OREAS 23a
OREAS 23a
A.B.N. 28 006 859 856 Enquiries: 61-3-9729 0333 Facsimile: 61-3-9761 7878
Email: [email protected] Web: www.ore.com.au
GRANITE BLANK
OREAS 23a
Prepared by:
Ore Research & Exploration Pty Ltd
March 2011
REPORT 10-885-23a
INTRODUCTION
OREAS geochemical reference materials are intended to provide a low cost method of
evaluating and improving the quality of precious metal analysis of geological samples. To the
analyst they provide an effective means of calibrating analytical equipment, assessing new
techniques and routinely monitoring in-house procedures. To the geologist they provide a
means of implementing quality control in analytical data sets generated in exploration, from
the grass roots level through to prospect evaluation, and in grade control at mining
operations.
SOURCE MATERIALS
OREAS 23a has been prepared from barren I-type hornblende-bearing granodiorite sourced
from the Late Devonian Lysterfield granodiorite complex located in the Melbourne Province of
Australia. It is characterised by very low background gold of less than 4 parts per billion.
The presence of a small oversize fraction is intentional in that it more closely resembles a
typical sample pulp prepared in a laboratory ring mill.
Seven laboratories participated in the analytical program to certify Au, Ag, As, Ba, Bi, Cd, Co,
Cu, Mo, Ni, Pb, Sb, Sn, Th, U, W and Zn. Their results together with uncorrected means,
medians, one sigma standard deviations, relative standard deviations and percent deviation
of lab means from the corrected mean of means (PDM3) are presented in an appendix
(Tables A2 – A18). The analytical methods employed by each laboratory are indicated as
codes at the head of each laboratory data set and explained in Table A1 of the appendix.
Each laboratory has been randomly designated with letter codes A through G in all tables.
For gold, all the laboratories used a lead fire assay collection on 40-50g charges with an ICP-
MS (5 labs), ICP-OES (1 lab) or solvent extraction AAS (1 lab) finish. The results indicate
uniform impoverishment in gold making it an ideal natural blank for monitoring contamination
levels in routine assay work. For the other elements, a four acid (HF-HNO3-HClO4-HCl)
digest was employed with an ICP-OES or ICP-MS finish.
ni
1
xi =
ni
x
j=1
ij
p
1
x =
p
x
i=1
i
where
x ij is the jth result reported by laboratory i;
p is the number of participating laboratories;
ni is the number of results reported by laboratory i;
x i is the mean for laboratory i;
x is the mean of means.
The confidence limits were obtained by calculation of the variance of the consensus value
(mean of means) and reference to Student's-t distribution with degrees of freedom (p-1).
p
Vˆ (x) = 1
p(p-1) (x - x )
i=1
i
2
where t1-x/2(p-1) is the 1-x/2 fractile of the t-distribution with (p-1) degrees of freedom.
The distributions of the values are assumed to be symmetrical about the mean in the
calculation of the confidence limits.
The test for rejection of individual outliers from each laboratory data set was based on z
scores (rejected if zi > 2.5) computed from the robust estimators of location and scale, T
and S, respectively, according to the formulae
xi - T
zi =
S
The z-score test is used in combination with a second method of individual outlier detection
that determines the percent deviation of the individual value from the median. Outliers in
general are selected on the basis of z-scores > 2.5 and with percent deviations > 1.5%. In
certain instances statistician’s prerogative has been employed in discriminating outliers.
Each laboratory data set is tested for outlying status based on z-score discrimination and
rejected if zi > 2.5. After individual and lab data set outliers have been eliminated a non-
iterative 3 standard deviation filter is applied, with those values lying outside this window also
relegated to outlying status.
Individual outliers and, more rarely, laboratory means deemed to be outlying are shown in
bold in the tabulated results (Appendix) and have been omitted in the determination of
certified values. The magnitude of the confidence interval is inversely proportional to the
number of participating laboratories and interlaboratory agreement. It is a measure of the
reliability of the certified value, i.e. the narrower the confidence interval the greater the
certainty in the certified value.
