orientation surveys
Optimum species based on distribution (must be widespread), contrast of anomalies,

homogeneity of anomalies, ease of recognition, ease of sampling and depth of root
system.
Part of plant to be sampled (twigs, leaves, fruits, bark, wood).
Best indicator element or elements.
Effects of aspect (sunlight), drainage, shading, antagonistic effects of other elements.
Amount of vegetation needed to give adequate ash.
Contamination from dust or other sources.
Sampling pattern and interval.
TABLE 11.5 Check list of factors to be optimized and evaluated by an orientation survey
preparatory to biogeochemical sampling. (Coker, pers. comm., 1983)
11.3.4. Examples
A survey conducted over gold-silver vein mineralization at Mt. Nansen in the Yukon
Territory (Coope, 1966) illustrates the application of the orientation approach. This area
is characterized by strong relief, an absence of glaciation at higher elevations, permafrost,
and mainly residual soil cover. A thin (2-4 inch) volcanic ash is widely distributed beneath
the shallow rooted vegetation. Detailed profile sampling of soil and overburden exposed
in a trench across virgin mineralization produced distinctive patterns of lead, antimony,
and zinc as illustrated in Figure 11.9. It is apparent from these patterns that the
dispersion behavior of lead and antimony are similar, but differ significantly from that of
zinc. All metals have been influenced by down slope movement in the overburden, but
the zinc pattern is consistent with dispersion in solution along the bedrock surface.
Examination of the patterns also indicates that near-surface sampling (0 to 12 in. or 0-30
cm.) would not reliably indicate the mineralized vein. This is due, at least in part, to the
presence of the volcanic ash layer. It was concluded that a sample depth of 18 to 24 in.
(45-60 cm.), and a sample interval of one-half the anomaly width at this depth (15 ft. or
5 m.) were the optimum parameters necessary for routine surveying (Fig. 11.10).
83
Nansen area. Trench crosscut mineralized vein at right angles and maximum
topographic slope was parallel to trench direction. (Coope 1966)
84
Observation of these sampling criteria led to the discovery of several previously unknown
veins.
The need for extreme care in the implementation of geochemical orientation

studies, and the dangers inherent in attempting to apply orientation results for specific
elements to other elements in the same general region is illustrated by experience in the
Saudi Arabian desert. Following a substantial number of orientation studies over and
around a variety of base metal and tin-tungsten deposits, it was generally concluded that
due to the dominantly mechanical nature of dispersion and the common occurrence of
eolian dilution, the sieved coarse fractions of soil and stream sediment samples provide
the optimum surficial sample media. For example, Thomson (1987) demonstrated that
analysis for zinc of the -10 + 35 mesh fraction of soil collected at a depth of 20 cm from
a partially residual regosol provided optimum contrast over lead-zinc mineralization (Fig.
11.11). In contrast zinc data for the -150 mesh fraction show far weaker and more
restricted anomalous response, which were presumed to reflect dilution by barren wind
blown dust.
in soils over lead-zinc mineralization, Ar Ridaniyak, Kingdom of Saudi Arabia.

(Thomson, 1986)
85
Use of coarse fractions was later extended to gold exploration in Saudi Arabia,
despite the limited nature of the orientation studies of gold in the local environment
(Barbier, 1987). However, unfortunately, a regional survey based on this approach was
a complete failure (Salpeteur, et al., 1989). Subsequent careful detailed geochemical
orientation studies of eight gold prospects in the central pediplain of the Saudi Arabian
Shield indicate that the earlier limited gold orientation results were influenced by
contamination from old gold mine workings. The coarse fraction of the skeletal soils and
wadi sediments is in fact not representative and yields erratic results. It is most effective
in the location of quartz-gold veins, of low economic potential, which were mined in
ancient times. The data demonstrate that gold is enriched and more homogeneously
distributed in the ultrafine (i.e. -80 micron) fraction of these surficial materials (Fig. 11.12)
than in the coarse. Concerns regarding eolian dilution might be misplaced, at least in this
case, as tests indicate that the -80 micron commonly constitutes only a minor constituent
of eolian sediments in the region (Fig. 11.13).
A stream sediment orientation survey can help define the appropriate sample
interval for a geochemical reconnaissance survey. In the example illustrated in Figure
11.14, closely spaced samples were collected both upstream and downstream of the
Wankatana molybdenum mineralization in the Sula Mountains of Sierra Leone, West Africa
(see Figure 5.2a for location). The area is characterized by moderate relief, forest cover,
and the presence of lateritic soils. Stream sediment samples were collected from the
Sende River which flows adjacent to the mineral occurrence. The sample intervals were
progressively increased downstream of the deposit. Analytical results indicated the
background level for molybdenum in the minus 80-mesh stream sediment fraction was
2 to 3 ppm Mo and that anomalous values extend downstream in the tributary sediments
for approximately 1.2 mi. (2.0 km) prior to being diluted by the background sediments in
the main stream. The moderate nature of the anomalous response in the stream
sediments is probably related to substantial dilution by background material from the
extensive catchment upstream of the occurrence. However, it is reasonable to conclude
that in this area sampling along drainages at half this anomalous distance (0.6 mi. or 1
km) with mandatory collection in each drainage immediately upstream of each tributary
junction will satisfactorily indicate the presence of similar, or more extensive, molybdenum
occurrences in a routine reconnaissance survey.
86
MORPHOLOGY
SOURCE Au
TYPE ppp
AH>l50m .«oo I Aklyoh prospect ( Au MAA )
Sub-parralel 400 Wadi A flat width ISO m
vein / , \»OO Eetimated
system / Background
PPb
Wodi B . flat width < so m
2-Jabal Ghadarah (Au AA )

Gold
pyritized
granite
AH>30m isoo- 3-Jodib Ghuzzayyil prospect (AA )

400-
.—------
"""’Ouorfe ^<n^
Ancient ah> 20m •*»- 4-Shignoh prospect ( A A )

workings w,.
(dumps) rrrm X
quartz '
vein
Ancient awzom ■•<»- 5-Bari prospect
workings 4O0.
(dumps) x
quartz
vein
Ancient AH<i0m «oo 6-Sir Tawilah prospect (Au NAA)
workings «oo •
(dumps) x
"*•'--------- -------------------------------------------------------------9
quartz ---------- r~
vein
7-Ash Shoktalyah
Ancient AH«5m >«x> .............
workings <oo
(dumps) x‘
d vri t ize d ---------
metavolcanics 8-Um Ar Rjum prospect (Au A.A.)
. AH<Sm 'Soo
Ancient
workings 400
VIOO
______
________________________ 100 500 1000 '500 m MO»llOWT*L OtSTANCC
X Source worked by oncient mow SOuoct
OH Altitude difference
B G Bockground___________
FIG 11.12 Summary of maximum gold dispersion trend obtained in the minus 80 n m fraction of wadi
sediments for 8 gold prospects. (Salpeteur, 1989)
87
CUMULATIVE CURVE ANO FREQUENCY HISTOGRAM
FIG 11.13 Grain-size distribution of some eolian materials

from the Central pediplain (Kingdom of Saudi
Arabia). (Salpeteur, 1989)
88
FIG 11.14 Stream sediment survey of River Sende, Sierra Leone. Data on -80 mesh fraction.
(Rose, Hawkes, and Webb, 1979).
89
12. FIELD SURVEY PROCEDURES
12.1. General
Effective sampling of any surficial media requires well-trained personnel capable

of recognizing and describing the correct sample material and the sample site
characteristics. Samplers should be able to recognize and, if possible, avoid situations
where contamination from human activity or changes in the natural physicochemical
conditions can produce spurious or unusual results. In most situations, these sampling
duties can be undertaken by trained technical personnel under the supervision of a
geochemist or geologist with adequate geochemical exploration experience. In some
surveys (e.g. where identification of the correct sample material is critical, as in
biogeochemical or glacial till sampling programs), it is prudent to employ qualified
specialists (e.g. botanists and Quaternary geologists) to both conduct orientation surveys
and instruct and supervise the sampling teams.
Sampling tools vary according to the medium and the field situation. Non
contaminating equipment is essential and care should be exercised in not only choosing
non-contaminating steels for shovels, trowels, augers etc. but also in ensuring that any
associated lubricants, adhesives, welds, and solders will not cause problems. Leaded
gas can sometimes constitute a potential problem in field vehicles when samples are
transported in proximity to leaking containers. This awareness of geochemical cleanliness
extends to the dress of the sampler who should avoid wearing metal buckles, rings, etc.
and handling coins which might lead to contamination by chipping or transfer of metal on
fingers.
The same caution is necessary in the choice of sample containers. Kraft paper
(with non-contaminating water-proof glue and closures), olefin, and plastic bag containers
of appropriate size are frequently used. Kraft and olefin allow samples to be dried without
transfer. Plastic bags are commonly used for larger samples. More rigid polypropylene
and special glass bottles can be utilized in water sampling and a variety of sampling
devices, many of them patented, are available for the sampling of gases and particulates.
It is strongly advised that all samples be allocated simple unique sequential

numbers which at least include a project (or regional office) designator prefix and a
sample type designator suffix. These are best provided by pre-numbered Assay/
Geochemical Sample Tag Books. The potential for error and misunderstanding is thereby
minimized and problems in subsequent data management and interpretation are avoided.
Some form of coordinates should also be assigned to every sample in order to assist
sample location and computer plotting of sample locations and analytical data. In the
case of widely spaced regional reconnaissance samples (e.g. stream sediment) the
Universal Transverse Mercator (U.T.M.) grid location of each site can be determined using
topographic base maps of suitable scale or possibly, a locator instrument (e.g. Magellan).
90
In more detailed studies the U.T.M. grid can be used to define the area boundaries, whilst
individual samples are located by reference to a local grid.
12.2. Sample Media
Some discussion of the potential role of available geochemical sample media in the
exploration sequence has been provided in previous chapters. Media selection will of
course be decided on the basis of orientation studies which will in turn be influenced by
the local environment as well the nature of the exploration problem. Reiterating earlier
statements concerning the applicability of the more widely used sample media in
reconnaissance studies, the methods used might include:
(i) drainage surveys: sampling stream or lake sediment, stream or lake water,
groundwater, etc.;
(ii) glacial deposit surveys: sampling of till, etc.;
(iii) rock surveys;
(iv) soil surveys: this approach is becoming increasingly popular at sampling
densities as low as 1 sample per 25 km2.
Follow-up studies of promising leads detected in the reconnaissance phase might involve:
(i) closer spaced sampling of one or more of the above mentioned media
and/or;
(ii) stream bank (residual soil or colluvium) surveys;
(iii) biogeochemical surveys;
(iv) soil gas surveys, or more rarely;
(v) geobotanical surveys;
(vi) particulate surveys, and
(vii) microorganism surveys.
Exotic techniques such as surveys based on animal tissue sampling, are currently
primarily of academic interest, and unlikely to provide solutions to actual practical
exploration problems.
12.2.1. Rocks
Geochemical exploration surveys based on systematic bedrock sampling are in

essence an extension of routine prospecting based on the collection and analysis of
relatively small numbers of "specimens" or rock chip "samples" from potentially interesting
bedrock exposures. However, the former aim to achieve consistently representative
material, and are generally capable of detecting and interpreting far more subtle
expressions of the possible presence of mineralization than the "character" sampling
normally carried out in prospecting. Unless exposure is exceptionally good, sample
91
spacing in geochemical rock surveys tends to be less consistent than that achieved in,
say, soil surveys.
As with other types of geochemical surveys, the sampling procedures and the
sample material collected in geochemical rock surveys should be standardized as much
as possible. However, considering the large number of variables that can be introduced
by the processes of weathering and oxidation, the ideal of collecting similarly weathered
material is sometimes impractical. Nevertheless, the geologist or the geochemist
conducting the survey should ensure that individual samples at all sample sites are
essentially comparable and that observed variations in weathering intensity are properly
recorded for interpretation purposes.
Geochemical rock sampling necessarily must take into account the geological
environment and the type of mineral deposit of interest to the explorer. The precise scale
of sampling necessary for detection of syngenetic and epigenetic patterns will be
determined by orientation surveys (see Chapter 8). Detection of syngenetic patterns may
necessitate the regional sampling of individual plutons or more detailed sampling of
specific parts of an exposed stratigraphic section. The latter patterns will require a
different approach. Surveys designed to detect leakage anomalies will focus on
systematic sampling of fault or fracture zones and, possibly, bedding structures. In
contrast, the preferred geochemical rock sample material for the detection of diffusion
haloes is likely to be unfractured and the scale of sampling much more detailed. In all
instances, analysis of geochemical rock survey material has the potential of delimiting
dispersion patterns beyond visible alteration associated with mineralization. Table 12.1
summarizes the elements determined and the sampling densities used in past exploration
programs for a variety of mineralization types.
A good example of a regional approach capable of discriminating between

productive and barren intrusions is provided by the work of Garrett (1973), which was
based on whole rock analysis of samples from felsic intrusions in the Yukon Territory,
Canada (Fig. 12.1). Using a variety of techniques, including residual scores from a
multivariate statistical analytical procedure (principal component analysis), comparisons
of metal concentrations (Fig. 12.2) and degree of skewness of frequency distributions, he
was able to demonstrate that most plutons associated with mineralization could be
recognized, and certain additional plutons with no known mineralization merited further
investigation. In strong contrast the work of Church et al (1976) demonstrates the
potential value of district scale geochemical rock sampling programs in the detection of
vein and replacement deposits. Their case history study was carried out in an area of
British Columbia, Canada which includes the Mesozoic volcanic sequence hosted Sam
Goosly replacement (?) massive sulfide deposit, and the Upper Cretaceous andesitic
volcanic sequence hosted Brandina vein type occurrences (Fig. 12.3). Both types of
mineralization are reflected by large As and somewhat more limited Cu anomalies (Fig.
12.4).
92
Scale Target Elements Sampling density
non-ore ore
Regional identification of K, Rb. Sr. Ba, U, e.g. Cu. Pb, Zn. min. 30/intrusion
productive Na", Ca- Sn. W. Mo. U. Ni but see Appendix
plutons massive Fe. Na, Mg. Mn, Cu. Zn. (Pb) 3. 0.2-5/krrr
sulphides Na,
(K), (Ca), (Ba) e.g. Cu, Pb, Zn 1-10/km2
vein and As. Sb, Ta. Bi* Au. Ag
replacement
local and Mine porphyry K, Ca, Rb. Sr. Cu. Zn. Mo. S 2-30/km2
Mn. (MG)
massive sulphides Fe, Mn, Na. K. Cu. Pb. Zn. (S) 150-200 m interval
Ca. Mg.
vein and (KjO). (Rb). (Sr) e.g. Cu, Pb, Zn. 5-10 m interval
replacement Au, Ag
TABLE 12.1 Summary of elements to be determined and surface sampling density for different
targets in regional , and local and mine scale exploration. Elements in parentheses
have been shown to be useful in some cases but have uncertain status; elements with
asterisk are expected to be useful but there are little data Si should be determined
in all cases where petrological variation is expected to cause variation to the content
of other elements. (Govett, 1983)
93
o 36 38
° O°.°o39
20 54
40 16 _OJ
4 V04^- - 69#
0'5
I-Ô"^.*23
65^*° ~ ?8 19 ®°Ôr
«%°6J M
On
130°
_i___
FIG 12.1 Cretaceous granitoids in the Canadian Cordillera sampled by Garrett, 1973. Black circles
are granitoids containing mineralization of the following type: 2 = Ag-Pb; 3 = Cu-Sb; 4 = Au;
5 = Au-Pb; 6 = Au; 8 = Pb-Zn; 9 = W, Au-Pb; 11 = no data; 12 = Zn-Ag-Pb; 13=W; 16 = Cu-W;
17 = Cu-Zn; 21 =W; 22 = Cu-Zn-W; 25 = Sb (Govett, 1983)
FIG 12.2 Distribution of mean Zn content in granitoids in northwest Territories (N.W.T.) and Yukon
Territory (Y.T.), Canada. (Govett, 1983)
94
FIG 12.3 Simplified geology, location of Bradina and Sam Goosly mineral deposits, and location
of rock samples, Goosly-Owen Lake area, British Columbia, Canada. (Govett, 19B3)
FIG 12.4 Distribution of As and Cu in rocks around the Bradina and Sam Goosly deposits, British
Columbia, Canada. (Govett, 1983)
95
Additional indications of some possible roles rock geochemistry might play in

exploration are provided by the discussion in Chapter 8 of the large primary haloes
associated with various types of mineralization. Many of these haloes should be readily
detectable by systematic geochemical rock sampling, if there is sufficient outcrop. The
hot spring-type gold mineralization (i.e. Round Mountain - Figure 8.11) and the sediment
hosted fine disseminated gold deposit (Pinson - Figure 8.12) examples are of particular
relevance in terms of current exploration priorities. The extensive nature of the
geochemical haloes commonly associated with sediment hosted fine disseminated gold
deposits are also illustrated by data from the Carlin District, Nevada, which was obtained
by Evans and Peterson (1986) in the course of a routine geological mapping program
(Figs. 12.5a, 12.5b and 12.5c). They provide further evidence of the potential value of
systematic geochemical rock surveys in exploration for this type of mineralization.
An interesting review of the application of bedrock geochemistry in mineral

exploration is provided by Govett (1989). A more recent discussion of the subject by
Franklin and Duke (1991) is primarily concerned with Canada, but their conclusions
regarding the need for close geological control and the potential value of parallel
mineralogical studies are of universal relevance.
Despite the potential advantages of rocks as sample media in many types of

geochemical exploration program, their use is often precluded by a lack of sufficient
exposure and/or a need for composite samples representing substantial areas. Hence
attention must frequently be concentrated on their surficial derivative products (e.g. soils,
stream sediments, etc.).
96
FIG 12.5a Carlin District, Nevada. Locations of samples

collected for analysis. See Figure 12.5c for
explanation of geologic symbols. (Evans and
Peterson, 1986)
FIG 12.5b Carlin District, Nevada. Map showing areas with
anomalousconcentrationof gold,arsenic, mercury,
antimony, copper, and lead and centers of aeroma
gnet ic anomalies. See Figure 12.5cfor explanation
of geologic symbols. (Evans & Peterson, 1986)
97
Tailing* pond Mine dump at

Carlin mine
QUATERNARY
Pliocene
and (or)
Miocene
TERTIARY
- Ollgocene
TERTIARY
OR
CRETACEOUS
CRETACEOUS
SIUCEOUS (WESTERN) ASSEMBLAGE TRANSITIONAL ASSEMBLAGE CARBONATE (EASTERN) ASSEMBLAGE
|______ | I-Upper Devonian DEVONIAN

Unnamed llmestona J Popovich Formation
I PSI | | OSa |
Undifferentiated Umeatone
DSI. Umeatone DEVONIAN
DSa. hydrothermally AND
altered Umeatone SILURIAN
| DSrm |
I °°b I ■ Roberta Mountain* Formation
II „ I SOh I SILURIAN
SOc 1I 1L SILURIAN
AND Brecdated AND
and altered
Chert and ihale J ORDOVICIAN carbonate Hanaon Creek Formation ORDOVICIAN
rocks
| 0« |
Eureka Quartzite ORDOVICIAN
| OP |
Pogonlp Group
I Ch I
CAMBRIAN
Hamburg Dolomite
.................................... CONTACT
......................... .......... FAULT —Dotted where concealed
—* a a a............... THRUST FAULT —Dotted where concealed
Teeth on upper plate
X LOCATION OF MINE AND (OR) DEPOSIT
FIG 12.5c Carlin District. Geological Legend

98
12.2.2. Soils
Soils vary considerably in composition and appearance according to their genetic,

climatic, and geographic environment. Classified into residual and transported types
according to their relationship to their substrate, soils are mixtures of mineral and biologic
matter and may be distinctively differentiated into a series of soil horizons.
Soils are most often sampled along traverses or grids in the follow-up or detailed
prospecting stages of geochemical programs. In rugged terrain initial follow-up surveys
of reconnaissance stream sediment anomalies is sometimes most readily achieved by
sampling soils along ridge and spur (Fig. 12.6), and/or base of slope (Fig. 12.7)
traverses. In recent years increasing attention has been given to low density soil
sampling (i.e. _< 1 sample per km2) in geochemical reconnaissance surveys and geochem
ical mapping. As has been previously stressed, orientation programs define criteria such
as sample depth or soil horizon to be sampled, sample interval, and the size-fraction for
analysis. It is essential that these criteria be observed resolutely through the survey.
Residual soils characteristically contain detectable dispersion patterns developed

during the weathering of mineralization in the underlying bedrock, and these patterns are
revealed by careful sampling of appropriate soil horizons. As might be expected, in view
of the size of the deposits and associated primary geochemical haloes, near surface
sediment hosted fine disseminated gold deposits in semi-arid areas, such as Nevada, are
commonly reflected by extensive geochemical anomalies in the immature residual soils.
It is therefore not surprising that geochemical soil (generally C - horizon) sampling has
assisted in the discovery of a number of these deposits (e.g. Alligator Ridge, Jerritt
Canyon, etc.). Some indication of the size and nature of soil anomalies which might be
expected in the vicinity of such mineralization is provided by Bagby, et al., (1984) in a
study of soils over the Dee Deposit, Nevada. The minus 80 mesh sieved fraction of 159
C horizon soil samples were analyzed for a number of elements including Au, As, Sb, Ag,
and Hg. The resultant geochemical data display anomalous patterns over and in the
immediate vicinity of the known "shallow" (> 100 feet - 40 m) and "deep" (>300 feet -120
m) ore zones (Figs. 12.8 and 12.9). These could be readily detected in routine
geochemical soil surveys based on, say, a 30 m grid.
Deeply weathered residual soils can also provide useful geochemical sampling
media. An example of use of lateritic soils as a regional geochemical reconnaissance
sample medium is provided by Lewis et al (1989). Lateritic soils were sampled on a 400
m grid in a UN exploration reconnaissance program for Archean metavolcanics hosted
massive sulfide (i.e. VMS) mineralization in the West African nation of Burkina Faso.
Follow-up soil sampling on a 25 m grid spacing of small weak anomalies detected in the
reconnaissance phase (Fig. 12.10) confirmed the existence of a distinct 550 by 250 m Zn
anomaly (i.e. >200 ppm) (Fig. 12.11). Subsequent drilling resulted in the delineation of
a major VMS deposit.
99
500 meters
FIG 12.6 Example of ridge-and-spur soil-sampling

pattern. Cebu Project, Republic of Philip
pines. Data on -80-mesh fraction. (Rose,
Hawkes, & Webb, 1979)
Lemieux District, Quebec. Data on -1cm

fraction. (Rose. Hawkes & Webb, 1979)
100
FIG 12.8 Spatial variation of anomalous soil samples. Symbols represent the histogram groups.
Outlined samples are those that have element concentrations in the upper two histogram
groups and are considered anomalous for this sample population. Deep ore =; shallow
ore \\\\ and UH- (Bagby et al., 1984)
101
FIG 12.9 A) Outlines of areas with samples that contain anomalous

values. The large outlined area contains samples that are
anomalous for more than one element, whereas the two
smaller areas contain samples that are anomalous in only
one element. Ore zones are shown as in Figure 12.8. B)
Outlines of the anomalous areas from Figure 12.9a with the
addition of smaller anomalies defined by areas containing
three or more samples with concentrations in the uppermost
histogram group. (Bagby et al, 1984)
102
-ISO - 500 - 600

Maule de 50m ■ 25 m
FIG 12.10 Regional soil geochemistry (Zn) in

the area around the Perkoa Deposit,
Burkino Faso. Values in ppm. (Lewis,
et al., 1989)
FIG 12.11 Detailed geochemistry (Zn) in the

vicinity of the Perkoa Deposit, Bur
kino Faso. Values in ppm. (Lewis, et
al., 1989)
103
Geochemical soil sampling can also constitute a useful technique in gold

exploration over lateritic terrain. The potential effectiveness of this approach is illustrated
by a recent study of surface pisolitic laterites over the Saddleback Greenstone Belt, in
Western Australia (Smith, 1989). The data reveals that the large (45 million tonnes at 1.8
g/t Au) Boddington gold deposit, which comprises extensive laterite, saprolite and
supergene reserves over a primary volcanogenic massive sulfide source, displays q
surface chalcophile element halo measuring some 30 km by 4 km (Fig. 12.12b). In
contrast the surface gold halo extends over an area of some 3 km by 1 km (Fig. 12.12a).
The large size of the chalcophile element anomaly in the surface laterite is thought to
reflect the retention of As, Sb, Bi, etc. in the Fe-oxyhydoxides and Sn and W in resistant
minerals during the laterite soil profile development, and subsequent lateral mechanical
dispersion (Fig. 12.13). (Thus the soils are not completely residual, in the strictest sense.)
The "mushroom-form" of the zone of gold concentration in the subsurface saprolites (Fig.
12.13) is thought to reflect leaching and supergene enrichment during post-laterite
modification of the weathering profile. Both low density (i.e. < 1 per km2) reconnaissance
and higher density follow-up geochemical soil sampling techniques could obviously play
useful roles in exploration for Boddington-type gold occurrences. The Boddington
example also demonstrates the need for care when using residual soils as geochemical
exploration sample media. Hydromorphic dispersion can sometimes produce epigenetic
soil anomalies located some distance from the bedrock source.
A similar "soil" sampling method developed in recent years for deeply weathered
semi-arid areas with long weathering histories, utilizes the surface residual concentrations
of hard rock fragments (generally siliceous and/or ferruginous) which remain after most
of the fines have been blown away. In Australia this sample media is known as "lag"
(Carver, et al., 1987), and has been successfully used in exploration for gold and base
metal sulfides. Figure 12.14 illustrates the far larger size of a gold anomaly defined by
"lag" samples from a 400x50 m reconnaissance grid, compared to that displayed by
follow-up bulk soil samples from a 100/20 m grid in the Eastern Goldfields Province of
Western Australia. Some success in comparable terrain (Australia and Botswana) has also
been claimed (Farrell, 1984) on both regional and local scales for a geochemical
exploration method based on the heavy mineral concentrate fraction of soils (i.e. "loam"
concentrates).
Transported soils present especially difficult sampling problems, but meaningful

surveys are possible in many areas once the genetic origins of the transported cover are
understood. In glaciated areas, for example, soils derived from glacial dispersion trains
can present far larger targets than the suboutcropping source mineralization. At Buchans,
Newfoundland, extensive soil anomalies, overlying tills, reflect glacial dispersion trains
which extend for some miles "down-ice" (i.e. southwestward) from suboutcropping
volcanogenic massive sulfide mineralizations (Fig. 12.15). Anomalous "hot-spots" reflect
locally enriched (or better exposed) portions of the dispersion train which are often far
104
Chalcoptvle Index
CHI - ®*x
FIG 12.12 Reconnaissance laterite geochemistry over the Saddleback Greenstone Belt. Western
Australia, showing dispersion patterns about the Boddington Au deposit. (Smith,
1989)
FIG 12.13 Diagrammatic cross-section depict-ing retention of chalcophile elements such as As,
Sb, Bi, In, Mo, and perhaps Ge in the Fe-oxyhydroxides and Sn and W in resistant
minerals in lateritic duricrust, whereas Au has undergone leaching and supergene
enrichment during post-laterite modification of the weathering profile. (Smith, 1989)
105
soils, Eastern Goldfields Province, Western Australia.

(Carver et al., 1987)
FIG 12.15 Zinc anomalies in soils, Buchans District. (James and Perkins, 1981)
106
from their bedrock source. In this type of situation, unless the nature of the surficial
environment is fully appreciated, time and effort could be wasted in fruitless searches for
mineralized bedrock sources in the immediate vicinity of many of the anomaly "peaks".
In some areas with barren exotic overburden the soil humus horizon (alternatively
known as mull, Ao, or Ah material) constitutes an effective geochemical sampling medium.
As discussed below in the section dealing with geochemical surveys based on vegetation
sampling, the root penetration of plants sometimes exceeds the thickness of barren cover •
and obtains nutrients from underlying mineralized bedrock and/or anomalous ground
water. In glaciated areas, deep rooted plants can sometimes obtain nutrients from
anomalous till dispersion trains (related to nearby suboutcropping mineralization) which
are obscured by barren oveburden. The seasonal fall of leaves and needles transfers
some of the accumulated metals to the surface soil where they are incorporated in the
humus. An early demonstration of the potential effectiveness of mull sampling in gold
exploration was provided by Curtin et al. (1971) in a research study of the Empire mining
district, Colorado. Au distribution patterns in mull (Fig. 12.16) were found to more clearly
reflect glacial sediment covered gold bearing quartz/sulfide veins than the Au distribution
patterns for the C horizon soils (Fig. 12.17). More recently, considerable attention has
been given to the use of humus as a geochemical sample medium in the Canadian
Shield. Gleeson and Sheehan (1987) report an absence of humus response around the
Doyon gold deposit in Quebec Province, presumably due to the presence of 1 m of
relatively impermeable glaciolacustrine clay and silt that overlies the 1 m to 2 m of i
anomalous, locally derived till. At the Williams property, in the Hemlo district, generally
poor response is reported for "B" horizon soils due to the presence of several meters of
exotic calcareous till. However, humus samples show well defined gold anomalies (Fig.
12.18) over gold occurrences and associated anomalous glacial dispersion trains (Fig.
12.19) . They conclude that in the Hemlo district humus sampling is an effective
geochemical exploration medium over terrain underlain by up to 5 m of permeable
overburden (exotic or otherwise), whilst "B" horizon sampling should be confined to areas
where the till cover is thin or absent (i.e. <1 m).
Attention is drawn to a useful check list for the organization of soil surveys (Table
12.2) which also has some relevance to other types of sample media.
12.2.3. Stream Sediments
Stream sediment is one of the more commonly used media for regional
geochemical surveys. The sediment at any point in a stream is a natural composite
sample of erosional materials from upstream in the drainage basin and can include clastic,
hydromorphic, and biogenic contributions from any weathering mineralization present.
The length of anomalous dispersion trains will vary with the nature of the mineralization,
source, and the physicochemical environment of the field area or drainage basin. In
humid, actively oxidizing environments, dispersion trains from sulfide-rich base metal
deposits may extend downstream for some miles.
FIG 12.16 Empire Mining District, Colorado. Gold distribution in
mull ash. Light stipple, ash contains 0.2-0.59 ppm
gold; heavy stipple, ash contains at least 0.6 ppm
gold. Heavy lines are veins. (Curtin, et al., 1971)
107
FIG 12.17 Empire Mining District, Colorado. Gold distribtuionin

soil (6-to 12-inch depth). Light stipple, soil contains
0.2-0.59 ppm gold; heavy stipple, soil contains at
least 0.6 ppm gold. Heavy lines are veins. (Curtin et
al., 1971)
108
FIG 12.18 Hemlo Gold District, Ontario. Williams Option - gold in humus.
(Gleeson and Sheehan, 1987)
FIG 12.19 Hemlo Gold District. Ontario. Williams Option - gold in basal till,
-250 mesh fraction. (Gleeson and Sheehan, 1987)
109
Item Check
FIELD PARTY numbers, composition, experience. leader
TRAINING when, where, by whom
BASE MAPS appropriate scale, topography, etc.
NUMBERING SCHEMES simple unambiguous, avoid complex alphanumerics
FIELD NOTES make sure they are taken correctly
QUALITY CONTROL collect field duplicate samples and insert, with standards, in batch submitted to laboratory
COMMUNICATIONS must be simple and direct. Only designated personnel should actually give instructions to the
WITH LABORATORY laboratory.
SHIPPING LISTS must accompany every consignment sent to the laboratory
INSTRUCTIONS give clear unambiguous instructions to the laboratory
RETURN OF DATA check duplicates, standards, etc. for quality of analytical data, request reanalysis when in doubt
DATA HANDLING manual or computer aided. What procedures are best for your project?
INTERPRETATION MAPS prepared to summarize geochemical features
INTEGRATION OF FIELD used to qualify interpretation of geochemical data
NOTES
STORAGE OF DATA need to be able to retrieve for reinterpretation
ARCHIVE OF SAMPLES at laboratory, office or warehouse
INTEGRATION WITH ensure good communication with management and other project personnel
OTHER EXPLORATION
PROCEDURES
REPORTING author of report must be familiar with field program
TABLE 12.2 Checklist for the organization of a geochemical soil survey. (Thomson, 1987)
As has been recently pointed out (Plant, et al., 1989) stream sediment samples fall
into two broad categories:
(i) representative samples;

(ii) samples designed to enhance patterns or anomalies related to specific
mineral deposit types.
Representative samples are the basis of most regional geochemical mapping

programs conducted by national survey organizations, as well as some regional
geochemical exploration surveys undertaken by mining companies. They commonly use
active stream sediment (i.e. material constantly or frequently washed by stream waters)
that is most representative of catchment erosion products, including petrogenic elements,
in a wide variety of climatically influenced weathering environments. In most of these
survey programs, approximately 500 to 1000 g of fine-grained material is collected from
the upper few inches of the sediment near the center of a drainage, avoiding sites that
may be contaminated or influenced by bank collapse. In most situations samples are
best collected with the aid of a (non-contaminating) steel shovel or plastic scoop.
Ballantyne (1991) recommends use of the latter in flowing streams as the scoop walls
help minimize loss of fines.
110
RIVER RIVERPLAIN
SUSPENDED RIVERPLAIN SEDIMENTS

load
mVo'^-'XT MAj c
rJ.CV. YQ t>,.,
5 BED LOAD
•^PÂ:
FIG. 12.20a Water discharge of a river under ordinary conditions with

normal amounts of water. (Otteson et. al., 1989)
FIG 12.20b Water discharge of a river during a major flood. Overbank

sedimentation takes place on the river plain.
(Otteson et. al., 1989)
Where active stream sediment is unrepresentative due to localized nature of current

fluvial erosion (Figs. 12.20 and 12.21), as in many parts of Scandinavia and else-where,
vertical composite samples of "overbank" (i.e. levee or flood plain) material have proven
more effective (Otteson, et al., 1989). These are derived from many episodes of flood
sedimentation and are therefore far more likely to constitute a representative sample of
the whole catchment than regular active sediment samples. Avoidance of more recent
(i.e. near surface) sediment in and around industrialized areas helps minimize possible
effects from industrial contamination.
111
patterns for active stream sediment and overfcank

sediment may be influenced by mineralization and
sediment sources. In the stream on the right hand side,
the active stream sediment is dominated by sediment
source No. 1, a reason why the anomaly can be detected
only in the overbank sediment. In the middle river, where
no active sediment sources exist in the upper part, a
stream-sediment anomaly has developed where the
stream crosses the mineralization due to influence from
paleo-sources and a presently small, diffuse sediment
production occurring along the stream bed. This anomaly
is diluted by sediments from source 3. (Otteson et al.,
1989)
Regional geochemical mapping programs based on representative stream

sediment samples generally cover areas of thousands or even tens of thousands of
square miles. A majority of these surveys employ sampling densities greater than 1 per
5 km2, although the recent Nordkallott Project in Northern Scandinavia used a sample
density of 1 sample per 30 km2. Even lower density sampling (i.e. 1 sample per 500 km2)
was applied in a recent geochemical mapping survey (Fig. 12.22) of the whole of Norway
based on "overbank" sampling (Otteson, et al., 1989).
As mentioned above, representative stream sediments are frequently also used as

geochemical sample media in regional reconnaissance exploration programs. The results
of a fairly small but successful survey based on this medium are described by Webster
112
FIG 12.22 Hot nitric acid soluble Mo in overbank sediment, Norway. An anomalous sample down
stream from the Nordli deposit is indicated with an arrow. (Otteson et al, 1989)
113
and Skey, 1979). Geochemical analysis of stream sediment samples collected at a

density of 3 to 5 samples/km2 over an area of Cambrian volcanic rocks in northwestern
Tasmania (Fig. 12.23), resulted in the discovery of the Que River massive Pb/Zn sulfide
deposit. Frequently, anomalous response from target mineralization types can be
enhanced by subjecting stream sediment samples to selective analytical methods, as in
the Bulk Leach Extractable Gold (BLEG) or Bulk Cyanide Leach (BCL) technique which
has been used extensively in Australian gold exploration in recent years (Elliott and
Towsey, 1989). Large (often 5-10 kg) samples of active stream sediment (minus the
coarser fractions) are exposed to a weak cyanide solution which leaches out accessible
gold. The gold content of the leachate can then be analyzed. The method is extremely
sensitive and helps minimize "nugget effects'*. Obviously it can only be used where gold
is freely accessible (i.e. in fine particulate form, exposed on mineral surfaces, etc.) to the
leachate, and is most effective in deeply weathered areas and in samples which are free
of refractory materials and the gold is not occluded.
Geochemical exploration efficiency can in many cases be increased by collection

and analysis of specific fractions of active stream sediments or even alternative drainage
sediment components which, in certain circumstances, display more distinct and more
consistent indications of the presence of target mineral deposits than do representative
samples of active stream sediments. Probably one of the better examples of this type of
approach is provided by heavy mineral concentrates. These improve contrast for
elements such as tungsten (e.g. Turiel, et al, 1987), barium (Coats, et al., 1981) and gold
(Fletcher, 1985 and Maurice, 1991) when they are held in resistate mineral phases. They
are sometimes also useful in lateritic terrain where elements of interest are held in iron
oxides.
In some areas (e.g. southeastern U.S.A.) selective analysis of manganese and iron
hydroxide coatings on stream sediment particles (boulders down to fines) is an effective
method of detecting hydromorphically dispersed ore and pathfinder elements (Figs.
12.24a and 12.24b) which have been adsorbed and concentrated by these coatings
(Chao and Theobald, 1976; Carpenter, et al., 1975; Nowlan, 1976; Whitney, 1981; Hale
et al., 1984). However, interpretation of the resultant data can sometimes be difficult.
The ultra fine sieved fractions (e.g. minus 200 mesh - minus 75 microns) of stream
sediments have been shown to be effective geochemical exploration sample medium in
some arid and semi-arid environments. Observed advantages in both base metal
exploration in Australia (Mazzuchelli, 1980; Beeson, 1984), and gold exploration in Nevada
(Mehrtens, pers. comm. 1986) include more extensive and consistent anomalous
dispersion trains than those provided by other sample media such as heavy mineral
concentrates and the coarser sieved sediment fractions. In contrast Moeskops and White
(1980) found the +35 to -18 mesh (+0.5 to -1.0 mm) sieved coarse fraction to be
especially effective in a base metal exploration program in South Australia, whilst Zeegers
114
FIG 12.23 Geochemical results for the 1970-71 stream sediment survey. Que River Prospect,
Tasmania. (Webster and Skey, 1979)
115
FIG 12.24a Sample location map for Magruder Mine area, Georgia.
(Meyer et al., 1979)
FIG 12.24b Downstream dispersion from zinc, copper, and lead in

minus-80-mesh stream sediments and oxide coatings,
Magruder Mine area. (Meyer et al., 1979)
116
et al. (1985) recommended use of the
+ 250 mesh ( + 62 micron) fraction in
desert areas to avoid problems with
dilution by fine eolian sand.
Organic drainage samples have

been used in northern Scandinavia
(Fig. 12.25) and elsewhere due to lack
of normal sedimentary material for long
distances in stream channels (Larsson,
1976). In Scandinavia the samples
comprise organic debris in various
stages of humification and often
penetrated by the living roots of
various bog plant species. Elsewhere
other potential drainage sample media
have also been examined. For
example, aguatic mosses were studied
by Erdman and Modreski (1984) to FIG 12.25 Copper content of organic stream sedi
determine whether they might provide ments in the Vehkavaara area, Pajala
effective geochemical sample media in district. (Larsson, 1976)
areas where steep terrain prevented
accumulation of stream sediment fine fractions. This clearly constitutes a biogeochemical
exploration method and is therefore described in more detail in Section 12.2.6. However,
an interesting variant of the aguatic moss biogeochemical technigue was described by
Smith (1976) following a limited study of mineralized areas in Norway. Moss-trapped
stream sediment material was found to provide similar but higher contrast geochemical
patterns to those produced by normal stream sediment samples.
In the regional reconnaissance prospecting mode, stream sediment surveys can

be designed to systematically cover areas up to several thousand sguare miles. Average
sampling densities tend to be significantly higher than those employed in geochemical
mapping programs as the emphasis is on detection of dispersion trains related to
individual mineral districts and/or deposits, rather than broad mineral provinces.
Densities are freguently in the range 1 sample per 1-3 km2, whilst 1 sample per 20 km2
would be considered unusually low.
As has been discussed previously, in all surveys in new areas, the critical
parameters of sample interval, sediment size fraction, appropriate analytical procedures,
significant anomaly contrasts, and background levels are determined through orientation
surveys. In areas where no previous experience exists, a short interval of 150 ft. (50 m)
over an initial downstream distance of 1050 ft. (350 m) is recommended. This interval
should then be progressively expanded with distance from the metal source to the limits
of the known or anticipated dispersion pattern. Samples must also be collected from non
117
mineralized areas to establish the

background range and sufficient material
should be collected at each site to allow
for the determination of optimum size
fractions, analytical techniques, and other
factors listed in Tables 11.1, and 11.4).
12.2.4. Lake Sediments
Lake sediment sampling has been

developed into an effective geochemical
reconnaissance technique, particularly
within the Canadian Precambrian Shield,
but also within the Fennoscandian Shield
and the Cordilleran and Appalachian
regions of North America. The ideal
terrain for this technique is where lakes
are common, conditions are swampy,
and/or where stream drainages are
inaccessible or poorly developed (Coker
et al., 1979). In low relief regions, the lake
sediment medium is dependent on the
hydromorphic dispersion of metals into the
lake environment through ground waters FIG 12.26 Cut-away section of sample bailer for
and the adsorption of this metal onto lake-sediment sampling. (Rose et al,
hydrous oxides and the organic rich muds 1979)
(i.e. gytia) being deposited on the lake
bottoms. The sampling generally focuses on the collection of these organic muds using
specially designed sampling devices (Fig. 12.26). In more mountainous areas, fine
grained clastic dispersion into the lake sediment becomes a more important factor. In
most areas satisfactory sample locations-are found well away from lake shores and are
reached using boats, float planes or helicopters. However, near shore materials have
been successfully used in some programs in the northern part of the Canadian Shield
although these are generally subaqueous equivalents of glacial and postglacial sediments
on the margins of lakes and not true lake sediments. Lake water samples (see Section
12.2.7.) are commonly collected at the same sites as the lake sediments.
The lake sediment technique has successfully indicated the presence of several
important forms of mineralization as the following examples clearly demonstrate. In
Saskatchewan the Key Lake and Rabbit Lake uranium mineralizations and associated
anomalous glacial dispersion trains are reflected by extensive lake sediment anomalies
(Figs. 12.27 and 12.28). Equally impressive anomalies are found in the vicinity of the
118
Key Lake U-Ni deposit, Saskatchewan. (Coker et al.,

