310 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No.

2,1995

AGRICULTURAL MATERIALS

Determination of pH of Soils by Different Methods:

Collaborative Study
YASH P. KALRA
Canadian Forest Service, 5320-122 St, Edmonton, AB, T6H 3S5, Canada

Collaborators: H.R Agrawal; E. Allen; J. Ashworth; P. Audesse; V.W. Case; D. Collins; S.M. Combs; C. Dawson; J. Denning;

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S.J. Donohue; B. Douglas; B.G. Drought; M.A. Flock; J.B. Friedericks; G.J. Gascho; Z. Gerstl; L. Hodgins; B. Hopkins; D.
Horneck; R.A. Isaac; P.M. Kelly; J. Konwicki; J. Kovar; G. Kowalenko; G. Lutwick; R.O. Miller; R. Munter; I. Murchison; A.
Neary; R. Neumann; M. Neville; C.B. Nolan; R. Olive; W. Pask; L. Pastorek; T.R. Peck; T. Peel; J. Ramakers; W.S. Reid; V.
Rodd; R. Schultz; R. Simard; R.S. Singh; J. Sorrels; M. Sullivan; S. Tran; D. Trenholm; J. Trush; M.R. Tucker; E. Turcotte; A.
Van Niekerk; P.N. Vijan; J. Villanueva; C. Wang; D.D. Warncke; M.E. Watson; L. Wikoff; P. Yeung

Fifty-three laboratories (including author's) from efore 1990, none of the methods used for soils analyses
Canada, India, Israel, and the United States partici-
pated in a collaborative study for the measurement
of pH of different types of soils. A method with 2 al-
B had been validated by AOAC INTERNATIONAL. In
1990, the Soil Science Society of America (SSSA) and
AOAC INTERNATIONAL decided to conduct collaborative
ternative procedures was used for pH measure- studies of soils methods. The first methods chosen for valida-
ments of mineral soils (alternative I for soils tion were for pH measurements, since pH is one of the most
containing less than 17x organic carbon and alter- important properties of soils.
native II for soils with variable salt content), a sec- The pH of mineral soils is normally determined in a 1:1
ond method was used for saline-sodic soils, and a soil-to-water mixture (1). Schofield and Taylor (2) suggested
third method was used for organic soils (soils con-
the use of CaCl2 solution for mineral soils to minimize interfer-
taining at least 17x organic carbon). The pH was
ences from suspension effects (due to particles suspended in
measured potentiometricaIly. The methods were se-
the soil-solution mixture) and variable salt content. The recom-
lected by the Soil Science Society of America, S889
mendations for management of saline-sodic soils are related to
Committee on Coordination of Official Methods of
Soil Analysis. Each laboratory used all 4 proce- pH values obtained with the saturated paste method (3,4). The
dures to analyze 10 blind duplicate samples per results by the saturated paste methods were obtained during
procedure. The repeatability relative standard de- over 30 years' work by the U.S. Department of Agriculture Sa-
viation values (RSDr) were 1.45-7.80% for mineral linity Laboratory and other research laboratories. For organic
soils tested by the alternative 1,0.95-6.91% for min- soils, a 1:4 soil-to-water mixture is recommended (5).
eral soils tested by the alternative II, 0.74-7.09% for
saline-sodic soils, and 0.73-4.66% for organic Collaborative Study
soils. The corresponding reproducibility relative
standard deviation (RSDR) values were 2.67- Fifty-three laboratories from Canada, India, Israel, and the
10.75%, 2.03-7.54%, 2.45-9.93%, and 2.15-6.32%. United States participated in this collaborative study. To make
Repeatability and reproducibility data indicated that the methods as widely applicable as possible, a broad range of
the results are within acceptable levels. The 3 meth- soils differing in pH, texture, organic matter, and other proper-
ods for pH measurements of mineral, saline-sodic, ties, was selected. Descriptions of soils used in the study are
and organic soils were adopted first action by presented in the Appendix.
AOAC INTERNATIONAL. Copies of the protocol including methods and data sheets
were sent to the participants in September 1992. Eighty heat-
sealed plastic bags containing the appropriate amounts of well-
mixed representative soil samples (20 g for the method used for
Submitted for publication July 12,1994. mineral soils [10 g for each alternative], 50 g for the method for
The recommendation was approved by the Committee on Feeds, saline-sodic soils, and 5 g for the method used for organic soils)
Fertilizers and Agricultural Related Topics, and was adopted by the Official
Methods Board of the Association. See "Official Methods Board Actions" were mailed to each of the participants by Fred Kaisaki from
(1994) J. AOAC Int. 77,203A, and "Official Methods Board Actions" the National Soil Survey Laboratory, U.S. Department of Ag-
(1994) The Referee 18, October issue.
riculture, Lincoln, NE, on October 1,1992.
 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995 311