Table 1. Certified values and 95% confidence intervals for OREAS 23a
Constituent Certified 95% Confidence Interval
Value Low High
Gold, Au (ppb) 3 2 4
Silver, Ag (ppm) 0.10 0.08 0.13
Arsenic, As (ppm) 37 35 39
Barium, Ba (ppm) 1092 1028 1156
Bismuth, Bi (ppm) 0.15 0.14 0.16
Cadmium, Cd (ppm) 0.15 0.02 0.29
Cobalt, Co (ppm) 14.8 14.3 15.3
Copper, Cu (ppm) 42.1 41.3 42.9
Molybdenum, Mo (ppm) 9.6 9.1 10.1
Nickel, Ni (ppm) 40.5 39.1 41.9
Lead, Pb (ppm) 21.3 20.3 22.3
Antimony, Sb (ppm) 0.45 0.41 0.48
Tin, Sn (ppm) 3.1 3.0 3.2
Thorium, Th (ppm) 20.9 19.3 22.4
Uranium, U (ppm) 6.2 5.8 6.5
Tungsten, W (ppm) 3.7 3.3 4.2
Zinc, Zn (ppm) 69 66 73
*IND - indeterminate; intervals may appear asymmetric due to rounding
Statement of Homogeneity
The standard deviation of each laboratory data set includes error due to both the imprecision
of the analytical method employed and to possible inhomogeneity of the material analysed.
The standard deviation of the pooled individual analyses of all participating laboratories
includes error due to the imprecision of each analytical method, to possible inhomogeneity of
the material analysed and, in particular, to deficiencies in accuracy of each analytical method.
© Ore Research & Exploration Pty Ltd 3
The calculation of tolerance was not practical for most elements in OREAS 23a due to their
low concentrations and corresponding assay values close to the reading resolution of the
analytical instruments employed. In determining tolerance intervals for Cu, Mo and Ni the
component of error attributable to measurement inaccuracy was eliminated by transformation
of the individual results of each data set to a common mean (the uncorrected grand mean)
according to the formula
p ni
x ij
x ij = x ij - x i + i= 1
p
j= 1
n
i= 1
i
where
The homogeneity of each constituent was determined from tables of factors for two-sided
tolerance limits for normal distributions (ISO 3207) in which
where
The meaning of these tolerance limits may be illustrated for copper, where 99% of the time
at least 95% of subsamples will have concentrations lying between 39.5 and 44.7 ppm
(see Table 2). Put more precisely, this means that if the same number of subsamples were
taken and analysed in the same manner repeatedly, 99% of the tolerance intervals so
constructed would cover at least 95% of the total population, and 1% of the tolerance
intervals would cover less than 95% of the total population (IS0 Guide 35).
The corrected grand standard deviation, sg", used to compute the tolerance intervals is the
weighted means of standard deviations of all data sets for a particular constituent according
to the formula
p
( s (1 - s
si
i ))
s g =
i=1 g
p
(1 - s
si )
i=1 g
The weighting factors were applied to compensate for the considerable variation in
analytical precision amongst participating laboratories. Hence, weighting factors for each
data set have been constructed so as to be inversely proportional to the standard deviation
of that data set. A weighting factor of zero was applied to those data sets where sI / 2sg’ >1
(i.e. where the weighting factor 1- sI / 2sg’ < 0). It should be noted that estimates of
tolerance by this method are considered conservative as a significant proportion of the
observed variance, even in those laboratories exhibiting the best analytical precision, can
presumably be attributed to measurement error. Outliers were removed prior to the
calculation of tolerance intervals and a weighting factor of zero was applied to those data
sets where sI / 2sg’ >1 (i.e. where the weighting factor 1- sI / 2sg’ < 0).
Ag (ppm) 0.10 0.02 0.07 0.14 0.05 0.16 16.83% 33.66% 50.49% 0.10 0.11
Ba (ppm) 1092 62 968 1216 906 1278 5.67% 11.33% 17.00% 1037 1147
Bi (ppm) 0.15 0.04 0.07 0.23 0.03 0.27 27.37% 54.75% 82.12% 0.14 0.16
Cd (ppm) 0.15 0.13 -0.10 0.41 -0.23 0.54 83.12% 166.3% 249.4% 0.15 0.16
Co (ppm) 14.8 0.6 13.7 15.9 13.1 16.5 3.83% 7.65% 11.48% 14.1 15.5
Cu (ppm) 42.1 1.7 38.7 45.5 37.0 47.2 4.03% 8.05% 12.08% 40.0 44.2
Mo (ppm) 9.6 0.7 8.3 10.9 7.6 11.6 6.92% 13.84% 20.75% 9.1 10.1
Ni (ppm) 40.5 1.7 37.1 43.9 35.4 45.6 4.18% 8.35% 12.53% 38.5 42.5
Pb (ppm) 21.3 1.0 19.3 23.3 18.3 24.3 4.71% 9.42% 14.14% 20.2 22.3
Sb (ppm) 0.45 0.04 0.36 0.53 0.32 0.58 9.70% 19.41% 29.11% 0.43 0.47
Sn (ppm) 3.1 0.1 2.9 3.4 2.7 3.5 4.35% 8.69% 13.04% 3.0 3.3
Th (ppm) 20.9 1.7 17.5 24.2 15.8 25.9 8.03% 16.06% 24.09% 19.8 21.9
U (ppm) 6.2 0.4 5.4 7.0 4.9 7.4 6.70% 13.41% 20.11% 5.9 6.5
W (ppm) 3.7 0.7 2.4 5.1 1.7 5.8 18.21% 36.42% 54.63% 3.6 3.9
The granodiorite reference material OREAS 23a has been prepared and certified and is
supplied by:
Ore Research & Exploration Pty Ltd
6-8 Gatwick Road
Bayswater North, VIC 3153
AUSTRALIA
It is available in laminated foil pouches in unit sizes of 10g and 60g and in plastic jars in
0.5kg units.