1979)
FIG 12.28 Uranium (ppm) in lake sediments near the Rabbit Lake
uranium deposit, Saskatchewan. Location of deposit
shown by solid triangle. (Coker et al., 1979)
119
Agricola massive sulfide

deposit, Northwest Territories
(Fig. 12.29), and in fact assisted
in its original discovery (Coker,
1979). More recently a number
of authors have reported on the
application of lake sediment
geochemistry to gold explora
tion. McConnell and Davenport
(1989) carried out extensive
orientation studies in
Newfoundland based on the
geochemical analysis of organic
sediment collected from lake
centers. It was determined that
most, but not all known Au
occurrences were distinguished
by anomalous Au concentra
tions in nearby lake sediments
(Figs. 12.30 and 12.31).
Pathfinder elements (Sb, As, Pb,
Cu and Zn) display inconsistent FIG 12.29 Distribution of Zn (ppm) in nearshore lake bottom
materials, Agricola Lake area, N.W.T. (Coker et al,
relationships to gold mineraliza
1979)
tion and it was concluded that
Au is the only universal
indicator. They suggest that for detailed exploration a sampling density of at least 1
sample per 4-5 km2 is necessary.
Useful reviews of the application of lake sediment geochemistry in mineral

exploration in Canada are provided by Hornbrook (1989) and Friske (1991).
12.2.5. Glacial Sediments
Extensive Quaternary glacial deposits occurring over most of Canada and the
northern United States, northern Europe, northern Asia, Geenland, and a number of high
elevation areas in the southern hemisphere have presented major challenges to
exploration. As a better understanding of the origin and formation of these glacial
sediments has grown, their blanketing presence has become progressively less
formidable and effective exploration techniques have been developed.
Mineralized boulder tracing in glaciated regions is an established technique of the

traditional prospector in Scandinavia and parts of Canada. In Scandinavia, dogs have
been trained to assist the prospector by sensing SO2 released from oxidizing sulfide
boulders at shallow depths below the surface. In Finland, methods were developed for
120
DEVONIAN
6 Wmoowgiatt Hili G'*n>i« eieaarfe
S Windsor Ponl Group mal>c ano Zer»< tullt
SILURIAN - ORDOVICIAN Georog>ce> Pounder*
« Cam Ra* Granite
'bull
ORDOVICIAN
Giactai no* tfrrecrion
3 FoMrM/OflAMe Antf g'ArtifpW rQcAl
3 Ptlitrt ICfHII A«C A"lp'«'0OZ<f» fA local B. nagionan
CAMBRO ORDOVICIAN
1 Long Range Ma*< - (M*enw*c Como/er
FIG 12.30 Gold In lake sediment, Cape Ray Fault area, Newfoundland.
(McConnell and Davenport, 1989)
CARBONIFEROUS
6 Ow Lake Group cnii't iac>fnontary >oc»i
DEVONIAN
7 Gu" LA*e Intrusive Suite gran,re g<anoo-or>ia
tonaino, gabbro
SILURIAN
6 Sops Arm Group sedimentary roc* I Iblt-C ano
minor mahc •oicanrc roc*s
CAMBRO ORDOVICIAN
S Southern While Ba* Aliocntho" tonsure
greenicn>if me«agre»wac*e •noângt
4 Cone* Arm G»oup matacaibonata ano caat'C
rocei
PRECAMBRIAN
3 Oevii ■ Room G>Anne
2 2a Fionch Chi'di gr*nocior'’e 2t> giomta
1 Gneui emph<Do'>re pAOOro
GoW Minere'rjetron ■
Gooiogicoi bovnoary — ——
fault — — —
Gtociol HO- OiffChon .
fA. eerr*. B nrej
el
FIG 12.31 Gold in lake sediment, White Bay area, Newfoundland.

(McConnell and Davenport, 1989)
121
1979)
sampling tills in the 1950’s, and this technique is now the preferred sampling method in
most Finnish geochemical exploration programs. Esker sampling and till sampling for
distinctive heavy mineral suites have been used for kimberlite and diamond prospecting
in the Canadian Shield.
Approximately 70% of lodgement till is locally derived, and most of the early
success with till sampling was in areas of shallow till cover (less than 30 ft or 10 m) where
the sample medium is reasonably accessible. In the 1960’s, lightweight percussion drills
such as the Pionjar and Cobra models, were adapted to collect small samples of till from
immediately above the suboutcropping bedrock to geochemically categorize anomalous
geophysical features at depths of up to 70 to 80 ft (23 to 25 m) (Gleeson et al., 1971).
Overburden drilling technology, particularly reverse circulation (Fig. 12.32) and sonic
drilling, advanced rapidly with the utilization of larger drills in programs for uranium, base
metal and gold deposits in glaciated areas.
Because most types of gold deposits are not detectable by conventional

geophysical methods, lodgement till sampling using overburden drills to depths of 330 ft
(100 m) has been routinely used in prospecting for gold in the Canadian Shield since the
early 1980’s. In these programs large samples of till (approximately 20 lb or 10 kg) are
122
FIG 12.33 Idealized geochemical dispersion model for lodgement till. (Miller, 1984)
generally recovered and the heavy mineral fraction is separated and examined both
visually and chemically for gold and other metals. It is essential that the whole of the
lodgement till section is routinely sampled as indicator trains tend to rise down-ice along
smear or thrust planes within individual till formations as shown in Figure 12.33. Even in
this simple example, significant parts of the dispersion train will not necessarily be
detected if attention is restricted to till immediately adjacent to bedrock. Adequate
sampling becomes even more critical when there are several lodgement tills related to
distinct glacial episodes in an area with pronounced bedrock topography (Fig. 12.34).
In the hypothetical example shown in the figure three mineral deposits suboutcrop
beneath lodgement tills which have been sampled by six vertical drill holes. Samples of
till from hole 01 will not contain anomalous indications because the site is up-ice of
mineralization. Hole 02 will contain anomalous material related to Mineralization A in
"basal" till (2). Hole 03 will contain a strong anomaly in "basal" till (1) related to
Mineralization B and a weaker, distal anomaly in an "upper" till (2) related to Mineralization
A. Hole 04, because of the effect of bedrock topography and the constriction of till
deposition and possibly accelerated erosion of earlier till over the bedrock escarpment,
will contain no anomalous material related to either Mineralizations A or B. Hole 05 will
contain anomalous material related to Mineralization C in its "basal" till (4) but hole 06 with
123
ICE MOVEMENT ----------------------------------------------------
01.02.. OVERBURDEN DRILL HOLE SITES
FIG 12.34 Diagrammatic overburden profiles in the Abitibi clay belt, Ontario.
124
no lodgement till will not provide material suitable for sampling. The correct interpretation
of till data is obviously dependent on a thorough understanding of local glacial sediment
stratigraphy and provenance. The technique is expensive, with combined drilling, sample
treatment, and analytical costs ranging from $20 to $30 per foot ($66-$99 per m), but it
is cost effective in deep overburden covered environments where other exploration
methods have not been as successful, especially in gold exploration.
Up to now the majority of the glacial overburden drilling programs in North America
have primarily relied on geochemical analysis of the heavy mineral concentrate fraction
of overburden samples. Several significant gold deposits have been discovered in Canada
by this method. For example, in the Casa Berardi area of Quebec the technique was
successfully used in follow-up of favorable stratigraphic zones delineated by geophysical
methods (Sauerbrei, et al., 1987). Initially, orientation studies of glacial overburden
overlying a portion of this stratigraphic sequence known to contain pyrite-arsenopyrite-
native Au bearing quartz-carbonate vein mineralization (Golden Pond deposit) had
enabled determination of optimum geochemical procedures for the district. Targets were
first tested with overburden drill holes located 25-100 m down-ice at 300-400 m intervals
along strike (Fig. 12.35a). Closer spaced overburden drilling was used to further define
anomalous dispersion trains prior to diamond drilling of bedrock (Fig. 12.35b) which
resulted in the discovery of the Golden Pond East zone. The gold content of heavy
mineral concentrate samples from the overburden were determined both visually and by
analysis. The samples were also analyzed for As and Sb. It should be noted that in this
particular area glacial dispersion of gold is only of the order of 200 to 400 m.
The degree of complexity sometimes observed in till stratigraphy and glacial

dispersion, which was previously alluded too, is clearly shown by the work of Bird and
Coker (1987) in the vicinity of the Owl Creek gold mine, Timmins, Ontario. They defined
four distinct glacial episodes each with different ice movement directions. In the lowest
(older) till, which directly overlies bedrock, gold dispersal (as determined by analysis of
heavy mineral concentrates) is very limited-, as it is truncated against a bedrock ridge (Fig.
12.36). The highest gold concentrations are located adjacent to the subcropping gold
occurrence. The overlying till has not been in contact with the mineralization and has
derived it’s gold from the lower till. This disperal train is longer (approximately 600 m, and
maximum gold values in heavy mineral concentrates are displaced 300 m down-ice from
the mineralization (Fig. 12.37).
A successful gold exploration program using both geophysical and geochemical

techniques is described by Harron, et al. (1987). Around 90 overburden sampling drill
holes were completed to test specific geophysically defined targets in an area virtually
devoid of outcrop. On the first pass, sampling of overburden drill holes at 800 to 1200
ft intervals perpendicular to the ice transport direction yielded anomalous gold values in
the heavy mineral concentrate fraction of till and carbonatized quartz pyrite-rich bedrock
chips. Subsequent induced polarization-resistivity surveys defined the areal extent of a
pyritic carbonate alteration zone. A second pass till sampling and shallow bedrock
125
FIG 12.35a Plan showing results of reverse-circulation drilling from the Golden Pond
orientation survey and exploration follow-up east and west of Golden Pond,
Quebec. Anomaly classification is based on the highest heavy mineral
concentrate (HMC) gold assay from the bottom three samples. (Sauerbrei
et al., 1987)
Gold in Heavy
Mineral Concentrates • Phase I
UJ
• Au > 2.0 ppm • Phase II
« Au 0.5 - 2.0 ppm
o Au < 0.5 ppm
FIG 12.35b Plan showing the results of the initial and follow-up phases of reverse
circulation drilling at Golden Pond East, Quebec. (Sauerbrei, et al., 1987)
126
HG 12.36 Owl Creek Gold Mine, Timmins, Ontario. Gold

values for "Older" till. (Bird and Coker, 1987)
FIG 12.37 Owl Creek Gold Mine, Timmins, Ontario. Gold
values for Matheson till. (Bird and Coker,
1987)
127
sampling program was then

used to determine the gold
potential of this zone. The
heavy mineral concentrate
fraction of the till samples
delineates an anomalous (i.e.
reportedly 22000 ppb) gold
dispersion train of fairly limited
extent as shown in Figure 12.38
(i.e. extending for hundreds
rather than thousands of feet
down ice). The short dispersion
train is thought to be related to
the presence of a bedrock ridge
down ice from the auriferous
veins.
Despite the exploration

successes resulting from the FIG 12.38 Murphy-Hoyle J. V., Timmins area. Ontario,
use Of heavy mineral Canada. Gold in till anomaly plotted in relation to
concentrates from till, caution is induced polarization/resistivity and horizontal loop
recommended. In view Of the electromagnetic survey results. (Harron, et al.,
variable nature of target 1987)
mineralizations and the
weathering history of the glacial overburden, heavy mineral concentrates will not
necessarily always constitute the optimum sample medium for geochemical analysis.
There have in fact been a number of reports of the successful use of the ultra fine sieved
fractions (e.g. <2 microns) of glacial overburden samples in Canada and Scandinavia
(Coker and DiLabio, 1989, Shilts, 1984, Nikkarinen, et al., 1984). It is thought probable
that in weathering tills the fine grain size phyllosilicate and secondary minerals act as
scavengers, and adsorb trace metals released during the breakdown of sulfide and other
minerals. However, in view of the practical problems associated with the preparation of
sufficient <2 micron material for analysis, the <63 micron (<250 mesh) is more
commonly used. Shelp and Nichol (1987) demonstrate, using data from the Hemlo Au
district and the area containing the Owl Creek Au deposit, Ontario Canada, that the <63
micron fraction can be a more effective geochemical sample medium than heavy mineral
concentrates, at least when target mineralizations contain ultrafine gold. At Hemlo the
HMC gold anomaly decays far more rapidly than that associated with the sieved fines
(Fig. 12.39). At Owl Creek they are broadly comparable in extent (Fig. 12.40). It should
be noted that Scandinavian explorers place a greater routine reliance on the minus 63
micron (minus 240 mesh) fraction of till than do the Canadians. This fraction has
successfully indicated the presence of several types of mineralization, including gold, in
Scandinavia.
128
heavy-mineral fraction of till assocated with

mineralization at Hemlo, Ontario. (Shelp and
Nichol, 1987)
mineral concentrate and the -63 p,m fraction of

tills from Owl Creek, Ontario. (Shelp and Nichol,
1987)
129
In view of the general complexity of glacial sediments and the need for correct
identification of the material being sampled, effective geochemical exploration in glacial^
terrain reguires the participation of Quaternary geologists or at least geologists with some
training in Quaternary geolQQV (Coker, 1991).
Probably the best recent reviews of geochemical exploration in glacial terrain are
provided by Coker and DiLabio (1989), Coker (1991) and Shilts (1991).
12.2.6. Vegetation
Early scientific observers dating from the eighth and ninth centuries recorded that
the morphology and distribution of certain plants were affected by the presence of metals
in the soils. Such visible variations in a plant species are referred to as geobotanical
indicators. Many other plants, while not showing any visible variations, are capable of
concentrating metals in their tissues and the presence of anomalous metals in the soils
or ground waters is often reflected in the metal content of leaves, twigs, or other plant
organs. These invisible metal concentrations are known as biogeochemical indicators
(Brooks, 1972).
Geobotanical and biogeochemical indicators are of greatest potential interest ..as

mineral exploration tools jn areas where soil sampling is ineffective (e.g. jn areas with
barren transported overburden). Deep penetrating root systems can sometimes provide
surface evidence of bedrock and ground water geochemistry (i.e. they allow the
prospector to "see through" the overburden). Conseguently, these techniques, in
particular biogeochemistry, have been applied with varying degrees of success in
glaciated regions of North America (Boyle et al., 1969), Europe and Asia, and in arid and
semi-arid areas, like the Southwestern United States, where pediment, colluvial, and
alluvial cover is extensive (Chaffee, 1977).
Although a number of papers and books on geobotany have been published over
the years, there is little evidence of extensive direct surface application in mineral
exploration field surveys. The bulk of the published studies are of an academic nature
(e.g. Cannon, 1979) rather than case histories of successful exploration programs. This
presumably, at least to some degree, reflects the fact that effective application of
geobotany requires highly developed botanical skills which are unlikely to be found in the
majority of exploration groups. In addition, effective programs for large areas are difficult
to design as the results of orientation studies are often likely to have only restricted
applicability due to the wide variety of environmental factors which can influence plant
growth. Probably the greatest potential value geobotanical features have in mineral
exploration is indirect. Suitably enhanced satellite imagery may sometimes detect
distinctive spectral responses related to vegetational associations, together with other
surface features, whose distribution patterns disclose significant (i.e from a mineral
exploration point of view) regional structural and lithological features (Cole, 1980). In
130
addition anomalous plant communities associated with mineralization may sometimes be

recognized on conventional air photographs.
Some of the few well documented examples of the use of geobotany in a mineral
exploration program are provided by Cole and Le Roex (1978), and Cole (1980). Initial
air and ground reconnaissance and orientation surveys of large areas with hot and semi-
arid climate in South West Africa and Botswana revealed distinctive vegetation
associations that distinguished areas of near surface Proterozic bedrock from those with
thick cover of Kalahari Sand and calcrete. The recognition of anomalous plant
communities (Figs. 12.41a, 12.41b and 12.42) at one of these locations with thin cover
resulted in the discovery of sedex-type copper mineralization. It should be noted that the
mineralization is also reflected by distinctive soil anomalies (Fig. 12.43) which could also
have assisted in the discovery. Subsequently, regional exploration of some 1000 km
strike length of thinly covered potential host strata, using a combination of geobotanical,
biogeochemical and geochemical (soil) techniques, resulted in the discovery of a number
of similar mineral occurrences.
An interesting application of geobotany in gold exploration in Finnish Lapland is

described by Pulkkinnen, et al. (1989). They found that host rocks for gold mineralization
(i.e. carbonatized and mica-altered zones within a volcanic sequence) support a distinctive
vegetation despite the presence of glacial overburden (mainly lodgement till). Hence
potential target areas could be effectively delineated during follow-up of anomalies '
detected in the course of regional geochemical mapping based on till and drainage
sampling.
Although biogeochemistry has found wider acceptance than geobotany in mineral

exploration, it is still generally far less popular than the techniques described in the
preceding sections (i.e geochemical methods based on rock, soil, stream sediment, etc.,
sampling), mainly due to the difficulties associated with program design and data
interpretation. Plants are complex organisms and so is their metabolism. Different
species respond differently to the same conditions and consequently some species are
more effective biogeochemical indicators than others. For example, deep-rooted plants
(e.g., the mesquite) are much more effective prospectors of the deeper ground waters
than the shallow-rooted flora of the southwestern U.S. deserts and are, therefore,
generally preferred species in biogeochemical work in this particular region.
Nevertheless, shallow rooted plants growing in transported cover may reveal meaningful
patterns in some desert regions. Evapotranspiration has been suggested as a
mechanism for movement of metals into the nutrient depth of these plants.
131
Areas of Helichrysum leptolepis and associated Fimbristvlis exitis.

Aristida congesta and Eragrostis denudata
Scattered occurence of Helichrysum teptolepis
Association of Aristida congesta, Eragrostis denudata

and Anthephoro pubescens
0 100 200 m
Areas of Stipogrostis uniplumis U -L-------- J
Association of Ocimum americonum. Nidorello resedifolio,

Enneapogon brachystachus and Fingerhuthia africano
Dense shrub cover
FIG. 12.42 Vegetation assocations and Helicbrysum leptolepis (DC) occurrences over one area near
Witvlei, Namibia. (Cole, 1980)
132
FIG 12.41b (Cole, 1980)

(— f— I I
133
FIG 12.41a Species distribution,geology along a transect across several zones of Helichrysum leptolepis(DC) occurrencesin Witvlei
area, Namibia. (Cole, 1980)
134
FIG 12.43 Copper values in surface soil in area shown in Fig. 12.42. (Cole, 1980)
Some species preferentially concentrate metals in specific tissues such as leaves,

twigs, bark, or wood. It is therefore very important to establish the most favorable tissues
for sampling once a useful species has been identified. This complexity is accentuated
by the fact that metal uptake may vary with aspect and season (Table 12.3). In temperate
forest regions, accelerated uptake and higher concentration commonly occurs during the
spring growth following a dormant winter season. In hot desert regions, following the
exhaustion of available near-surface water during the dry season, deep rooted plants will
tap the deeper groundwaters. Because of these seasonal variations, biogeochemical
surveys must be completed quickly in the optimum period(s) defined by the orientation
studies.
These variables make biogeochemical sampling a very specialized exercise. Some

expertise in botany as well as exploration geochemistry is essential for both the
orientation studies and the supervision of vegetation surveys. On the other hand the
basic field equipment required for biogeochemical sampling is very simple (Dunn, 1991):
135
-
Alder Twigs Alder Leaves
Gold (ppb) in ash Gold (ppb) in ash
1984 1985 1984
Site Early Early Mid Mid June August September

June August September April
1 32 7 23 250
2 53 6 17 47
3 58 9 20 130 43 6 19
4 34 6 15 166 48 7 15
5 29 8 10 37 27 18 11
6 35 7 11 34 21 6 12
7 23 6 13 57 25 7 13
8 25 8 13 41 21 13 13
9 25 11 20 27 21 11 16
10 8 20 14 20 6 <5
11 29 20 23 75 11 8 22
12 35 10 22 58 8 7 8
13 23 8 14 51 6 6 9
14 12 17 18 33 10 8 8
15 24 10 11 53 14 7 18
16 25 11 12 42 5 10 13
17 14 11 9 66 13 <5 13
18 21 10 38 48 8 7 14
Mean1 28 10 17 69 18 8 14
(0.56) (0-2) (0-34) (1-38) (0-9) (0-4) (0-7)
i Values in parentheses have been recalculated to dry weight basis.

Ash yield of dry twigs is about 2 percent; Ash yeield of dry leaves is 5 - 6 percent.
TABLE 12.3 Seasonal changes in the gold content of ashed alder twigs and leaves. (Dunn.
1991)
136
(i) a pair of anvil-type non-contaminating (e.g. brass-free) pruning shears,
preferably Teflon coated;
(ii) fairly large sampling bags (e.g. 20 x 30 cm). Use heavy duty coarse brown
paper bags when conditions are dry and cloth bags when conditions are
wet;
(iii) roll of masking tape or stapler to close bags;
(iv) very large pack. Although samples are not heavy they are extremely bulky;
(v) hunting knife or hatchet for bark sampling.
Dunn (1991) also provides a useful summary of the procedures to be used and the
precautions to be observed when conducting a biogeochemical survey (Table 12.4).
Dunn (1987) has pointed out that with some species, sampling of bark (a dead
tissue) can be an effective technique that is not subject to seasonal metabolic variations.
The potential value of humus as a geochemical sampling medium has already been
discussed in the section on soil surveys. This again avoids the effects of seasonal
variations as the accumulated material constitutes an integrated sample. Weathering,
leaching, and bacterial decomposition will work to diminish the metal contents, but
signatures in mull are generally preserved.
In view of current interest in gold exploration, some examples of recent

biogeochemical studies in gold areas are probably particularly appropriate. Unfortunately,
the few case histories published to date on the application of biogeochemistry in gold
exploration over alluvial and colluvial covered semi-arid areas in the western United States
are mostly somewhat inadequate. One by Busche (1989) suggests the presence of
possibly anomalous concentra-tions of gold in the leaves of creosote bushes over both
exposed and colluvium covered epithermal quartz stockwork vein gold at Standard Hill
in the Mojave District, California (Fig. 12.44). As no soil data are provided it is uncertain
whether the apparent anomalous geochemical response is confined to the plant cover.
Another test survey has been described by Erdman, et al. (1988) of the U.S.G.S.
Limited studies were made of sage-brush geochemistry over skarn-, disseminated gold
and silver-, and hot springs-type mineral occurrences in Nevada. The results are again
far from definitive, but apparently anomalous gold was detected in ashed stem and leaf
sagebrush samples from one traverse adjacent to known gold mineralization (Figs. 12.45
and 12.46). Again no information is provided on the geochemistry of soils along this
traverse!
Published data for the Canadian Shield are somewhat more comprehensive. For
example, Cohen et al. (1987) describe an extensive investigation in the Hemlo Gold
District designed to establish the potential usefulness of biogeochemistry in gold
exploration over areas with shallow exotic till cover. Balsam fir was shown to have an
uneven, if not erratic, distribution along the tree within all organs (Fig. 12.47). In contrast,
gold distribution in Mountain Maple displayed generally higher concentrations in the base
section than in the crown. However, this did not prevent delineation of distinct
137
Basic Rules Reasons
1. Collect same species. Every species has a different

chemical composition, and trace
element requirements and
tolerances.
2. Collect same plant organ. Each plant organ has different

capacity to store trace elements.
3. Collect same amount (i.e. There are chemical variations along

age) of growth, from same a twig (see Table 4). Heterogeneity
area of tree (e.g. chest in bark scales can be minimized by
height), preferably from all scraping from around the tree.
sides.
4. Try to collect samples from This is the basic inter-site

plants of similar age and consistency that is required for any
appearance. geochemical sample medium.
5. If living tissue is the selected There are significant seasonal

medium, collect at same changes in plant chemistry.
time of year (i.e. conduct
survey in 2-3 week period).
[Dead tissue (e.g. outer No appreciable seasonal change]

bark) can be collected at
any time
6. Do not return to a This is unrealistic in view of the

previously sampled tree and heterogeneity of element
expect to obtain exactly the distributions and seasonal variations
same analyses. ? in composition (and to a leser
extent annual variations). Be
satisfied if an anomaly is the same
order of magnitude.
TABLE 12.4 Basic rules to be applied at each sampling station when conducting a
biogeochemical survey. (Dunn. 1991)
138
FIG 12.44 Sample sites and contoured Au values for the Standard
Hill area, California. Gold in plants determined by INAA.
(Busche, 1989)
139
FIG 12 .45 Base map showing site locations

along traverses A and B, and
prospects, adits, and shafts of the
Gold Run mining district, Nevada.
(Erdmann, et al. (1988)
FIG. 12.46 Gold levels in ashed stem-and-

leaf samples of sagebrush along
traverse A. Samples with traces
of Au (reported as less than the
limit of determination) are given a
value of 4 ppb and shown as <;
those in which no Au was
detected are indicated by N. Qa
= alluvium, Qg = gravels and «p
= Preble Formation. (Erdmann,
et al., 1988)
140
FIG 12.47 Variations in the gold content of a

variety of organs in a balsam fir
growing over mineralization, sampled
at varying heights. (Cohen, 1986)
geochemical patterns in the vicinity of mineralization. For example, in areas of poor

drainage or exotic overburden the needles of balsam fir and the leaves of birch and alder
display far more extensive anomalous response than the local soils (Figs. 12.48 and
12.49). In well drained areas both soils and plants display good geochemical response
for gold (Figs. 12.50 and 12.51). Response for most of the pathfinder elements (i.e. Mo,
Sb and Ba), except As, is good in both poor and well drained areas. However, the
multielement data do not provide unique information and their main value is probably as
backup in the event of undetected problems with the gold analysis. The data suggest
that in this district biogeochemistry would be more effective than geochemical soil
sampling in poorly drained areas. In well drained areas geochemical soil sampling would
probably be preferable as biogeochemistry appears to offer no clear technical advantages
and is certainly more expensive.
141
FIG 12.48 Hemlo District, Ontario. Comparison for poorly drained ground between the Au
contents of needles and bark of Balsam Fir (Abiles balamea) and Spruce (Picea
glauca, P. mariana) and B horizon soils and humus. (“M" represents location of
mineralization). (Cohen, et al., 1987)
FIG 12.49
contents of Alder leaves, first year twigs and bark, White Birch (Betula papyrifera)
leaves and bark and B horizon soils and humus. ("M“ represents location of
mineralization). (Cohen, et al.. 1987)
142
FIG 12.50 Hemlo District, Ontario. Comparison for freely drained ground between the Au
contents of needles and bark of Balsam Fir (Abies balamea) and Spruce (Picea
glauca, P. mariana) and B horizon soils. ("M" represents location of mineralization.).
FIG 12.51 Hemlo District, Ontario. Comparison for freely drained ground between Au contents
of Alder (Alnus rugosa, A. crispa) leaves, first year twigs and bark and B horizon soils.
(“M‘ represents location of mineralization). (Cohen, et al., 1987)
143
Dunn (1989) provides an interesting demonstration of the potential value of

biogeochemistry in regional gold reconnaissance programs. Analytical data for samples
ol the outer scales of spruce bark, collected on sample density of only.site per 50 km
over 5000 km2 in Nova Scotia, broadly define the known god distr'cts2 bes
indications of these districts are provided by Au, As, Sb and Se (Figs. 12.52a, , ,
d).
An interesting variant of biogeochemistry based on the analysis of aquatic mosses
in drainage channels has been the subject of a number of studies. These suggest tha
these mosses might provide effective alternative geochemical sample media in areas
where steep terrain prevented accumulation of stream sediment fine factions,
example Erdman and Modreski (1984) found good correlation between the Cu and Co
data for aguatic moss and regular stream sediment samples in the vicinity of the; iron
Creek stratabound Cu/Co occurrence in Lehmi County Idahojt°aX XmatiJe
the absence of stream sediment, aquat.c mosses might be a su table aI ernative
reconnaissance sample medium. Jones (1985) reached a similar conclusion fol owing a
study of the Au, Ag, As, Cd and Sb content of aquatic bryophytes from the DolgeHau gold
district in North Wales. However, arsenic, rather then gold, appears to be the most
effective pathfinder element for gold mineralization in this particular area. Other studies
have been carried out for uranium in the northwestern U.S.A. (Shacklette and Erdman,
1982) and for base metals in Alaska (Smith, 1986).
144
FIG 12.52a&b Elements in ash of outer scales of spruce bark, Nova Scotia: (a) (above) gold, (b) (above
arsenic, (c) (next page) antimony, (d) (next page) selenium (Dunn, 1989)
QUOTES*”
CELSQ L. PALACIOS CARRILLO J
145
FIG 12.52c&d (Dunn, 1989)

146
Excellent reviews of recent developments in exploration biogeochemistry are
provided by Dunn (1989 and 1991). Although it is now a little dated, a useful bibliography
on the use of plants in prospecting for gold was compiled by Erdman and Olson (1985).
12.2.7. Water
The detection and interpretation of aqueous dispersion haloes in surface and

groundwaters related to mineralization form the basis of hydrogeochemical prospecting.
Geochemical surveys, especially regional reconnaissance based on water sampling offer
potential theoretical advantages in many environments (Table 12.5), especially in the case
of highly mobile elements such as uranium and zinc. However, where there are
alternative effective geochemical sample media (e.g. soils, stream sediments, etc.) these
commonly tend to be used in preference to water. This is due to certain potential
difficulties associated with geochemical exploration programs based on water samples,
in particular:
(i) relatively large samples generally required. These can present transportation
difficulties.
(ii) chemical instability of untreated samples;
(iii) the frequent need for ultra sensitive analytical methods;
(iv) the extreme sensitivity of aqueous dispersion processes to a variety of interacting
environmental factors, some of which might be seasonal in nature and not all of
which will be necessarily recognized.
Water samples are generally collected in clean acid rinsed 500 ml or 1000 ml
polyethylene or polypropylene bottles as these are more practical than glass bottles under
field conditions. However, several important trace metals are incorporated in plastics
during the manufacturing process and are often present in leachable form. This applies
particularly to zinc. Therefore thorough cleaning prior to use is required. Prolonged
soaking in 50% hydrochloric or nitric acids followed by repeated rinses with distilled or
deionized water is recommended. Prior'to sampling in the field the bottles should be
rinsed several times with the water to be sampled. Samples that are to be analyzed for
trace elements should be acidified to pH <2 with metal free nitric or hydrochloric acid to
keep the dissolved metals from precipitating or adhering to the bottle walls. Turbid water
should be filtered using a 0.45 micron membrane before addition of the acid, otherwise
leaching of elements from the suspended sediment might occur. When both trace and
major elements are to be determined, at least two samples must be collected so that
material without introduced cations and anions is available for the major element analysis.
In order to minimize growth of algae (Miller, 1979) in samples prior to analysis they should
be stored in a cool place away from sun light. If this is not possible, chloroform should
be added. pH, conductivity and certain other measurements are commonly made at the
sample site.
147
Areas of arid conditions Areas of swamps Areas of mountainous terrain

Areas of permafrost
High values for pH and salinity Low pH values and flow rales Chemically aggressive walers.
Characterization Geochemical movement is The maximum contrast is
of waler partly electrochemical, and slightly high background and slightly high background
values for many trace elements values for many trace elements obtained for moderate relief
with waler in lhe active and rainfall; higher relief or
zone above the permafrost but with low contrast. but with low contrast.
rainfall lends to decrease
gradually becoming enriched contrast.
in trace components.
Fair to moderate mobility of many Movement and precipitation Good mobility of many
Mobility ul elements Mineralized bodies lhal emerge elements because of the
al lhe surface usually have elements because of flat landscape of chemical elements are
oxidation zones and high contrast and lack of chemically aggressive governed mainly by the aggressive walers, the
waters. Elements capable of concentration, pH, and greater relief, and the more
(difference between anomalous
forming negatively-charged ions contents of humic and fulvic likely chance for oxidizing
and background values); conditions.
dispersion patterns traceable in or soluble compounds are the acids, and organic material
lhe active zone by both surface most mobile such as U, Mo, V, As, in contact with the waler.
and spring walers. and Se.
When the number of springs end Most limes except during Usually after spring runoff
Optimum lime for Either lhe first part or the* when the streams have
sampling the Iasi part of lhe summer. ephemeral streams will be lhe runoff or flooded periods.
greatest, usually in the spring returned to normal flow or
and fall. during low streamflow, which
is usually during the fall
and winter.
Good sample density is Fair to poor sampling density, Abundant waler, good Usually abundant water with
Abundance ol possible good sampling density for
sample sites possible for both spring and usually ephemeral streams and sampling density.
some springs both spring and surface
surface walers. walers. First-order streams
and springs are probably lhe
best source for water
samples.
General comments Chemical weathering There is an accumulation of Dispersion patterns of The dissection of terrain
reduced because of cold sails and secondary minerals mineralization may be increases the possibilities for
temperalures, organic and lhe lack of organic material. characterized by a set of lhe intersection of mineral
material is abundont. elements which may not ization and oxidizing
correspond exactly to their conditions.
paragenic associations in
the mineralization. Dispersion
patterns are reduced oecause
of little dissection and less
favourable mobility under more
reducing conditions and
abundant organics.
TABLE 12.5 A summary for the application of hydrogeochemical prospecting in different environments. (Miller, 1979)
148
One the more effective applications of hydrogeochemistry has been in regional
reconnaissance programs based on lake water (and lake sediment) sampling, particularly
within the Canadian Precambrian Shield, but also within the Fennoscandian Shield and
the Cordilleran and Appalachian regions of North America. As in the case of lake
sediment sampling the ideal terrain for this technique is where lakes are common,
conditions are swampy, and/or where stream drainages are inaccessible or poorly
developed (Coker et al., 1979). In low relief regions, the lake water medium is dependent
on the hydromorphic dispersion of metals into the lake environment through ground
waters. In areas with higher relief surface hydromorphic dispersion could also be an
important factor. An early example of a hydrogeochemical survey based on lake water
sampling was provided by Dyck et al. (1971) and Dyck (1979) in the course of a
experimental study of a variety of sample media over a 500 square mile area including the
Beaverlodge Uranium District in Saskatchewan. Surface lake water samples were
collected at an average density of 1.3 samples/ square mile. The resultant anomalous
uranium distribution patterns clearly outlined known uraniferous zones as well as
additional areas of potential interest (Figs. 12.53a and 12.53b). It was concluded that
organic sediments, bicarbonate and pH control the migration of U in the surface
environment. The presence of high organic concentrations severely restricted uranium
dispersion.
Regional reconnaissance for selected metals can also be achieved by sampling the
waters ^f actively flowing streams where metal is dispersing in solution. A prospecting
approach similar to the sampling of stream sediments is necessary. Sampling of ground
water seepage sites is an integral part of stream water surveys. In view of the paucity of
recently published examples of stream water sampling, it is again necessary to refer to
fairly old studies. For example Dyck et al. (1971) sampled stream water in addition to lake
water (see above) in their experimental uranium exploration program in the
BeaverlodgeDistrict of Saskatchewan. Stream water (and stream sediment) samples were
collected at an average density of 1 sample/square mile. Sample temperature was
recorded at the sample site, whilst radoo, pH and alkalinity were determined in a field
laboratory. The samples were then acidified and transported to a central laboratory for
uranium and other trace element analyses. Although the regional uranium distribution
patterns (Figs. 12.54a and 12.54b) were found to be broadly similar to those displayed
by the lake waters, it was concluded on economic grounds (i.e. ease of sample
collection) that the latter were the preferred sample medium.
Groundwater can also play a useful role in mineral exploration, especially when the
targets and large potential target hosts are obscured by post mineral overburden or
unmineralized bedrock, and target and/or associated pathfinder elements are mobile in
the prevailing groundwater environment. Interesting examples of the attempted
application of groundwater geochemistry in mineral exploration are provided by work
carried out by the U.S.G.S. (Huff, 1970), and various companies in the southwestern
U.S.A, in the 1960’s and 1970’s. Here the primary interest was in locating porphyry
copper deposits under pediment and alluvial sediment cover. The exploration technique
149
FIG 12.53a Regional uranium concentration levels in lake waters