Table 1. Soils used in the collaborative study for pH measurements'

Sample No. Soil Sample No. Soil Sample No. Soil Sample No. Soil

1-1 Malbis 1-11 Laurentides 1-111 Houston 21-IV Peck 90-9

2-1 Peck 90-9 2-11 Peck 90-11 2-111 Houston 22-IV Peck 90-10
3-1 Peck 90-12 3-11 Houston 3-111 Peck 90-12 23-IV Peck 90-11
4-1 Saline soil 4-11 Peck 90-12 4-111 Halii 24-IV Peck 90-9
5-1 Peck 90-11 5-11 Peck 90-11 5-111 Peck 90-11 25-IV Houghton Oa3
6-1 Halii 6-11 Peck 90-12 6-111 Peck 90-10 26-IV Houghton Oa4
7-1 Peck 90-10 7-11 Myakka 7-111 Myakka 27-IV Peck 90-12
8-1 Myakka 8-11 Malbis 8-111 Peck 90-12 28-IV Houghton Oa3

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9-1 Halii 9-11 Peck 90-10 9-1II Peck 90-11 29-IV Houghton Oa5
10-1 Laurentides 10-11 Halii 10-111 Peck 90-9 30-IV Houghton Oa2
11-1 Peck 90-10 11-11 Peck 90-10 11-111 Saline Soil 31-IV Peck 90-12
12-1 Saline Soil 12-11 Myakka 12-111 Peck 90-10 32-IV Houghton Oa5
13-1 Peck 90-11 13-11 Halii 13-111 Saline soil 33-IV Laurentides LFH
14-1 Peck 90-9 14-11 Peck 90-9 14-111 Laurentides 34-IV Peck 90-11
15-1 Myakka 15-11 Malbis 15-111 Peck 90-9 35-IV Houghton Oa1
16-1 Houston 16-11 Peck 90-9 16-111 Laurentides 36-IV Laurentides LFH
17-1 Malbis 17-11 Saline Soil 17-111 Myakka 37-IV Houghton Oa4
18-1 Laurentides 18-11 Houston 18-111 Halii 38-IV Houghton Oa2
19-1 Peck 90-12 19-11 Laurentides 19-111 Malbis 39-IV Peck 90-10
20-1 Houston 20-11 Saline Soil 20-111 Malbis 40-IV Houghton Oal

a
Roman numbers indicate the method used for the analysis: I = method 994.16—Alternative I; II = method 994.16—Alternative II; III = method
994.17; and IV = method 994.18.