INTENDED USE
OREAS 23a is a reference material intended for the following:
i) for the calibration of instruments used in the determination of the concentration of Au,
Ag, As, Ba, Bi, Cd, Co, Cu, Mo, Ni, Pb, Sb, Sn, Th, U, W and Zn;
ii) for the verification of analytical methods for Au, Ag, As, Ba, Bi, Cd, Co, Cu, Mo, Ni, Pb,
Sb, Sn, Th, U, W and Zn;
iii) for the preparation of secondary reference materials of similar composition;
Ore Research & Exploration Pty Ltd has prepared and statistically evaluated the property
values of this reference material to the best of its ability. The Purchaser by receipt hereof
releases and indemnifies Ore Research & Exploration Pty Ltd from and against all liability
and costs arising from the use of this material and information.
CERTIFYING OFFICER
REFERENCES
Table A2. Results for Au in OREAS 23a (abbreviations as in Table A1; values in ppb).
Lab Lab Lab Lab Lab Lab Lab
Replicate A B C D E F G
No. FA*MS FA*MS FA*MS FA*MS FA*SXAAS FA*OES FA*MS
50g 40g 50g 50g 50g 40g 50g
1 3 <1 <1 2 4 4 1
2 3 <1 11 2 6 4 1
3 3 <1 2 3 4 4 2
4 3 <1 3 2 4 4 2
5 3 <1 3 3 4 4 2
6 2 <1 3 3 4 5 1
Mean 3 #DIV/0! 4 3 4 4 2
Median 3 #NUM! 3 3 4 4 2
Std.Dev. 0 #DIV/0! 4 1 1 0 1
Rel.Std.Dev. 14.41% #DIV/0! 84.43% 21.91% 18.84% 9.80% 36.51%
3
PDM -5.99% #DIV/0! 45.99% -17.05% 43.78% 38.25% -50.23%
Table A3. Results for Ag in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 0.13 <0.5 <0.1 0.13 <0.1 0.70 <0.1
2 0.13 <0.5 <0.1 0.09 <0.1 0.70 <0.1
3 0.11 <0.5 <0.1 0.11 <0.1 0.60 <0.1
4 0.11 <0.5 <0.1 0.09 <0.1 0.70 <0.1
5 0.10 <0.5 <0.1 0.07 <0.1 0.70 0.10
6 0.11 <0.5 <0.1 0.10 <0.1 0.60 <0.1
Mean 0.12 #DIV/0! #DIV/0! 0.10 #DIV/0! 0.67 0.10
Median 0.11 #NUM! #NUM! 0.10 #NUM! 0.70 0.10
Std.Dev. 0.01 #DIV/0! #DIV/0! 0.02 #DIV/0! 0.05 #DIV/0!
Rel.Std.Dev. 10.65% #DIV/0! #DIV/0! 20.76% #DIV/0! 7.75% #DIV/0!