(a) with and (b) without contaminated samples.
(Dyck et al.. 1971)
.nnniiii
FIG 12.53b (Dyck et af, 1971)

150
FIG 12.54a (a) Radon and (b) uranium

stream waters without contaminated samples (Dyck
et al.. 1971)
FIG 12.54b (Dyck et al. 1971)

151
was based on the known mobility of molybdenum, a significant component of most

porphyry copper deposits, in the neutral to alkaline conditions prevalent in local
groundwater. Samples were generally collected from domestic and irrigation wells, and
natural springs. Early results, as for example in the Pima Mining District, showed
anomalous molybdenum was indeed present in the groundwaters around known deposits
(e.g. Fig. 12.55) and elsewhere, but the anomalies were so large (i.e. tens or even
hundreds of square miles) that source location in routine surveys was not apparently
economically feasible. In addition, anomalous contrast appeared to often correlate with
total dissolved solids, a feature presumably unrelated to mineralization. Later studies by
Trost and Trautwein (1975) indeed found molybdenum concentration in groundwater to
correlate strongly with conductivity (an indirect measure of total dissolved solids), weakly
with pH and not at all with Eh (Fig. 12.56). On theoretical grounds they concluded that
this reflected a relationship between the solubility of molybdate salts, such as CaMoO4,
due to an increase in ionic strength and corresponding decrease of the activity
coefficients. They suggested utilizing the ratio of log [Mo/K] in conjunction with a plot of
log [Mo/K] vs. log [Mo] to determine the proximity of a buried oxidizing porphyry copper
deposit. The possibility of applying sophisticated hydrogeochemical models to mineral
exploration purposes was discussed by Runnells and Lindberg (1981). They determined
that the saturation index is a reliable indicator of the presence of uranium mineralization,
but the requirement for reliable Eh measurements could present certain practical
difficulties in routine surveys.
12.2.8. Gases
Under certain conditions, mineral deposits produce gaseous emanations which can
be detected by specialized measurements. There are two broad categories of soil gas
sampling technique:
(i) instantaneous;
(ii) integrated.
With the instantaneous method, specific volumes of soil gas are extracted through a
probe, from some predetermined optimal depth which is normally somewhere in the range
of 20 to 40 inches (50 to 100 cm).1 These can then be either:
(i) analyzed on site by a field instrument (e.g. CO2 and O2 analyzers or one of
the new generation of portable micro gas chromatographs). Mobile mass
spectrographic systems, such as that used by Howard McCarthy of the
U.S.G.S., should probably be classified more as research systems at this
time in view of high capital and operating cost as well as interpretational
uncertainties;
(ii) or placed in a special container for transportation to an analytical laboratory

(e.g. Barringer Technique, etc.);
152
FIG 12.55 Map showing distribution of molybdenum in ground water, Pima Mining District, Arizona. (Huff, 1970)
153
A.
FIG 12.56 Correlation plots for groundwaters in southern Arizona: (a) pH vs. log [Mo],
suggesting a slight correlation between the molybdenum content and pH; (b) Eh vs.
log [Mo], showing poor correlation between molybdenum content and Eh; (c) log K
vs. log [Mo], suggesting a good correlation between increasing conductivity and
increasing molybdenum content. (Trost and Trautwein, 1975)
154
(iii) or adsorbed onto a special collector material and transported to the

laboratory for analysis.
The main potential problem with the instantaneous methods is that they are subject to any
short term gas flux variability which might occur. This could prove particularly serious in
large surveys during periods of climatic instability. Instantaneous methods are also
inappropriate when dealing with gases occurring in concentrations at or near the
detection limits of the available analytical equipment. The main advantage of the
instantaneous methods is that they only entail one visit to the sample site.
With the integrated method of soil gas sampling, special adsorbent or reactive
material, including molecular sieves or porous polymer sorbents (e.g. Clifton, 1984a and
1984b, etc.), or activated carbon (e.g. "Petrex" system), is buried in the soil at each
sampling site for specific periods of time (generally for several weeks). At the end of this
time the collectors are recovered and sent to the laboratory for analysis. Alternatively, use
can be made of natural soil gas collectors, including specific soil fractions (e.g. clays -
"Advol" system). The main potential advantage of the integration methods of soil gas
sampling is that results are unlikely to be influenced by short term fluctuations in the soil
gas flux. However, two visits to each sample site are required, except in the case of the
natural soil collectors. A problem with some of the collector systems (i.e. molecular
sieves) is that gas desorption in the laboratory requires heating to very high temperatures
which will likely modify the nature of some of the volatile species.
Much of the published information on the application of gas geochemistry in

mineral exploration relates to research and orientation studies. However, numerous
geochemical gas surveys were carried out some years ago during the last uranium
"boom". These were mainly concerned with measurement of radon produced during the
radioactive decay of uranium and radium. Although some radon in stream and lake water
studies were undertaken (e.g. Dyck et al., 1971), most of the programs were based on
integrated measurements of radon in soil gases. Some of the better known procedures
(e.g. "Track Etch") use detectors which respond to alpha particles emitted during radon
decay (e.g. Gingrich, 1984). The "Track Etch" procedure utilizes small pieces of radiation
sensitive film. These are processed in an etching solution to provide visible track-like
images of the alpha particles which, can then be counted to provide an indication of the
average amount of radon present during the exposure time (Fig. 12.57). Later versions
include plastic filters to prevent exposure of the detectors to thoron. In “Track Etch"
surveys the integrative detectors are buried at shallow depth (i.e. normally around 0.5 m
in inverted plastic cups (Fig. 12.58) and left for a specific period of time. In the Baker
Lake area in Northern Canada (Fuchs et al., 1982) cups were buried for the full winter
season at 100 ft intervals along traverses with 200 ft separation. The unusually long
exposure produced improved results over those obtained with detectors left in place for
shorter periods during the summer. Follow-up of several high contrast anomalies
resulted in the discovery of the Lone Gull Uranium Deposits (Fig. 12.59).
155
ALPHA PARTICLE
BOMBARD FILM
FH.M
TRACKS RETAINED
ETCH FILM
ETCHED TRACKS VISIBLE
FIG 12.57 The Track Etch Process.

(Gingrich, 1974)
(Gingrich, 1974)
156
FIG 12.59 Radon contour map of the Lone Gull U discovery. (Gingrich. 1984)
Mercury-bearing minerals which can include sphalerite and other sulfides, often
release mercury vapor during oxidation. This vapor can be measured in soil gas directly
(i.e. generally using integrative collectors which are analyzed in the laboratory) or
adsorbed Hg can be released from conventional soil samples by heating to 210-390°F
(100-200°C) (Landa, 1978). Over the past twenty or so years there have been many
studies of the possible application of mercury vapor surveys to mineral exploration, but
the published results have often been poorly documented and frequently inconclusive.
Fedikow and Amor (1990) recently described their evaluation of commercially available
mercury detectors (i.e. "Aurex") following test studies at a number of Canadian mineral
deposits. The detector consists of a thin silver wire in an open ended glass vial (Fig.
12.60). These are buried in overburden'at a depth of 40 cm (Fig. 12.61) for a period of
32 days. They concluded that the system does not measure mercury in soil gas in a
consistent manner in proximity to mercury enriched base and precious metal deposits in
the rest areas.
The oxidation of moist sulfides leads to the generation of CS2 and COS (Taylor, et
al., 1982). Oakes and Hale (1987) describe an experimental exploration technique based
on the selective thermal desorption of COS from the < 150 micron fraction of overburden
materials and quantitative determination by a rapid gas chromatographic method. At
Johnson Camp, Arizona the surface microlayer of the soil was sampled on 30x60 m grid.
Analysis disclosed distinct COS anomalies over suboutcropping sediment hosted
replacement sphalerite/chalcopyrite mineralization despite the presence of considerable
thicknesses of pediment gravel and alluvium (Fig. 12.62). Elsewhere comparable
157
integrative detector. (Fedikow and Amor,

1990)
FIG 12.61. Schematic representation of Hg-vapour

measurement utilizing the Aurex detector
(Fedikow and Amor, 1990)
158
anomalies were delineated over
sulphide mineralizations covered by a
variety transported overburden,
sometimes exceeding 90 m thickness
and ranging from arid highly porous
sand and gravel to moist, clay-rich
glacial till.
Because of the consumption of

oxygen in the oxidation process, the
atmospheric proportions of CO2:O2
change in the vicinity of oxidizing
sulfides and these imbalances can be
measured in the soil gas (Lovell, et al.,
1983). Lovell and Reid (1989) used
this approach in northern Arizona to
evaluate the subsurface potential for FIG 12.62 Plan of simplified geology and COS
dispersion pattern in surface microlayer
structurally controlled mineralization in at Johnson Camp, Arizona. (Oakes and
82 collapse breccias. They collected a Hale, 1987)
little under 5000 soil gas samples with
a sample probe and transported them in special containers to a laboratory for analysis
by gas chromatography. Although the presence of buried sulfide accumulations was
found to be reflected by strong CO2 anomalies (Fig. 12.63), these anomalies were
extremely sensitive to climatic change (e.g. rainfall). In recent years CO2 and O2 in soil
gas surveys have also been applied in a number of exploration programs for sediment
hosted gold deposits in the western U.S.A. These surveys have reportedly resulted in the
determination of lithology changes, location of faults and the presence of alteration
beneath transported overburden (Jaacks, 1989).
Recent studies in Sweden (Malmqvist et al., 1986) have identified an upward fluxing
of GEOGAS in the near-surface sections of the earth. This GEOGAS enters the ground
waters as dissolved air. The circulating meteoric waters and changing pressure
conditions in the subsurface cause the GEOGAS to rise as small streaming bubbles. The
bubbles contain other gases and can also collect metallic ions and particles that can be
trapped in collectors set out in the surface soil. Anomalous patterns in GEOGAS have
been recorded over mineralization buried under thicknesses up to 100 ft (30 m) of
transported cover.
It should be noted that biogenic activity in the soil can produce methane (CH4),
hydrogen (H2), carbon monoxide (CO), hydrogen sulfide (H2S), dimethyl sulfide ((CH3)2S),
dimethyl disulfide ((CH3)2S2), methyl mercaptan (CH3SH), carbonyl sulfide (COS)and
carbon disulfide (CS2) (Taylor, et al., 1982). Therefore, near-surface detection of these
gases can be suspect. Methane is found at depth in several types of mines, but a
genetic association with mineralization is not always clear.
159
FIG 12.63 CQ> content of soil air over

mineralized breccia pipe, Arizona.
(Lovell and Reid, 1989)
A recent volume of the Journal of Geochemical Exploration (Kesler, 1990) provides

a useful review of a number of soil- and rock-gas geochemistry studies.
12.2.9. Particulates
Solid particles down to the size range of large molecules are present in the
atmosphere. Weiss (1971) developed an airborne geochemical prospecting technique
for arid terrain based on the collection of dust particles suspended in the atmosphere.
The AIRTRACE and SURTRACE techniques of Barringer Research Ltd. were designed to
sample a variety of particulates in the lower atmosphere including spores, pollen, dust,
microorganisms, organometallics, and hydrocarbon complexes. The collected particulates
were analyzed using a laser pulse/inductively coupled plasma spectrometry (ICP)
procedure in the laboratory. The same airborne platform could be equipped with a
mercury sensor for real-time measurements. According to the Barringer organization
AIRTRACE was successful in sensing gas and oil resources and produced positive results
over mineral deposits. Reproducibility of the technique in the search for mineral deposits
was hampered by variable weather conditions and temperature inversions. The
SURTRACE method was designed to overcome these climatic problems by sampling
160
FIG 12.64 Plot of log B. cereu$ (colony forming units/gram of soil) in ^>and B horizon soils
overlying and adjacent to Au-quartz veins in the Empire Mining District, Colorado
(from Parduhn and Watterson, 1984). (Parduhn, 1987)
particulate matter from the ground surface (i.e. microlayer) using a helicopter-based or
manually transported system. Despite the fact they have been available for a number
ofyears neither method has yet been -used extensively in routine metallic mineral
exploration programs. AIRTRACE was used in some large scale hydrocarbon surveys
in the 1980’s.
12.2.10. Microorganisms
Parduhn and Watterson (1984) and Parduhn et al. (1985) have demonstrated that
the population of the common microorganism, Bacillus cereus, increases with natural
increases in the base and precious metal content of soils in the vicinity of known mineral
deposits. It has also been noted that the increased antibiotic resistance of these bacteria
correlates with increased metal concentrations in soils (Watterson et al., 1986). On the
basis of very limited sampling Parduhn and Watterson (1984) reported anomalous Bacillus
cereus populations over quartz/gold/sulfide veins, overlain by 15-20 feet of glacial
overburden, near Empire, Colorado (Fig. 12.64). However, earlier work by Curtin, et al.
161
(1971), determined that although the B horizon soils were not particularly effective sample
media in this district, the Au, Cu and Bi content of the forest humus layer (mull) clearly
define the mineralized veins. Thus no particular advantage appears to be provided by the
Bacillus cereus data in this example. The same appears to be true in certain other test
areas (e.g. Vista Pit area, Mesquite Deposit, Imperial County, California) studied by
Parduhn (1987).
An interesting alternative approach to the possible application of microbiology to

mineral exploration is discussed by Michaels and Riese (1986). They suggest
determination of the metal tolerance of bacteria by the addition of suitable metal
concentrations to culture media prepared from stream sediment, stream water, and
organisms on stream water surfaces. Peliminary data indicate bacteria populations are
more metal tolerant in mineralized areas.
Mineral exploration methods based on microbiological features are still in their

infancy and should be approached with extreme caution.
12.2.11. Animal Tissues
Animal tissues have not been used extensively as a geochemical medium. Warren
et al. (1971) analyzed 96 trout livers from locations in British Columbia and identified a
general correlation between the zinc and copper contents of these livers and known
mineral regions. As part of an environmental monitoring program, the government of
Ontario has sampled fish tissues for their mercury content. Recent work has investigated
the use of the trace element content of bee pollen as an exploration tool. Variations in
concentrations were noted showing a general relationship with known mineralization, but
follow-up is complicated by the territorial wandering of the insects.
162
13. FIELD-LABORATORY LIAISON
Geochemical field surveys can produce large numbers of samples of various types
which require often complex processing and analysis. Despite the fact that this is a
critical stage in the geochemical exploration sequence, there is a common tendency for
field staff to avoid serious involvement. However, effective programs require that they
have a clear understanding of the sample preparation and analysis needs established in
the orientation studies, and they ensure these are fulfilled by the selected laboratory. As
in all other stages of a geochemical exploration program good communication is
absolutely imperative. All too often samples are sent to commercial laboratories with
minimal information other than a list of elements to be determined. Project staff need to
have a clear idea of laboratory capabilities and ensure the laboratory understands project
needs including:
(i) the number and type(s) of samples to be analyzed, and probable timing and
rate of submittal;
(ii) sample preparation procedures;
(iii) elements of interest;
(iv) analytical accuracy and precision (i.e. whether quantitative, semi-quantitative
or qualitative analysis is needed);
(v) if a total or a partial analysis is needed, and
(vi) how rapidly the results are required.
Laboratory staff should provide:
(i) an honest assessment of their ability to meet the required standards and
schedules;
(ii) an indication of problems, if any, which might be encountered in sample
preparation and analysis and what effect these might have on the results;
(iii) "in-house" quality control information.
Periodic contacts between project and laboratory staffs over the life of a project help
ensure rapid solution of any problems which might arise.
163
14. LABORATORY PROCEDURES
The following chapter deals with some of the more common preparation and
analytical procedures to which geochemical samples from mineral exploration programs
might be subjected. This work is mostly carried out by independent commercial
laboratories, which with modern air transportation are generally accessible from even the
most remote areas where mineral exploration field surveys are undertaken. Although
geologists and geochemists responsible for geochemical exploration programs do not
normally become directly involved in laboratory operations, some basic knowledge of
these activities is essential. It enables the explorationist to assess probable laboratory
capabilities, as well as actively participate in the selection of sample preparation and
analytical methods. Total reliance on the laboratory personnel is inadvisable as they do
not generally possess the requisite field knowledge, and unless given clear direction, can
make inappropriate decisions or recommendations.
The discussion follows a typical sequence of activities from sample preparation

through analysis to analytical data reporting. It borrows heavily from published work by
Fletcher (1981), and to a lesser degree, Hall (1991).
14.1. Sample Preparation
Geochemical field samples can rarely be analyzed directly on arrival at the

laboratory as a variety of preliminary steps are required. These fall into the general
category of sample preparation procedures and might include simple drying, sieving,
crushing, grinding, mineral separation, etc.
The basic aims are to ensure that:
(i) the generally small proportion of the original sample which is submitted for
analysis is reasonably representative of the whole;
(ii) when a specific sample fraction (or component) is selected for analysis, it
is effectively separated from the other sample constituents;
(iii) the material analyzed is in an appropriate form for the chosen method of
analysis.
(iv) there is no contamination of the sample by the sample preparation
equipment.
As has been discussed previously in Chapter 11 the relative importance and

interdependence of the various components of a geochemical exploration program can
be likened to a "House of Cards". Inappropriate sample preparation procedures or
sample preparation errors can completely nullify the careful work of the sampler who has
invested time and expertise in the selection and collection of representative material.
Furthermore, it is impossible to restore the integrity of the poorly prepared sample by
enterprising analytical treatments and interpretational procedures. Hence, sample
164
preparation requires just as much attention as other, possibly more exciting aspects of
geochemical exploration! Unfortunately, all too often sample preparation is carried out
by inadequately trained and insufficiently supervised temporary laboratory help.
Consequently, errors resulting from sample mixups and incorrect procedures are not all
that uncommon, and if undetected can cause serious harm. Recent Newmont experience
suggests that on average 6% of all geochemical data are suspect as a result of sample
preparation and/or analytical errors.
14.1.1. Drying
Prior to mechanical treatment, non-lithified clastic and rock geochemical samples

have to be dried. In some climates this can be achieved by exposure to the sun, but
specially constructed ovens are generally necessary. Heating these ovens to
temperatures in excess of 160°F (70°C) can lead to the loss of volatile elements (e.g.
mercury) which may be of value to the exploration program. It can also result in the
baking of clay-rich samples, which makes subsequent disaggregation difficult.
Vegetation and humus samples are normally dried at temperatures of less than
160°F (70°C) in a standard drying or microwave oven. Ideally, these samples should
contain no clastic material. Dust on leaves and twigs can be removed by rinsing with
demineralized water, but humus material is rarely 100% organic. The presence of
excessive clastic material may prevent accurate determination of the metal content of the
organic component.
14.1.2. Crushing and Grinding
Since sample weights analyzed in geochemical work are small (0.1 to 50 g)

compared with the original sample size, sample homogeneity is very important if the
analytical split is to be representative. Achievement of the requisite degree of
homogeneity with rock and non-lithified coarse clastic samples generally requires
reduction of the whole, or an appropriate sample portion, to a powder, and careful
blending prior to splitting and analysis. Homogeneity can be significantly improved by
pulverization of coarser fractions to the minus 200 mesh (i.e., 75 micron) size. The
sample is rarely reduced to this fipe grain size in its entirety, but as a general rule, the
finer the sample can be crushed or ground prior to sample splitting, the more
representative the analytical split is likely to be.
Sample preparation procedures can be roughly evaluated by means of specially

constructed graphs or nomographs based on sampling theories originally developed by
Gy (1979a). Where the concern is primarily with base metals Gy’s Sampling Safety Curve
might be used (Fig. 14.1). This is based on a general safety rule (Gy, 1979b) which
states:
165
400 200 80 60 35 18 10 6 # (ASTM)

100
MAXIMUM PARTICLE SIZE
FIG 14.1 Sample preparation safety curves for gold bearing materials.
BIBLIOTEQA
CELSQ L. PALACIOS CARRILLO
166
W_> 125,000 d3
where W is the sample weight (in grams) and d is the diameter of the largest particle in
the sampled material fin centimeters). It should be noted that Gy states that this curve
is not designed for gold bearing materials or low grade ores. However, this does not
prevent its use as a general guide to minimal acceptable sample sizes at each stage of
geochemical sample comminution, especially prior to base metal analysis. The degree
of precision required in geochemical analysis is generally less than that needed in regular
assay studies for which the curve was primarily designed. The more conservative "Rule
of Thumb Curve" (Fig. 14.1) is probably more appropriate in the case of materials
containing fine disseminated gold. This curve is based on two widely accepted rules of
thumb (Ottley, 1983):
(i) there should be at least 20 particles of the valuable mineral or metal in the
sample subjected to analysis;
(ii) no particle should represent more than 1/20,000 of the weight of the
sample.
Where the presence of relatively coarse gold is suspected, nomographs developed

by Clifton et al. (1969) can be used to guide decisions regarding sample size in both field
and laboratory (Figs. 14.2 and 14.3). These are also based on Gy’s sampling theories
and were originally applied to placer and other gold deposit types. To simplify the
determination of the major factors influencing sampling precision, Clifton et al. made
certain assumptions concerning sample characteristics:
(i) gold particles in the sample material are all of uniform mass;
(ii) gold particles are randomly distributed through the sample;
(iii) gold particles make up <0.1% of all sample particles;
(iv) analytical error is absent.
Although these conditions are not all precisely fulfilled in nature, inclusion in the
calculations should not significantly detract from the conclusion that sampling precision
is primarily influenced by the number of gold particles in a sample. Thus achievement of
an acceptable minimum precision level of, say, 50% at the 95% confidence level requires
the presence of twenty gold particles. This is in fact the basic criteria applied in the
published nomographs shown in Figures 14.2 and 14.3.
At the evaluation stage of gold programs when sample representativity is even

more important, consideration might be given to the use of various formulae developed
by Pitard (1987), an associate of Gy.
There are situations when achievement of adequate homogeneity is not

economically feasible, as for example in the case of coarse particulate gold.
167
PARIICU MASS. IN MICROCRAMS
FIG ---------- Size of sample required to contain an expected 20 particles of gold as a function of the
combination of gold particle size and grade, assuming all gold particles to be of uniform
size and randomly distributed in the deposit. (Clifton et al., 1969)
169
Comminution of these gold particles can sometimes prove difficult due to heir malteaWity.
Representative samples would be far too large for any of the normal gold analyt'ca
procedures. The solution generally lies in some form of preconcentration involving either
"gravity separation" or "scrgfiD assay". In the first, analysis of a carefully prepared heavy
mineral concentrate, representing a large (and. if necessary, crushed and I ghfiy
pulverized) sample, provides an indication of the free metallic gold con ent of the materia
In the second a fairly large sample (i.e. several Kg) is crushed and Pênzed untla'' ût
50-60 q is less than 100 mesh. The whole of the coarse fraction and two splits of the fine
fraction are then assayed. The results for the coarse and fine fractions are combmed.
taking into account the relative total coarse and fine sample weights.
Reduction of rock fragments to powder involves crushing in a laboratory jaw

(and/or more rarely a roller) crusher, followed by pulverization in a disc ring, hammer,
swing or ball mill. Disc mills can quickly reduce relatively large volumes of material to
minus 100 mesh (i.e., 150 microns). This is sufficiently fine for some purposes (e.g. many
base metal programs). However, where further reduction is necessary due to sample
heterogeneity (e.g. some gold programs) and/or where loss of sample representativity
might result through "smearing" of soft minerals (e.g. native gold, native copper,
molybdenite, etc.) on the disc plates, pulverizers with a different comminuting action (e.g.
ball, ring, hammer or swing mills) should be used. Larger pulverizers (eg. Labtechnics
Mixermills) have more recently been developed which are capable of reducing up to 3kg
of minus 6mm material to over 90% minus 100 mesh in just a few minutes.
When a particular mineral fraction is required for analysis, rather than a

representative sample of the whole rock, a special procedure must be followed. The rock
should only be ground sufficiently to release monomineralic grains without excessive
production of fines. Mineral separation techniques can then be applied. (See Section
14.1.4.).
Laboratory crushing and grinding equipment is made from a variety of materials
including chrome steel, tungsten carbide, etc. some of which are potential sources of
sample contamination as a result of wear (Table 14.1). Where contamination is a
potential problem it is advisable that alternative equipment be selected. However, it
should be noted that an even greater problem in sample preparation results from materia^
carryover between samples. Careful cleaning of equipment between samples with
compressed air is essential. In addition, batches of clean quartz sand should be run
through the system between each sample.
When dry, vegetation samples are macerated in a Wiley Laboratory Mill to a minus
2 mm size. This material is commonly compressed into either 8.0 g or 30.0 g pellets for
direct analysis by neutron activation, or can be ashed in a muffle furnace at 450 C to
470°C for approximately 15 hours. The plant ash is then analyzed in a similar manner to
clastic sample material.
170
Material Potential contaminants
Grinding equipment
Steel and iron grinding plates Fe, Co, Cr, Cu, Mo, Mn, Ni, V
Alumina ceramic plates 1 Al, Cu, Fe, Ga, Li, Ti, B, Ba, Co, Mn, Zn, Zr
Tungsten carbide Co, Ti. W
Lubricants Mo
Packaging materials ’
Polythene Ti, Ba, Zn, Cd

Polypropylene Ti
PVC Ti, Zn, Na, Cd
Brown paper Si
Rubber Zn
1 Thompson and Bankston (1970).

2 Scott and Ure (1972).
TABLE 14.1 Potential contaminants from laboratory materials. (Fletcher, 1981)
14.1.3. Sieving
After drying it is necessary to ensure non-lithified clastic samples are

disaggregated. This might require simple agitation or even light pounding with a pestle
and mortar or other suitable non-contaminating mechanical device that can be thoroughly
cleaned between samples. As the objective is generally to obtain the natural grain size
distribution, care must be taken to avoid any crushing of component particles.
In earlier geochemical prospecting work, orientation studies on soils, stream

sediments, and other non-lithified clastic materials revealed that the separation of minus
80 mesh (-177 micron) material for analysis was appropriate in many surveys. With some
elements, such as those commonly concentrated in residual minerals, and other elements
dispersed in weathering products in arid/semi-arid environments, fractions coarser than
80 mesh give superior geochemical patterns with better contrasts. Examples of the use
of the coarse sieved fractions of soils and stream sediments in arid and semi-arid areas
have been given previously, (i.e. soil - see Section 11.3.4 and Figure 11.10 - Thomson
(1987); stream sediment - see Section 12.2.3 - Moeskops and White (1982)). Some
surveys in glacial till environments benefit from the analysis of the minus 240 mesh (i.e.
minus 63 micron), or even finer, clay-size fractions (see references to the work of Shilts,
172
FRENCH.
114. COMPARISON TABLE OF U.S.A.. TYLER. CANADIAN. BRITISH.
AND GERMAN STANDAR 5 SIEVE SERIES
BRITISH* FRENCH' GERMAN*

USA 1 TYLER' CANADIAN’
—■ ■ Nominal Nominal Opening
Meih Opening
Standard Alternate aperture MahNo (mm. No
"Si a ndjrd Alternate Designation
1'.' •
JI 5 mm 1'•' 31.5 mm
1 06" 1 05- 26 5 mm 1 06'
26 5 mm 25.0 mm
25 0 mm r 25 0 mm 1'
22 4 mm 883’ 22.4 mm
20 0 mm
|9 0 mm ».• .742' 19.0 mm •t
18 0 mm
160 mm
16 0 mm 624' 160 mm
13.2 mm 530- 525' 13 2 mm .530'
12.5 mm 12.5 mm
12 5 mm 4*
11 2 mm * k .441' 11.2 mm
10 0 mm
9 5 mm .371' 9.5 mm
8 .0 mm
8 0 mm 8 0 mm Ha'
265' 3 6.7 mm .265'
6 7 mm 6.3 mm
6.3 mm 6.3 mm '<«
No. 3’i 5.6 mm No. 3'.

5 6 mm 5000 38 5 0 mm
4 4 4.75 mm 4
4 ?5 mm 4 4000 37 4.0 mm
5 5 4 00 mm 5 *00 mm
6 6 3.35 mm 6 3.35 mm 5
.' 35 mm
3.150 36 3.15 mm
7 2 80 mm 7 2.80 mm 6
2.80 mm 7 2.500 35 2.5 mm
8 2.36 nun 8 2.40 mm 7
2.36 mm 8 2.000 34 2.0 mm 1
2.00 mm 10 2.00 mm 8
2 00 mm 10 9 1 600 33 16 mm
10 1.70 mm 12 1.68 mm 10
1.70 mm 12
12 1 40 mm 14 1.40 mm >2
1 X> mm M 1.250 32 1 25 mm
14 1.18 mm 16 1 20 mm 14
1 14 mm 16 I.C00 31 1.0 mm
16 1.00 mm 18 1.00 m n 16
1 00 mm s 850 Mm 18
20 850 ^m 20
850 -m
■ — — --------------- 0800 30 800 Mm
25 24 710 nm 25 710 m» 22
710 -m 0 630 29 630 Mm
30 600 Mm 30 600 Mm 25
600 -m 500 Mm 30 0 500 28 500 Mm
500 -m 35 32 500 Mm 35
40 35 425 >un 40 420 Mm 36

425 0.400 27 400 Mm
42 355 Mm 45 355 Mm 44
355 -m 45 26 315 «un
0.315
48 300 Mm 50 300 Mm 52
>00 1 50
250 60 250 Mm 60 0250 25 250 Mm
60 60
70 65 212 Mm 70 210 Mm 72
213 -m 0 200 24 200 Mm
so 80 180 Mm 80 180 Mm 85
180 -m 0.160 23 160 Mm
•
100 ISO Mm 100 150 >*m 100

150 -m 100 125 Mm
115 125 Mm 120 125 Mm 120 0.125 22
PS -m 120
140 150 106 Mm 140 105 Mm 150
106 0 100 21 100 Mm
90 Mm 170 90 Mm 170 90 Mm
90 Mm 170 170
0080 20 80 Mm
200 75 Mm 200 75 Mm 200
75 »m 200 71 pm
250 63 Mm 230 63 Mm 240 0.063 19 63 M«n
63 230 56 Mm
270 53 Mm 270 53 Mm 300

53 ^m 270 50 Mm
0050 18
45 Mm 325 45 Mm 350 45 Mm
45 Mm 325 323 40 Mm
J___ «°_____ 0.040 17
38 Mm 400 _ 1 —
38 Mm 400 *,~ISt> ‘
e-n-n. •T\rtr
1. u A j—< 5»-x> ASTM SmM>«*
X Tr " Sctir S"*« rrrar<*t
] Ct Sr'*, 4-Gr-H
t *
3 Fr afw~. AfNOH X II-301.
4 G.
TABLE 14^ Comparison table of U.S.A., Tyler, Canadian, British, French, and German standard sieve
series. (Berkman and Ryall, 1976)
173
174
FLOW SHEET
DRAINAGE
BASIN
...... COMMONLY OBSERVED MINERALS

|-UNMINERALIZED AREAS
ZIRCON
BARITE
SPHENE
APATITE
IN MINERALIZED AREAS
COMMONLY OBSERVED MINERALS FLUORITE
LIMONITE CASSITERITE
HORNBLENDE GALENA
BIOTITE PYRITE
GARNET WULFENITE
SPHENE VANADINITE
EPIDOTE SCHEELITE
OTHER OXIDIZED ORE
MINERALS
FIG 14.5 Flow sheet from separation of sediment samples into magnetic (M) and nonmagnetic (NM) fractions, (after Meyers and
others, 1979)
175
14.2. Sample Analysis

Geochemical sample analysis generally comprises several major components.
fi) decomposition. Most analytical methods require the elements of interest to

be in solution form. Therefore solid state samples require some type of
partial or total dissolution.
(ii) separation. Once the elements of interest have been released from the
sample it may be necessary to separate them from other elements which
create interference in the chosen analytical process.
(iii) measurement xjf element concentrations. Generally carried out by some
form of instrumental technique.
14.2.1. Decomposition
Many analytical methods, including colorimetry, inductively coupled plasma (ICP)
and atomic absorption spectrometry (AAS) require that elements of interest be introduced
to the instruments in solution. This entails some form of sample decomposition (Table
14.3) which might involve:
(i) digestion and leaching with concentrated or dilute acids;

(ii) fusion with acid or alkaline fluxes;
(iii) liberation of volatile constituents by pyrolysis.
Decomposition procedures fall into two broad categories:
(i) strong decompositions capable of releasing a large proportion of the trace

constituents from mineral lattices. These are sometimes erroneously
classified as total extractions, although they generally do not release all the
trace constituents present.
(ii) weak or partial dissolutions intended to remove only weakly bonded
elements or elements associated with a particular fraction of the sample (i.e.
phase selective leaches). These are sometimes loosely referred to as cold
extractions, although their efficiency is strongly influenced by even small
changes in ambient temperature.
Decomposition therefore provides the opportunity to liberate and determine either all or
only a particular fraction of the element(s) of interest (Fig. 14.6). For example, Coope
(1975) determined that the cold extractable heavy metal (primarily copper) content of
reconnaissance soil samples clearly defines the area containing the Sheslay porphyry
copper mineralization in British Columbia. However, the use of cold extractable methods
in the analysis of geochemical soil samples from this area is likely to give misleading
176
Strong digestions Reagents

Total decomposition
Fusions
acid fusions KHSO4, K2S2O7
ammonium halide sublimations nh4i, nh4ci
alkaline fusions Na2CO3, NaOH, LiBO2, LiB2O7
oxidative-alkali fusions Na2CO3 or NaOH with KNO3 or Na2O2
Acid digestions
Hot strong mineral acids hf-hno3-hcio4. hf-hcio4, hf-hno3-hci
Partial decomposition
Hot strong mineral acids HF, HCIO4, HNO3, HCI, HBr, Aqua, Regia
Partial digestions or leaches

Non-selective extractions
cold dilute inorganic acids: 0.1 - 1 N HCI
organic acids: acetic acid (pH 5.5)
oxalic acid
buffers: NH4-citrate NH3OH (pH 2-8)
chelating agents: 0.05-0.25 M EDTA (pH 4-7)
NH4-citrate-hydroxylamine hydrochloride (pH
8.5)
Selective extractions
exchangeable metals NH4-acetate; MgCI2, CaCI2 BaCI2
organic matter: H2O2; NaOCI; Na4P2O-, or K4P2O7
carbonates: cold weak acetic acid
manganese oxides: 0.1 M hydroxylamine hydrochloride in 0.01 M
HNO3 (pH 2)
•
iron oxides:
amorphous 0.175 M (NH^CjO.-O.IO M H2C2O4
0.25 M hydroxylamine hydrochloride
crystalline 1 0.02-1 M hydroxylamine hydrochloride
-0.25 M acetic acid
Na-dithionate
Hydrazine chloride (pH 45)
NH4-oxalate 0.2 M oxalic acid in 0.1 M ascorbic
add
sulfides: H2O2-ascorbic add
KCIOj/HCI followed by 4 M HNO3
_______________________________________________________________________ —
TABLE 14.3 Classification of some dissolution techniques useful in exploration geochemistry. (Church
et al.. 1987)
177
RETENTION MODE
EXTRACTANT
Ion Surface Precipitated Co. pptod. Co.ctdmatod Occluded l ettice
TYPE Eictiongp adsorption CO3. S. OH) amorphous to orgonici icrretellme ccmpeem
Sitoi hydrous hydrous (mineral)
ondeii oxidosl
E lactrol j to M.jCI2
Acetic Acid HOAc HOAc/OAc'

(iul for) HOAe ♦ NH;0M__
(reducing)
Oxalic Acid HOi ♦ NHnO.- u?hiju_vi^
ibul far)
CL4 m HCI ____
dil. Acid —.................
(cold)
Acid (hot) HCI ♦ UNOj: HMO3 * HCIOn
Mixture! HCI ♦ HMO3 ♦ HF
k-HH
Choloting EOTA DTPA
<
Agents NA4P2O7
NajPÔ? c.Ko;S2O7
I
N02S2O7 ♦ citrate ♦ _HCOJ
1
Belie (alk.ppte) looH
Soln*. NeF
Fuiion N02C0j
(♦Acid leach)
— __________ 1_________
Schematic representation of the ability of different extractants to release metals

retained in different modes or associated with specific sediment fractions. Dashed
lines indicate areas of uncertainty. (Hall, 1991)
results if the mobility of copper in the local environment is not fully appreciated. In
seepage areas hydromorphic dispersion of copper has resulted in the development of
broad strong cold extractable heavy metal (cxHM) anomalous patterns in soils which do
not pinpoint areas of copper mineralization as well as the "total" copper data (Fig. 14.7a).
On the other hand, due to the absence of significant hydromorphic dispersion in well
drained soils, there is good correspondence between the distribution patterns of cxHM
and "total" copper, and the relative proportion of cxHm is much less (Fig. 14.7b).
Selection of an appropriate decomposition technique can greatly assist in the
enhancement of geochemical dispersion patterns related to mineralization, and in the
avoidance of spurious anomalies related to extraneous factors.
Choice of decomposition method will depend largely on the dispersion

characteristics of the elements of interest and their mode of occurrence within the sample
material. Other factors to be considered include:
(i) the final method of analysis and the need to avoid interferences;
(ii) the desirability of determining several elements in the same solution;
(iii) ease of handling the desired number of samples;
(iv) availability and cost of procedure.
178
XL 88 N
N0M120NVAI KALt
VtMTCAL KALI Of
TC*O«A **•«•£ MCT«*
FIG 14.7a Distribution of copper, molybdenum, and cold-

extractable heavy metals in soils, Sheslay area.
British Columbia, (Coope, 1975)
extractable heavy metals in soils, Sheslay area.