The soil samples conformed to all known regulations of the B. Apparatus

United States concerning biological pest abatement. The soil
(a) pH meter.—Equipped with glass electrodes (indicating
samples did not require special handling or disposal measures,
and reference), or combination electrode.
nor did the participating laboratory need to be licensed or in-
spected to receive, handle, or dispose of these samples. The (b) Automatic pipet.—Capable of accurately delivering
"blind duplicate" design was used. A number was assigned to 10 mL.
each soil sample as follows: duplicate 1 x 2 in. cards containing (c) Stirrer.—Glass rod or portable mechanical stirrer, capa-
numbers from 1 to 20 were placed in a large kraft paper bag ble of stirring at 1550 rpm. Small stirrer motor mounted on
and mixed for 1 min by vigorous shaking. The cards were then handle with short, slightly bent plastic or glass rod agitator is
removed (blind selection) one at a time and samples received acceptable.
the numbers in the order they were removed from the bag. This (d) Glassware.—Paper cups holding 28 g; or glass beak-
procedure was repeated for every set of samples prepared for ers, 50 mL.
each procedure. Numbers assigned to all samples are presented C. Reagents
in Table 1.
(a) H20.—Distilled or deionized.
(b) Standard buffers.—pH 4.00, 7.00, and 10.00. Use
994.16 pH Measurement of Mineral Soils
pH 4.00 and 7.00 for acid soils, and pH 7.00 and 10.00 for al-
kaline soils.
First Action 1994
D. Calibration
Alternative I Calibrate pH meter to appropriate setting using 2 standard
buffers, C(b), depending on type of test sample. If reading of
(Applicable to pH measurement of mineral soils [soils con- second standard buffer is not within 0.05 pH unit after adjust-
taining <17% organic carbon].) ing to first standard buffer, follow manufacturer's instructions.
Method Performance:
E. Preparation of Standard Soils
See Table 994.16A for method performance data.
Use 3 different standard soils (air-dried) of known pH, cov-
A. Principle ering pH range of test samples. Weigh 10 g air-dried soil into
paper cup. {Note: Calibrated volume measurement of soil may
Air-dried soil sample is mixed with H 2 0 (1 + 1). pH is be substituted for weighing.) Add 10 mL H 2 0, C(a), to soil
measured potentiometrically. with automatic pipet. {Note: For fine-textured soils containing
312 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995

Table 994.16A . Method performance for pH measurements of mineral soils using alternative 1
Repeatability Reproducibility
Overall mean of Repeatability Reproducibility relative standard relative standard
laboratory values standard standard Reproducibility deviation (RSDr), deviation
Soil (x) deviation (sr) Repeatability (r) deviation (sR) (R) % (RSDR), %

Malbis 5.62 0.30 0.86 0.40 1.14 5.28 7.20

Peck 90-9 6.13 0.19 0.54 0.23 0.66 3.04 3.69
Peck 90-12 4.88 0.18 0.51 0.28 0.80 3.60 5.73
Saline soil 9.74 0.16 0.46 0.26 0.74 1.67 2.67
Peck 90-11 7.86 0.39 1.11 0.44 1.25 4.92 5.54
Halii 4.55 0.18 0.51 0.29 0.83 3.94 6.35

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Peck 90-10 5.87 0.18 0.51 0.24 0.68 3.14 4.00
Myakka 5.94 0.29 0.83 0.34 0.97 4.80 5.80
Laurentides 4.28 0.33 0.94 0.46 1.31 7.80 10.75
Houston 7.73 0.11 0.31 0.22 0.63 1.45 2.81

high level of organic matter it may be necessary to add addi- G. Determination

tional 10 mL H 2 0 to make suspension.) Mix thoroughly 5 sec
with glass rod or mechanical stirrer. Let soil-H 2 0 suspension Perform pH measurement at 20°-25°C. Before analysis stir
stand for 30 min. Measure pH of each standard as in G. pH test sample from F with glass rod or mechanical stirrer. Insert
values are acceptable within ± 0.1 pH unit of known values. If electrode(s) of calibrated pH meter from D into container and
pH values fall outside this range, recalibrate instrument with swirl soil-H 2 0 suspension slightly. (Note: Position of reference
electrode with respect to glass electrode and flow rate from
standard buffers and check pH of standard soils again. Follow
reference electrode may affect pH determination; follow
manufacturer's instructions for recalibration. Replace elec-
manufacturer's instructions for electrode[s].) Read pH imme-
trodes if they cannot be calibrated within acceptable limits.
diately (after 30-60 s) to the nearest 0.1 pH unit. After remov-
If pH values of all standard soils are >0.1 pH unit lower or ing electrode(s) from soil-H 2 0 suspension rinse them with
higher than known pH of soil, recheck reference electrode. H 2 0; blot off excess H 2 0 with filter paper.
Repeat pH measurements of standard soils just before Follow manufacturer's instructions for storing and main-
analysis of test sample. taining pH electrodes.
F. Preparation of Test Sample
Alternative II
Air dry soil at 20°-40°C for 1-4 days depending on the rela-
tive humidity and soil properties. Grind air-dried soil to pass (Applicable to pH measurement of mineral soils with vari-
2 mm sieve and mix well. Prepare soil sample-H 2 0 suspension able salt content.)
as in E, beginning "Weigh 10 g air-dried soil into paper Method Performance:
cup...". See Table 994.16B for method performance data.