3
PDM 10.11% #DIV/0! #DIV/0! -5.85% #DIV/0! 538.30% -4.26%
Table A5. Results for Ba in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 >500 1060 1142 1060 1095 1027 1136
2 >500 1050 1155 1040 1089 1039 1100
3 >500 1050 1187 1120 1108 984 1136
4 >500 1020 1185 1090 1110 1009 1104
5 >500 1040 1206 1110 1111 1032 1114
6 >500 1030 1267 1090 1087 1010 1025
Mean #DIV/0! 1042 1190 1085 1100 1017 1103
Median #NUM! 1045 1186 1090 1102 1019 1109
Std.Dev. #DIV/0! 15 44 30 11 20 41
Rel.Std.Dev. #DIV/0! 1.41% 3.71% 2.78% 1.00% 1.96% 3.72%
3
PDM #DIV/0! -4.61% 9.01% -0.64% 0.73% -6.87% 0.96%
Table A6. Results for Bi in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 0.14 0.20 0.10 0.11 0.16 0.20 0.20
2 0.15 0.10 0.10 0.13 0.16 0.20 0.20
3 0.20 0.10 0.20 0.13 0.12 0.20 0.10
4 0.13 0.20 0.20 0.15 0.16 0.20 0.20
5 0.19 0.10 0.50 0.15 0.13 0.20 0.10
6 0.22 0.20 0.10 0.13 0.16 0.20 0.10
Mean 0.17 0.15 0.20 0.13 0.15 0.20 0.15
Median 0.17 0.15 0.15 0.13 0.16 0.20 0.15
Std.Dev. 0.04 0.05 0.15 0.02 0.02 0.00 0.05
Rel.Std.Dev. 21.30% 36.51% 77.46% 11.29% 12.37% 0.00% 36.51%
3
PDM 15.30% 0.75% 34.33% -10.45% -0.37% 34.33% 0.75%
Table A8. Results for Co in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*OES 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 14.5 15.0 15.0 13.5 13.5 14.6 15.0
2 15.5 15.0 14.9 13.7 13.5 14.8 14.5
3 14.5 20.0 16.1 14.3 13.2 14.3 15.2
4 14.8 15.0 15.8 14.6 13.2 14.6 15.2
5 14.5 15.0 15.3 14.7 13.2 14.8 14.8
6 15.2 15.0 15.9 13.7 13.0 14.8 14.1
Mean 14.8 15.8 15.5 14.1 13.3 14.7 14.8
Median 14.7 15.0 15.6 14.0 13.2 14.7 14.9
Std.Dev. 0.4 2.0 0.5 0.5 0.2 0.2 0.4
Rel.Std.Dev. 2.88% 12.89% 3.24% 3.66% 1.48% 1.35% 2.93%
3
PDM 0.22% 6.98% 4.73% -4.85% -10.36% -1.02% 0.00%
Table A9. Results for Cu in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*OES 4A*MS 4A*MS 4A*OES 4A*MS 4A*MS
1 38.9 44.0 44.0 39.6 38.0 41.3 47.6
2 44.5 42.0 45.0 39.1 43.0 41.6 43.0
3 38.4 42.0 46.0 42.1 42.0 37.7 44.0
4 43.3 38.0 44.0 42.8 40.0 38.8 43.4
5 41.1 42.0 45.0 43.4 42.0 38.3 43.2
6 42.3 40.0 48.0 44.0 43.0 39.4 42.4
Mean 41.4 41.3 45.3 41.8 41.3 39.5 43.9
Median 41.7 42.0 45.0 42.5 42.0 39.1 43.3
Std.Dev. 2.4 2.1 1.5 2.0 2.0 1.6 1.9
Rel.Std.Dev. 5.85% 5.00% 3.32% 4.85% 4.76% 4.05% 4.26%
3
PDM -1.60% -1.80% 7.71% -0.61% -1.80% -6.11% 4.38%
Table A11. Results for Ni in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*OES 4A*MS 4A*MS 4A*OES 4A*MS 4A*MS
1 39.8 42.0 44.0 39.1 38.0 41.0 45.5
2 41.7 40.0 44.0 40.6 40.0 44.0 41.8
3 39.1 40.0 46.0 38.1 38.0 43.0 42.4
4 40.6 38.0 47.0 40.4 40.0 41.0 42.7
5 44.8 38.0 44.0 40.8 39.0 44.0 40.8
6 40.9 40.0 47.0 40.1 37.0 41.0 41.3
Mean 41.2 39.7 45.3 39.9 38.7 42.3 42.4
Median 40.8 40.0 45.0 40.3 38.5 42.0 42.1
Std.Dev. 2.0 1.5 1.5 1.0 1.2 1.5 1.7
Rel.Std.Dev. 4.86% 3.80% 3.32% 2.62% 3.13% 3.56% 3.92%