(Coope, 1975)
179
The following discussion of decomposition procedures is in part based on material

included in a recent publication by Hall (1991).
14.2.1.1. Strong Acid Decomposition

Geochemical exploration samples are commonly subjected to some form of strong
acid decomposition procedure. In most cases, acids are used in combinations of two or
more; the actual selection depending on the properties of the individual acids, the nature
of the samples and the desired degree of decomposition.
Hot hydrofluoric acid (HF) is the only acid decomposition medium that will
completely dissolve silicate minerals in the typical geochemical clastic or rock sample.
HF breaks downs the Si-O bond to form SiF4 which volatilizes upon heating and thereby
reduces the sample solution salt content - a considerable advantage in many anal^.cal
procedures. However, it should be noted that fluorides of As, B, Ti, Nb, Ta, Ge and Sb
may be volatilized to varying degrees at the same time.
Hydrochloric acid (HCI) is effective in the dissolution of carbonates Phosphates

borates and sulfates (except baryte) and is therefore widely used (Hall, 1991 . I s
capacity to decompose Fe and Mn oxides is superior to that of nitric acid (HNO3), but
although HCI effectively breaks down certain sulfides (e.g. pyrrhotite, sphalerite and
marmatite), it barely touches pyrite. Sulfides, together with selenides, te lundes,
arsenides, sulfoarsenides, phosphates, and the majority of uranium oxide minerals are in
fact more readily decomposed by hot, concentrated nitric agid- This acid also has he
useful property of dissolving the majority of native metals found in nature, with the
exception of Au and Pt. Perchloric acid (HCIO4) is effective in decomposing sulfides as
well as organic matter. Its high boiling point can greatly assist in the removal of HF and
other more volatile acids.
A strong acid digestion, which is pften used when there is a need to determine the
metal content of a range of minerals, including silicates, involves hot HE, EO04,
and HCI The HF decomposes silicates, oxides and sulfides, whilst the HCIO4
decomposes organics, its action being moderated by the presence of HNO,. The
presence of HCIO4 also enables the evaporation of any remaining HF which could
otherwise damage the analytical instruments. These acids are evaporated to dryness and
the residue dissolved in weak HCI prior to analysis. It should be noted that the presence
of HF does not guarantee total decomposition. Refractory minerals such as cassiterite,
wolframite, chromite, spinel, beryl, zircon, tourmaline, magnetite and high concentrations
of baryte are not dissolved.
A commonly used less rigorous but still strong digestion involves hot H£l and
HNO Ci e aqua regia) with or without HCIO4. This strongly oxidizing digestion is an
efficient solvent for numerous sulfides, arsenides, selenides, tellurides, sulfosalts and
native Au, Pt and Pd. It also takes into solution many metals sorbed on to clays or other
180
Chromium extracted (ppm)
Lithology_____________ _____________ ______ —

600 140 nd
Chromite 11.00% 930
1550 480 nd
2900 1600
Pyroxenite 1400 390 nd
Chlorite schist 5800 135°
2050 740 nd
2500 2200
Serpentinite 42 18 nd
270 H5 ___ _
Quartzite
hot aqua regia; C - hot nitric add; D - hot 0.5N hydrochloric add; E
•A = alkaline fusion; B =
= cold 0.25% EDTA; nd = not detected
TABLE 14.4 Variation of Cr from different lithologies with five digestion procedures. (Fletcher.
1987)
readily decomposed mineral phases such as simple oxides and their hydrates (e.g.
Fe/Mn), most sulfates except baryte, some silicates such as zeolites, uranium oxides, etc.
Evaporation to dryness with concentrated HCI (except in the case of As, Sb, Bi, Se and
Te analyses) converts salts to chlorides ready for final solution in weak acid solution prior
to analysis.
The amount of metal extracted by the strong decompositions achieved with nitric,
hydrochloric, perchloric acids, or their mixtures is not total and will vary with the
mineralogy of the sample (Tables 14.4 and 14.5). In addition, as emphasized by Fletcher
(1981 1987) even with similar acid mixtures, extraction efficiency will vary with the acid
(Table 14.4),’sample to acid ratio, and the duration and the temperature of extraction.
Table 14.6 demonstrates how nickeliferous magnetite is more readily dissolved by
hydrochloric acid than perchloric acid, nitric acid, or aqua regia.
As previously indicated,' some resistant minerals may not be soluble in hot

concentrated acids. These must be decomposed by fusion with a compound which
lowers the melting point. The resultant reactions are of either acid-base or oxidation
reduction types. Alkaline flux reagents include Na and K carbonate (and bi-carbonate),
Na and K hydroxide, and sodium tetraborate; acid fluxes include Na and K hydrosulfate,
Na and K pyrosulfate, boron trioxide an hydrofluoride. Oxidative reagents are Na2O2,
KNO and KCIO3, whilst carbonaceous substances such as flour and starch are added
to flux mixtures for reducing action. Some examples of fusions used to decompose
certain resistant minerals are shown in Table 14.7.
181
/- o-«
Ni Zn
CU Fe HF NP PE
Cr NP PE HF NP PE
PE HF NP PE HF
HF NP
60 25 >100 50 15
15 95 75 10 >100
55 50 <10 >100 70
Pisolites in clays
95 55 >100 80 45
(ultramafic) 70 100 85 - >100
55 40 25 95 80
Ferruginous clays
(ultramafic) 90 80 >100 95 75
75 65 95 90 45 100
Silicified clays 65 60 30 80
95 75 100 100 70
80 80 65 95 95 40 95
Silicified serpentinite 70 65 30
100 100 95 100 90 65
80 75 75 95 90 50
Saprolite serpentinite 55 55 . 35
>100 >100 >100 >100 120 90
45 75 80 80 90 90 45
Fresh serpentinite 60 55
95 45 <10 85 40 <10
<10 85 65 10 90 65 <10
Weathered talc- 55 30
carbonate >100 40 35 90 60 35
40 90 85 75 90 70 50
Fresh talc- 60 60
carbonate >100 35 15 >100 50 25
35 20 90 60 35 80 65 15
Weathered dacite > ■100
>100 85 45 >100 90 35
25 <10 95 80 35 85 90 25
Saprolitic mica 90
schist - >100 60 45 >100 50 35
90 35 15 90 70 45 80 70
Saprolitic amphibilite
- perchloric acid digestion.
HF - hydrofluoric + perchloric acid. NP - nitric perchloric acid; PE
- Highly variable data
TABLE 14.5 Accuracy of acid digestions. Mean extraction (percent) determined by comparing AAS results (with simultaneous
background correction) with XRF results. (Butt and Smith, 1980)
182
Preparation jq.
crushing fraction Digestion (ppm)
Lab A no minus 80 70% HC1O4 20

Lab B no minus 80 1:3 HNO3 60
Lab C no minus 80 HNO3/HC1 150
Lab D no minus 80 1:1 HC1 320
Lab E yes minus 100 1:1 HC1 14
Lab F no minus 100 1:1 HQ 1120
Sample description
stream sediment with 0.5% magnetite
magnetite contains an average of 0.28% Ni
80% of magnetite is minus 80 mesh
99% of sample is plus 100 mesh and 96% is plus 80 mesh
TABLE 14.6 Comparison of six stream-sediment analyses for Ni. (Fletcher, 1987)
Decomposition techniques
Mineral Fusion Add extraction
Barite NaÔ, —
Beryl NajCOj; NaOH —
Cassiterite NHJ; Na,O; —
Chromite NaOH; NajO, Hacr.
Columbite/tantalite NaOH; Na.O, HF
Fluorite Na;COv NaOH Be nitrate solution
Gold Fire assay Aqua regia; bromine; alkaline
cyanide solutions
Monazite Na,Oi H;SOV HQO., H,PO.
Zircon NaOH; Na.Oj, borax
TABLE 14.7 Decomposition techniques for some resistant minerals. The presence of significant
concentrations of an element as a constituent of these minerals will cause relatively
low results to be reported if routine geochemical decomposition techniques are used.
(Fletcher, 1987)
183
The drawbacks of fusion for fusion/acid solution/ instrumental determination

methods include:
(i) the potential addition of contaminants due to high flux:sample ratio (3:1 to
10:1);
(ii) the high salt concentration introduced and subsequent need for a higher
dilution factor;
(iii) the difficulties associated with attempts to achieve high productivity.
Fusion techniques are of course also used in qla$$iQal fire assay (Fig. 14.8).
Typically, 30 g of finely ground sample is thoroughly mixed with 140 g of premixed (alkali
reductive) flux, 10-20 g of SiO2 and 3-5 g of flour. The precise nature and quantities of
the flux components depend on the mineralogy of the samples (Haffty, et al., 1977), but
always includes a substantial amount of litharge (PbO) which provides lead for precious
metal collection. Samples with high concentrations of sulfides and arsenides are
pretreated at 600-800°C to oxidize and volatilize S and As which could otherwise interfere
with the fusion. In the fusion process, all gold present is concentrated in the lead button.
In the cupellation stage the Pb is driven off and the Au remains in the dore bead. This
bead can be dissolved in cone. HNO3 and cone. HCI. The gold in solut>on is then
normally determined by AAS or ICP-AES. Alternatively, the Ag is dissolved from the bead
with HNO3 and the gold annealed and then weighed on a sensitive balance (i.e.
gravimetric method).
14.2.1.2. Phase Selective Leaches (Partial Extraction; Sequential Extraction)
Comparison of the quantities of metals extracted by techniques capable of different

degrees of decomposition can be very informative. Metals in silicate lattices of rock
forming minerals commonly constitute the background or threshold level of the
geochemical sample material. The mineralization component of an anomalous sample
is generally contained in sulfides, iron or manganese oxides, or in adsorbed positions on
clay minerals. The metal on the clays, and that contained in the sulfides and hydroxides,
is more easily extractable than the background/threshold component contained in the
rock-forming minerals. Stronger decompositions which break down the rock-forming
minerals, will effectively dilute the anomalous metal components by releasing the lower
concentrations of metal in the background component. Partial decomposition techniques
utilizing cold or weaker acids, and other reagents that do not break down the rock
forming silicates, enhance the more readily extractable mineralization component, resulting
in a much greater contrast between the anomalous and background values in the survey
(Table 14.18). In numerous geochemical surveys, therefore, the data from partial
decompositions, or partial decompositions ratioed against total decompositions, can be
much more definitive in target delineation than data from strong or total decompositions.
The potential theoretical advantages of this approach have been recognized for many
years. Canney and Hawkins (1958) and Bloom (1955) developed colorimetric tests for
cold-extractable copper (cxCu) and cold extractable heavy metals (cxHM) which have the
additional practical advantage of being readily adaptable for field-use.
184
procedure. (Hall, 1991)

r i r i i I r r i
185
Host Mineral Form

Extraction Sample
______----------
Silicate Analysis Ratio

Oxide Sulfide
Total
5 100 110
TOTAL Background 5
5.0
200 100 550
Anomalous 250
5 5 15
PARTIAL "A” Background 5
30.3
200 5 455
Anomalous 250
5 1 1 7
PARTIAL ”B" Background
37.0
•
250 8 1 259
Anomalous
Total - Dissolution of oxides, sulfides and s ilicates

Partial "A” - Dissolution of oxides, sulfides
Partial ”B" - Dissolution of oxides
TABLE 14.8 Hypothetical examples of metal extracted (ppm) by Total and ‘Partial" methods from background and anomalous
samples.
186
Chao (1984) provides a fairly comprehensive discussion of partial dissolution

tprhninups He sudoests that these techniques can be classified as ginglg or sequential
SZ J! S and 'ngn-sW sub-classes. It should be noted that he
terms^selective- and "non-selective" are strictly relative, whilst sequential exrac ion
techniques are more commonly used in research projects than routine exp o aton
programs. Many of the more frequently applied partial extraction reagents are
Table 14.3.
Viets Clark and Campbell (1984) reported that a solution of dilute hydrochloric
acid ascorbic acid and potassium iodide dissolves many weakly bound metals in soils,
Xam sediment and oxidized rocks. More recently Church et al. (1987).havemade a
useful comprehensive study of multi-element partial extractions using Inductively Coupled
Plasm^XX Emission Spectroscopy (ICP-AES) following oxalic acid and aqua reg.a
leaches They chose oxalic acid, as it primarily attacks compounds formed in secondary
qeochemical processes, whereas aqua regia will digest sulfides as well as the secondary
phafe! They concluded that oxalic acid leach is most useful in areas where here is
strono chemical weathering. In contrast the aqua regia leach is more useful w e e
mecharical weathering is predominant and the mineralization is exposed or near the
surface.
14.2.2. Separation
Once the trace element under study has been released from the sample, it may
be necessary to separate it from interfering elements liberated at the same tima Many
separations^ “race analysis involve liquid-liquid solvent extractton which permits the
transfer of dissolved material between two immiscible liquid phases, usually water and an
organic “quid sXnt extraction requires vigorous mechanical shaking of the system to
emX the two component phases and thus increase the effective surface area across
which the transfer of dissolved components takes place. Separation may be facilitated
b /the use of appropriate complexing agents that modify the solubilities of he trace
element in the two phases. Solvent extraction is the basis of many of the colorimetric
tests that have been extensively employed in geochemica prospecting. Pape
chromatography (adsorption on paper in a flowing capdiary film) and other types of
chromatography can also be used to separate elements.
A solid phase containing the desired elements may be separated from a liquid
chase bv ion exchange or by precipitation. These methods may be applied to samples
natural water or to aqueous solutions obtained by some of the sample extraction
procedures mentioned above.
Although separation is most commonly required prior to colorimetric analysis it is
also useful in some atomic absorption procedures (e.g. for natural waters, trace gold,
etc.) where the process of separation concentrates the element(s) of interest and/or helps
187
avoid potentially interfering elements, and thus improves the effective sensitivity. Common
separation techniques used include solvent extraction (MIBK, DIBK, etc.), ion-exchange,
and precipitation methods. For example, in addition to the previously mentioned (Section
14.2.3) partial extraction procedure, Viets, Clark and Campbell (1984) describe an organic
separation technique for a number of elements of common exploration interest. Ag, Bi,
Cd, Cu, Mo, Pb, Sb, and Zn are selectively separated from the extraction solution by a
mbrture of Aliquat 336 (tricaprylyl methyl ammonium chloride) and MIBK (methyl isobutyl
ketone). Since potentially interfering major and minor elements do not extract, the
organic separation allows interference-free determinations of the elements of interest, and
extremely low detection limits are possible.
A multi-element organic extraction/separation procedure which reportedly provides

essentially interference-free geochemical analyses in gold exploration has been recently
developed by the U.S.G.S. (Clark and Viets - 1990). The Methyl isobutyl ketone-Amine
synerGistic Iodide Complex (MAGIC) extraction method separates Au, Ag, As, Sb, Bi, TI,
Hg, Se, Te, Ga , Pt, Pd, Cu, Zn, Cd, In, Sn, Pb, and Mo from interferences in geological
matrices. Quantitative extraction is accomplished over a broad range of acid normality,
allowing determination by ICP or AAS of 19 elements from a single digestion or leach
solution!
14.2.3. Measurement
A prime requirement for cost-effective geochemical exploration surveys is the

availability of analytical procedures capable of high productivity, low detection limits, and
acceptable precision and accuracy, all at moderate cost. These criteria were met in the
1950’s, by a series of colorimetric analytical techniques with man-day productivity ranging
from 20 to 100 samples per day. Technological developments subsequently led to the
introduction of atomic absorption spectrophotometry (AAS), inductively coupled plasma
spectrometry (ICP), X-ray fluorescence (XRF), and instrumental neutron activation analysis
(INAA) which permit vastly increased productivity (See Table 14.15 below). Along with
the multielement capability of ICP, XRF, and INAA, these techniques provide accurate,
precise determinations with detection limits of less than 5 ppb to 1 ppm for many of the
elements commonly measured in exploration geochemical surveys. The inductively
coupled plasma - mass spectrometer (ICP-MS) instrument is capable of even greater
sensitivity, and other techniques including direct current plasma (DCP), and ICP-atomic
fluorescence analysis (ICP-AFS) are particularly well-suited for some element groups. The
DC-arc emission spectrograph is still used for some geochemical work, but the method
has lost ground to the other techniques that have been described. Available analytical
instrumentation allows the better equipped commercial laboratories to offer analyses for
a remarkably wide range of elements (Table 14.9).
188
ELEMENT AAS ICP i XRF NNA FA EC c JISC. LEGEND

Li 1 Atomic Absorption
Be 0 1 AAS -
5 Spreclrocopy
B 100
c
20 KP - Inductively Coupled
F
100 Plasma
“fl
Al §g 100 XRF - X-ray
SI
p 10 Fluorescence
10
s 100
Cl INAA - Induced Neutron
K 100 Aclivotion Analysis
Sc 0.5
Ti 10 FA - Fire Assay etc.
V 5
Cr 2 Electrochemical
Mn 5 EC -
too
Co 1 C - Colorimetric
NI 1
Cu 1 MISC. - Miscellaneous
Zn 1
Go 1
5
1
0.1
0.5
Rb 1
Sr 1
Y 5
Zr 5
Nb s
Mo 1
Ru 0.005
Rh 0.005
0.002
S3
0.2
Cd 0.1
In 1
2
Sn
Sb 0.2
0.05
1 2.0
Ci 0.5
Ba 10
La 1
Co 2
Pr 5?
Nd 5
$rr 0.1
Eu 0.5
Gd 50?
Tb 0.1
Dy 17 •
Ho 1?
Er 20?
Tm 17
Yb 0.1
0.1
HI 2
To 2
W 2
Ao 0.005?
01 0.005
ir 0.005
Pt 0.005
Au 0.001
Hg 0.01
TI 0.1
Pb 1
Bl 0.1
Th 1
U 0.27
TABLE 14.9 Preferred analytical methods and analytical detection limits (ppm) for solid state geologica
materials at a typical major commerical geochemical laboratory (Chemex).
189
The following paragraphs include general descriptions of a number of these

analytical methods together with brief discussions of their advantages and limitations.
They borrow heavily from the work of Fletcher (1981) which, together with the recent
publications by Baedecker (1987) of the USGS and Hall (1991) of the GSC provide useful
sources if more detailed information should be required.
By way of explanation, the terms "working range" and "linearity" are often used in
descriptions of the operational capabilities of specific analytical procedures. The working
range of an analytical technique is the concentration range over which the relationship
between metal content and instrument response is linear. This defines the normal upper
and lower detection limits for the method (Fig. 14.9). Thus for example the linear working
range for many colorimetric and AAS techniques is only two orders of magnitude of
concentration, whereas the ICP technique typically has a linear response of four to five
orders of magnitude of concentration.
14.2.3.1. Colorimetry
Colorimetry is based on the formation of colored compounds in solution by

reaction of an element with a specific chemical reagent. Quantitative determination of the
element concentration is possible if the intensity of the color is proportional to the
concentration of the compound causing the color. Estimation of the intensity or hue of
the color in the solution can be made by visual comparison with standards of known
concentration, or instrumentally by measurement of the intensity of those wavelengths
most strongly absorbed by the colored solution (spectrophotometry). A few colorimetric
reagents form colored compounds with only one element, but most react with several
elements. Therefore, preliminary exclusion of the interfering elements by complexing or
separation is usually required. It is also necessary to control solution pH conditions in
order to optimize reagent selectivity. Thus most colorimetric procedures involve:
(i) sample decomposition;

(ii) transfer of an aliquot of sample solution;
(iii) addition of a buffer, and if necessary, a complexing agent;
(iv) addition of the colorimetric agent;
(v) extraction of the colored complex into a suitable organic solvent;
(vi) estimation of color intensity.
190
Linear working range. (Coker, pers. comm., 1983)

FIG 14.9
191
Mercutic chloride
paper
ABSORPTION O ring
HEAD
Absorption tube
) ARSINE I
I GENERATOR I
Silver
Oiethyldithiocarbamate
solution
FIG 14.10 Determination of As by generation of arsine and its reaction with (A) mercuric chloride
paper, or (b) silver diethyldithiocarbamate dissolved in pyridine or quinoline.
(Fletcher, 1981)
A few determinations deviate from this sequence. For example, in the

determination of As, arsine gas is produced by reduction of As with nascent hydrogen;
the arsine is then allowed to react with filter paper soaked in mercurous chloride giving
a colored spot, the intensity of which reflects the As concentration (i.e. Gutzeit Method).
Alternatively, the arsine is bubbled through a solution of silver diethyldithiocarbamate (Fig.
14.10).
The advantages of colorimetry in geochemical exploration are simplicity, low cost,
equipment portability, and the wide range of elements which can be determined (Table
14.10). The disadvantages are the inability to determine more than one element at a time,
the sensitivity of many reagents to interferences and aberrant chemical conditions and,
in some cases, the carcinogenic nature of the solvents used (e.g. carbon tetrachloride,
benzene, etc. Although widely used in the early days of exploration geochemistry,
colorimetric methods have been mainly replaced by more rapid and sensitive instrumental
techniques.
14.2.3.2. Fluorimetry
When a fluorescent substance is exposed to ultraviolet radiation, it emits visible

light at a longer wavelength than the excitation source. The intensity of the fluorescence
192
Some colorimetric reigents used in analysis of geochemical samples Reference

Element Reagent
Brillant Green 2.5.82

Element Reagent Sb
Rhodamine B 3. 6-8
56
Ag dithizone 3 3' dumino lienzidine 2.54
catalytic oxidation Mn' 55 Se
1-3, 58. 59.60.67
1-3.9-11 Gallein
Sn
As HgCI2 dithiol 61
silver diclhyldilhiocarbamatr 4. 12.75
4 Th Arsenazo III 1.57. 83
Molybdenum Blur
Cassius gold purple 84 2. 3
Ti Tiron
Brilliant Green 2, 27 as phospholungstovanadic acid 1-3, 68, 69
Au V
4,4'bisthiobenzophenonc (TMK) 28
1.2. 33. 62-64
29 W dithiol
crystal violet 3. 65, 66
thiocyanate
methylene blur 1. 17
B dithizone 1-3. 70. 71
2. 3. 13 Zn
Ba sulphate
2. 14 References I - Stanton (1976); 2 ■ Stanton (1966). 3 - Ward el al (1963). 4 • W ard
Be berylion II
(1975) 5 -Stanton and McDonald (1962). 6 - Ward and Lukin (1954). 7 - J.rdme
dielhyldithiocar hamate 1-3, 15. 16
Bi 1963). 8 • Schnepfe (1973); 9 - Almond (1953a). 10 - Stanton (1964). 11 • Lynch. and
2 nilroso l napthol 3. 19 Mihailov (1963). 12 • Rundle et al. (undated); 13 ■ Brobat and Ward (1965). 1 1 - Jun
Co
tri-n bulylamine 2, 20 et al (1959 60); 15 - Ward and Crowe (1956); 16 - SUnlon (197 la). I 7 ■ Stanton and
2, 3. 18 McDonald (1966). 18 - Wood and Stanton (1956 -57), 19 • Almond (1953b). 20-
Cr as chromate Stanton and McDonald (1961—62a); 21 - Almond (1955), 22 - Holman (1963) 23 ■
dipbenylcarbazide 2, 18
Holman (1956-57). 24 - Warren and Del.v.ult (1958). 25 - Kaur.nne and Norm.
2,2' biquinoline 2. 3, 21,77 (1967); 26 ■ Almond et al (1955). 27 - Stanton and McDonald (1964). 28 - Lakm and
Cu
1.22. 23
dithizone Nakaeawa (1965); 29 - Kolhny (1969), 30 - Grimaldi and Schnepfe (1971), 31-
rubeanic acid 24. 76 Almond (1953c); 32 ■ Ward and Bailey (1960). 33 - North (1956) 34 - Stubb. (1968).
Neocuproine 25 35 • Stanton and Hardwick (1967); 36 - Stanton (1970a). 37 - Marshall (1968) 38 -
phenylfluorone 2,3.26 Marshall (1964), 39 = Stanton el al (1973); 40 - Hoffman and Waakel Myers (1974).
Ge
41 - Baker (1965); 42 - Ward (1951a); 43 - Lapointe (1968), 44 - Barakso (1967) 45 -
dithizone 1, 3, 72 -74
Heavy metals Stanton and Coope (1958 59); 46 - Nowlan (1970); 47 - Lyneh (1967). 48 ■ Bloom
dithizone 2. 3. 32 (1962), 49 = Peachey et al (1973); 50 - Thompson (1967), 51 - Kothny (1974). 52 ■
Hg
30 Rose (1969); 53 - Mahaffey (1974); 54 ■ Stanton and McDonald (1965). 55 - Nakagawa
1 as iodine
and Lakin (1965). 56 - Bloom (1966). 57 ■ Stanton (1971b). 58 - Wood (1959). 59 -
as permanganate 2. 3, 31
Mn Stanton and McDonald (1961-626). 60 ■ Smith (1967). 61 ' Cogger (1974). 62 ■
1.2, 33 41. 78, 85 Sunton (1970b); 63 - Bowden (1964). 64 - Quin and Brook. (1972). 65 • Ward
Mo dithiol
thiocyanate 3, 42-44 (1951b); 66-Cogger (1976), 67 ■ McDonald and Stanton (1962). 68 - Sunton and
Hardwick (1971), 69 = RoberU (1971); 70 - Lakin et al (1949), 71 - Sunton (1962).
thiocyanate 3. 79
Nb 72 - Bloom (1955). 73 - Hawke. (1963); 74 - Smith (1964). 75 • Manh.ll (19781.76 -
a-furildioxime 2. 3. 45-47 Delavault (1977). 77 ■ Peachy et al. (1978). 78 - GrifitU el al. (1976); 79 ■ Ward and
Ni
dimethylglyoxime 48 Marranzino (1955); 80 - Stanton (1975); 81 - Rom (1976). 82 - Sunton and McDonald
as phosphomolybdovanadic acid 2.3,49 (1961-62C); 83 - Aly et al (1977). 84 - Krings et al (1976); 85 - Clark and Alley
P
reduction of phosphomolybdic acid 1. 50. 80 (1955)
Pa
dithizone 1-3
Pb
reduction of phosphomolybdic acid 1.50.80
Pl
Rhodamine 6G 51
(several methods) 52. 81

Rare earths
thiocyanate 53
Re
TABLE 14.10 Some colorimetric reagents used in analysis of geochemical samples. (Fletcher, 1981)
193
is proportional to the concentration of the fluorescent material and can be estimated

visually, by comparison to standards or measured in a fluorimeter. Uranium is especially
amenable to this technique when samples are fused with a K2CO3/Na2CO3/NaF flux.
A number of elements including Mn, Cr, Co, Ni, Fe, Ag, Pb, Pt, etc. tend to suppress
fluorescence, but special precautions can be made to minimize possible interferences.
The method has the advantages of speed and simplicity, particularly in the hands of an
experienced and skilled analyst. More complex versions involve separation of the uranium
from other elements by solvent extraction in order to avoid potential analytical
interferences.
14.2.3.3. Atomic Absorption Spectrophotometry (AAS)
Atomic Absorption Spectrophotometry has been one of the principal methods of

exploration geochemical sample analysis for over 25 years. It involves conversion of
compounds to their constituent atoms and then excitation of these ground state atoms
by absorption of radiant energy. The amount of energy absorbed is measurable and is
proportional to the concentration of absorbing atoms.
FIG 14.11a & b Schematic diagram of atomic absorption

spectrophotometers: (A) single-beam, and (B) a double
beam instrument, h = hollow cathode light source; m =
monochromator; and p = photomultiplier. is the
intensity of the signal from the light source and its
intensity after absorption by analyte atoms in the flame.
194
In its simplest single beam form (Fig. 14.11a) an AAS unit comprises:
(i) a light source emitting the sharp line spectrum of the element to be
determined. This is generally provided by a sealed hollow cathode lamp
containing the element(s) of interest;
(ii) a means of generating a cloud of atomic vapor (i.e. ground-state atoms);
(iii) a monochromator and slit to select the desired absorption line;
(iv) a detector, amplifier and readout system.
A beam of radiant energy of the desired wavelength provided by the light source,
is passed through the atomized sample. The amount of absorbed energy is measured
by a suitable detector after the atomic absorption wavelength has been isolated from any
neighboring non-absorbing wavelengths emitted by the light source. In many cases this
isolation can be achieved with a simple narrow slit through which the light beam passes.
However, for elements with more complex spectra (e.g. Ni and Mn) a small grating
monochromator is required.
Components of the double-beam instrument (Fig. 14.11b) are identical to those of

the single-beam discussed above, but the light from the source is split into two beams,
one of which bypasses the atomic cloud and provides a reference against which instability
in the output source can be corrected. The double- beam instrument also allows use of
a continuum light source, either a hydrogen or deuterium lamp in the UV region, in
addition to the primary hollow cathode lamp. Intermittent passage of light from this
secondary source permits determination of background absorption resulting from
absorption by molecular species in the flame, and possibly also by light scattering by
solid particles. This interference absorption can then be automatically subtracted from
the total absorption of the primary light beam to give a corrected value for each sample
(Table 14.11 and Fig. 14.12). Such corrections are advisable for a number of elements,
especially Ag, Cd, Co, Ni, and Pb. These and other common corrections are listed in
Table 14.12.
Conventional AAS requires that the elements of interest be in solution. Hence

water samples can often be analyzed direct, but as previously discussed, solid samples
must first be subject to some forrri of decomposition process, and a dilute acid or other
aqueous extract prepared. If analytical sensitivity is too low for direct determination of the
analyte in the original solution it may be concentrated into an organic phase by solvent
extraction. Usually the sample solution is aspirated by a venturi powered by the pressure
of the oxidant gas, into a chamber where the resulting aerosol mixes with fuel gas before
entering the flame through a narrow laminar-flow burner slit. The requisite cloud of atomic
vapor is then produced in the flame. A variety of gas mixtures have been used, but the
lean oxidizing air/acetylene flame has the most general application. Its temperature
(2200°C) is sufficiently high to ensure breakdown of most compounds and production of
ground state atoms, but not high enough, except in the case of alkalies, to allow forma-
195
Pb added Absorbance Pb found (ppm) 1

(PPm) *
cathode lamp H2 lamp corrected uncorrected corrected
0.0 0.015 0.015 0.000 24.8 0.0

20.0 0.025 0.015 0.010 47.7 21.0
50.0 0.041 0.015 0.026 82.1 53.5
100.0 0.063 0.016 0.047 122.2 95.5
200.0 0.111 0.015 0.096 217.7 190.9
1 Dilution factor = 50
TABLE 14.11 Correction for background absorption in lead analysis of a synthetic rock solution.
(Fletcher, 1981)
FIG 14.12 Errors in uncorrected and background-corrected measurement of Pb in the presence

of 4000 ppm Fe. (Fletcher, 1981)
196
Element 1 Inter Comments

ference
Ag B background correction
Ba* C, I suppression by Si, Al and

P — add oxine or NH4CI;
enhancement by alkalies and
alkali earths — add
K radiation buffer
Be* C suppression by Al
Cd, Co B background correction
Cr C suppression by Fe, Na and K;

enhancement by Al, Mg, Ca —
interference and sensitivity
reduced in NjO/CjHj flame
Mo* C suppression by alkalies, Ca,

Fe — add up to 1000 pg/ml Al
Ni, Pb B background correction
Rh I add K radiation buffer
Sr* C. I add K radiation buffer and La

releasing agent
V* C suppression by Fe and Ti —
add 1000 pg/ml Al
Zr* C add NH4F
1 Determined in lean air/acetylene flame except (*) in nitrous oxide/acetylene flame.