Table 994.16B . Method performance for pH measurements of mineral soils using alternative II
Repeatability Reproducibility
Overall mean of Repeatability Reproducibility relative standard relative standard
laboratory values standard standard Reproducibility deviation (RSDr), deviation
Soil (x) deviation (sr) Repeatability (r) deviation (sR) (R) % (RSDR), %

Malbis 5.09 0.07 0.20 0.13 0.37 1.40 2.47

Peck 90-9 5.53 0.12 0.34 0.17 0.48 2.21 3.13
Peck 90-12 4.39 0.14 0.40 0.20 0.57 3.09 4.51
Saline soil 9.25 0.09 0.26 0.19 0.54 0.95 2.03
Peck 90-11 7.36 0.18 0.51 0.33 0.94 2.41 4.47
Halii 4.34 0.08 0.23 0.18 0.51 1.75 4.16
Peck 90-10 5.40 0.06 0.17 0.13 0.37 1.13 2.41
Myakka 4.31 0.04 0.11 0.12 0.34 0.99 2.86
Laurentides 3.69 0.25 0.71 0.28 0.80 6.91 7.54
Houston 7.48 0.15 0.43 0.16 0.46 2.02 2.17
 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995 313

H. Principle M. Preparation of Test Sample

Salt content in soil influences ionic activity, which affects Air dry soil at 20°-40°C for 1-4 days, depending on relative
pH value of soil-water suspension. H+ anions are displaced by humidity and soil properties. Grind air-dried soil to pass 2 mm
cations. Exchangeable Al is displaced, which increases con- sieve and mix well. Prepare soil sample-CaCl2 suspension as
centration of H+ in solution. pH is decreased by ca 0.5 pH unit in L, beginning "Weigh 10 g air-dried soil into paper cup...."
if CaCl2 is used instead of H 2 0. N. Determination
/. Apparatus Proceed as in G.
Same as in B.
Ref.: J. AOAC Int. 78,310 (1995).
J. Reagents

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994.17 pH Measurement of Saline-Sodic Soils
See C(aHb).
(c) CaCl2 solution.—0.01M. Dissolve 14.7 g CaCl2 2H 2 0 First Action 1994
in 10 L H 2 0. pH of solution should be 5.0-6.5. If required, (Applicable to pH measurement of saline-sodic soils [i.e.,
adjust pH with Ca(OH)2 or HC1. Specific conductivity should containing large amounts of soluble salts and sufficient ex-
be 2.32 ± 0.08 mS/cm at 25°C. changeable sodium to interfere with growth of most crop
K. Calibration plants].)
Method Performance:
Perform as in D. See Table 994.17 for method performance data.
L. Preparation of Standard Soils A. Principle

Use 3 different standard soils (air-dried) of known pH, cov- H 2 0 is added to air-dried soil until saturated paste is ob-
ering pH range of test samples. Weigh 10 g air-dried soil into tained and then pH is measured. For determination of sodium
paper cup. {Note: Calibrated volume measurement of soil may adsorption ratio, salt analysis is performed on saturation extract
be substituted for weighing.) Add 10 mLO.OlM CaCl2, J(c), to from paste.
soil with automatic pipet. {Note: For fine-textured soils con- B. Apparatus
taining high level of organic matter it may be necessary to add
additional 10 mL 0.01M CaCl2 to make suspension.) Mix thor- (a) pH meter.—Equipped with glass electrodes (indicating
oughly 5 s with glass rod or mechanical stirrer. Let soil-CaCl2 and reference), or combination electrode.
suspension stand for 30 min. Measure pH of each standard as (b) Glassware.—Paper cups holding 25-250 g; or glass
in G. pH values are acceptable within ± 0.1 pH unit of known beakers, 50-400 mL.
values. If pH values fall outside this range, recalibrate instru- (c) Spatula.
ment and check pH of standard soils again. Follow manufac-
turer's instructions for recalibration. Replace electrodes if they C Reagents
cannot be calibrated within acceptable limits. (a) H20.—Distilled or deionized.
If pH values of all standard soils are 0.1 pH unit lower or (b) Standard buffers.—pH 4.00, 7.00, and 10.00. Use pH
higher than known pH of soil, recheck reference electrode. 4.00 and 7.00 for acid soils, and pH 7.00 and 10.00 for alkaline
Repeat pH measurements just before analysis of test sample. soils.