3
PDM 1.57% -2.09% 11.89% -1.64% -4.56% 4.49% 4.70%
Table A12. Results for Pb in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 20.6 22.0 24.0 17.7 22.0 22.8 20.2
2 22.1 22.0 20.0 17.8 21.0 23.2 19.8
3 21.2 21.0 21.0 18.5 22.0 22.2 20.8
4 20.6 21.0 21.0 19.1 22.0 22.8 20.8
5 20.4 21.0 20.0 19.0 22.0 23.6 20.5
6 21.2 21.0 21.0 18.7 22.0 22.3 19.3
Mean 21.0 21.3 21.2 18.5 21.8 22.8 20.2
Median 20.9 21.0 21.0 18.6 22.0 22.8 20.4
Std.Dev. 0.6 0.5 1.5 0.6 0.4 0.5 0.6
Rel.Std.Dev. 2.99% 2.42% 6.95% 3.22% 1.87% 2.33% 2.94%
3
PDM -1.19% 0.30% -0.48% -13.18% 2.65% 7.27% -4.87%
Table A14. Results for Sn in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 3.1 3.0 3.0 2.9 3.1 3.1 3.1
2 3.4 3.0 3.1 2.9 3.3 3.2 3.1
3 3.1 3.0 3.2 3.0 3.1 3.0 3.1
4 3.3 3.0 3.2 3.2 3.1 3.1 3.1
5 3.1 3.0 3.4 3.1 3.3 3.2 3.3
6 3.3 3.0 3.4 3.0 3.3 3.1 2.9
Mean 3.2 3.0 3.2 3.0 3.2 3.1 3.1
Median 3.2 3.0 3.2 3.0 3.2 3.1 3.1
Std.Dev. 0.1 0.0 0.2 0.1 0.1 0.1 0.1
Rel.Std.Dev. 4.13% 0.00% 4.98% 3.88% 3.42% 2.42% 4.08%
3
PDM 2.97% -3.96% 2.97% -3.43% 2.44% -0.23% -0.76%
Table A15. Results for Th in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 21.3 23.0 21.5 17.2 21.9 19.2 21.3
2 24.0 24.3 20.7 17.2 22.2 19.9 21.0
3 21.5 23.6 20.5 18.6 22.2 18.9 20.7
4 22.5 22.8 20.7 17.1 23.0 19.2 20.7
5 22.0 22.5 20.3 19.5 22.4 19.7 20.3
6 22.0 22.8 21.6 18.4 21.3 19.5 21.3
Mean 22.2 23.2 20.9 18.0 22.2 19.4 20.9
Median 22.0 22.9 20.7 17.8 22.2 19.4 20.9
Std.Dev. 1.0 0.7 0.5 1.0 0.6 0.4 0.4
Rel.Std.Dev. 4.37% 2.87% 2.58% 5.48% 2.58% 1.90% 1.88%
3
PDM 6.42% 10.97% 0.03% -13.78% 6.20% -7.07% 0.03%
Table A17. Results for W in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 4.40 2.50 3.50 3.30 4.80 3.60 3.40
2 4.50 2.50 3.70 3.50 3.20 3.40 3.00
3 4.30 3.00 4.30 3.30 3.50 3.50 3.50
4 5.40 3.50 4.40 3.30 5.60 5.00 4.70
5 3.80 3.00 3.50 5.70 4.50 3.80 2.90
6 4.40 3.50 6.00 4.40 4.60 4.20 4.10
Mean 4.47 3.00 4.23 3.92 4.37 3.92 3.60
Median 4.40 3.00 4.00 3.40 4.55 3.70 3.45
Std.Dev. 0.52 0.45 0.95 0.97 0.88 0.60 0.69
Rel.Std.Dev. 11.65% 14.91% 22.44% 24.83% 20.21% 15.35% 19.08%
3
PDM 19.44% -19.78% 13.21% 4.74% 16.77% 4.74% -3.73%
Table A18. Results for Zn in OREAS 23a (abbreviations as in Table A1; values in ppm).
Replicate Lab Lab Lab Lab Lab Lab Lab
No. A B C D E F G
- 4A*OES 4A*MS 4A*MS 4A*MS 4A*MS 4A*MS
1 NR 72.0 79.0 67.0 66.0 82.9 70.0
2 NR 74.0 78.0 67.0 67.0 82.6 69.0
3 NR 70.0 82.0 71.0 69.0 81.2 69.0
4 NR 70.0 81.0 71.0 66.0 81.7 70.0
5 NR 72.0 82.0 73.0 67.0 85.0 67.0
6 NR 72.0 83.0 70.0 66.0 82.1 71.0
Mean #DIV/0! 71.7 80.8 69.8 66.8 82.6 69.3
Median #NUM! 72.0 81.5 70.5 66.5 82.4 69.5
Std.Dev. #DIV/0! 1.5 1.9 2.4 1.2 1.3 1.4
Rel.Std.Dev. #DIV/0! 2.10% 2.40% 3.44% 1.75% 1.61% 1.97%
3
PDM #DIV/0! 3.24% 16.45% 0.60% -3.72% 18.97% -0.12%