2 B = background absorption; C = chemical (suppression); I = ionization (enhancement).
TABLE 14.12 Some interferences in the determination of trace elements in geological matrices by flame
atomic absorption spectrophotometry. (Fletcher, 1981)
197
tion of complex chemical and/or ionization products which can cause serious analytical
interferences. The hotter (2955°C), fuel-rich nitrous oxide/acetylene flame is more prone
to these interferences, but it provides a reducing environment for determination of
elements (e.g. molybdenum) which otherwise tend to form refractory oxides. The hotter
flame generally necessitates particular attention be given to removal, by separation, of
potential interference sources prior to analysis.
Variants of the conventional AAS procedure, using electrothermal furnaces (e.g.

graphite or silica tube) rather than flames to produce ground state atoms, allow more
efficient use of the sample (i.e. smaller samples required) and generally have better
sensitivities. However, productivity is often low, and interferences from non-specific
absorption (due to smoke and high atom densities, etc.) necessitate special separation
procedures with most samples other than dilute aqueous solutions (e.g. water samples).
Hence, the methods are generally only applied when adequate data are otherwise
FIG 14.13 Apparatus for AAS determination of elements forming gaseous hydrides. Cell A is a
18 mm x 16 mm plastic test tube with a hole, 30 mm from the bottom, to take the tip
of a micropipet. A 1-^1 volume of sample is injected into the borohydride solution in
the cell. Gaseous hydrides are then swept by a flow of nitrogen into the silica
absorption cell (D) heated by the air/acetylene flame of a triple-slot burner. (Fletcher,
1981)
198
by atomic absorption spectrophotometry

Application of Ifydride generation to analysis of geochemical samples
Comments Reference 1
Generator Atomizer Detection limit
Element Decomposition
0.16 ppm on interference from Ni 1

2% NaBH4 flame heated
As aqua regia prevented by addition of
solution quartz cell 0.5-g sample
HF/HCIO4/HNO3
0.01 M EDTA
6 M HCI
semi-automated Technicon 2
1% NaBH4 resistance 0.25 ppm on
As HNO3/HCIO4 system for analysis of
heated 0.1 g sample
solution
soil and vegetation
quartz cell
modification for rapid 3
5% NaBH« Nj/Hj/air
A* analysis of exploration
flame
samples
KI added as a pre-reduc 4
resistance 10 ng/ml in
HCI 1% KI/ tant; rapid technique for
As solution
1% NaBH4 heated
analysis of soils, walers
quartz cell
HNOj/HClOa and vegetation
KMnO4 added to avoid w
Ar/Hj flame 0.04 ppm for
HF/HCIOJ Kl/SnClj/Zn
As 1 g sample volatilization losses;
HNOj/KMnO« interference from Pb
minimized by addition
Fe”
no interferences from Cd, 7
resistance 0.001 pg/ml
HNOj/HjSO* 2% NaBH4 Cu. Pb. Zn, Mg. Ca, Fe
As
heated silica
and Al at concentrations
tube
found in soil samples
interference from Ni and 1
flame heated • 0.08 ppm on
Aqua regia 2% NaBH4 Ag reduced by addition of
Sb quartz cell 0.05-g sample
HF/HCIO4/HNO3 0.01 M EDTA
6 M HCI no serious interferences 6
resistance 5 ppb on 0.25-g
HF/HCIO«/HNOj 5% NaBH4 for most samples: up to
Te heated quartz sample
200 ppm Cu can be
cell
tolerated
; 2 - Vijan et al. (1976); 3 = Kokoi (1976); 4 * Wauchope (1976); b = lerasluma (19 , b) ; 6 = Green-
1 References: 1 “ Aslin (1976,
= Thompson and Thoresby (1977)._____________________________ ____
lonrl and Campbell (1976); 7
atomic absorption spectrophotometry, (neicrwr.
TABLE 14.13 Application^ hydride generation to analysis of geochemical samples by
1981)
199
unobtainable at reasonable cost. A case in point is the hydride generation technique

which provides a rapid and sensitive approach to analysis of elements forming gaseous
hydrides (e.g. As, Sb, Se, Sn, and Te). The hydrides are swept into a transparent
argon/hydrogen or nitrogen/hydrogen flame or flame heated cell (Table 14.13 and Fig.
14.13).
Estimation of mercury by flameless AAS after its release by acid digestion followed
by reduction in solution to elemental mercury (i.e. cold vapor method) or pyrolysis,
predates conventional AAS by many years. The cold vapor method is readily adaptable
for use on any conventional atomic absorption spectrometer with a quartz window
equipped glass tube replacing the burner head (Fig. 14.14). The pyrolysis method,
however, suffers from problems, especially with samples rich in organic matter or sulfides.
These produce smoke or SO2 which cause serious interferences due to non-specific
absorption. Several procedures have been developed to help overcome this problem,
including a double beam instrument which permits corrections to be made for non-atomic
absorption (e.g. Fig. 14.15).
Atomic absorption has become one of the most widely used analytical methods in
exploration geochemistry because of:
(i) the wide range of elements which can be determined (Fig. 14.16);
(ii) the low detection limits for most elements of interest;
(iii) the specificity for individual elements;
(iv) the opportunity to determine several elements in one solution
(v) the relatively inexpensive and simple equipment required.
200
FIG 14.14 Cold vapour generation and determination of Hg by AAS. In the gas washing bottle
H</* is reduced to Hcf with Sn2’ and then swept into the absorption cell by a stream
of air. The IR heater lamp prevents condensation of water vapour in the cell.
(Fletcher. 1981)
FIG 14.15
one of which passes though glass wool loaded with palladium chloride, to remove Hg
but not constituents causing non-atomic absorption, before entering the reference
absorption cell on the right side of the instrument. Output from the two
photomultipliers is compared. (Fletcher, 1981)
201
ELEMENTS BY AAS
H KEY -----------
COMPLEXITY
uTBel
a
C
• FIRE ASSAY PRECONC
-CVAA
r b' C~N S’ Fira
1 SIMPLE
a - EXTRACTION PRECONC-
I- PAA 2 MODERATE F Al SI SI Cl Ar
Na Mg
g GFAA 3 MOST | ,
h ■HGAA ___
CoT Nl “Cu Ga Ge As Se Br Kr
K Ca Sc; tTl Cr Mn
g®j'«2
tE Ru Rh Pd Agl Cdl In Sn Sb ~T8
Xe
Sr Y', Zr Nb Mo
Rb fa. ja fa, a» W. g®
;• ;a 9® 9® HOT 'V n. g*
Pb B At Rn
Csi Ba Lai HtrrST-N rEI 08 It- Pt
9® gas® S< i fa n. <a
Fr Ra Ac (Rn (Ha)i
:-----------
Pr Nd Pm _ Gd Tb Dy Ho Er Tm Yb Lu
J Ce Sm Eu
5 Th i Pa U Np Pu Am Cm Bk Ct Fm Md No (Lr)
indicates "best' element by this technique
Analysis by AAS. Sensitivities with respect to crustal abundances (Hall, 1991)

FIG 14.16
A disadvantage for most conventional AAS equipment is the restriction of analysis to one
element at a time Freedom from interferences is often cited as one of the principal
advantages of AAS; however, if samples and standard solutions differ in bulk
composition, a variety of interferences can cause enhancement or depression of the
signal unrelated to the actual concentration of the element being measured. The
Newmont 1988 SRS round robin study found that one laboratory using non-matrix
corrected standard solutions obtained results which were one half the acceptable value.
Needless to say they are now using matrix corrected standards.
14.2.3.4. Emission Spectroscopy - DC Arc (DC-ES) and

Inductively Coupled Plashia (ICP-ES or ICP-AES)
Almost all elements, when vaporized and ionized in intense heat emit radiation of
characteristic wavelengths in the visible and ultraviolet range as a result of electrons
refilling the outer electron orbital. The spectra emitted by the excited atoms can be
separated by a quartz prism or diffraction grating and then either recorded
photographically or, in the case of direct reading spectrometers, measured
instantaneously with photomultipliers (Figs. 14.17a and 14.17b). Elements can be
identified by the wavelengths emitted, and the concentrations determined by the intensity
of the emissions.
202
In the past the most common
excitation source for emission
spectroscopy was the DC source
(Fig. 14.17a) in which a generally small (10-
50 mg) solid-phase sample was placed in
the lower electrode. Temperatures
achieved in the arc (i.e. 7000-8000°C
under optimum conditions) are significantly
higher than those encountered in AAS and
the proportion of atoms excited to energy
levels above the groundstate is
correspondingly increased. The technique
was at one time widely applied in
multielement analysis of geochemical
exploration samples, particularly in
regional reconnaissance programs in
which it is desirable to determine as wide
a range of elements as possible. All grating and D.C. - arc source.
elemental analyses by this method are (Coker, pers. comm., 1983)
based on comparisons of measured
spectral signals between samples and
standards with similar compositions.
Under ideal circumstances (i.e. consistent
matrices and concentration levels)
quantitative analyses that are accurate to
within ±10 percent can be achieved for
many (up to 35 or more) elements (Fig.
14.18.) However, when dealing with
typical highly variable geological materials _
such as stream sediments, matching of
standards and samples is difficult, if not
impossible, and analytical errors of ±50%
or more are common! The analytical data
are at best only semi-quantitative- In
addition, detection limits for some of the
elements commonly considered in
geochemical exploration (e.g. As, Sb, Zn,
etc.) are unacceptably high. Matrix
modification (diluents and buffers) and the
standard addition method can sometimes
help overcome some of the interferences
and improve data quality, but potential
representativity problems related to the small sample size remain. With typical
__ - • ‘
203
FIG 14.17c Inductively coupled plasma. (Coker, pers.

comm., 1983)
FIG 14.17d Direct current plasma. (Coker, pers. comm.,

1983)
204
He
H
B C N O F Ne
Li Be
Al Si P s Cl Ar
Na Mg
Zn Ga Ge As Se Br Kr
K Ca Sc Ti V Cr Mn Fe Co Ni Cu
Rh Pd Ag Cd In Sn Sb Te 1 Xe
Rb Sr Y Nb Mo TC Ru
.....
W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
Cs Ba La HI Ta
Fr Ra Ac
Pr Nd Pm Sm Eu Gd Tb Oy Ho Er Tm Yb Lu
Ce
Np Pu Am Cm Bk Ct Es Fm Md Lw
Th Pa U
Analysis of exploration samples by DC-ES. Emission lines of elements in bold face

FIG 14.18. and Stipple are almost invariably present in the DC-arc spectra of geochemica
samples^ elements in stipple only are often visible and those in^’st'ppl® ®r®
occasionally visible. Remaining elements either cannot be determmed by ES,or are
only very rarely seen in emission spectra of rocks, soils and sediments. (Fletcher.
1981)
geochemical samples alternative methods (e.g. ICP-ES or ICP-AES) often provide superior
results with less effort.
inductively Coupled Plasma (ICP-ES or ICP-AES), a fairly modern variant of the
emission spectrographic method, has become the dominant geochemical analytic^
technique in many parts of the world. It uses a plasma cell as the sample excitation
source (Fig 14.17c). Argon passing thorough a strong magnetic field created by a
induct coil is seeded wim electrons. Heating
in the plasma gas produces temperatures of the order of 7000-10000 K, Sl9™fl™y
higher than those associated with the DC arc. Also in contrast to the DC arc method the
sample is introduced in aerosol form. Consequently, solid samples must first be
dissolved, but water samples can be analyzed directly or after a Ste5
This technique is capable of determining many elements over a wide range Q
concentrations (Fig. 14 19) Specific elements can be determined quantitatively with hig_
precision and accuracy.
205
ELEMENTS BY ICP-AES “h£

n
1 rriMPt fxity
___
U Be B c N 0 F Ne'
h • MVDRiDG 1 SIMPLE
P • PPFCDNCFNTRATlON 2
i 2 MODERATE
BY EXTRACTION. FIRE Al SI p 5 Cl Ar
Na Mg
ASSAY OR RESIN 3 MOST 1 1 1 !
1 1
V Cr Mn Co NI Cu Zn Ga Ge As Se br Kr
K Ca Sc Ti ,F- h n n
1 1 1 1 1 1 1 1 1 2 2 2 2 ------ 1
Zr Nb Mo Tc Ru I Rh Pd Cd In Sn Sb le Xe
Rb Sr Y 3 h n n 0
□ ■=? p p
1 1 1 2 i? 2 2 2 3 3
Hf Ta w Re Os I Ir Pt Au Hg I Pb b Po At Rn
Cs Ba La n L_!
0 | P p p
1 3 3 2 3 2 2 !’ 2
Fr; Ra Ac
® (Rf) (Ha j
c Ce Pr Nd Eu Gd Tb Dy Ho br Im Yb Lu |
0 p Pm D p p p p p p I
1 2 2 2 2 2 2 2 2 2 ;
2
s Th Pa u Np Pui Am Cm Bk Ct Es
Fm Md NO
(Lr)|
p p
3
indicates "best' element by this technique
FIG 14.19 Analysis by ICP-AES. Sensitivities with respect to crustal abundances, (Hall, 1991)
ICP offers better precision than DC arc, superior limits of detection for most
elements, and faster rates of analysis for multiple element request than flame atomic
absorption spectrometry. In addition, ICP-calibration curves are linear over a large range
of concentrations. The linear working range for many colorimetric and AAS techniques
is only two orders of magnitude of concentration, whereas the ICP technique typically has
a linear response of four to five orders of magnitude of concentration. Analytical precision
of most determinations will be ±5 percent, if properly performed. It is therefore not
surprising that the technique has assumed much of the analytical workload previously
accomplished by DC arc and, to lesser extent, AAS. A fundamental limitation arises from
one of ICP’s main features: the high excitation energy levels excite ground state and ion
electron transitions for most elements. Consequently, spectral overlap between elements
is common. Although the spectral overlap contribution from each element can be
corrected mathematically, the degree of overlap and the concentration of the interfering
element combine to modify the limit of detection. The recently developed MAGIC
multielement extraction system (Clark and Viets, 1990), which has been previously
described in Section 14.2.2., avoids some of these problems by providing a virtually
uniform sample solution matrix.
206
The advantages of ICP include:
(i) the ability to determine many elements simultaneously;

(ii) high sensitivity and precision;
(iii) good stability;
(iv) correctable interferences;
(v) reproducibility in the introduction of samples, and
(vi) convenience of operation.
The disadvantages include:
(i) the high cost and sensitive nature of equipment;

(ii) the need to often compromise when selecting a sample digestion method.
(A single digestion is generally not optimal for all elements in an analytical
suite. It is therefore necessary to be aware of which elements do not
respond well to the selected digestion).
Direct current plasma (DCP) is another type of sample excitation source sometimes
used in emission spectroscopy (Fig. 14.17d). Its operational characteristics are
somewhat similar to those of ICP.
( 14.2.3.5. X-Ray Fluorescence Spectrometry (XRF)
When a sample is bombarded by sufficiently energetic X-rays, secondary X-rays

are emitted at wavelengths (or energies) and intensities that are determined by the
elemental composition of the sample. Measurement of the intensity of this characteristic
radiation is the basis of XRF.
All X-ray emission spectrometers _ provide some means of exciting secondary

fluorescence from a sample, selecting the desired characteristic line and measuring its
intensity. These goals can be achieved with:
(i) a conventional wavelength-dispersive spectrometer;
(ii) an energy dispersive spectrometer;
(iii) a portable unit with an isotope source.
In the conventional XRF spectrometer, characteristic radiation, excited by a primary

X-ray beam produced in a high-voltage X-ray tube, is dispersed by crystal diffraction. It
is then measured at the appropriate wavelength by a proportional or scintillation detector
on the movable arm of a goniometer (Fig. 14.20a). The operation of the gnergy-
dispersive XRF spectrometer (Fig. 14.20b) is somewhat different in that the secondary X-
2Q7
rays are sorted solely on the basis of their energies. This is achieved with a semi
conductor detector which both resolves and measures the intensity of the secondary
fluorescence. Interferences from background radiation are minimized as far as possible
by using as an excitation source either a radio-isotope or monochromatic radiation,
generated by bombarding a secondary target with primary X-rays. Its outstanding
advantage compared to conventional XRF is that simultaneous multi-element analyses are
possible with a relatively inexpensive instrument. A serious disadvantage is that the
detector must be maintained at low temperature by means of liquid nitrogen. With
portable XRF instruments (Fig. 14.20c) weight and bulk are important factors so radio -
isotopes are used as primary energy sources, and characteristic lines are isolated with
balanced filters having absorption edges immediately adjacent to and on either side of the
analyte’s characteristic line. Readings are taken first with one filter in position and then
the other, the difference in readings giving the intensity of the characteristic line.
Because of the wide compositional variations of solid-state geochemical samples,

and differential excitation of different components of individual samples as a result of
textural and mineralogical effects, it is only possible to obtain reliable results if sample
preparation is designed to minimize textural variations, and if corrections are made for
mass absorption differences between samples and standards. Sample preparation can
in some cases simply involve fine grinding (<50 microns) prior to insertion in the sample
holder. Alternatively, the pulverized sample can be mixed with a binding agent and
formed into a pellet under pressure. When very accurate whole rock analyses are
required, possible problems from mass absorption coefficient variations can be minimized
208
A. WAVELENGTH DISPERSIVE
Detector HV, Amplifier.

Electronic*. PHA, Readout
FIG 14.20a X-ray spectrometer. Wavelength dispersive.

(Fletcher, 1981) V >
FIG 14.20b X-ray spectrometer. Energy dispersive

(Fletcher, 1981)
C. PORTABLE UNIT WITH

ISOTOPE SOURCE
Nat Ci Filter pair on
rotating mount
Source
Electronics Photomultiplier ----- Sample
Safety
shutter
Cable to power supply, Window

electronres and readout
FIG 14.20c X-ray spectrometer. Portable unit with

isotope source. (Fletcher, 1981)
209
by fusion of the sample to produce a homogeneous glass disc. This can then be
pulverized, mixed with a binding agent and pressed into a pellet.
XRF can also be used to analyze natural waters (or analytical digests) by collection
of particulate and dissolved metals on ion-exchange loaded filters. Alternatively,
precipitates can be collected as a thin film on a filter paper which can then be analyzed.
XRF has found wide acceptance for determination of the major constituents of
rocks, and is also capable of providing useful data for many trace elements in
geochemical matrices (Fig. 14.21). However, the detection limits for elements of low
atomic number, notably Na, Mg, Al and Si, are relatively high (Fig. 14.22) due to the
internal re-absorption of secondary X-rays. Limitations on the method which affect
precision, accuracy, and sensitivity, arise from spectral overlap, matrix absorption and
enhancement effects, and sample heterogeneity. Inter-element and matrix effects are
treated by one or more methods including matrix matching of samples and standards,
dilution, preconcentration of the element of interest, and/or mathematic corrections.
The main advantages of XRF are:
(i) good analytical precision;

(ii) sample preparation can be extremely simple.
The main disadvantages include:
(i) the high detection limits for some elements of potential interest;
(ii) the need to correct data for matrix effects;
(iii) high cost of the conventional wavelength dispersive X-ray spectrometer.
210
ELEMENTS BY XRF He
H
SENSITIVITY
Li Be B C N 0 ~F Ne|
f • FUSED OISC 1. HIGH
p PRESSED POWDER 2 MODERATE
Na Mg SI S Cl Ari
'ipl i(pF 3 LOW t(p> np> np) D p
i t 1 1 1' 2 2
K Ca Sc TI V Cr Mn
Fe Co NI Cu Zn Ga Ge As Se Br Kr
<(P) t(p) p p (p>
'(P) I p t p t p tp p p 0
'(?) 1 t 1 1 1 1 1
i i i 1 1 J 3
Rb Sr Y Z r Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
p ip ip tp t.P 2 p p p
1 t t 1 t 3
Cs Ba La Hf Ta w Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
ip p p tp 0
1t |'z 2 I______33 I 3 1 Li— 3
Fr' Ra>Ac|(Rf) (Ha)i
Ce Pr Nd Eu Gd Tb Dy Ho Er| Trn Yb Lui

Pm Sm
Th Pa u Np Pu Am Cm Bk Cf Es Fm Md No (Ur)
pffi Ptn
i 2 —
Inoicates best" element by this technique
FIG 14.21 Analysis by XRF. Sensitivities with respect to crustal abundances (Hall, 1991)
Atomic numoer
FIG 14.22 Detection limits (ppm) by XRF at the 95% confidence level: based on 100 seconds
counting time for pressed powder pellets. Broken lines join results between which
unmeasured elements occur. (Fletcher, 1981)
| B.lBLlQTECA
CELSQ L. PALACIOS CAPKILLO !
211
14.2.3.6. Instrumental Neutron Activation Analysis (INAA)
Instrumental neutron activation analysis is based on the fact that non-radioactive

elements can be converted into radioactive elements by bombardment with neutrons or
other atomic particles. This radioactivity can then be measured. The best source of the
high density neutron flux required for this purpose is a nuclear reactor. Bombardment
induces the formation of radioactive isotopes peculiar to the elements in the sample. As
these isotopes decay, they emit characteristic gamma radiation which is directly
proportional to the elemental concentrations. Measurement of specific spectral intensities
allows a quantitative evaluation of specific elemental concentrations.
Some of the most significant benefits neutron activation offers over other analytical
methods is the simplicity of the sample treatment prior to analysis, its non-destructive
nature, extreme sensitivities for many elements (Fig. 14.23) and the possibility of
multielement analysis. It is particularly attractive in the case of elements difficult to analyze
at trace levels by other standard methods (i.e. rare earth elements, platinum group
metals, Au, etc.) In most cases, all that is required is the reduction of the sample to a
particle size suitable for encapsulation. Where sample homogeneity might be a problem
sample preparation can include a preconcentration step. Thus for gold analysis a dore
bead suitable for irradiation can be produced by fire assay fusion of a fairly large sample
ELEMENTS BY INAA
Li Be B C N 0 F Ne
p PGAA 1 HIGH p
d DNC 1
2. MODERATE Al Si P s Cl Ar
Na Mg a ASSAY
PRECONCENTRATION 3. LOW
i
K Sc Ti V -Cr Mn FeiiCo Ni Cu Zn Ga Ge As Se Hr Kr
2 1-1 ’ 3 3 3 1 3 1 :
3 3 1 ■t
Rb Sr Y Zr ND Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
8- a a
1 3 3 2 1 1 1 3 3 3 1
Cs Ba La Hf Ta w He Os Ir Pt Au Hg TI Pb Bi Po At Rn
• a a a (•)
2 1 i 1 1 1 1 1 1 1 2J1L. 3
Fr Ra 4Ac|(Rf)
(Ha)
€ I Ce Pr Nd Eu Gd Tb □y Hoi Er Tm Yb Lu
Pm Sm <p)
1 3 1 1 i 2 1 3 3 3 1 1
3 Th Pa U Np Pu Am Cm Bk Cf EsFm
Md No (Lr)
0
(? 1
Indicates "best" element by this technique
FIG 14.23 Analysis by INAA. Sensitivities with respect to crustal abundances. (Hall, 1991)
212
(Hoffman and Ernst, 1982). In biogeochemical prospecting, samples can be macerated
and then briquetted prior to irradiation. This avoids possible loss of gold in the sample
ashing procedure required by a number of the more commonly used gold analytical
methods.
Application of INAA is not widespread due to the limited availability of suitable

reactors and properly equipped laboratories, and the practical and regulatory problems
associated with the handling of radioactive materials.
14.2.3.7. Electroanalytical Methods (pH, Eh, Specific

Ion Electrodes and Jerome Hg Analyser)
Measurement of pH by the potential of a glass electrode and Eh by the potential

of a platinum electrode are the best known electroanalytical methods. Analogous
methods using special electrodes can also determine concentrations of F-, CI-, Cu2 + and
other ions in solution (Table 14.14).
A pH electrode consists of a thin-walled bulb of pH sensitive glass sealed to the

end of a glass tube (Fig. 14.24). The bulb holds dilute hydrochloric acid or a buffered
chloride solution into which dips a silver/silver chloride electrode connected to a sheathed
cable. When the electrode is placed in a solution in which hydrogen ion activity differs
from that inside the electrode, protons accumulate at different rates on either side of the
glass membrane and a potential develops across it. In specific ion electrodes the proton
sensitive membrane is replaced by a solid state or liquid ion exchange membrane
sensitive to the ion to be determined. The pH (or specific ion) electrode is used in
conjunction with a reference electrode which provides a stable reference potential.
pH meters are easy to use in both field and laboratory. It should be noted that
drying of soils prior to pH determination can result in erroneous readings. Soil pH is very
sensitive to oxidation-reduction reactions (including microbial activity) and to the balance
of carbon dioxide between soil gases and the atmosphere. Hence soil samples for pH
determination are best kept under field conditions.
Specificion electrodes are easy to use and have sensitivities generally less than 1
ppm, but they can be subject to interferences from other ions (Table 14.14). The
electrodes measure the chemical activity of the ions rather than their total concentration
in solution, so that careful calibration and selection of the chemical medium are important.
The Jerome Portable Mercury Analyser, which can be used under both field and
laboratory conditions, is based on the principle that a thin gold film undergoes a
significant increase in electrical resistance upon adsorption of mercury vapor. Mercury
bearing vapor from heated samples is first passed through moisture and acid scrubbers
and then over a noble metal collector which strips the mercury. This mercury is
subsequently driven off by electric heating and adsorped by the gold film detector. The
BIBLIOTEC ••
CELSQ L, PALACIOS CARRILLO ;
213
Concentration range Interferences

Electrode
(ppm) (M)______________ _
>3 X 10’” Br. 5 X IO'10 I;

Chloride (Cl ) 1.8-35,500
2 X IO’10 CN; >3 X 10"7 S
6.4 X 10"4 to saturated >10" 7 S2". Ag*. Hg2*, high *

Cupric (Cu2*)
levels of Cl . Br , Fe , Cd‘
0.02 to saturated >10"4 OH"

Fluoride (F )
>2 x 10"2 NO'j; 0 2 Br",
Fluoroborate (BFa) 0.26 to saturated
OAc", HCOi, F'.Cl", OH",
SO," at 10"3 M BFi
5 X 10"3 to 127,000 >10"7 s

Iodide (I )
(can be used to measure Hg)
>10"7 Ag*. Hg2*,Cu2*;
Lead(Pb2*) 0.2-20,700
high levels Cd2*, Fe3*
(can be used to measure SO^ )
S2': 0.003-32,100 >10"7 Hg2*
Silver/sulphide
(Ag'/S2") Ag*: 0.01—107,900
TABLE 14.14 Characteristics of some specific ion

literature) (Fletcher, 1981)
1981)
214
resultant electrical resistance change in the detector provides a measure of the sample
mercury content.
14.3 Data Reporting
Most laboratories report data electronically as well as in hard copy form. It is

preferable, from the point of view of both speed and accuracy, that the data be
transferred electronically if they are going to be placed in a computer database. The
Geochemistry Department is therefore encouraging the laboratories that Newmont uses
on a regular basis to standardize data formats, as there is currently considerable
variation. Rbase procedures have been written to automatically load electronically
transferred data into the standard NEL database system, along with the location and field
observation information, and to simultaneously evaluate the enclosed SRS results.
To avoid any possible confusion, all data reports should include precise information
on the analytical methodology which can be clearly understood. This can have an
important bearing on both immediate and future data interpretations. Reevaluation of old
data, when personnel involved in the related project are no longer to hand, is especially
difficult without adequate supporting documentation.
When results fall outside the analytical range they are reported as below (<) or
above (>) the applicable dilution limits. These annotations are easily understood on
printed reports, but cause some problems when the data are manipulated as numbers
in data processing. They cannot be omitted as this would bias any statistical analyses.
Therefore, they must be replaced by actual numbers before mathematical calculations,
such as mean value, are carried out. Conventionally, samples that are recorded as <
detection limit are given a value 1/2 the detection limit. Samples that are reported as
greater than the upper detection limit are recorded as the upper detection limit or the
upper detection limit plus one.
14.4. General Conclusions
It is apparent from the previous sections that a bewildering array of geochemical

sample preparation and analytical techniques are nowadays available to the mineral
explorationist. It is more important than ever that choices be made on a rational basis.
As has already been discussed, this requires that each project include careful orientation
studies. These should aim to determine optimum sample type(s) in the prevailing local
environment as well as sample preparation and analysis procedures, and interpretational
techniques which best enhance significant anomaly contrast and reduce the likelihood of
false anomalies being pursued. General outlines of typical procedural combinations which
can be developed for the major sample types are shown in Figure 14.25.
As sample preparation and analysis are generally carried out by independent

commercial laboratories outside the immediate control of the project personnel, particular
215
care need be taken in their

selection. All too often choice is
more influenced by price and
salesmanshipthan competence.
Knowledge of the range and
quality of the services available,
and the relative strengths and
weaknesses of the techniques
employed is essential. For
purposes of reference, the
performance characteristics of
the more commonly available
analytical methods discussed in
the previous sections are briefly
summarized in Table 14.15.
The range of minor and trace
elements, which each method
is typically used to determine, is
indicated in Figures 14.16
(AAS), 14.18 (DC-ES), 14.19
(ICP-ES), 14.21 (XRF) and
14.23 (INAA). It is apparent that and analysis of exploration samples. (Fletcher,
no one technique is likely to 1981)
satisfy all analytical needs for an
individual project, let alone
several projects. It should be noted that in view of the cost of the various analytical
instruments (Table 14.15), and the need for specialists to operate the more sophisticated
types, few laboratories are completely equipped to determine all elements of potential
importance at the required abundance levels.
216
_______ _ __________ —------------- ------------------------- -------------------------
Freedom Multi Deter Solid Comments
Method Cost Precision
from inter element minations samples
($)
ferences capa per man
bility day
no 20-100 no very simple: adaptable

1 Colorimetry 1 X 103 poor-good good
to field use; special
reagents needed for
each element
X 10" good very good no 500 no easy to set-up and

2. Atomic absorption 2
operate: several ele
ments can be deter
mined on same solu
tion; special methods
for Hg, As, Te. Se;
dilutions required for
high concentrations
3. Emission spectroscopy
4 X 10* very poor very poor yes 500 yes simple robust equip-
visual comparison
ment: requires com
parator and darkroom,
results semi-quantita-
tive
1-2 X 10s poor poor yes >1000 yes sophisticated equip
direct reader
ment: requires ex
perienced analyst to
set-up and supervise
ICP-direct reader 1-2 X 10s good good yes >1000 no operations, requires
dedicated computer
or access to computer
wavelength dispersive 3 X 10s good good yes >1000 yes sophisticated equip
ment: requires super-
energy dispersive 1 X 10s good (?) good (?) yes >500 yes vision by a skilled
analyst; dedicated com
puter or access to
computer; very simple
sample preparation
TABLE 14.15 Evaluation of performanceof analytical methods commonly used in exploration geochemistry. (Fletcher, 1981)
217
15. QUALITY CONTROL
15.1. General
The "house of cards" analog (Fig. 11.1) illustrating the relative importance and
interdependence of the various phases of geochemical exploration programs has been
previously discussed (Chapter 11). However, careful adherence to the basic principles
of program design and planning (including conceptual model development and
orientation), and determination of optimum sampling, sample preparation, analysis, etc.
does not guarantee avoidance of error. Proper training and efficient project management
can help to minimize this risk, but the possibility of the occasional introduction of human
and technical error, despite all of these efforts, must be recognized and accepted. The
best solution is to have in place effective quality control procedures which permit potential
problems to be quickly recognized, particularly in the sampling, sampling preparation and
analytical stages, where unrecognized problems can have extremely damaging and
expensive consequences. Properly designed quality control procedures permit routine
FIG 15.1 Random and systematic errors. The variation in concentration caused by random
errors is represented by the normal curve with an average value X: p is the true
concentration of the analyte. A. The dispersion (width) of the normal curve is narrow
and symmetrical around n - i.e. x = n and results are both accurate and precise.
B. The dispersion is greater but symmetric about p - precision is therefore relatively
poor and although the average value (X) is accurate, this is not necessarily true of
individal analyses. C. Dispersion is narrow but a systematic positive error has been
introduced (x > p) - results are precise but inaccurate. D. Systematic error and poor
precision. (Fletcher, 1981)
218
monitoring of project data so that errors can be quickly detected and corrective action
taken before serious problems develop.
15.2. Principles
Quality control (or monitoring) in exploration geochemistry is based on the

evaluation of data produced by a variety of routine check analysis procedures. These are
designed to detect evidence of sampling and/or analytical error. Two types of error are
responsible for any problems observed (Fig. 15.1). These are:
(i) random errors which arise from variations inherent to any sampling
or measurement process; and
(ii) non-random errors which produce systematic negative or positive
deviations from the true result.
The reliability of geochemical data is evaluated in terms of accuracy and precision (Fig.
15.2). Accuracy is a measure of how close the determined value is to the true value, and
is dependent on both random and systematic error. On the other hand precision, which
is a measure of the reproducibility of the analytical determinations, is related to random
error alone.
219
Random errors are assumed to follow a normal Gaussian distribution about their
mean concentration. Hence precision is conveniently specified as the Perce,]t r®
variation at the two standard deviation (95%) confidence level. Thus for example an
analytical precision of ±20% for a sample with an apparent Au content of 10Ci ppb
indicates that 95 out of 100 analyses of the sample will likely fall within the range 80-120
ppb The 5 remaining results will be outside this range. The Pot®ntia sources ^ random
error are many and varied and can be encountered during sample collection,
and analysis. They are best minimized by careful application of properly designed
procedures at each stage of a geochemical exploration program.
Svstematic errors, giving rise to spurious geochemical trends, can result from a
number of factors including contamination, instrumental drift or physical and chemical
interferences. Again, careful attention to procedural details helps ensure systematic errors
are kept to a minimum.
15.3. Procedures
15.3.1. Systematic Duplicate Analyses

The precision of analyses can be determined by multiple determinations of a single
sample or preferably, systematic duplicate analyses of many samples from the survey
lreaP assuming good prepared sample homogeneity. Duplicate analyses of many
samples is preferable as multiple determinations of a single sample does not allow-an
estimate of precision over the range of concentrat.ons encountered. Another potent.a
advantage of the duplicate sample approach is that it can help in the detection of
occasional errors resulting from procedural mistakes m.snumbenng, etc.A< graphica
presentation of duplicate results is an adequate, effective and expedient method of
determining analytical precision (Fig. 15.3).
15.3.2. Standard Reference Samples-

Specially prepared suites of standard reference samples, having known metal
contents provide essential material for checking the accuracy and precision of an
analytical data on a batch basis, and also for monitoring analytical drift wrth time when
numerous batches are forwarded to the same laboratory over the life of a project. The
chemical composition of the reference samples is carefully documented numerous
analyses (>25) at one or, preferably more, laboratories. Graphical presentat.on of
standard reference sample data provide a strong indication of analytical accuracy (Fig.
15.4).
15.3.3. Duplicate Field Sample Analyses

Another type of variation that should be periodically assessed, although not
necessarily as often as analytical precision and accuracy, is sample material homogenerty
220
D uplicate
FIG 15.3 Graphical plot of duplicate analytical data.

221
LABORATORY ROUND GO2

ROBIN RESULTS
* 1988
---------- mean + 20%

----------- mean Acceptable range O Excluded from calculations
----------- mean - 20%
FIG 15.4 Graphical plot of SRS analytical data.

222
SAMPLE IDENTIFIER SAMPLE STATUS
83267C0OO1 80 (BD) ----- Blind duplicate split

002 00 Of 83267C0O18
003 00
004 00
005 00
006 00
007 00
008 9G (RC) ------ Reference Control "G"
009 00
010 00
Oil 00
012 00
013 10
014 11 (FD1)
015 20 Field duplicate array
016 21 (FD2)
017 00
018 00
019 00
83267C0O2O 00
FIG 15.5 Model for insertion of control samples to determine analytical accuracy and
precision. (Coker, pers. comm., 1983)
as reflected by elemental variation at the sample site. Field sample duplicates are
collected at selected sites and, after preparation, split in two for analyses. This approach
allows confident assessment of both the analytical and sample site component on any
variation.
15.4. Recommended Procedure
Objections to the inclusion of thorough quality control procedures in programs are

sometimes made on the basis of cost. This is just not acceptable, as recent studies by
the Newmont Geochemical Department, and others, demonstrate that around 5% of all
analytical data suffer from some form of gross error. Unless these errors are detected
and corrected at an early stage the potential cost in terms of lost exploration opportunities
and unproductive field follow-up is far greater.
It is very important to know that analytical data collected at all stages of a project
are comparable. The usual practice of the routine addition of one of a suite of standard
reference samples with every 30 project samples and the inclusion of blind sample and
analytical duplicates at a similar frequency will provide a 10% quality control volume (Fig.
15.5). Duplicate field samples are generally inserted into analytical batches less
frequently. Routine inspection of the graphical plots of the analytical results for these
223
standards and duplicates will give an immediate indication of unsatisfactory precision and
accuracy, and sample inhomogeneities.
Insertion of quality control samples requires care and forethought. Ideally, this
should be done prior to the transmittal of sample batches to the analytical laboratory so
that all laboratory staff are totally unaware of their location. In practice this is generally
not feasible as sample preparation and analysis is carried out in one facility. In addition,
Standard Reference Samples are of pre-prepared material and therefore easily
recognized. Nevertheless, provision should be made to include standard reference
samples in the same numbering sequence as batch samples by reserving appropriately
spaced numbers during field sampling for subsequent SRS insertion. It is generally
necessary to rely on the integrity of the laboratory staff with respect to standard reference
samples by ensuring that the persons responsible for the actual analysis were unaware
of their location in the sample sequence.
Since it is the responsibility of the geochemical laboratory to produce reliable data

and provide good service to the client, they must give close attention to quality control
in their operations. Every reputable laboratory will have its own standard reference
sample suite and other controls and should include routine quality control information in
each analytical data report. If any irregularities are noted in reported quality control data,
the laboratory should be contacted immediately and the discrepancies discussed.
Laboratories should re-run samples without charge if the quality of any of their output can
be shown to be suspect in some way. If erratic analytical results are experienced with the
duplicate and batch samples, but not with the standard reference materials, sample
inhomogeneity ("nugget" effect) is indicated. Experienced commercial laboratory
personnel can assist in the solution of this type of problem by utilizing special techniques.
224
16. INTERPRETATION
16.1 Definition and General Procedure
As was noted previously (Chapter 11) the relative importance and interdependence
of the various components of a geochemical exploration program can be likened to a
"house of cards" with interpretation at the top of the pyramid (Fig. 16.1). In practice, the
successive phases generally overlap to varying degrees and despite the fact that
interpretation is the last phase to be completed, its implementation is not simply confined
to the concluding stage. Interpretation occurs throughout a program, from planning and
design onward, in fact wherever conclusions need be drawn from available data. The
interpretation phase shown in the illustration would probably be better designated "final
interpretation gf geochemical data SDd integration with dsta from other sources-"
Final interpretation of data from geochemical exploration programs is a complex

process as it involves so many interrelated factors which can influence the final outcome
(Fig. 16.2). The precise sequence of interpretational steps adopted in a geochemical
survey will be influenced by the nature of the survey as well as the accepted
interpretational philosophy. However, the preliminary phase always includes the
compilation and display of the geochemical and other relevant data. In the case of
geochemical data the primary aim is to delineate potentially significant patterns which
could be related to significant mineralization of the type(s) sought. The characteristics of
these patterns will have been determined in the orientation studies prior to the main
survey program. The field and laboratory procedures will have been designed to detect
and, if possible, to enhance them.
The final interpretation process generally involves use of some simple statistical
procedures. Complex statistical methods are more rarely employed. Assessment of the
potential significance of geochemical patterns delineated should be strongly influenced
by the previously developed geochemical conceptual dispersion models and all other
relevant available information on the local environment. The final comparative rating of
patterns determined to have potential significance, and requiring follow-up, will depend
on a variety of technical and economic factors which will have been defined in the
program design and planning process. The ratings will normally influence the sequence
in which these are subjected to field follow-up study.
Many of the procedures involved in the interpretation of geochemical exploration

data are described and illustrated with numerous actual examples in a useful workbook
format by Levinson, et al. (1987).
In conclusion, it should be noted that the relatively small emphasis given to

statistics and particularly to computers in the following discussion is deliberate. This is
designed to reflect their optimum roles as available and generally useful, rather than
dominant procedures and tools, respectively, in the interpretational process.
225
The stages of exploration geochemistry related to a "House of Cards' (Source:

FIG 16.1
Modified after Lavin, Grant, and Nichol, 1987).
226
16.2. Data Compilation
Final interpretation of geochemical exploration program data requires compilation,

and effective presentation and integration of all relevant information. The precise nature
of this process will of course depend on the type and size of the survey. However, it
generally involves the preparation of a series of maps of convenient identical scales so
that all available relevant geochemical, geological, mineral occurrence, geophysical,
topographical, field note, etc., information can be observed, compared and effectively
integrated (Fig. 16.2). Comparison between different survey parameters is generally
simplified by the use of transparent data plots. It also helps if the salient significant
features of each parameter are clearly shown. In the case of geochemical data this
necessitates clear delineation of geochemical patterns and anomalies.
With large regional programs which cover many map sheets it is advisable to
prepare small scale compilations of the salient features of the various parameters so that
any potentially significant regional correlations, are not overlooked.
16.3. Geochemical Pattern Delineation
In the early days of exploration geochemistry, final interpretation was often a

relatively simple process as most programs were concerned with the search for exposed
or near surface mineralization in areas with residual cover, which had not been previously
systematically explored with modern techniques. The emphasis was on detection of
strongly anomalous geochemical patterns which needed little in the way of sophisticated
interpretative technique to define, interpret and evaluate. However, more recently, as
mineral exploration has become increasingly concerned with mineralization overlain by
barren bedrock and/or obscured by transported overburden, detectable geochemical
expression of mineralization frequently tends, at best, to be fairly subtle. Delineation and
effective interpretation of these significant geochemical patterns requires a far more
refined approach, with greater emphasis on full appreciation of underlying factors. These
are determined during the orientation study and include the dispersion characteristics of
the metallic elements, the nature of,the overburden, and the overall general geochemical
environment. Such recognition contributes to the formulation of conceptual geochemical
dispersion models and interpretational procedures, and impacts directly on the sampling,
sample preparation and analytical procedures that are selected for the geochemical
program.
As has been discussed previously (Chapter 11), the orientation study data, in
conjunction with cumulative relevant experience gained elsewhere, enables geochemists
to compile conceptual models that pictorially represent likely geochemical dispersion
behavior in the survey area environment. The model should portray dispersion as a
series of geochemical patterns related to and controlled by a variety of identifiable natural
factors. Fundamentally, final geochemical interpretation involves the recognition of these
227
FIELD NOTES
AND OBSERVATIONS
FIG 16.2 Diagrammatic representation of the data integration process in geochemical

interpretation
228
patterns, the identification of the factors causing them, and the extrapolation of the
patterns back to a mineralized or other source.
The importance of the preferred emphasis on dispersion patterns rather than the
magnitude of the geochemical values in, say, ppm or ppb units can be illustrated by
reference back to Figure 11.2. Precipitation and accumulation of hydromorphically
transported metal in a seepage area adjacent to a stream channel can commonly result
in concentrations markedly higher than in the surface horizons of a residual soil anomaly
on a well drained slope. In such a situation, reference only to the magnitude of values
would result in first priority for follow-up being assigned to the seepage anomaly, whereas
recognition of the location and shape of the seepage anomaly would immediately indicate
its origin and direct the interpretation to the source areas upslope. With the gradual
acceptance of these concepts geomorphological mapping through ground and air
photograph observations is proving to be an invaluable tool in the interpretation of
geochemical patterns particularly in areas of mature landscapes.
From the preceding discussion it is readily apparent that spatial display of

geochemical data on maps plays a major role in pattern delineation and interpretation.
This is therefore the subject of the following section. Graphical display of geochemical
data using frequency distribution histograms, probability plots, etc., which can also assist
data interpretation, are examined in the discussion of univariate statistics (Section 16.5.1).
16.3.1. Data Display Maps
Effective presentation is essential for good communication and fundamental to the

understanding and interpretation of geochemical data. It involves compilation of maps
which show the spatial distribution of element concentration (or other geochemical
parameter) values in relation to relevant geological and geographical data. These
geochemical maps may be conveniently grouped into those which show element
concentrations at the sample locations' (i.e. value or poi.nt-symbo.l), and those which
emphasize element distribution patterns. Point symbols represent concentrations on the
basis of size and/or color and/or shading and/or shape, and, if carefully selected, do
permit potentially significant patterns to be distinguished. Contours are commonly used
229
2 km
FIG 16.3 Map showing relation of Cu in dambos

and outlet-stream sediments to location
of ore horizon, Baluba area, Zambia.
Data on -80-mesh fraction. (Rose et al.,
1979)
in geochemical display maps, but many of the computer display techniques originally
developed for geophysical data are now also being applied in geochemical exploration.
These include computer imaging, shaded relief, color coded contouring, etc. Although
these techniques can be very useful in some instances, they are not always appropriate
for geochemical data.
For the sake of visual clarity, both point-symbol and distribution pattern maps are
commonly restricted to the display of a single element (or some parameter derived from
multivariate geochemical data), however, multivariate data are sometimes displayed on
special point-symbol or composite image maps. Geochemical maps may also include
various other types of relevant information such as geography and/or topography and/or
geology and/or geophysical features, etc. It is sometimes more convenient to present
some or all of this additional information on under- or overlays.
In view of the extreme importance of pattern recognition in geochemical data

interpretation, some of the more commonly used data display techniques are discussed
in the following sub-sections.
230
FIG 16.4 Cu data obtained from the organic soil horizon samples at the end of the second field
season (25 x 100 m grid). (Levinson et al., 1987)
16.3.1.1. Posting Geochemical Values
Posting of values near sample site locations on base maps of suitable scale has
long been the most common initial form of data display (Figs. 16.3 and 16.4). This should
be done for every geochemical survey and these maps must be referenced when
evaluating output from other mapping or statistical procedures. Advantages of posted
value maps are:
(i) gives sample identification and actual data values;

(ii) provides location of each sampling point, and
(iii) assists review of other displays during interpretive phase of project.
Some of the disadvantages are:
(i) may become cluttered by closely spaced sampling points at the mapping
scale used;
(ii) often difficult to determine trends, and
(iii) limited number of parameters (generally 3-4) which may be posted on any
one map.
231
■ o® ®• •
• •o •O • O
. *- ♦□ B ■
« • *□□■■<»
CONCENTRATION I
FIG 16.5 Examples of sets of symbols used in point-symbol geochemical maps.