Table 994.17. Method performance for pH measurements in soil paste

Repeatability Reproducibility
Overall mean of Repeatability Reproducibility relative standard relative standard
laboratory values standard standard Reproducibility deviation (RSDr), deviation
Soil type (x) deviation (sr) Repeatability (r) deviation (sR) (R) % (RSDR), %

Malbis 5.47 0.05 0.14 0.18 0.51 1.00 3.27

Peck 90-9 5.99 0.22 0.63 0.25 0.71 3.59 4.14
Peck 90-12 4.82 0.21 0.60 0.28 0.80 4.43 5.78
Saline soil 9.48 0.07 0.20 0.26 0.74 0.74 2.76
Peck 90-11 7.64 0.12 0.34 0.22 0.63 1.58 2.94
Halii 4.35 0.09 0.26 0.17 0.48 2.02 3.95
Peck 90-10 5.83 0.17 0.48 0.22 0.63 2.84 3.82
Myakka 5.42 0.10 0.29 0.17 0.48 1.80 3.22
Laurentides 4.18 0.30 0.86 0.42 1.20 7.09 9.93
Houston 7.51 0.11 0.31 0.18 0.51 1.46 2.45
314 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995

D. Calibration Repeat pH measurements of standard soils just before

analysis of test sample.
Calibrate pH meter to appropriate setting using 2 standard
buffers, C(b), depending on type of test sample. If reading of F Preparation of Test Sample
second standard buffer is not within 0.05 pH unit after adjust- Air dry soil at 20CM0°C for 1-4 days, depending on relative
ing to first standard buffer, follow manufacturer's instructions humidity and soil properties. Grind air-dried soil to pass 2 mm
for recalibration. sieve and mix well. Prepare soil paste as in E, beginning
"Weigh 50-250 air-dried soil...."
E. Preparation of Standard Soils
G. Determination
Use 3 different standard soils (air-dried) of known pH, cov-
ering pH range of test samples. Weigh 50-250 g air-dried soil Perform pH measurement at 20°-25°C. Insert electrode(s)

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into paper cup or glass beaker. (Note: Use smaller amounts of of standardized pH meter from D almost to the bottom of con-
soil for pH measurement only; use larger amounts to obtain tainer containing soil paste. Gently rotate container to remove
sufficient volume of saturation extract for other measure- air bubbles and provide good contact between electrode(s) and
ments.) Wet soil with H 2 0, C(a), while stirring with spatula. soil paste. Remove hands from container while measuring pH
(Note: Calibrated volume of soils may be substituted for of soil paste.
weighing. Alternatively, add sufficient amount of soil to known Read pH immediately (after 30-60 s) to the nearest 0.1 pH
volume of H 2 0 to obtain saturated paste. Moisture content in unit. After removing electrode(s) from soil paste, rinse them
soil may vary [25-100%] depending on soil texture, clay min- with H 2 0; blot off excess H 2 0 with filter paper.
eralogy, and content of organic matter.) Follow manufacturer's instructions for storing and main-
taining pH electrodes.
Tap container gently against workbench to settle soil paste.
Ref.: J. AOAC Int. 78, 310 (1995).
At saturation, surface of paste should glisten but no supernatant
H 2 0 should be present. (Note: Saturated soil paste also slides
freely and cleanly from spatula when blade is turned vertically. 994.18 pH Measurement of Organic Soils
At saturation, soil will slowly flow together after it has been
parted by spatula.) Add more H 2 0 if needed to obtain saturated First Action 1994
paste. If excess H 2 0 is present, add small amount of soil, stir,
and tap container again. Add H 2 0 or soil until proper moisture (Applicable to pH measurement of organic soils [soils con-
content is obtained. taining >17% organic carbon].)
Cover container with watch glass and let stand for 1-4 h. Method Performance:
After 60 min some high clay soils may require addition of more See Table 994.18 for method performance data.
H 2 0, as interstitial spaces in some clays become saturated with A. Principle
H 2 0. After further saturation let soil paste stand longer.
Measure pH of each standard as in G. pH values are accept- Dried soil sample is mixed with H 2 0 (1 + 4). pH is meas-
able within ±0.1 pH unit of known values. If pH values fall ured potentiometrically.
outside this range, recalibrate instrument and check pH of
B. Apparatus
standard soils again. Follow manufacturer's instructions for re-
calibration. Replace electrodes if they cannot be calibrated (a) pH meter.—Equipped with glass electrodes (indicating
within acceptable limits. and reference), or combination electrode.