(Howarth, 1983)
The posted value map may be enhanced by the application of color to each
sample site location. Specific colors are assigned to concentration ranges often selected
following inspection of probability plots and histograms. The resultant color patterns aid
in the visualization of trends and patterns within the data.
16.3.1.2. Symbol Maps
Maps with symbols representing specific geochemical concentrations or ranges

can be used effectively to display data relating to both evenly and sparse irregularly
spaced samples. Many types of symbol presentations based on shape, size, shading,
and color are available (Figs. 16.5 and 16.6). Each has certain advantages and
disadvantages. However, an advantage common to all is the ability to present unevenly
or widely spaced data. A potential disadvantage is that locally high sample densities may
render maps difficult to read if inappropriate scales are used.
232
Examples of point-symbol (b-e) and “worm diagram’ (f) representations used for
FIG 16.6
stream sediment or water geochemical maps. Original data (a), heavy metal content
(ppb) of steam water of Missouri Creek, Colorado, U.S.A. (Howarth, 1983)
233
There are two commonly used size symbol formats. One depends on several
uniquely sized symbols representing specific ranges of values (e.g. Fig. 16.5c). tlean be
effective in presenting geochemical data from a variety of sample types mcludmg soils
(Fig. 16.7) and stream sediments (Fig. 16.8). .
The other format uses symbols bearing a proportional size relationship !° c°nc®^t'nat
as clearly shown in an example of regional nickel distribution in glacial tills from the
Nordkallot project in Scandinavia (Fig. 16.9). Advantages provided by s.ze symbols are.
(i) can show continuous range of values; .

(ii) may be combined with pplpr, shading or shape to enhance visual
interpretation.
Stream sediment and water samples differ from a number of other common
geochemical sample types in that they represent portions of drainage basins.rather than
restricted sample sites. This can result in somewhat misleading geochemical data
representation Especially at the local scale, if symbols are simply plotted at sample
locations. So-called "worm-maps" (Fig. 16.6F), which are a form of s.ze symbo provide
an effective method of at least partially overcoming this problem. Lines, whose thickness
234
Sn -28*65 mesh ppm
---------------------------- 300
•
---------------------------- 160
_*_________________ 100
•
__________________ 41
FIG 16.7 Sn content of -28 + 65 mesh soils. (Sirinawin et al.. 1987)

235
FIG 16.8 Sn content of -80 mesh drainage

sediments. (Sirinawin etal., 1987)
236
FIG 16.9 Nordkallott Project. Ni content of heavy mineral traction or iiiisp

Surveys of Finland, Norway and Sweden, ISBN-91-7158-383-1).
237
and/or color reflect the concentrations of the element of interest, are plotted along
drainage traces, upstream of sample sites, as far as the next sampling points. Stream
sediment data from East Africa illustrate the effectiveness of this approach (Figs. 16.10
and 16.11).
Symbol maps using the shapes to represent different value intervals is another
possible approach (Figs. 16.5B and D through H). They can also be used for
geochemical data from various sample types including stream sediments (Fig. 16.12).
Figure 16.13 demonstrates that properly selected series of shape symbols (in this case
representing lake sediment data) can provide a clear picture of the regional distribution
of an element despite the presence of a large amount of other useful visual information.
A particular advantage is clear differentiation of value ranges. Disadvantages of using
only different shaped symbols include:
(i) trends sometimes difficult to discern;
(ii) limited number of symbols possible;
(ii) data values must be in discrete classes.
Symbols based on shading have also been used. An advantage of shading is that
it is very effective in black and white publications. A possible disadvantage is that it can
be difficult to distinguish between the various value classes, if inappropriate shading
classes are employed.
A combination of one or more of the above symbol types can be particularly

effective and several European countries have adopted combined symbol maps for the
presentation of government geochemical surveys and national geochemical atlases. The
Finnish Government has started using a modified version of the proportional symbol for
all of its geochemical atlases. The size has a continuous range that is an exponential
function based on the frequency distribution of the data as has already been shown in
Figure 16.7 (Bjorklund and Gustavsson, 1987). The Finnish national map for gold in the
minus 63 micron sieved fraction of glacial tills (Fig. 16.14) also illustrates the effectiveness
of this data presentation approach.
238
FIG 16.10 Distribution of Nb in stream sediments draining pyrochlore

carbonatite, Kaluwe, Zambia. Data on -80-mesh fraction.
(Rose, et al., 1979)
FIG 16.11 Distribution of Be in stream sediment, Ishasha area, south

western Uganda. (A) Indicates position of undisturbed
pegmatite discovered by sediment sampling.
(Rose, et al., 1979)
239
East Central Area
0 I mile
West Central Area
r..olo„ Nick.1 concent, pp-n
m J T IIn Iiir
I'C erinite ♦ < J 0 70-150
[.■J
□ Metasediments « 3-7 ® ISO-300
O 7 - IS @ 300 - 700
Basic rocks
Ultrabasic cocks O IS - 30 • 700 - 1500
, Acid volcanics O 30 - 70
FIG 16.12 Variation in nickel content of stream sediments

derived from different areas of basic rocks
(Nichol, et al., 1966)
240
FIG 16.13 Example of point-symbol usage in a regional ma

shown are lakes and numbered geological units. (Howarth, 1983)
241
Multivariate point-symbol maps are sometimes used (Fig. 16.15), but are generally
difficult to interpret, even when dealing with as few as three parameters. Ingenious
methods of multivariate data display based on "faces", "trees", castles , etc., are also
available, but have not been widely used in exploration geochemistry. Garrett (1989a)
applied "tree" displays, previously developed by Kleiner and Hartigan (1981), to
representmultivariate geochemical data (i.e. six elements) for stream sediment samples
(Fig. 16.16). Although it appears more effective than some of the other available
multivariate geochemical data display techniques, routine application and interpretation
might again prove difficult.
16.3.1.3. Contour Maps
In theory, contouring is not applicable to geochemical data as geochemical

concentration surfaces are generally not smooth and continuous. However, this normally
presents no problem in exploration geochemistry as, at the scales employed, the
emphasis tends to be more on broad spatial trends rather than precise local details of
element distribution patterns.
Manual contouring is still widely used in exploration geochemistry to display spatial

trends. With gridded, or at least fairly evenly distributed sample data points (e.g. soil,
vegetation, etc., surveys), potentially significant regional and local trends can often be
clearly defined by manual contouring (Figs. 12.12, and 16.17 and 16.18, respectively).
Where ambiguities occur, the highly subjective nature of this method can be both a
hindrance and a help. As contouring trends tend to be influenced by the prejudices of
the contourer, prejudices based on sound geologic, morphologic, etc., knowledge can
have beneficial consequences. However, without this knowledge, manual contouring in
ambiguous situations can produce misleading results. It should be noted that manual
contouring of geochemical data is generally assisted by application of colors or symbols
representing specific concentration ranges at each sample data point.
242
SAMPLE
IN
Au
FIG 16.14 Gold in Till (-63 g fraction) Geochemical Atlas of Finland. (Geological Survey of Finland)
243
FIG 16.15 Multivariate point-symbol maps: (a) pie diagram; (b) pseudo
histogram; and (c) windrose representation. (Howarth. 1983)
FIG 16.16 Stream sediment data displayed spatially in the form of Kleiner-
Hartigan trees. (Garrett, 1989)
244
MOLYBDENUM
CONTENT OF
SOIL SAMPLES
COLLECTED
. AT A CONSTANT
DEPTH,
MAINLY
A" HORIZON
MOLYBDENUM
CONTENT OF
/F. SOILS AFTER
RESAMPLING
B'HORIZON
CENTRAL
BRITISH
COLUMBIA
FIG 16.17. Molybdenum distribution in soils as shown by

sampling at a constant depth (mainly A horizon)
and uniformly from the B horizon. (Thomson,
1987)
A Ore boulder C*HM content

Of humus (ppm)
« 6 ■ 1012
200 meters
FIG 16.18 Rectilinear soil sampling

grid, Petolahti, Finland.
(Rose, Hawkes, and
Webb, 1979)
245
FIG 16.19 Contour map for zinc (ppm) in 2156 B-horizon soil samples, Key Anacon, New
Brunswick, Canada. Sample stations at 100 ft (30 m) along lines 400 ft (122 m) apart.
(Howarth, 1983)
Machine (i.e. computer) contouring is also becoming increasingly used in

geochemical exploration due to the widespread availability of contouring software for both
gridded and ungridded data. This is a far more complex process than manual
contouring, but when correctly applied offers many of the same advantages, in particular
clear definition of local and regional trends (Fig. 16.19). Unfortunately, however, it is
sometimes misapplied, especially to data from widely and/or irregularly distributed sample
points.
Machine contouring involves two distinct processes:
(i) gridding;
(ii) contouring.
Many of the problems associated with machine contouring relate to the gridding process
which involves creation of an artificial rectangular grid. Consequently, the data actually
contoured are the values calculated for the grid nodes and not the original geochemical
concentrations. Due to the nature of many gridding algorithms, uniform sized areas are
generally evaluated to assign values. Therefore when geochemical samples are not
representative of uniformly sized and shaped areas, misleading values are sometimes
246
FIG 16.20 Example of a moving (circular) window in two successive positions. Weighted, or
unweighted, average of data points in current window assigned to grid node to
yield the moving average map. Proportion of overlap between successive window
positions chosen by user. (Howarth, 1983)
assigned to the grid nodes. Unlike manual contouring, machine contouring is in fact a
smoothing process, and the resultant contours do not always necessarily correspond with
the data displayed by individual sample points. This smoothing can help eliminate or at
least reduce random "noise", but it can also distort data trends, especially where gridding
errors and/or improper interpolations occur.
Artificial data grids for contouring can be achieved by a variety of techniques

including moving average interpolation, whereby data points within a moving "window",
which may be circular (Fig. 16.20) or square, are used to determine values for the
window center point (i.e. grid node), with or without corrections for distance of data points
from the grid node. The effect of increasing the size of non-overlapping windows on
geochemical patterns and corresponding frequency distributions for some soil data are
shown in Figures 16.21, 16.22 and 16.23. Broad scale trends are preserved and even
enhanced, but potentially important local details are often lost. In another commonly used
method, the values for grid nodes may be determined from 4 to 16 nearest neighbors
247
FIG 16.21 Contour map for zinc (ppm) in B-horizon soil samples. Key Anacon, New Brunswick,
Canada, averaged over 602 non-overlapping 400 x 400 ft (122 x 122 m) blocks.
(Howarth, 1983)
(Fig. 16.24). The results of this treatment on data from the lake sediment samples in
Figure 16.25 are shown in Figure 16.26. Again it is apparent that as the grid spacing and
number of nearest neighbors are both increased, the map becomes progressively
generalized.
Alternatively, techniques such as kriging, which permit directional changes in the
behavior of the sampled medium to be taken into account in calculating grid note values
are also sometimes applied to geochemical data. Kriging procedures have been used
to prepare regional geochemical maps (e.g. Armour-Brown, et al., 1983), but have mainly
been applied to local scale data where true distance related spatial variability in the data
is not overwhelmed by differences related to lithologically controlled backgrounds (Garrett,
1989b).
Computer contouring involves calculation of the locations of specified concentration
lines throughout the grid (Sampson, 1975). The perimeter of the grid is first searched
until the range in value between two successive points includes the value of the contour
line. The location of the contour line at the perimeter is found by interpolation and then
248
Canada averaged over 300 non-overlapping 600 x 600 ft (183 x 183m) blocks.
(Howarth, 1983)’
Canada, averaged over 186 non-overlapping 800 x 800 ft (244 x 244m) blocks.
(Howarth, 1983)
249
FIG 16.24 Examples of 8 nearest-neighbours to a central grid node located by octant, quadrant,
or unconstrained searches on (a) irregularly spaced or (b) traverse data. (Howarth,
FIG 16.25 920 lake sediment samples in a portion of NTS sheet 64N, Kasmere Lake sheet,
northwest Manitoba, Canada. (Howarth, 1983)
250
FIG 16.26 Contours of uranium (ppm) in lake sediments. Kasmere lake sheet, northwest
Manitoba, Canada, as a function of grid cell-size (CS; inches) and unconstrained
nearest-neighbour (NN) search using the Calcomp GPCP contouring package (R.E.
Ellwood and R.G. Garrett, personal communication; reproduced with permission of the
Geological Survey of Canada). Original map scale 1:1000000. Contours enclosing
50 and 100 ppm filled with stipple and solid tone respectively. (Howarth, 1983)
extended through the grid matrix to its end. When all contour lines that intersect the edge
of the map have been located, the interior of the grid is searched for closed contour lines.
At this time, the interiors of closed contours are searched to determine whether they
represent highs or lows. Consistent rules govern ambiguous situations where diagonally
opposite corners of a grid cell display higher and lower values, respectively, than the
value of the contour line entering the cell. Finally, prior to plotting, the contour lines can
be smoothed to reduce their angularity, again according to consistent rules.
16.3.1.4. Image Analysis
Computer image analysis is primarily used for geophysical data, but may also be
applied to geochemical data. It is similar to contouring in terms of advantages and
disadvantages. Since images are based upon the pixel representation of an area (Figs.
16.27 and 16.28), the data must be gridded as in contouring. Each pixel is assigned a
distinct color or shade dependent on the calculated value. Depending on the size of the
251
47’ 15 W 46’ 00 W
--------- 16’ 00 S
47“ 15 W 46’ 00 W
-------- 16° 00 S
<22.9
<20.0
122.9-35.0
20.0-35.0
35.0-45.0
J43.5-55.0
4 5.0-57.5
$§55 0-65 0
i 57.5-70.0
§§65.0-80.0
70.0-86.2
■ >80.0
>86.2
100
-100
- 50 km
19* 00’S
19’ 00 S
FIG 16.27 Distributionof cell averaged Zn in stream sediments, FIG 16.28 Distribution of gap-filled unsmoothed Zn in stream
Bambui area, Brazil. U = Unai, P = Paracatu, M = sediments, Bambui area, Brazil. U = Unai, P =
Morro Agudo, V = Vazante. Classes are 20, 40, 60, Paracatu, M = Morro Agudo, V = Vazante. Classes
80, 90, and 95th percentiles for corresponding are 20, 40, 60, 80, 90, and 95th percentiles for
values of 20.0,35.0,45.0,57.5, 70.0,86.2, and >86.2 correspondingvalues of 22.9, 35.0,43.5,55.0,65.0,
ppm. (Chorkand Mazzucchelli, 1989) 80.0, and > 80.0 ppm. (Chork and Mazzucchelli,
1989)
252
area being imaged and the resolution of the images, the amount of data that pixels
represent may vary considerably. Once gridded, the data may be imaged in various
ways Fig 16 29 presents Ba data from Finland as proportional dots (inset A) and as
smoothed moving-mean surfaces, after both log-and linear-transformations, illuminated
from different directions. Particularly useful effects can be obtained with color imaging of
the smoothed moving average data and overlaying point symbol data as a ratio of the
smoothed data (Fig. 16.30). This same diagram illustrates additional versatility by
presenting Cu data as graytone colors allowing comparison with the Ni distribution.
This Finnish data is based on a sample density of 1 site/300 km2. The innovative
data handling and data presentation of this very low density data has revealed patterns
not directly correlatable with mapped geological units or lithologies but possibly reflecting
deeper crustal structural patterns of metallogenic significance. Alignment of geochemical
patterns and significant mineral deposits (Fig. 16.31) supports this prediction.
A color correlation image can be created by selecting two to three elements of

interest and assigning one of the three primary colors (red, green, or blue) to each. The
relative intensity of the pure colors is proportional to the element they represent Areas
where all three elements are high (relative to the rest of the data in the image) will be
white and areas where the three elements are low, will be dark. Areas which are
predominantly of a primary color (red, green, or blue) possess high dominant
concentrations of the corresponding element. An interesting application of this technique
to stream sediment data from the southwest Highlands of Scotland is described by Plant,
et al. (1989). An additive color image for arsenic, antimony and bismuth shows
geochemical zoning features not clearly defined by the individual element images (Figs.
16.32 and 16.33). '
253
FIG 16.29 The Geochemical Atlas of Finland. Barium contents in the - 62 pm fraction of till. Map
A: contents visualized with dots. Maps B-E: content-variation surfaces of the moving
mean shaded from the NW, N, NE, and E, after a log-transform of the contents to the
unit of the x- and y- coordinates. Map F: the same as Map D but a linear transform of
the contents. (Bjorklund and Gustavsson, 1987)
254
GEOCHEMICAL
ATLAS OF
FINLAND
TILL
COLOUR IMAGE
Ni
MOVING MEDIAN
10 20 40ppm
SIZE OF DOTS
Ni RATIO
MEASURED VALUE /
MOVING MEDIAN
0.7 1.0
FIG 16.30 The Geochemical Atlas of Finland. Nickel and Cu contents in the - 62 p m fraction of till.
The colour surface: the weighted moving median (background) of Ni contents calculated
from windows the radius of which is 50 km. The dot sizes: ratio between the measured
Ni contents and the weighted moving median surface. The gray-tone of the dots:
measured Cu contents. (Bjorklund and Gustavsson, 1987)
255
FIG 16.31 Geochemical Atlas of Finland. Alignment of geochemical patterns and significant minera
deposits. (A. J. Bjorklund)
256
FIG 16.32 Distribution of gold and pathfinderelementsin southwest Scotland: (a) gold in pan concentrates; (b) arsenic; (c) antimony;
(d) bismuth. (Plant et al., 1989)
( ( ( ( i r (~ r r r i ( r-i t r_
257
Plate 2a Argyll Geology with Bi anomalies Plate 2b

Bl Arsenic distribution
with Sb anomalies
(white)
w?St Nil-
ARGYLL GEOLOGY
S. «o'ue *.te
Plate 2d As. Sb, Bi additive RGB Image

Plate 2c As (red) and Sb(white) anomalies
K -Kilmelford
T - Tyndrum
C - Comrie
CELSO L. PALACIOS CAPPILLQ

BIBLIOTEC*
ARGYLL REGION
« UM Sb Cram S. Slug
FIG 16.33 Plate 2 image analysis of geochemical data for southwest Scotland: (a) Bi anomalies; (b) As distribution
with Sb anomalies shown in white; (c) As (red) and Sb (white)anomalies; (d) additive RGB image for As, Sb
and Bi. (Plant et al., 1989)
BIBUOTEC a
CELSQ L. PALACIOS CARR/LLO
258
FIG 16.34 Samples localities, streams and catchment basins

for a study area. (Bonham-Carter, et al., 1987)
16.3.1.5. Catchment Basin Maps
Geochemical data from stream sediment and water samples do not always lend
themselves to contouring, especially on a local scale due to the fact that they are
generally related to widely scattered and irregularly distributed sample sites which
represent drainage catchments with irregular shapes and sizes. In the early days of
exploration geochemistry an effort was made to overcome this problem by use of
distinctive patterned or shaded "Zipatone" to represent specific ranges of geochemical
values in samples from manually outlined'catchment areas (Fig. 5.2b). More recently,
shaded imaging of sample catchments has been employed to show element concentra
tions, and other parameters in drainage catchments (Figs. 16.34 and 16.35). Although
this method is effective, the need to digitize all catchment outlines would probably be
unacceptably time consuming in many routine geochemical surveys.
16.3.2. Class Selection
Effective delineation of significant geochemical patterns often requires careful

separation of the data into discrete classes which govern the concentration ranges
assigned to each symbol, and contour intervals, etc. These classes should aim to clearly
differentiate multiple data populations, should they occur, and highlight the data in each
population. The use of color will generally allow the use of up to ten or twelve clearly
differentiated classes, whilst only seven or eight are feasible with a single color or black-
259
FIG 16.35 Maps showing (a) observed and (b) residual zinc values. (Bonham-Carter et al., 1987)
/Vji
260
and-white. However, laser plotters permit mapped surfaces to be represented by nearly
continuous tonal changes which can be especially useful when subtle, low contrast
geochemical patterns are being sought.
Class selection techniques in common use fall into two broad categories:
(i) data specific;

(ii) serial.
16.3.2.1. Data Specific
Data specific classes are influenced by characteristics of the overall frequency

distribution of the data. One common approach utilizes "natural breaks" in the frequency
or the analogous cumulative frequency curve (see Section 16.5.1). These can be
especially effective when dealing with data comprising a small number of populations from
fairly small areas. However, when dealing with data from large areas, "breaks" or lack of
"breaks" are often an artifact of data distributions which comprise numerous overlapping
geochemical populations.
Another common approach, especially in regional geochemical maps, is based on

percentiles of observed distribution. The class intervals correspond to particular
cumulative percentages of these data (e.g. 10, 20, 40. 60, 80, 90, 95, 99, and 99.9th; and
25, 50, 75, 90, 98 and 99th percentiles). An advantage of using fixed percentiles on a
series of maps is that the same number of samples are displayed in the same
symbol/contour range. When individualized category cut points are used for each
element/map, a particular element can appear to be "better" than other elements because
it contains a greater number of samples in the highest category. Using fixed percentile
intervals eliminates this bias, and if sufficient categories are used, all relevant patterns
remain detectable. Practical experience in fact confirms that regional geochemical
patterns are generally better defined by percentile based classes than by classes chosen
by more traditional means (e.g. arbitrary or geometric). An example of application of
percentiles to data display is provided in Agure 16.36 which shows contoured distribution
of radon in the waters of a lake in Saskatchewan.
16.3.2.2. Serial
Serial classes are those in which class limits are in definite mathematical relation
to each other, and fixed in relation to statistical parameters such as the mean, standard
deviation, or range. Probably the simplest system uses equal intervals between class
limits based on division of the range into equal parts. These are generally not particularly
effective with trace element geochemical data sets due to the frequent occurence of
positive skewed distributions. Such distributions are better represented by geometric
class systems. Tbe most familiar of these employ a doubling of each successive class
261
FIG 16.36 Maps showing (a) Location of sample sites and (b) Spatial distribution of radon in lake
l bottom waters of "Dop" Lake. (Dyck and Car, 1987)
262
interval; such as 2, 4, 8, 16, 32.... or 25, 50 100 200 .... In general, a geometric class
system is one in which the difference between successive class division points is a
constant (log) value. The table below demonstrates this point:
class log of class difference

CUt point Cut point (in log value)
2 0.301
0.301
4 0.602
0.301
8 0.903
0.301
16 1.204
0.301
32 1.505
The examples above use a doubling progression, thus the difference between the log
values of successive cut points is the log of 2 (0.301). For a trebling geometric
progression (3,9, 27...) the difference between log values of successive cut points would
be the log of 3 (i.e. 0.477). Geometric progressions can readily cover a very wide data
range. This method has found widespread application in exploration geochemistry. A
good example was provided earlier in Figure 16.13. in which point symbols were used to
show regional distribution of uranium in lake sediments in part of Saskatchewan. Canada.
If a data set can be conveniently transformed to a near normal distribution, class limits
based on percentiles or centered on the mean and based on multiples of the standard
deviation are also sometimes useful.
16.4. Geochemical Anomalies

•
In parallel with pattern recognition, geochemical interpretation requires a knowledge
of the "anomalous", "threshold", and "background" values. As previously discussed in
Section 5.2, the normal element abundance level in an unmineralized geological material
is commonly referred to as the geochemical background for that particular material.
However, as element distribution in a specific geological material (e.g. rock, soil, stream
sediment, etc.) is rarely uniform, even when it is derived from an apparently homogenous
source, it is more realistic to visualize background as a range rather than an absolute
value. Any departures from normal ranges, be they positive or, more rarely, negative, are
viewed as anomalous. The upper and lower limits, above or below which, respectively,
values are considered to be anomalous are defined as anomalous thresholds. It must
be emphasized that each individual geological and geochemical environment will display
a characteristic anomalous threshold for each geochemical parameter. Recognition and
delineation of Ml environments present in a study area can be difficult, particularly in large
regional surveys.
263
Although a threshold value, of necessity, is set at a particular value, and is

designed to separate background from anomalous values, there can be considerable
overlap between background and anomalous populations and the threshold will ■error"
in classification (see Figure 11.8). The degree of overlap between the populations will be
different in each situation. Therefore, the effectiveness of a threshold can vary
significantly between surveys and elements.
Hawkes and Webb (1962) originally defined threshold as the upper limit £f.
background fluctuation. They went on to suggest that in cases of a single symmetrical
population, the mean plus two standard deviations could be used as a threshold. It is
quite clear from this section that they intended the threshold to be set at the mean plus
two standard deviations of the background population, not the total population. As they
go on to say:
"This is equivalent to saying that only 1 in 40 background samples is likely to

exceed the threshold content."
Unfortunately, the mean plus two standard deviations has been applied by many to the
total population; background plus anomalous and then cast in stone. Under this scheme,
only 2.5 percent of data from any survey are allowed to be classified as anomalous,
regardless of whether the survey was based on reconnaissance stream sediment or soil
samples collected directly over mineralization. This concept should be unacceptable to
any experienced geologist. However, the practice of arbitrarily using mean plus two
standard deviations of the total population unfortunately lives on. Garret (1989c) provided
a particularly eloquent discussion of this topic entitled "A cry from the heart". Obviously,
this pseudo- statistical practice is to be strongly discouraged. It simply results in attention
being concentrated on the highest values, which are not necessarily the most significant.
The fundamental observations leading to the identification of background ranges,

anomalous thresholds, etc. should come from the orientation survey. In the simplest
orientation scenario, background values are not influenced by the presence of
mineralization and in Figure 16.37 are represented by the relatively homogeneous areas
of low values at the extremities of the hypothetical soil traverse. (In practice they should
come from areas significantly removed from the anomalous traverse). Anomalous values
are, in this example, the higher values peaking a short distance down slope of the sub
outcropping vein zone. Weaker mineralization, disseminated in the rocks on either side
of the vein zone, also gives rise to anomalous, but less spectacular values which are also
influenced by the topographic slope. The upper limit of the background population is
referred to as the threshold and it is clear that contouring this data at the threshold level
will outline an anomalous pattern related to the mineralization in the bedrock.
Unfortunately, many explorationists apply this simple concept of anomaly definition

far too rigidly in their exploration programs. This reflects an erroneous conception of the
geochemical environment and totally ignores the geological influences on metal
264
GEOCHEMICAL
GEOLOGY AND TOPOGRAPHY

WEAKER. DISSEMINATED
FIG 16.37 Hypothetical soil profile across a mineralized zone.
distribution and the basic principles of dispersion illustrated by appropriate geochemical

models. For the majority of field areas this simple scenario, which assumes no variation
in bedrock type or environmental factors, is the exception rather than the rule. The
introduction of even a few of the commonly encountered geological and
geomorphological factors produces a far more complex picture, as is illustrated in Figure
16.38. Here a residual anomaly is again delineated in soils over a mineralization
comprising a vein and adjacent weak disseminations. Elsewhere, dispersion of
anomalous groundwater and sheetwash has produced a soil anomaly some distance
down slope of the mineralization (Fig. 16.39). Anomalies of unknown origin are found in
alluvium nearby (Fig. 16.38). Substantial variations in geochemical background levels
relate to the presence of several distinct rock types. It is apparent that without a
reasonable understanding of the local environment, effective interpretation of the
geochemical data would unlikely be achieved. Much time and effort could be wasted in
follow-up of spurious anomalies, even in this idealized simple situation which is far less
complex than those normally encountered in most mineral exploration surveys.
16.5. Statistical Analysis
In the recent past, geochemists have adapted statistical methods to assist in

geochemical interpretation. This has not been a simple evolution. As noted by Sinclair,
265
GEOLOGY AND TOPOGRAPHY

WEAKER, DISSEMINATED
GROUND WATER SEEPAGE MINERALIZATION
AREA
FIG 16.38 Hypothetical

geomorphological complexities.
FIG 16.39 Development of a break of slope anomaly, etc. in

mountainous areas (from Levinson, 1974). Anomaly may
have hydromorphic and clastic components. (Reimann,
1988)
266
(1987), "...to attempt to carry out a blind evaluation of data by submitting them to any one
of an increasing number of packaged software systems and expect a computer to do our
thinking for us is patently wrong..." Effective application of statistical methods, whether
univariate or multivariate, requires not only a full appreciation of the geochemical
environment, the geology and the chemistry of the elements as described in the
preceding paragraphs, but also an understanding of the statistical technique being
employed. In addition, effective application is dependent on correct design,
representativity and quality of the sampling and analytical phases of the program. It is
not difficult to appreciate that statistical treatment of a data set lacking in representativity
and quality will primarily highlight error, to the exclusion of relationships of geochemical
significance.
Given these essential understandings, statistical techniques provide useful and

often powerful tools for geochemical data analysis. They can assist in explaining
previously unrecognized characteristics in a data set and making significant patterns more
consistent, larger or otherwise more easily recognizable.
A basic assumption applied in the statistical treatment of geochemical data sets is

that they are unbiased and continuous. Most geochemical data are discrete but,
fortunately, in practice, these discrete values commonly are sufficiently abundant and
close that they can be assumed to be continuous. Such is generally the case if the
number of values is large and if the analytical uncertainty is small relative to the spread
of the values.
An extensive review of basic statistics is beyond the scope of this presentation, but
a useful summary has been prepared by Sinclair (1987) and a more comprehensive
treatment is presented by Howarth (1983). More recently (Kurzl, 1988) discussed
Exploratory Data Analysis which attempts to deal with the fact that in practice,
assumptions necessary for conventional classical statistics often fail to describe real data
behavior. He suggested that this problem can be overcome by use of a variety of
graphical techniques including density traces, one dimensional scatter plots, and boxplots
(see below).
16.5.1. Univariate
Univariate statistics allow the geochemist to quickly determine the basic properties
of voluminous data sets. Frequency distribution histograms, box-plots and probability
plots provide means of displaying data and revealing internal complexity. The resultant
information can be used to guide application and assist interpretation of the univariate
statistics.
A frequency distribution histogram (Fig. 16.40) has the obvious advantage of

providing visual information on the total range of values, the existence of one or more
267
populations and possible

thresholds separating
background and anomalous
populations. However, although
histograms have been, and
continue to be used extensively
in the presentation of
geochemical data, far better
ways of presenting data for
inspection are nowadays
available. Histograms suffer
from several disadvantages
including the fact that the
starting point and bin-widths
(i.e. data groups) are arbitrary,
and by choosing different
values alternate representations
of the data are obtained
(Garrett, 1991). In addition, the
behavior of individual data items
is hidden. Thus a variety of
FIG 16.40 Overlap of values in background and ore
subtle, but potentially important populations (derived as random samples from two
features may be overlooked by log-normally distributed populations). (Rose
the interpreter. Hawkes & Webb, 1979)
The box of the box-plot

(Fig. 16.41) defines the middle 50% of the data, The bar is plotted at the data-set median
and the box extends to the upper and lower "hinges" of the data (Garrett, 1991). These
"hinges" are the medians of the upper and lower halves of the data, and are
approximately equal to the 1st and 3rd quartiles and the 75th and 25th percentiles. The
difference between the two "hinges" is known as the H-spread or mid-range, and the so-
called "whiskers" extend from the "hinges" to the upper and lower "fences", which lie
1,5xH-spread beyond the hinges or to the maximum and minimum value, whichever
comes first. Therefore, if no points plot beyond the whisker ends there are no extreme
values. Extreme values (i.e. possibly anomalous outliers) can be plotted as asterisks up
to 3xH-spread, and open circles beyond. Box-plots provide a particularly effective
qraphical summary of a data set especially when used in conjunction with probability
plots. As mentioned above, Kurzl (1988), in a discussion of Exploratory Data Analysis,
suggested use of several graphical techniques including density traces and one
dimensional scatter plots (Fig. 16.42), in addition to boxplots.
268
(a) Definition of the boxplot as a graphical display of the 5 number summary.

(b) Introduction of the outlier cutoffs by fences and their graphical presentation in the
boxplot. (Kurzl, 1988)
FIG 16 42 (a) Empirical distribution of Al. and (b) Empirical distribution of Mn displayed by EDA-
techniques (histogram, density trace, boxplot, one-dimensional scatter plot; for
boxplot outliers see scatter plot). (Kiirzi, 1988)
269
(Coker, pers. comm., 1983)
When population separation is not feasible on the basis of readily identifiable

features, cumulative frequency and/or probability plots (Fig. 16.43), as described by
Sinclair (1976), and the "PROBPLOT' computer program of Stanley (1987), can also prove
useful. Depending on the statistical distribution of geochemical data, one axis of the
probability graph paper is either arithmetic or logarithmic, and the other axis, the
probability scale, is arranged such that a normal or lognormal distribution will plot as a
straight line (Fig. 16.43A). This type of graph is a very sensitive method of recognizing
the presence of multiple populations. A mixture of two distinct normal populations appears
as two nearly straight segments separated by curved segments containing an inflection
point (Fig. 16.43B).
270
FIG 16.44 Probability graphs (cumulative curves) tor Zn and

Cu in B horizon soil samples over the Daisy Creek
strata-bound copper prospect, western Montana.
Cumulated from high to low values (Sinclair,
1976)
In the example shown in Figure 16.44, the straight line plot for Zn indicates a single
lognormal population and the curved line for Cu indicates the presence of more than one
population. The inflection point of the Cu curve can be interpreted from the probability
plot to be at the 25 percentile (Fig. 16.45) indicating the curve to represent a mixture of
25% of the higher population A and 75% of the lower population B, both of which can be
mathematically derived. The two populations overlap slightly, but it is clear that if
populations can be defined in this way, an estimated or statistically calculated value can
be identified that can be contoured or otherwise differentiated that will separate the
populations, as much as possible, for interpretation purposes.
Used in conjunction with some basic statistical calculations these graphical data
plots can reveal an even wider range of useful information on the data distribution. Some
commonly used basic statistical parameters which describe central tendency, and thus
help differentiate populations, include:
271
FIG 16.45 Probability graph of Cu in soils (from Fig. 16.44) partitioned into two ideal
components, A and B. An arrowhead shows the interpreted position of an inflection
point in the curve. Black dots, are original data; open circles are construction points
determined by the partitioning procedure; open triangles are check points determined
by combining ideal populations A and B in their zone of overlap to compare with real
data. Thresholds of 58 and 66 ppm are determined at the lower 2.5 percentile of A
and the upper 2.5 percentile of B. (Sinclair, 1976)
Arithmetic Mean (x) of a set of measurements xv is

equal to the sum of measurements divided by n (Fig. 16.46):
X = Xy^L-Xj +._Xy^Xn
n
272
FIG 16.46. Frequency curves for (a) normal, (b) lognormal, (c) normal with outliers and (d
multipopulation distributions. (Coker, pers. comm., 1983)
274
values might be expected to exceed this so-called "threshold in the normal course of
events!)
(iV) Skewness is the degree of asymmetry of a distribution. If it is a symetrical

curve, skewness equals 0. If the curve is skewed to right (i.e. the mean lies
to the right of median and mode), skewness is positive, and if it is to the
left, skewness is negative (Fig. 16.48). The formula used to calculate
skewness can also be found in any basic statistics textbook. (For normal
populations which have symmetrical frequency distributions, the mean,
mode and median coincide. For asymmetrical curves the mean > median
>mode if skewed to the right and the mode > median > mean if skewed
to the left (Fig. 16.48).
(v) Kurtosis is the degree of peakedness of a distribution, usually taken relative

to a normal distribution (Fig. 16.49). A normal distribution has a kurtosis of
275
determined by direction of skewness. (Coker,

pers. comm., 1983)
(bell-shaped) data distribution. (Coker, pers.

comm., 1983)
276
untransformed (b) Mo data from a

granite body (Coker, pers. comm.,
1983)
around 3. If required, the formula used to calculate kurtosis can be found in any basic
statistics textbook.
Effective application of many of the commonly used statistical functions to a data

set generally requires a normal distribution. If this condition is not met, the data must be
normalized by applying some form of transformation such as the log10 transformation (Fig.
16.50). Other ways of satisfying the requirement for normal data include:
(i) removing outliers (extremely high or low values clearly distinct from the main
population);
(ii) identification and separation of two or more populations (related to different

rock types, soil horizons, variations is stream sediment composition, etc.).
16.5.2. Multivariate
Multivariate statistical analysis is sometimes used in the latter stages of

geochemical data interpretation to investigate complex inter-element relationships, and
277
can include other types of exploration parameters based on geological, geophysical, etc.,
data. A necessary prerequisite for more advanced multivariate analyses are correlation
studies between pairs of variables (scatter diagrams, correlation coefficients) and between
populations (analysis of variance). Based on this information, it is possible to investigate
intra-element and between-sample relationships using a variety of techniques (principal
component, factor analysis, cluster analysis, multiple regression discriminate, and
characterization analysis, etc.) (Howarth, 1983). However, the application of these
procedures is not without serious problems due to the distortion of the linear statistical
models by the sought-for anomalous samples in the data sets (Garrett, 1989a). Detailed
description of each of the multivariate statistical techniques is outside the scope of this
manual. In situations where multivariate techniques are required, individuals are
encouraged to contact the Geochemistry Department for assistance and guidance.
i
An example of the use of these multivariate techniques is the mineral resource
assessment map produced as a result of joint collaboration of the geological Surveys of
Finland, Norway, and Sweden in the Nordkalott Project north of the 66th parallel.
Discriminant and characterization analysis methods were applied to integrate twenty
geochemical, five geophysical and five geological variables to produce a resource
assessment map showing regional favorability for mineral deposits (Fig. 16.51). In
addition, scores were calculated representing each of 13 metallogenic provinces, and the
local favorability for the existence of each deposit type are shown as symbols in which
size indicates favorability, and color the most likely deposit model. The model areas are
shown as irregular polygons.
Garrett (1991) describes a simple but effective method of combining elemental

suites in a single number or index for map plots, without use of multivariate statistics.
This procedure involves use of weighted sums which allow the interpreter to determine
the elements to be considered as well as their relative contributions on the basis of
available knowledge of local geochemistry and metallogeny. It should be noted that in
some situations simple element ratios have provided exploration guides of equal or
greater value than complex multivariate statistical parameters.
16.6. Data Assessment and Integration
Once the geochemical patterns have been delineated they must be carefully
assessed. This process commonly involves the examination of the geochemical and
other relevant data maps for correlations between the patterns displayed by individual
geochemical parameters and between these parameters and other relevant features.
Where there is evidence in large scale surveys that patterns are controlled by regional
factors such as bedrock geology, surficial geology, soil type, geomorphology, etc., the
data should be disaggregated as much as possible on the basis of distinctive
"geochemical units". A second generation of histograms and/or probability plots and
geochemical pattern maps can then be constructed and interpreted for each subset. This
process can be repeated, as often as necessary, to eliminate broad scale regional
278
FIG 16.51 Northern Fennoscandia Mineral Resource Assessment Map, Northern Fennoscandia,
regions and locations highly favored for mineral deposits (reduced from Mineral
Resource Assessment Map, Northern Fennoscandia, 1:1 million scale., Geological
Surveys of Finland, Norway and Sweden, 1986, ISBN-91-7158-384-X).
(Legend continues, next page)
279
MINERAL DEPOSIT MODELS
1 Koilelainen (Cr. V PGE) ® 8 Store Allebuouda |Mo W)
• 2. Kemi-Penikat (Cr. PGE) V 9 rjjrrojjkka (Cu. Fe)
3 Bidjovagge (Cu. Au) ■' 10 Kiruna (Fe)
e 4 Viscaria (Cu) 11 Aitik (Cu Au)
• 5 Pahtavuoma (Cu. Zn U)
£ 12
Sarvisoaivi (Ni)
• 6 Kaunisvaara (Fe)
A 13
Raitevarre (Cu)
e 7 Hannukainen (Fe. Cu. Au)
Local favourability for mineral deposits
Symbol size --------- FavouraNlity
Cumulative frequency |
Regional favourability for mineral deposits
St fer
LOW
FIG 16.51 Legend (continued)

280
patterns unrelated to the presence of mineralization. This allows attention to be focussed
on generally local geochemical features of potential significance in terms of mineral
exploration.
Assuming the geochemical field, laboratory and data presentation methods were
selected on the basis of thorough orientation studies, the nature of patterns of potential
significance should be reasonably well defined. However, there will often be many similar
patterns produced by factors other than the local presence of mineralization of the type
sought. The significance of all potentially interesting patterns must therefore be assessed
using the previously developed conceptual geochemical dispersion models, in conjunction
with all available relevant information. The precise nature and extent of this information
will of course depend on the character of both the sample media and the study area
environment, as well as the scale of the survey, but must always include bedrock geology
and sometimes also information from other allied disciplines (e.g. geophysics, remote
sensing, etc.). When the geochemical sample media include some form of surficial
material, essential data might also include thickness and types of soils and overburden,
geomorphology, physicochemical conditions in surface and groundwater, vegetation, etc.,
etc. (Fig. 16.52).
The remaining unexplained patterns of potential interest, especially those in

reconnaissance programs where anomalous conditions might be represented by single
samples, should then be confirmed by check analysis. Once confirmed, each potentially
significant pattern should be considered in terms of the most appropriate conceptual
geochemical dispersion model so that the likely disposition of bedrock sources can be
determined.
Finally, surviving significant anomalous geochemical patterns are cataloged and

described. Priority ratings for follow-up are determined following comparison of anomaly
parameters with requirements imposed by the geological model controlling overall
exploration philosophy, exploration strategy, land status, economics and last, but by no
means least, data from allied disciplines such as geophysics, remote sensing, etc.
Effective integration of the data from the various disciplines naturally assumes good
communication, cooperation and coordination between the representatives of these
disciplines throughout the program (refer to Figure 10.2).
281
FIG 16.52 A diagrammatic representation of some typical factors which influence the selection and
rating of significant geochemical patterns.
282
16.7. Data Management
Interpretation of the large quantity of data usually produced in geochemical

exploration programs is greatly assisted by use of suitable computer database
management systems. Efficient data entry, documentation and archival systems, in
conjunction with appropriate statistical and plotting capabilities, assist in the achievement
of cost-effective exploration. The databases should not only include analytical data, but
also information on sample locations, field observations, sampling methodologies, sample
types, preparation and analytical techniques, etc.
Well constructed database management systems also simplify storage and retrieval
over the long term, an important consideration in view of the high cost of data acquisition,
and possible future need for data review as exploration ideas and conditions change.
Garrett (1989b) has written a useful review of the role of computers in exploration.
283
17. FOLLOW-UP
Follow-up of geochemical patterns of potential significance delineated in mineral

exploration programs is a normal part of the exploration sequence discussed previously.
Additional comment is provided here in order to stress the necessity of having a clear
idea of what follow-up might entail in terms of cost, time and technical difficulty from the
earliest stages of project design and planning onward. In the past, too many large
ambitious regional geochemical reconnaissance exploration programs have been initiated
without full realization that each successive stage of the exploration sequence tends to
be more costly than the previous one. Consequently, budgetary constraints have
prevented full effective follow-up or even definition of all promising geochemical patterns
and anomalies.
There is often some overlap between the initial survey and the follow-up stages.
The verification of potentially significant geochemical patterns, which was discussed
towards the end of the preceding discussion of interpretation, in fact constitutes one of
the final phases of the primary survey and the first stage in follow-up. It is necessary to
verify the pattern or anomaly of interest, especially if it relates to a small number of
samples and/or samples from a specific analytical batch. The possibility of undetected
analytical error or sample contamination in the field or laboratory must always be
considered. Revisiting the areas of interest is advisable at an early stage in order to
determine whether apparently signifcant geochemical patterns are related to previously
unsuspected extraneous factors (e.g. rock type with high geochemical background
concentration, surficial concentration resulting from natural geochemical processes,
environmental contamination from past industrial activity, etc.).
Once anomalies have been verified, follow-up can begin in earnest. Choice of
techniques will depend on both the nature of the favorable indications and the local
environment. For example, follow-up procedures for significant geochemical patterns
discovered in the course of large regional surveys with low sampling densities will be very
different from those required for significant patterns delineated by high density soil or rock
surveys over small mineral properties. Selection of geochemical procedures for follow-up
studies and interpretation of subsequent data must continue to take into account the
results of the original orientation studies and the conceptual geochemical dispersion
models. Additional orientation studies might be required, especially if the sample media
being considered for the follow-up program differ from those used earlier.
As drilling is the most expensive phase of the follow-up sequence, every effort,
within reason, should be made to localize suitable drill targets. The selected procedure(s)
will generally first involve collection and analysis of substantial numbers of closer spaced
samples than in the preceding survey stage, in order that the potentially significant
geochemical patterns can be better defined and possible source areas determined. In
the case of regional surveys, several successive stages of increasingly detailed study may
be required before drilling can even be considered. For example, anomalous stream
284
Problem __________________ _____ Solution

1 The anomaly is assumed to be valid No checks are made Check assumptions by re-analysis and resampling
2. Anomalies are poorly defined Use a more detailed sampling plan
3. The anomaly is defined by too many samples. Sample density shuld be selected by a synthesis ol geological
target, cost, orientation and experience
4a. Trenching and/or drilling of the anomaly site did not lead to Mechanical and hydromorphic dispersion of metal to the site
must be considered. The source lies upslope or up ice of the
discovery.
anomaly.
4b. Trenching of a contoured anomaly did not lead to discovery. As in (4a) or the point source nature of geochemical data must
be recognized
5. The anomaly is "explained away" when drilling is unsuccess Reinterpretation of the data is necessary Failure to locate a
ful source for a bona fide anomaly means the source remains to
be discovered.
6. A minor mineral occurrence explains the anomaly, even though A second source probably remains to be found
this is trivial considering the size/grade of the initial anomaly.
7. Rock types or alteration are not right where exposed near the The importance of geological observations must be tempered
anomaly. by uncertainty regarding what is not exposed
8. The anomaly does not fit the geological model. Refinements of exploration philosophy might be warranted
9. Geophysical features of economic importance are not identi Was the right geophysical method used’ Must the source have
fied under the anomaly. a geophysical response’ Consider mechanical and hydro
morphic dispersion as in (4)
10. Geophysical targets near the geochemical anomaly were tested Determine if geophysical and geochemical anomalies had to
and found to be uninteresting. be related
11. Geophysical targets were tested in prference to source areas Exploration bias is unavoidable An independent audit of ex
suggested by the geochemical interpretation_________________ ploration procedures may be needed.
TABLE 17.1 Common failings encountered in follow-up of geochemical soil surveys.

(Hoffman and Thomson, 1987)
sediment patterns can be followed-up with more detailed sediment sampling to pinpoint
source areas in greater detail. Follow-up sampling of seepage areas is particularly
effective in delimiting anomalous ground water sources containing metal derived from
oxidizing mineralization. If appropriate, soil sampling can then be used to define sub
outcropping mineralization in the anomalous source areas defined by the sediment
surveys.
It is important to always bear in mind that an anomaly may have multiple sources
so that the discovery of one source does not necessarily always provide the complete
answer. Many significant mineralized districts are characterized by widespread weak
mineralization, numerous small discrete occurrences as well as one or more orebodies.
Hoffman and Thomson (1987) have compiled a useful summary (Table 17.1) of
some common mistakes made in follow-up of geochemical soil anomalies as a result of
false assumptions or interpretation errors. This table, which is fairly self explanatory, also
has some relevance to other types of geochemical sample media.
285
18. REPORT WRITING
One of the final acts, and perhaps one of the most important, in any geochemical
exploration program sequence is report writing.
Unless the methodology, data, conclusions, recommendations, etc., are clearly

presented in an objective, accurate and concise manner, they will unlikely have the
desired impact on the decision making process. Much of the time, effort and
expenditures of the program might be thereby wasted. A brief summary of the report
contents, including conclusions and recommendation, should always be inserted in a
readily accessible position, preferably at or near the front. In conjunction with a contents
list it should enable a reader who is unfamiliar with the project to quickly determine and
locate items of particular interest. A report should also provide a permanent
comprehensive record (including references to relevant properly archived data files) of the
related project so that any future need for data review and/or reinterpretation can be
readily met.
In addition to the main data and/or interpretation maps which are often located in
appendices, the main body of the report should include small scale compilation maps and
figures which clearly show the main features of the geochemical data (e.g. anomalies) as
well as relevant significant features (e.g. surficial and/or bedrock geology, geophysical
anomalies, etc.) derived from other disciplines.
No attempt will be made here to provide a detailed dissertation on geochemical

report writing, instead attention is drawn to a useful brief discussion of the subject which
was published a few years ago by the Association of Exploration Geochemists (Hoffman
1986). It was primarily designed for Canadian environmental and regulatory conditions,
but the general format and recommended content could probably be modified for use
elsewhere. More general discussions of geological report writing, which have general
relevance to exploration geochemistry, -include those available the Geological Survey of
Canada (Blackadar, et al., 1975) and the American Geological Institute (Cochran, et al.,
1979).
286
19. LONG TERM STORAGE OF DATA AND SAMPLES
The need for hard copy records of project data has already been alluded to in the
section on report writing. It is also advisable that full data records be maintained in
readily accessible computer databases. This will simplify project data review and
potentially useful data access in future programs.
All too often samples are discarded on completion of projects. Long term this can
prove extremely wasteful, as new concepts, techniques, etc., often encourage re
examination of previously surveyed areas. Re-sampling, especially in remote areas,
and/or in large reconnaissance areas, and/or in areas now disturbed by deposit
development can be an expensive if not impossible task. Existing samples can
sometimes play a useful role in such cases, especially in the initial phase of a new project.
Centralized storage of geochemical samples is a fairly expensive process to initiate and
maintain, but can prove economic over the long term.
287
20. CONCLUSIONS AND RECOMMENDATIONS
Exploration geochemistry or geochemical prospecting is based on

a fundamental premise, which is substantiated by extensive empirical
data, that the chemical composition of certain constituents of the
natural environment in the vicinity of a mineral deposit differ from
those of similar constituents where there is no mineral deposit.
Unfortunately, in the past, exploration geochemistry has often been

presented and applied in an overly simplistic manner. Consequently,
the results obtained have sometimes been less than optimal.
"Cookbook" exploration geochemistry is in fact a recipe for disaster
as all areas have their own distinct geological and geochemical
peculiarities.
Geochemistry can make a useful cost effective contribution in many

types of mineral exploration, when the programs are properly
designed, planned and implemented.
A properly designed, planned and implemented geochemical

exploration program comprises a successive series of interdependent
components which can be likened to a "house of cards". Each
component is wholely dependent on those preceding, so that errors
or inadequacies in one will negatively effect all those that follow.
Successful geochemical exploration requires a basic understanding

of the geological and geochemical environment in which the program
is being carried out. This is best achieved by careful review of
available relevant information and thorough field and laboratory
orientation studies in the initial stages of the program. The data thus
acquired help ensure development of realistic conceptual
geochemical dispersion models and determination of optimum field,
laboratory and interpretational techniques.
Although imaginative selection and application of geochemical

techniques is to be encouraged, realistic assessment of their
performance in the area(s) of interest should be undertaken prior to
any decisions regarding application.
Quality control is an essential aspect of geochemical exploration.

High standards must be achieved at all stages of a program. There
is no point in applying sophisticated analytical or computer aided
interpretational techniques if sample collection and/or preparation
has been improperly undertaken.
288
yiii) Periodic objective reassessment of available data is essential at every

stage of all geochemical exploration programs in order that
unexpected factors or conditions are immediately recognized and
any necessary corrective action is quickly taken. Interpretation is not
something to be only undertaken in the closing stages of a project
when all samples have been collected and all data have been
prepared and compiled.
ix) Effective interpretation of geochemical exploration data

requires emphasis on patterns rather than absolute values. A variety
of computer based data presentation procedures are available to
assist this process. However in some cases, manual procedures
may be required to effectively display the data and all relevant
support information.
(x) Final interpretation is a complex process, not only involving study of

the geochemical data and the various factors which influence
geochemical dispersion, but also integration of the geochemical
results with those provided by other allied disciplines.
(xi) Univariate, and sometimes also multivariate statistics, can play a

useful contributory role in geochemical data interpretation. However,
the latter in particular should not be applied without specialist advice,
preferably from the Geochemical Department.
(xii) The Geochemical Department is in fact available to assist

exploration project staff in a number of ways, including:
(a) provide answers to general and specific geochemical

enquiries;
(b) carry out geochemical literature research;
(c) help design geochemical programs;
(d) carry out geochemical orientation studies;
(e) train field staff;
(f) assist in the supervision of geochemical surveys;
(g) recommend essential geochemical research;
(h) help to keep field staff up-to-date with respect to relevant
developments in geochemical exploration by means of
periodic provision of informational reports, short courses, etc.
Bid- i -
CELSQ L. PALACIOS CAPPILLO j
289
21. LIST OF REFERENCES
[Note: JGE = Journal of Geochemical Exploration]
AIMM, 1988
Prospecting In Arid Terrain.
Extended abstracts from the Second International Conference, Perth Western Australia,
26-30 April, 1988, Aust. Inst. Min. & Metall., 154 pp.
Amor, S.D., and Nichol, I., 1983

Identification of Diagnostic Geochemical Alteration in the Wall Rocks of Archean Volcanic-
Exhalative Massive Sulphide Deposits.
JGE 19 (1/3), p. 543-562.
Andrews-Jones, D.A., 1968

The Application of Geochemical Techniques to Mineral Exploration. Colorado School of
Mines, Mineral Industry Bulletin II, no.6, p. 1-31.
Armour-Brown, A., Steenfelt, A., and Kunzendorf, H., 1983

Uranium Districts Defined by Reconnaissance Geochemistry in South Greenland.
JGE 19 (1/3), p. 127-145.
Baedecker, P.A., 1987

Methods for Geochemical Analysis.
U.S. Geological Survey Bulletin 1770, 220 pp.
Baker, W.E., 1978

The Role of Humic Acid in the Transport of Gold.
Geochim. et Cosmochim. Acta, 42, p. 645-649.
Bagby, W.C., Goldfarb, R.J., Hill, R.A.,

and Pickthorn, W.J., 1984
Distribution of Selected Trace Elements in Soils Overlying The Dee Disseminated Gold
Deposit, Elko County, Nevada.
Preprint No. 84-319. SME-AIME Meeting, Denver, Colorado,
Oct 24-26, 1974.
Ballantyne, S.B., 1991

Stream Geochemistry in the Canadian Cordillera: Conventional and Future Applications
for Exploration.
Paper #6, GSC Exploration Geochemistry Workshop, Toronto,
March 28, 1991, p. 6-1 to 6-74.
290
Barbier, J., 1987

Arid Environment Geochemical Exploration in Saudi Arabia: The Problem of Aeolian
Contamination.
JGE 27 (1/2), p. 29-52.
Beeson, R., 1984

The Use of Fine Fractions of Stream Sediments in Geochemical Exploration in Arid and
Semi-Arid Terrains.
JGE 22 (1/3), p. 119-132.
Berger, B.R., and Bethke, P.M., (eds.), 1985

Geology and Geochemistry of Epithermal Systems.
Reviews in Economic Geology, Volume 2, Economic Geology Publishing Co., El Paso,
Texas, 298 pp.
Berger, B.R., and Silberman, M.L., 1985

Relationships of Trace Element Patterns to Geology in Hot Spring-Type Precious Metal
Deposits.
In: Geology and Geochemistry of Epithermal Systems. Reviews in Economic Geology,
Volume 2, B.R. Berger and P.M. Bethke, (eds.), Economic Geology Publishing Co., El
Paso, Texas, p.233-247.
Berkman, D.A. and Ryall, W.R., (eds.), 1976

Field Geologists Manual.
Aust. Inst. Min. & Metall. Monograph Series No. 9, 295 pp.
Bird, D.J., and Coker, W.B., 1987

Quaternary Stratigraphy and Geochemistry at the Owl Creek Gold Mine, Timmins, Ontario,
Canada.
JGE 28 (1/3), p. 267-284.
Bjorklund, A.J., (ed.), 1984

Geochemical Exploration 1983, Proceedings of the Tenth International Geochemical
Exploration Symposium, Espoo, Finland, August 29 - September 2, 1983.
JGE 21 (1/3), 501 pp.
Bjorklund, A., and Gustavsson, N., 1987

Visualization of Geochemical Data on Maps: New Options.
JGE 29 (1/3), p. 89-103.
Blackadar, R.G., Dumych, H., and Griffin, P.J., 1975

Guide to Authors - A Guide for the Preparation of Geological Maps and Reports.
Geological Survey of Canada, Miscellaneous Report 16, 199 pp.
291
Bloom, H., 1955

A Field Method for the Determination of Ammonium Citrate Soluble Heavy Metals in Soils
and Alluvium.
Economic Geology, Vol. 50, No. 5, p. 533-541.
Bolviken, B., et al., 1986

Geochemical Atlas of Northern Fennoscandia.
Nordic Collaboration, Geological Survey of Sweden, Uppsala, Scale 1:4,000,000.
Bonham-Carter, G.F., Rogers, P.J., and Ellwood, D.J., 1987

Catchment Basin Analysis Applied to Surficial Geochemical Data, Cobequid Highlands,
Nova Scotia.
JGE 29 (1/3), p. 259-278.
Boyle, R.W., 1967

Geochemical Prospecting - Retrospect and Prospect.
]n: Symposium on Geochemical Prospecting, Ottawa 1966, Proceedings, E.M. Cameron,
(ed.), GSC Paper 66-54, p. 30-43.
Boyle, R.W., et al., 1969

Research in Geochemical Prospecting Methods for Native Silver Deposits, Cobalt area,
Ontario, 1966.
Paper 67-35, Geological Survey of Canada, 91 pp.
Boyle, R.W., (ed.), 1971

Geochemical Exploration, Proceedings of the Third International Geochemical Exploration
Symposium, Toronto April 16-18, 1970.
Canadian Inst. Min. and Metall. Spec. Vol. 11, 594 pp.
Boyle, R.W., 1974

Elemental Associations in Mineral Deposits and Indicator Elements of Interest in
Geochemical Prospecting. [Revised].
Geological Survey of Canada Paper 74-45, 40 pp.
Bradshaw P.M.D., (ed.), 1975

Conceptual Models in Exploration Geochemistry.
JGE 4 (1), 223 pp.
Brookins, D.G., 1988

Eh-pH Diagrams for Geochemistry.
Spring-Verlag, 176 pp.
292
Brooks, R.R., 1972

Geobotany and Biogeochemistry in Mineral Exploration.
Carey Coneis, (ed.), Harper and Row, NY, 290 pp.
Brummer, J.J., Gleeson, C.F., and Hansuld, J.A., 1987

A Historical Perspective of Exploration Geochemistry in Canada - the First 30 Years.
JGE 28 (1/3), p. 1-39.
Bubar, D.S., and Heslop, J.B., 1985

Geology of the Gondar Volcanogenic Massive Sulphide Deposit, Slave Province, N.W.T.
Canadian Inst, of Mining and Metallurgy Bull., Vol. 78, p. 52-60.
Busche, F.D., 1989

Using Plants as an Exploration Tool for Gold.
JGE 32, (1/3), p. 199-210.
Butt, C.R.M. and Smith R.E., (eds.), 1980

Conceptual Models in Exploration Geochemistry.
JGE 12 (2/3), 367 pp.
Butt, C.R.M., and Wilding, I.G.P., (eds.), 1977

Geochemical Exploration 1976, Proceedings of the Sixth International Geochemical
Exploration Symposium, Sydney, August 1976.
JGE 8 (1/2), p. 1-494.
Cameron, E.M., (ed.), 1967

Symposium on Geochemical Prospecting, Ottawa 1966, Proceedings.
GSC Paper 66-54, 282 pp.
Canney, F.C., Bloom, H., and Hansuld, J.A., (eds.), 1969

Proceedings of the International Geochemical Exploration Symposium, Golden, Colorado,
April 17-20, 1968.
Colorado School of Mines Quart., Vol. 64, Part 1, 520 pp.
Canney, F.C., and D.B. Hawkins, 1958

Cold Acid Extraction of Copper from Soils and Sediments - a Proposed Field Method.
Economic Geology, Vol. 53, No. 7, p. 877-886.
293
Cannon, H.L., 1979

Advances in Botanical Methods of Prospecting for Minerals:
Part 1 - Advances in Geobotanical Methods.
In: Geophysics and Geochemistry in the Search for Metallic Ores: Proceedings of
Exploration 77, P.J. Hood, (ed.), Geological Survey of Canada, Economic Geology Report
31, p. 386-395.
Carpenter, R.H., Pope, T., and Smith, R.L., 1975

Fe-Mn Coatings in Stream Sediment Geochemical Surveys.
JGE 4 (3), p. 349-363.
Carr, G.R., 1984 . .

Primary Geochemical Mineralogical Dispersion in the Vicinity of the Lady Loretta Zn-Pb-Ag
Deposit, Northwest Queensland.
JGE 22 (1/3), p. 217-238.
Carr, G.R., Wilmshurst, J.R., and Ryall, W.R., 1986

Evaluation of Mercury Pathfinder Techniques: Base Metal and Uranium Deposits.
JGE 26 (1), p. 1-117.
Carver, R.N., Chenoweth, L.M., Mazzucchelli, R.H., et al., 1987

"1 ag" - a geochemical sampling medium for arid regions.
JGE 28 (1/3), p. 183-189.
Chaffee, M.A., 1977

Geochemical Exploration Techniques Based on Distribution of Selected Elements in
Rocks, Soils and Plants, Vekol Porphyry Copper Deposit Area, Pinal County, Arizona.
Bulletin 1278E, U.S. Geological Survey, 78 pp.
Champigny, N., and Sinclair, A.J., 1982.

Cinola Gold Deposit, Queen Charlotte Islands, B.C. - A Geochemical Case History.
In: Geology of Canadian Gold Deposits, R.W. Hodder and W. Petruk, (eds.), Canadian
Inst, of Mining and Metallurgy, Spec. Vol. 24., p. 121-137.
Chao, T.T., 1984

Use of Partial Dissolution Techniques in Geochemical Exploration.
JGE 20 (2), p. 101-135.
Chao, T.T., and Theobald, P.K., Jr., 1976

The Significance of Secondary Iron and Manganese Oxides in Geochemical Exploration.
Economic Geology, Vol. 71, p. 1560-1569.
294
Chork, C.Y., and Mazzucchelli, R.H., 1989
Spatial Filtering of Exploration Geochemical Data Using EDA and Robust Statistics.
JGE 34 (3), p. 221-243.
Chown, H., Hicks, J., et al.,1984

The Disseminated Archean Big Bell Gold Deposit, Murchison Province, Western Australia:
An Example of Pre-Metamorphic Alteration.
Jn: Gold ’82, the Geology, Geochemistry and Genesis of Gold Deposits, R.P.Foster, (ed.),.
A.A. Balkema, p. 305-324.
Church, B.N., Barakso, J.J., and Bowman, A.F., 1976

The endogenous distribution of minor elements in the Goosly-Owen Lake area of Central
British Columbia.
Can. Inst. Min. Metall. Bull., 69 (773), p. 88-95.
Church S E , Mosier, E.L., and Motooka, J.M., 1987 Mineralogical Basis for the
Interpretation’of Multielement (ICP-AES), Oxalic Acid, and Aqua Regia Partial Digestions
of Stream Sediments for Reconnaissance Exploration.
JGE 29 (1/3), p. 207-233.
Clark, J.R. and Viets, J.G., 1990

Multielement Extraction System for Determining 19 Elements in Gold Exploration Samples.
Abstract in Program for "Gold 90”, 1990 Annual Meeting AIME, Salt Lake City, Utah, Feb.
26 - Mar. 1, 1990 .
Clifton, C.D., 1984a . .

Examples of Primary Gas Dispersion in Several Disseminated Gold Deposits in Nevada
and California.
Unpublished Paper, Exploration Research Laboratories.
Clifton, C.D., 1984b

Interpretation of soil Gas Data.
Unpublished Paper, Exploration Research Laboratories.
Clifton, H.E., Hunter, R.E., et al., 1969

Sample Size and Meaningful Gold Analysis.
U.S. Geological Survey Prof. Paper 625-C, 17 pp.
Closs, L.G. and Nichol. I., 1989

Design and Planning of Geochemical Programs.
In: Proceeding of Exploration '87: Third Decennial International Conference on
Geophysical and Geochemical Exploration for Minerals and Groundwater, G.D. Garland,
(ed.), Ontario Geological Survey Spec. Volume 3, p. 569-587.
295
Coats, J.S., Gallagher, M.J., et al., 1981

Stratabound Barium-Zinc Mineralization in Dalradian Schist Near Aberfeldy, Scotland.
Final Report, Mineral Reconnaissance Programme, Institute of Geological Sciences,
Number 40, 116 pp.
Cochran, W., Fenner, P., and Hill, M., 1979

Geowriting: A guide to Writing, Editing, and Printing in Earth Science.
American Geological Institute, Falls Church, VA, 80 pp.
Cohen, D.R., 1986 . , _ .. . ,

Biogeochemistry. A Geochemical Method for Gold Exploration in the Canadian Shield.
M.S. Thesis, Queen’s University, Kingston, Ontario, 498 pp.
Cohen, D.R., Hoffman, E.L., and Nichol, I., 1987

Biogeochemistry. A Geochemical Method for Gold Exploration in the Canadian Shield.
JGE 29 (1/3), p. 49-73.
Coker, W.B., 1991

Overburden Geochemistry in Mineral Exploration.
Paper #3 - GSC Exploration Geochemistry Workshop, Toronto,
March 28, 1991, p. 3-1 to 3-60.
Coker, W.B., and DiLabio, R.N.W., 1989

Geochemical Exploration in Glaciated Terrain: Geochemical Responses.
In: Third Decennial International Conference on Geophysical and Geochemical Exploration
for Minerals and Groundwater, Proceedings of Exploration ’87, G.D. Garland, (ed.),
Ontario Geological Survey Spec. Volume 3, p. 336-383.
Coker, W.B., Hornbrook, E.H.W., and Cameron, E.M., 1979

Lake Sediment Geochemistry Applied to.Mineral Exploration.
Exploration 77, P. J. Hood, (ed.), Geological Survey of Canada, Economic Geology Report
31, p. 435-477.
Cole, M.M., 1980

Geobotanical Expressions of Orebodies.
Trans. Inst. Min. and Metall. (London), Sect. B, Vol. 89,
p. 73-91.
Cole, M.M., and Le Roex, H.D., 1978

The Role of Geobotany, Biogeochemistry and Geochemistry in Mineral Exploration in
South-West Africa and Botswana:
A Case History.
Geol. Soc. South Africa Trans. Vol. 81, p. 277-317.
296
Colvine, A.C., (ed.). 1983
The Geology of Gold in Ontario.
Ontario Geological Survey Miscellaneous Paper 110, 278 pp.
Coope, J. A., 1966

Geochemical Prospecting in the Dawson Range.
Mining Congress Journal, Vol. 25, No. 5, p. 62-69.
Coope, J.A., 1975

Sheslay Cu-Mo Prospect, British Columbia.
JGE 4 (1), p. 97-100.
Coope, J.A., 1992?

Geochemical and Other Prospecting Techniques.
jn: preparation.
Coope, J.A., and Davidson, M.J., 1979

Some Aspects of Integrated Exploration.
31, p. 575-592.
Crone, W., Larson, L.T., et al., 1984

A Comparison of Iron Oxide-Rich Joint Coatings and Rock Chips as Geochemical
Sampling Media in Exploration for Disseminated Deposits.
JGE 20 (2), p. 161-178.
Curtin, G.C., Lakin, H.W., Hubert, A.E., Mosier, E.L.,

and Watts, K.C., 1971 . . u . r>.
Utilization of Mull (Forest Humus Layer) in Geochemical Exploration in the Empire District,
Clear Creek County, Colorado.
U.S.G.S. Bull. 1278-B, 39 pp.
Davenport, P.H., 1982a

Prospecting In Areas of Glaciated Terrain - 1982.
Papers presented at an international meeting in St. John’s, Newfoundland, Canadian Inst.
Min. Metall., 339 pp.
Davenport, P.H., 1982b . ~

Regional Geochemical Mapping in Newfoundland - the Use of Lake and Sediment as
Sample Medium in a Glaciated Landscape.
jn: Prospecting In Areas of Glaciated Terrain - 1982,
P.H. Davenport, (ed.), Canadian Inst. Min. Metall., p. 57-81.
297
Davis, J.C., and McCullagh, M.J., (eds.). 1975

Display and Analysis of Spatial Data.
John Wiley, New York, N.Y., 378 pp.
Davies, J.F., Whitehead, R.E.S., et al., 1982 . T. . e

Regional and Local Patterns of CO2-K-Rb-As Alteration: a Guide to Gold in the Timmins
A roo
Davy, R., and Mazzucchelli, R.H., (eds.), 1984

Geochemical Exploration in Arid and Deeply Weathered Terrain.
JGE 22 (1/3), 368 pp.
Dean, W.E., (ed.), 1986

Organics and Ore Deposits.
Proceedings of Denver Region Exploration Geologists (DREGS) Symposium, 218 pp.
Duchaufour., P., 1982

Pedology - Pedogenesis and Classification. (Trans, by T.R. Paton)
George Allen & Unwin, London, 448 pp.
Dunn, C.E., 1987 ..

Gold Exploration in Northern Saskatchewan by Biogeochemical Methods.
Jn: Gold in the Western Shield, A. Clark, (ed.),
Special Vol 38, Canadian Institution and Metallurgy, p. 418-434.
Dunn, C.E., 1989 .

Reconnaissance-Level Biogeochemical Surveys for Gold in Canada.
Trans. Inst. Min. and Metall. (London) Vol. 98, p. B153-B161.
Dunn, C.E., 1991

Biogeochemistry in Mineral Exploration.
March 28, 1991, p. 7-1 to 7-25.
The°Natu’re of Hydrothermal Alteration Associated with the Madson and Starrett-Olsen

Gold Deposits, Red Lake Area. . _
In: The Geology of Gold in Ontario, A.C. Colvine, (ed.), Ontario Geological Survey,
Miscellaneous Paper 110, p. 123-140.
298
Dyck, W., 1979
Application of Hydrogeochemistry to the Search for Uranium.
Jit Geophysics and Geochemistry in the Search for Metallic Ores. Proceedings of
31, p. 489-510.
Dyck, W., and Car, D., 1987

Detailed Geochemical Studies of a He-U Lake Anomaly in Permafrost, Baker Lake, N.W.T. ■
JGE 28 (1/3), p. 409-429.
Dyck, W., Dass, S., Durham, C.C., et al., 1971

Comparison of Regional Geochemical Uranium Exploration Methods in the Beaverlodge
Area, Saskatchewan. .
In: Geochemical Exploration, Proceedings of the Third International Geochemical
Exploration Symposium, Toronto April 16-18,1970, R.W. Boyle, (ed.), Canadian Inst. Min.
and Metall. Spec. Vol. 11, p. 132-150.
Elliott, I.L., and Fletcher, W.K., (eds.), 1975

Geochemical Exploration 1974, Proceedings of the Fifth International Geochemical
Exploration Symposium, Vancouver,
April 1-4, 1974.
Elsevier Scientific Publishing Company, 720 pp.
Elliott, S.M., and Towsey, 1989

Regional Drainage Geochemical Gold Exploration Techniques Used in Queensland,
Australia
Proceedings NO Gold '89 Conference, Townsville, Queensland, April 1989, p. 51-61.
Erdman, J.A., Cookro, T.M., et al., 1988

Gold and Other Metals in Big Sagebrush (Artemisia tridentata Nutt.) as an Exploration
Tool, Gold Run District, Humboldt County, Nevada.
JGE 30 (3), p. 287-308.
Erdman, J.A., and Modreski, P.J.', 1984

Copper and Cobalt in Aquatic Mosses and Stream Sediments from the Idaho Cobalt Belt.
JGE 20 (1), p. 75-84.
Erdman, J.A. and Olson, J.C., 1985

The Use of Plants in Prospecting for Gold: A Brief Overview with a Selected Bibliography
and Topic Index.
JGE 24 (3), p. 281-304.
299
Eremeev, A.N. et al., 1973

Application of Helium Surveying to Structural Mapping and Ore Deposit Forecasting.
]n: Geochemical Exploration 1972: Papers Presented at the Fourth International
Geochemical Exploration Symposium, London, April 17-20, 1972, M.J. Jones, (ed.), Inst.
Min. Metall. (London),
p. 183-192.
Evans, J.G. and Peterson, J.A., 1986

Distribution of Minor Elements in the Rodeo Creek NE and Welches Canyon quadrangles,
Eureka County, Nevada.
U.S.G.S. Bull. 1657, 65 pp.
Farrell, B.L., 1984

The Use of "Loam" Concentrates in Geochemical Exploration in Deeply Weathered Arid
Terrains.
JGE 22 (1/3), p. 101-118.
Fedikow, M.A.F., and Amor, S.D., 1990

Evaluation of Mercury Vapour Detection System in Base and Precious Metal Exploration,
Northern Manitoba.
JGE 38 (3), p. 323-350.
Fletcher, R.J., 1985

Geochemical Exploration for Gold in the Red Sea Hills, Sudan.
In: Prospecting in Areas of Desert Terrain, Inst. Min. Metall. (London), p. 79-94.
Fletcher, W.K., 1981

Analytical Methods in Geochemical Prospecting.
Handbook of Exploration Geochemistry, Vol I, G.J.S. Govett, (ed.), Elsevier, 255 pp.
Fletcher, W.K., 1987

Analysis of Soil Samples.
Jn: Exploration Geochemistry: Design and Interpretation of Soil Surveys, Reviews in
Economic Geology, W.K. Fletcher, bt al.,
Vol. 3, SEG, p. 79-96.
Fletcher, W.K., Hoffmann, S.J., Mehrtens, M.B., Sinclair, A.J., and Thompson, I., 1987
Exploration Geochemistry: Design and Interpretation of Soil Surveys.
Reviews in Economic Geology, Vol. 3, SEG, 180 pp.
Foster, R.P., (ed.), 1984

Gold ’82, the Geology, Geochemistry and Genesis of Gold Deposits.
A.A. Balkema, 753 pp.
300
The Use of Landscape Geochemistry to Process Geochemical Exploration Data.