Table 994.18. Method performance for pH measurements of organic soils

Repeatability Reproducibility
Overall mean of Repeatability Reproducibility relative standard relative standard
laboratory values standard standard Reproducibility deviation (RSDr), deviation
Soil (x) deviation (sr) Repeatability (r) deviation (sR) (R) % (RSDR), %

Houghton Oa3 7.43 0.05 0.14 0.06 0.17 0.73 3.16

Peck 90-9 6.24 0.22 0.63 0.30 0.86 3.57 4.74
Peck 90-12 5.08 0.24 0.68 0.32 0.91 4.66 6.32
Houghton Oa4 7.07 0.06 0.17 0.18 0.51 0.87 2.51
Peck 90-11 7.96 0.21 0.60 0.38 1.08 2.62 4.82
Houghton Oa5 6.85 0.17 0.48 0.23 0.66 2.50 3.43
Peck 90-10 6.07 0.18 0.51 0.27 0.77 2.94 4.49
Houghton Oa2 7.73 0.26 0.74 0.34 0.97 3.32 4.36
Laurentides LFH 6.62 0.10 0.29 0.15 0.43 1.55 2.33
Houghton Oa1 7.37 0.06 0.17 0.16 0.46 0.77 2.15
 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995 315

(b) Automatic pipet.—Capable of accurately delivering Read pH immediately (after 30-60 s) to the nearest 0.1 pH
20 mL. unit. After removing electrode(s) from soil-H 2 0 suspension
(c) Stirrer.—Glass rod or portable mechanical stirrer, capa- rinse them with H 2 0; blot off excess H 2 0 with filter paper.
ble of stirring at 1550 rpm. Small stirrer motor mounted on Follow manufacturer's instructions for storing and main-
handle with short, slightly bent plastic or glass rod agitator is taining pH electrodes.
acceptable. Ref.: J. AOAC Int. 78, 310 (1995).
(d) Glassware.—Paper cups holding 28 g; or glass beak-
ers, 50 mL. Results and Discussion
C. Reagents
The results of analyses were received from 53 collaborators
(a) H2O.—Distilled or deionized. by February 5, 1993, and are presented in Tables 2-5. Results