JGE 4 (1), p. 3-7.
Fortesque, J.A.C., 1980

Environmental Geochemistry, A Holistic Approach.
Ecological Studies, Vol. 35, Springer-Verlag, 347 pp.
Franklin J.M. and Duke, J.M., 1991

Lithogeochemical and Mineralogical Methods of Base Metal and Gold Exploration.
March 28, 1991, p. 1-1 to 1-33.
ThÂpplica’tionôf Lake Sediment Geochemistry in Mineral Exploration.

March 28, 1991, p. 4-1 to 4-20.
Fuchs, H., Hilger, W., Prosser, E„ and Stuart, M., 1982

Exploration of the Lone Gull Property, Baker Lake Area, District of Keewatin, Northwest
Territories. .. .no_
Canadian Institute of Mining, Quebec City, Quebec, apnl 1982.
Fvon, J.A., and Crocket, J.H., 1982 .

Gold Exploration the Timmins District Using Field and Lithogeochemical Characteristics
of Carbonate Alteration Zones.
in: Geology of Canadian Gold Deposits, R.W. Hodder and W. Petruk, (eds.), Canadian
Proceeding of Exploration '87: Third Decennial International Conference on Geophysical

and Geochemical Exploration for Minerals and Groundwater.
Ontario Geological Survey Spec. Volume 3, 960 pp.
Regional geochemical study of Cretaceous acidic rocks in the Northern Canadian

Cordillera as a tool for broad mineral exploration.
In: Geochemical Exploration 1972: Papers Presented at the Fourth International
Geochemical Exploration Symposium, London, April 17-20, 1972, M.J. Jones, (ed.), Inst.
Min. Metall. (London),
p. 203-219.
301
Garrett, R.G., (ed.), 1987 .

Geochemical Exploration 1985, Proceedings of the Eleventh International Geochemical
Exploration Symposium, Toronto, April 28 - May 2, 1985.
JGE 28 (1/3), 494pp. and JGE 29 (1/3), 440 pp.
Garrett, R.G., 1989a

The Chi-Square Plot: A Tool for Multivariate Outlier Recognition.
JGE 32 (1/3), p. 319-341.
Garrett, R.G., 1989b

The Role of Computers in Exploration Geochemistry.
jn: Third Decennial International Conference on Geophysical and Geochemical Exploration
for Minerals and Groundwater, Proceedings of Exploration '87, G.D. Garland, (ed.),
Ontario Geological Survey Spec. Volume 3 p. 586-608.
Garrett, R.G., 1989c

A Cry from the Heart.
EXPLORE, The AEG Newsletter No. 66, p. 18-20.
Garrett, R.G., 1991

The Management, Analysis and Display of Exploration Geochemical Data.
March 28, 1991, p. 9-1 to 9-41.
Gingrich, J.E., 1974

Results from a New Uranium Exploration Method.
Am. Inst, of Mining Engineers, Feb. 24-28, 1974, Dallas, Texas.
Gingrich, J.E., 1984

Radon as a Geochemical Tool.
JGE 21 (1/3), p. 19-39.
Gleeson, C.F., and Cormier, R., 1971

Evaluation by Geochemistry of Geophysical Anomalies and Geological Targets Using
Overburden Sampling at Depth. .
In: Geochemical Exploration, Proceedings of the Third International Geochemical
Exploration Symposium, Toronto April 16-18, 1970, R.W. Boyle, (ed.), Canadian Inst. Min.
Gleeson, C.F., and Sheehan, D.G., 1987

Humus and Till Geochemistry Over the Doyon, Bousquet and Williams Gold Deposits.
CIM Bulletin, Vol. 80, No. 898, p. 58-66.
302
Goldschmidt, V.M., 1923
Geochemische Verteilungsgesetze der Elemente.
Videnskapsselskapets Skrifter I, Mat.-naturw. Cl 3.
Goldschmidt, V.M., 1954

Geochemistry.
Clarendon Press, Oxford. 730 pp.
Goodfellow, W.D., Jonasson, I.R., and Morganti, J.M., 1983

Zonation of Chalcophile Elements about the Howard’s Pass (XY) Zn-Pb Deposit, Selwyn
Basin, Yukon.
JGE 19 (1/3), p. 503-542.
Govett, G.J.S., (ed.), 1976

Exploration Geochemistry in the Appalachians.
JGE 6 (1/2), p. 1 - 298.
Govett, G.J.S., 1983

Rock Geochemistry in Mineral Exploration.
Handbook of Exploration Geochemistry, Vol. 3, Elsevier, Amsterdam, 461 pp.
Govett, G.J.S., 1989

Bedrock Geochemistry in Mineral Exploration.
Guha, J., Gauthier, A. et al., 1982

Gold Mineralization Patterns at the Doyon Mine (Silverstack), Bousquet, Quebec.
jn: Geology of Canadian Gold Deposits, R.W. Hodder and W. Petruk, (eds.), Canadian
Gy, P.M., 1979a

Sampling of Particulate Materials - Theory and Practice.
Elsevier Scientific Publishing Company.
Gy, P.M., 1979b

Sample Preparation.
]n: Computer Methods for the 80's in the Mineral Industry,
A. Weiss, (ed.), Soc. Mining Engineers, New York, p. 163-169
Haffty, J., Riley, L.B., and Goss, W.D., 1977

A Manual on Fire Assaying and Determination of the Noble Metals in Geologic Materials.
U.S.G.S. Bulletin 1445, 58 pp.
303
Hale, M., Thompson, M. and Wheatley, M.R., 1984 .iti^mant

Laser Ablation of Stream Sediment Pebble Coatings for Simultaneous Multielement
Analysis in Geochemical Exploration.
JGE 21 (1/3), p. 361-367.
Hall, G.E.M., 1991

Analytical Methods Used in Exploration Geochemistry.
March 28, 1991, p. 8-1 to 8-90.
Harron, G.A., Middleton, R.S., Durham, R.B. and Philipp, A., 1987
Geochemical and Geophysical Gold Exploration in the Timmins Area, Ontario: A Case
History.
CIM Bulletin, Vol. 80, No. 898, p. 52-57.
Harvey, J.D., and Hinzer, J.B., 1981

Geology of the Lyon Lake Ore Deposits, Noranda Mines Ltd., Sturgeon Lake Area.
Canadian Inst, of Mining and Metallurgy Bull. Vol. 74, p. 77-84.
Hawkes, H.E., 1957

Principles of Geochemical Prospecting.
Bulletin 1000-F, U.S. Geological Survey, p. 225-355.
Hawkes, H.E., 1982

Exploration Geochemistry Bibliography to January 1981.
Special Volume No.11, The Association of Exploration Geochemists
Hawkes, H.E., 1985

Exploration Geochemistry Bibliography - Jan. 1981 to Oct. 1984.
Spec. Vol. No.11, Supplement 1, Assoc. £xpl. Geochem.
Hawkes, H.E., 1988

Exploration Geochemistry Bibliography - Nov. 1984 to Oct. 1987.
Spec. Vol. No.11, Supplement 2, Assoc. Expl. Geochem.
Hawkes, H.E., and Webb, J.S., 1962

Geochemistry in Mineral Exploration (first edition).
Harper & Row, New York, 415 pp.
Heberlein, D.R., Fletcher, W.K., and Godwin, C.I., 1983

Lithogeochemistry of Hypogene, Supergene and Leached Cap Samples, Berg Porphyry
Copper Deposit, British Columbia.
JGE 19 (1/3), p. 595-609.
304
Hem, J.D., 1972
Chemistry and Occurrence of Cadmium and Zinc in Surface Water and Groundwater.
Water Resources Research Vol. 8, p. 661-679.
Hodder, R.W., and Petruk, W., (eds.), 1982

Geology of Canadian Gold Deposits.
Canadian Inst, of Mining and Metallurgy, Spec. Vol. 24., 286 pp.
Hoffman, E.L., and Ernst, P.C., 1982

Analytical Geochemistry Advanced by Neutron Activation.
Jour. Radioanalytical Chemistry, 71, (1-2), p. 447-462.
Hoffman, S.J., 1986

Writing Geochemical Reports - Guidelines for Surficial Geochemical Surveys.
Association of Exploration Geochemists, Spec. Vol. No. 12, 29 pp.
Hoffman, S.J., 1987 t

Case History and Problem 4: The Volcanogenic Massive Sulfide, A Second Example.
In: Exploration Geochemistry: Design and Interpretation of Soil Surveys, Reviews in
Economic Geology, W.K. Fletcher, et al.,
Vol. 3, SEG, p. 147-154.
Hoffman, S.J. and Thomson, I., 1987 .

Models, Interpretation and Follow-up. Exploration Geochemistry. Jn. Exploration
Geochemistry: Design and Interpretation of Soil Surveys, Reviews in Economic Geology,
W.K. Fletcher, et al.,
Vol. 3, SEG, p. 117-128.
Hood, P.J., (ed.), 1979

Geophysics and Geochemistry in the Search for Metallic Ores:
Proceedings of Exploration 77.
Geological Survey of Canada, Economic Geology Report 31, 811 pp.
Hornbrook, E.H., 1989 1

Lake Sediment Geochemistry: Canadian Applications in the Eighties.
In: Third Decennial International Conference on Geophysical and Geochemical Exploration
Howarth, R.J., 1983

Statistics and Data Analysis in Geochemical Prospecting. Handbook of Exploration
Geochemistry, Vol. 2, G.J.S. Govett (ed.), Elsevier, 437pp.
305
Huff, L.C., 1970

A Geochemical Study of Alluvium-Covered Copper Deposits in Pima County, Arizona.
U.S. Geol. Survey Bull. 1312-C, 31 pp.
IMM, 1977
Prospecting in Areas of Glaciated Terrain 1977.
Papers presented at an international conference in Helsinki, Finland, 1977, Inst. Mm.
Metall. (London), 140 pp.
IMM, 1979
Papers presented at an international conference in Dublin, Ireland, 1980, Inst. Min. Metall.
(London), 110 pp.
IMM, 1984
Papers presented at an international conference in Glasgow, Scotland, 1984, Inst. Min.
IMM, 1985
Prospecting in Areas of Desert Terrain.
Papers presented at an international conference in Rabat, Morocco, 14-17 April, 1984,
Inst. Min. Metall. (London), 283 pp.
IMM, 1986
Papers presented at an international conference in Kupio, Finland, 1986, Inst. Min. Metall.
(London), 269 pp.
Jaacks, J.A., 1989

Carbon Dioxide Soil-Gas Signatures Over Sediment Hosted Gold Deposits in the Western
U.S,
Abstract of informal presentation made at DREGS Meeting,
Lakewood, Colorado, April 3, 1989.
James, L.D., and Perkins, E.W., 1981

Glacial dispersion from sulphide mineralization, Buchans Area, Newfoundland.
In: The Buchans Orebodies: Fifty Years of Geology and Mining,
E.A. Swanson, D.F. Strong and J.G. Thurlow, (eds.), Geol. Assoc. Canada Spec. Paper
22, p. 269-283.
306
Jenness, S.E., (ed.). 1989

Geochemical Exploration 1987, Proceedings of the Twelfth International Geochemical
Exploration Symposium, April 23-26, 1987, Orleans, France.
JGE 32 (1/3), 491 pp.
Jones, K.C., 1985

Gold, Silver and Other Elements in Aquatic Bryophytes from a Mineralized Area of North
Wales, U.K.
JGE 24 (3), p. 237-246.
Jones, M.J., (ed.), 1973a

Geochemical Exploration 1972: Papers Presented at the Fourth International Geochemical
Exploration Symposium, London, April 17-20, 1972.
Inst. Min. Metall. (London), 458 pp.
Jones, M.J., (ed.), 1973b

Prospecting in Areas of Glacial Terrain.
Papers presented at an international meeting in Trondheim, Norway, 1973, Inst. Min.
Jones, M.J., (ed.), 1975

Prospecting in Areas of Glaciated Terrain.
Papers presented at an international meeting in Edinburgh, Scotland, 1975, Inst. Min.
Joyce, A.S., 1984

Geochemical Exploration.
TFie Australian Mineral Foundation Inc., 183 pp.
Kauranne, L.K., (ed.), 1976a

Conceptual Models in Exploration Geochemistry, Norden, 1975.
JGE 5 (3), p. 173-420.
Kauranne L.K., 1976b

Introduction to Conceptual Models in Exploration Geochemistry. JGE 5 (3), p. 175-198.
Kesler, S.E., (ed.), 1990

Soil and Rock Gas Geochemistry. (Special Issue).
JGE 38 (1/2), p. 1-245.
Kleiner, B. and Hartigan, J.A., 1981

Representing Points in many Dimensions by Trees and Castles.
J. Am. Stat. Assoc., 76 (374), p. 260-269.
307
Kral, V.E., et al., (eds.), 1983

Papers Given at the Precious Metals Symposium, Sparks, Nevada,
November 17-19, 1980.
Nevada Bureau of Mines and Geology Report 36, 172 pp.
Kurzl, H., 1988 . . ._ t

Exploratory Data Analysis: Recent Advances for the Interpretation of Geochemical Data
JGE 30 (3), p. 309-322.
Landa, E.R., 1978

The Retention of Metallic Mercury Vapor by Soils.
Geochimica et Cosmochemica Acta, Vol. 42, p. 1407-1411.
The^Geoc’hemistry of the Sedimentary Rocks in the Vicinity of the Tom Pb-Zn-Ba Deposit,
Yukon Territory, Canada.
JGE 15 (1/3), p. 203-217.
Larsson, J.O., 1976

Organic Stream Sediments in Regional Geochemical Prospecting, Precambrian District,
Sweden.
JGE 6 (2), p.233-249.
Lavery, N.G., 1985 .

Quantifying Chemical Changes in Hydrothermally Altered Volcanic Sequences - Silica
Enrichment as a Guide to the Crandon Massive Sulphide Deposit, Wisconsin, U.S.A.
JGE 24 (1), p. 1-27.
Lavin, O., A. Grant, and I. Nichol, 1987

The Optimization of Geochemical Exploration Techniques for Gold Deposits in Areas
Covered by Glacial Till.
Report 4 - Two Year Summary, April 1985 to March 1987, Department of Geological
Sciences, Queens University, Kingston, Prepared on behalf of the Ontario Ministry of
Colleges and Universities, U.R.L'F., 140 pp.
Lerman, A., and Maybeck, M., (eds.) 1988

Physical and Chemical Weathering in Geochemical Cycles.
(Proc. NATO Advanced Study Institute, France, Sept. 1985).
NATO ASI Series 251, Kluwer Academic Publishers.
Levinson, A.A., 1974

Introduction to Exploration Geochemistry.
Applied Publishing, Calgary, 612 pp.
308
Levinson, A.A., McCammon, R.B., and Hitchon, B., 1980
Introduction to Exploration Geochemistry, 2nd. edition.
Levinson, A.A., Bradshaw, P.M.D., and Thomson, I., 1987

Practical Problems in Exploration Geochemistry.
Lewis, M., Mage, R., Dakio, J., and Ouedraogo, J., 1989
L’Application des Methodes Geophysiques et Geochimiques pour la Recherche des
Gisements de Sulfures Massifs de Type Perkao.
Jn: Third Decennial International Conference on Geophysical and Geochemical Exploration
Lovell, J.S., Hale, M., and Webb, J.S., 1983

Soil Air Carbon Dioxide and Oxygen Measurements as a Guide to Concealed
Mineralizations in Semi-Arid and Arid Regions.
JGE 19 (1/3), p. 305-317.
Lovell, J.S., and Reid, A.R., 1989

Carbon Dioxide/Oxygen in the Exploration for sulphide Mineralization.
In: Third Dicennial International Conference on Geophysical and Geochemical Exploration
Lovering T.G. and McCarthy J.H. Jr., (eds.), 1978

Conceptual Models in Exploration Geochemistry - the Basin and Range Province of the
Western United States and Northern Mexico; JGE 9 (2/3), p. 113-276.
MacDonald, D.P., (ed.), 1988

Prospecting in Areas of Glaciated Terrain.
Papers presented at an international meeting in Halifax, Nova Scotia, 1988, Canadian
Institute of Mining and Metallurgy,
641 pp.
MacGeehan, P.J., Sanders, T., and Hodgson, C.J., 1982

Meter-Wide Veins and Kilometer-Wide Anomaly: Wall-Rock Alteration at the Campbell Red
Lake and Dickenson Gold Mines, Red Lake District, Ontario.
Canadian Inst, of Mining & Metallurgy Bull., Vol. 75, p. 90-102.
Malmqvist, et al., 1986

Method for Indicating Concealed Deposits.
U.S. Patent 4,587,847, May 13.
309
Marcotte, D., and David, M., 1981

Target Definition of Kuroko-Type Deposits in Abitibi by Discriminant Analysis of
Geochemical Data.
Canadian Inst, of Mining & Metallurgy Bull., Vol. 74, p. 102-108.
Mattinen, P.R., and Bennett, G.H., 1986 ...............

The Green Mountain Massive Sulphide Deposit: Besshi-Type Mineralization Within the
Californian Foothills Copper-Zinc Belt.
JGE 25 (1/2), p. 185-200.
Maurice, Y.T., 1991 . .

The Use of the Heavy Fraction of Stream Alluvium: Application to Low-Energy Glaciated
Environments in Eastern Canada.
March 28, 1991, p. 5-1 to 5-24.
Mazzucchelli, R.H., 1991

Warburton Range Cu Prospects, Musgrave Block, Western Australia.
JGE 12 (2/3), p. 236-239.
McConnell, J. and Davenport, P., 1989

Gold and Associated Trace Elements in Newfoundland Lake Sediment: Their Application
to Gold Exploration.
JGE 32 (1/3), p. 33-50.
Meyer, W.T., Theobald, P.K., and Bloom, H., 1979

Stream Sediment Geochemistry.
31, p. 411-434.
Michaels, G.B., and Riese, W.C., 1986

Microbiological Exploration for Mineral Deposits: A New Technique.
Applied Geochemistry, Vol. 1, p. 103-109.
Miller, J.K., 1984

Model for Clastic Indicator Trains.
Jn: Prospecting in Areas of Glaciated Terrain 1984.
Inst. Min. Metall. (London), p. 69-77.
310
Miller, W.R., 1979
Application of Hydrogeochemistry to the Search for Base Metals.
jn: Geophysics and Geochemistry in the Search for Metallic Ores: Proceedings of
31, p. 479-510.
Moeskops, P.G., and White, A.H., 1980

Ediacara Pb-(Zn)-(Cu) Deposit, Adelaide Geosyncline, South Australia.
JGE 12 (2/3), p. 272-275.
Nichol, I., James, L.D., and Viewing, K.A., 1966

Regional Geochemical Reconnaissance in Sierra Leone.
IMM Trans (London), Vol. 75, p. B146-B161; discussions Vol. 76, p. B69-B72; Vol. 78, p.
B52-B54.
Nikkarinen, M., Kallio, E., Lestinen, P., and Ayras, M., 1984
Mode of Occurrence of Cu and Zn in Till over Three Mineralized Areas in Finland.
JGE 21 (1/3), p. 239-238.
Nowlan, G.A., 1976

Concretionary Manganese-Iron Oxides in Streams and their Usefulness as a Sample
Medium in Geochemical Exploration.
JGE 6 (2), p. 193-210.
Nurmi, P.A., and Isohanni, M., 1984

Rock, Till and Stream Sediment Geochemistry in the Search for Porphyry-Type Mo-Cu-Au
Deposits in the Proterozoic Rautio Batholith, Western Finland.
JGE 20 (2), p. 209-228.
Oakes, B.W., and Hale, M., 1987

Dispersion Patterns of Carbonyl Sulphide above Mineral Deposits.
JGE 28 (1/3), p. 235-249.
Ong, H.L., and Swanson, V.E., ,1969

Natural Organic Acids in the Transport, Deposition and Concentration of Gold.
Jn: Proceedings of the International Geochemical Exploration Symposium, Golden,
Colorado, April 17-20,1968, Canney, F.C., Bloom, H., and Hansuld, J.A., (eds.), Colorado
School of Mines Quart., Vol. 64, Part 1, p. 395-426.
Otteson, R.T., Bogen, J., Bolviken, B., and Volden, T., 1989
Overbank sediment: a representative sample medium for regional geochemical mapping.
JGE 32 (1/3), p. 257-278.
311
Ottley. D.J., 1983

Calculation of Sample Requirements and Development of Preparation Procedures for
Reliable Analyses of Particulate Materials.
jn: Papers Given at the Precious Metals Symposium, Sparks, Nevada, November 17-19,
1980, Kral, V.E., et al., (eds.), Nevada Bureau of Mines and Geology Report 36, p. 132-
144.
Parduhn, N.L., 1987

The Ecology and Distribution of Bacillus Cereus and other Microorganisms in Soils
Associated with Gold Deposits.
Ph.D. Thesis, Colorado School of Mines, 193 pp.
Parduhn, N.L, Watterson, J.R., and Silberman, M.L., 1986 Distribution of Bacillus Cereus
Spores in Soil Over Four
Subsurface Gold Deposits: a Progress Report.
Jn: Organics and Ore Deposits, Proceedings of Denver Region Exploration Geologists
(DREGS) Symposium, W.E. Dean, (ed.),
p. 115-118.
Parduhn, N.L., and Watterson, J.R., 1984

Preliminary Studies of Bacillus Cereus Distribution Near a Gold Vein and Disseminated
Gold Deposit.
USGS Open File Report 84-509, 6 pp.
Parslow, G.R., (ed.), 1983

Geochemical Exploration 1982, Proceedings of the Ninth International Geochemical
Exploration Symposium, Saskatoon, May 12-14, 1982.
JGE 19 (1/3), 743 pp.
Pirie, J., 1982

Regional Geological Setting of Gold Deposits, Eastern Red Lake Area, Northwestern
Ontario.
Jn: Geology of Canadian Gold Deposits, R.W. Hodder and W. Petruk, (eds.), Canadian
Pitard, F„ 1987
Sampling of Gold - Theory and Practice.
Short Course, Mackay School of Mines, Reno, Nevada, May 1987.
Plant, J.A., Breward, N., Forrest, M.D., and Smith, R.T., 1989
The Gold Pathfinder Elements As, Sb and Bi - Their Distribution and Significance in the
Southwest Highlands of Scotland.
Trans. Inst. Min. Metall. (London), Sect. B, Applied Earth Science, Vol. 98, p. B91-101.
312
Plant, J.A., Hale, M., and Ridgway, J. 1989
Regional Geochemistry Based on Stream Sediment Sampling.
Pulkkinen, E., Raisanen, M.-L, and Ukonmaanaho, L., 1989

Geobotanical and Biogeochemical Exploration for Gold in the Sattasvaara Volcanic
Complex, Finnish Lapland.
JGE 32 (1/3), p. 223-230.
Reimann, C., 1988

Comparison of Stream Sediment and Soil Sampling for Regional Exploration in the
Eastern Alps, Austria.
JGE 31 (1), p. 75-85.
Rose, A.W., and Gundlach, H., (eds.), 1981

Geochemical Exploration 1980, Proceedings of the Eighth International Geochemical
Exploration Symposium, April 10-15, 1980, Hannover, Germany.
JGE 15 (1/3), 698 pp.
Rose, A.W., Hawkes, H.E., and Webb, J.S., 1979

Geochemistry in Mineral Exploration (second edition).
Academic Press, New York, 657 pp.
Rossler, H.J., and Lange, H. 1972

Geochemical Tables.
Elsevier, 468 pp.
Rugless, C.S., and Govett, G.J.S., 1984

Exploration Rock Geochemistry for Pinnacles-Type Mineralization at Broken Hill, New
South Wales, Australia.
JGE 22 (1/3), p. 133-160.
Runnells, D.D., and Lindberg, R.D., 1981

Hydrogeochemical Exploration for Uranium Ore Deposits: Use of the Computer Model
WATEQFC.
JGE 15 (1/3), p. 37-50.
Salpeteur, I., 1989

Orientation Studies for Gold in the Central Pediplain of the Saudi Arabian Shield.
JGE 34 (2), p. 189-215.
313
Salomons, W., and Forstner, U., 1984

Metals in the Hydrocycle.
Springer-Verlag, 349 pp.
Sampson, R. J., 1975

The SURFACE II Graphics System.
Jn: Display and Analysis of Spatial Data, Davis, J.C., and McCullagh, M.J., (eds.),
John Wiley, New York, N.Y., p. 244-266.
Sauerbrie, J.A., Pattison, E.F., and Averill, S.A., 1987

Till Sampling in the Casa-Berardi Gold Area, Quebec: A Case History in Orientation and
Discovery.
JGE 28 (1/3), p. 297-314.
Shacklette, H.T. and Erdman, J.A., 1982

Uranium in Spring Water and Bryophytes at Basin Creek in Central Idaho.
JGE 17 (3), p. 221-236.
Shaver, S.A., 1986

Elemental Dispersion Associated with Alteration and Mineralization at the Hall (Nevada
Moly) Quartz Monzonite-Type Porphyry Molybdenum Deposit, with a Section on
Comparison of Dispersion Patterns with those from Climax-Type Deposits.
JGE 25 (1/2), p. 81-98.
Shelp, G.S. and Nichol, I., 1987

Distribution and Dispersion of Gold in Glacial Till Associated with Gold Mineralization in
the Canadian Shield.
JGE 27, (3), p. 315-336
Shilts, W.W., 1984

Till Geochemistry in Finland and Canada.
JGE 21 (1/3). p. 95-117.
Shilts, W.W., 1991

Principles of Glacial Dispersal and Sedimentation.
Paper #2 - GSC Exploration Geochemistry Workshop,
March 28, 1991, p. 2-1 to 2-42.
Sinclair, A.J., 1976

Applications of Probability Graphs in Mineral Exploration.
The Association of Exploration Geochemists, Special Vol. No. 4,
Richmond Printers, 95 pp.
314
Statistical Interpretation of Soil Geochemical Data, Exploration Geochemistry

h: Exploration Geochemistry: Design and Interpretation of Soil Surveys, Reviews in
Vol. 3, SEG, p. 97-115.
Sirinawin T Fletcher, W.K., and Dousset, P.E., 1987 .

Evaluation of Geochemical Methods in Exploration for Pomary Tin Deposits: Batu Gajah-
Tanjong Tualang Area, Perak, Malaysia.
JGE 29 (1/3), p. 165-181.
D*nprosRpecting7|n the Abitibi Clay Belt; Overburden Drilling Program ■ Methods and
Costa.
Geol. Survey Canada, Open File Report 116.
Smee B W and Bailes, R.J., 1986 .

The Use of Lithogeochemical Patterns in Wall Rock as a Guide to Exploration Drilling at
the Jason Lead-Zinc-Silver-Barium Deposit, Yukon Territory.
JGE 25 (1/2), p. 217-230.
Sto'rvatne?and Rettbekken: Moss-Trapped Stream Sediment Material as a Prospecting
Medium.
JGE 5 (3), p. 338-341.
Smith, R.E., (ed.), 1982

Geochemical Weathering in Deeply Weathered Terrain.
CSIRO, Floreat Park, Western Australia, 190 pp.
Smith, R.E., 1989

Using Lateritic Surfaces to Advantage in Mineral Exploration.
in- Third Decennial International Conference on Geophys.cal and Geochemical ^P'oration
Smith, R.E., and Butt, C.R.M., 1982

Sample Preparation.
jn: Geochemical Weathering in Deeply Weathered Terrain,
R.E. Smith, (ed.), CSIRO, p. 23-25.
315
Smith, R.E., and Hallberg, J.A., 1982
Element Associations in Mineral Deposits, Some Host and Background Rocks,
h: Geochemical Weathering in Deeply Weathered Terrain,
R.E. Smith, (ed.), CSIRO, p. 3-8.
Smith, S.C. 1986

Base Metals and Mercury in Bryophytes and Stream Sediments From a Geochemical
Reconnaissance Survey of Chandalar Quadrangle, Alaska.
JGE 25 (3), p. 345-365.
Stallard, R.F., 1988

Weathering and Erosion in the Humid Tropics.
jn: Physical and Chemical Weathering in Geochemical Cycles,
(Proc. NATO Advanced Study Institute, France, Sept. 1985),
A. Lerman and M. Meybeck, (eds.), NATO ASI Series 251, Kluwer Academic Publishers,
p. 225-246.
Stanley, C.R.,1987
PROBPLOT, An Interactive Computer Program to Fit Mixtures of Normal (or Log Normal)
Distributions with Maximum Likelihood Optimization Procedures.
The Association of Exploration Geochemists, Special Vol. 14.
Stoffregen, R., 1986

Observations on the Behavior of Gold During Supergene Oxidation at Summitville,
Colorado, U.S.A., and Implications for Electrum Stability in the Weathering Environment.
Applied Geochemistry, Vol. 1, p. 549-558.
Taylor, C.H., Kesler, S.E., and Cloke, P.L, 1982

Sulfur gases produced by the decomposition of sulfide minerals:
application to geochemical exploration. .
JGE 17 (3), p. 165-185.
Thompson, I.S., 1979 1

Till Prospecting for Sulphide Ores in the Abitibi Clay Belt of Ontario.
Can. Inst. Min. and Metall. Bull. 72 (807), p. 65-72.
Thomson, I., 1987

Getting It Right.
In: Exploration Geochemistry: Design and Interpretation of Soil Surveys, Reviews in
Vol. 3, SEG, p. 1-18.
316
Trost, P.B., and Trautwein, C., 1975
Interpretation of Molybdenum Content in Groundwater Utilizing Eh, pH and Conductivity.
In: Geochemical Exploration 1974, Proceedings of the Fifth International Geochemical
Exploration Symposium, Vancouver,
April 1-4, 1974, I.L. Elliott and W.K. Fletcher, (eds.),
Elsevier Scientific Publishing Company, p. 531-545.
Valiant, R. J., Mongeau, C., and Doucet, R., 1982

The Bousquet Pyritic Gold Deposit, Bousquet Region: Descriptive Geology and
Preliminary Interpretations on Genesis.
Viets, J.G., Clark, J.R., and Campbell, W.L., 1984

A Rapid Partial Leach and Organic Separation for the Sensitive Determination of Ag, Bi,
Cd, Cu, Mo, Pb, Sb, and Zn in Surface Geologic Material by Flameless Atomic
Absorption.
JGE 20 (3), p. 355-366.
Warren, H.V., Delavault, R.E., and Fletcher, K., 1971

The Copper, Zinc and Lead Content of Trout Livers as an Aid in the Search for Favorable
Areas to Prospect.
Jn: Geochemical Exploration, Proceedings of the Third International Geochemical
Exploration Symposium, Toronto April 16-18,1970, R.W. Boyle, (ed.), Canadian Inst. Min.
Watterson, J.R., Nagy, L.A., and Updegraff, D.M., 1986

Penicillin Resistance in Soil Bacteria is an Index of Soil Metal Content Near a Porphyry
Copper Deposit and near a Concealed Massive Sulfide Deposit.
Jn: Mineral Exploration: Biological Systems and Organic Matter, Rubey Vol. V, D. Carlisle,
et al., (eds.), Prentice-Hall, NJ, p. 328-350.
Watterson, J.R., and Theobald, P.K., (eds.), 1979

Geochemical Exploration 1978, Proceedings of the Seventh International Geochemical
Exploration Symposium.
Association Exploration Geochemists, 504 pp.
Webster, J.G., and Mann, A.W., 1984

The Influence of Climate, Geomorphology and Primary Geology on the Supergene
Migration of Gold and Silver.
JGE 22 (1/3), p. 21-42.
317
Webster, S.S., and Skey, E.H., 1979

Geophysical and Geochemical Case History of the Que River Deposit, Tasmania,
Australia. Jn: Geophysics and Geochemistry in the Search for Metallic Ores: Proceedings
of Exploration 77, P.J. Hood, (ed.), Geological Survey of Canada, Economic Geology
Report 31, p. 697-720.
Weiss, A., (ed.), 1979

Computer Methods for the 80's in the Mineral Industry.
Soc. Mining Engineers, New York.
Weiss, D.O., 1971

Airborne Geochemical Prospecting.
]n: Geochemical Exploration, Proceedings of the Third International Geochemical
Exploration Symposium, Toronto April 16-18, 1970, R.W. Boyle, (ed.), Canadian Inst. Min.
Whitney, P.R., 1981

Heavy Metals and Manganese Oxides in the Genessee Watershed: Effects of Geology
and Land Use.
JGE 14 (1), p. 95-117.
Yu, C„ 1981
Mechanisms of Ore Formation and Primary Dispersion at the Dexing Porphyry Copper
Deposit, Jianghzi, and their Implications in Geochemical Exploration.
JGE 15 (1/3), p. 115-137.
Zeegers, H., Al Shanfari, S.M., Muflehi, Y.A.,

and Letalnet, J., 1985
Aspects of Regional Geochemical Prospecting in Desert Conditions.
jn: Prospecting in Areas of Desert Terrain, Inst. Min. Metall. (London), p. 131-140.
Zhang, B., Han, Y., Ma, Z., et al., 1984

Mechanisms of Ore Formation and Primary Dispersion at the Porphyry Molybdenum
Deposits in the Nannihu Metallogenetic Field, Henan.
27th International Geological Congress, Moscow.

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EXPLORATION GEOCHEMISTRY

SHORT COURSE MANUAL

Newmont Exploration Limited

SHORT COURSE MANUAL

Newmont Exploration Limited’

'COPYRIGHT ©Newmont Exploration Limited 1991

LIST OF TABLES........................................................................ XIV

5.1. Geochemical Environment..................................................... 7

7. WEATHERING AND SOIL DEVELOPMENT.................................................. 27

8. PRIMARY GEOCHEMICAL HALOES AND PATTERNS ASSOCIATED WITH

8.4. Sedimentary Exhalitive Deposits............................................. 48

9. SECONDARY GEOCHEMICAL PATTERNS ASSOCIATED WITH MINERAL

10. ROLE OF GEOCHEMISTRY IN THE MINERAL EXPLORATION

10.1 Mineral Exploration Sequence................................................. 60

11. PROGRAM DESIGN AND PLANNING OF GEOCHEMICAL EXPLORATION

12. FIELD SURVEY PROCEDURES............................................................ 89

13. FIELD/LABORATORY LIAISON........................................................ 162

14. LABORATORY PROCEDURES............................................................. 163

14.1. Sample Preparation.......................................................... 163

15. QUALITY CONTROL..........;....................................................... 217

15.1. General..................................................................... 217

16. INTERPRETATION.................................................................... 224

16.1. Definition and General Procedure.......................................... 224

17. FOLLOW-UP.......................................................................... 283

18. REPORT WRITING................................................................... 285

19. LONG TERM STORAGE OF DATA ANDSAMPLES............................. 286

20. CONCLUSIONS AND RECOMMENDATIONS..................................... 287

21. LIST OF REFERENCES.............................................................. 289

FIG 2.1 The stages of exploration geochemistry related to a "House of

FIG 8.8 Distribution of O and Mn in limestone ............................................... 49

FIG 12.21 A diagrammatic depiction of how geochemical dispersal patterns

FIG 14.4 A Heavy-mineral concentration procedure using a shaking table

TABLE 5.1 Geochemical characteristics of selected elements. • • • • ................... 9

TABLE 14.4 Variation of Cr from different lithologies with five digestion

Although geochemistry is being used appropriately within many company

Geochemical Department personnel are always available to assist in the planning

The objective of exploration geochemistry, or geochemical prospecting, is to apply

Although exploration geochemistry involves many of the basic principles of the

Exploration geochemistry is of course only one of a cost effective number of

FIG 2.1 The stages of exploration geochemistry related to a 'House of Cards'.

Levinson (1974) records that modern methods of exploration geochemistry were

The successful application and adaptation of geochemical exploration techniques

Through multi-element analysis, geochemical data can reveal multi-parameter

1966 - Ottawa, Canada (Cameron, 1967)

1973 - Trondheim, Norway (Jones, 1973b)

1984 - Rabat, Morocco (IMM, 1985)

(i) The Canadian Cordillera and Canadian Shield - (Bradshaw, 1975);

(i) Exploration Geochemistry in the Appalachians (Govett, 1976);

Thorough English language treatments of the basic principles of exploration

Anyone involved in exploration geochemistry would be well advised to consider

5.1. Geochemical Environment

Geologically and geochemically the earth constitutes a dynamic system in which

The deep-seated environ­

Geochemists have long recognized systematic behavior amongst certain element

(i) siderophile, affinity for iron, concentrated in the Earth’s core;

In the recent past, modified versions of Goldschmidt’s classification have been

5.2. Characteristic Element Abundances and Associations

In exploration geochemistry the normal element abundance level in an

GEOCHEMICAL CHARACTERISTICS OF THE ELEMENTS

The deep-seated environ