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(b) Standard buffers.—pH 4.00, 7.00, and 10.00. Use pH were analyzed using statistics software and worksheets devel-
4.00 and 7.00 for acid soils, and pH 7.00 and 10.00 for alkaline oped by the Statistics Committee, AOAC INTERNATIONAL
soils. (6-8). Results of statistical analyses are presented in Tables
994.16A-B, 994.17, and 994.18.
D. Calibration
All 53 participants provided results obtained by the meth-
Calibrate pH meter to appropriate setting using 2 standard ods for mineral and organic soils, while 51 laboratories pro-
buffers, C(b), depending on type of test sample. If reading of vided data from the method for saline-sodic soils. In general,
second standard buffer is not within 0.05 pH unit after adjust- the more diluted the soil suspension, the higher pH of the soil.
ing to first standard buffer, follow manufacturer's instructions. The alternative I for mineral soils and the method for saline-so-
dic soils use a mixture of soil and water. In alternative I for
E. Preparation of Standard Soils
mineral soils the amount of water is fixed (100%). However,
Use 3 different air-dried standard organic soils of known for saline-sodic soils the amount of water needed to prepare a
pH, covering pH range of test samples. Weigh 5 g air-dried soil saturated paste depends on soil properties such as texture and
into paper cup. (Note: Calibrated volume measurement of soil organic matter. For soils that require 100% water for saturated
may be substituted for weighing.) Add 20 mL H 2 0, C(a), to paste, the pH will be the same as when using alternative I for
soil with automatic pipet. Mix thoroughly 5 sec with glass rod mineral soils; it will be lower if less water is needed. Halii soil
or mechanical stirrer. Let soil-H 2 0 suspension stand for uses less water to make a paste (method for saline-sodic soils)
30 min. Measure pH of each standard as in G. pH values are than in the alternative I for mineral soils; therefore, the pH
acceptable within ± 0.1 pH unit of known values. If pH values would be lower by 0.2 unit. For Mykka soil, the pH differences
fall outside this range, recalibrate instrument and check pH of are large because this type of soil is a fine sand and, therefore,
standard soils again. Follow manufacturer's instructions for re- much less water is required to prepare a paste.
calibration. Replace electrodes if they cannot be calibrated All valid data were included in the statistical analyses. The
within acceptable limits. tests used for determination of outliers were: (1) Cochran test
If pH values of all standard soils are >0.1 pH unit lower or for removal of laboratories showing significantly greater
higher than known pH of soil, recheck reference electrode. within-laboratory variability than the other laboratories, and
Repeat pH measurements of standard soils just before (2) Grubbs (Single and Double Grubbs) test for removal of
analysis of test sample. laboratories with extreme values. The repeatability relative
standard deviation (RSDr) values were 1.45-7.80% by the al-
F. Preparation of Test Sample ternative I of the method for mineral soils, 0.95-6.91% by the
Pass dried soils (at 30°C) through 2 mm sieve and mix well. alternative II of the method for mineral soils, 0.74-7.09% from
(Note: Many organic soils become hydrophobic when they are the method for saline-sodic soils, and 0.73-4.66% from the
dried and may require longer time to wet.) Weigh 5 g dried soil method for organic soils. The corresponding reproducibility
sample into paper cup. (Note: Calibrated volume measurement relative standard deviation (RSDR) values were 2.67-10.75%,
of soil may be substituted for weighing.) Add 20 mL H 2 0, 2.03-7.54%, 2.45-9.93%, and 2.15-6.32%. There were out-
C(a), to soil with automatic pipet. Mix thoroughly 5 sec with liers indicated but repeatability and reproducibility standard
portable mechanical stirrer. Let soil-H 2 0 suspension stand for deviations show that these values are well within acceptable
30 min before pH measurements. limits for pH measurement in soil (9). Therefore, no laborato-
ries were deleted from statistical analysis. It is interesting to
G. Determination note that one sample (Laurentides) gave the highest RSDr and
Perform pH measurement at 20°-25°C. Before analysis stir RSDR values by the methods for mineral and saline-sodic soils;
test sample from F with glass rod or mechanical stirrer. Insert this sample was not analyzed by the method for organic soils.
electrode(s) of calibrated pH meter from D into container and
swirl soil-H 2 0 suspension slightly. (Note: Position of reference Collaborators' Comments
electrode with respect to glass electrode and flow rate from
reference electrode may affect pH determination; follow The participants were asked to indicate any questions, prob-
manufacturer's instructions for placement of electrode[s].) lems, and suggestions regarding their work with these methods.
316 KALRA: JOURNAL O F AOAC INTERNATIONAL VOL. 78, No. 2,1995

Table 2. Collaborative study results for pH measurements of mineral soils using alternative I
Sample
Lab. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

1 5.90 6.35 5.13 9.61 8.04 4.50 6.12 6.08 4.51 4.37 6.13 9.62 8.08 6.49 6.10 7.83 5.95 4.38 5.15 7.83
2 5.48 6.01 4.82 9.77 7.98 4.43 6.14 5.90 4.48 4.25 5.84 9.77 7.88 6.11 5.91 7.71 5.69 4.28 4.85 7.65
3 5.50 6.10 4.80 9.65 7.80 4.20 5.90 5.80 4.20 4.05 5.80 9.60 7.85 6.00 5.80 7.80 5.50 4.05 4.80 7.70
4 5.45 6.04 4.84 9.97 7.93 4.38 5.90 5.91 4.33 4.26 5.85 9.99 7.87 6.04 5.85 7.91 5.52 4.30 4.87 8.04
5 5.37 6.19 5.13 9.33 7.52 4.76 5.92 5.67 4.44 4.20 5.89 9.44 7.73 6.19 5.70 7.68 5.59 4.24 4.87 7.42
6 5.18 5.80 4.59 9.67 7.85 4.38 5.74 5.75 4.30 4.03 5.70 9.65 7.89 6.10 5.75 7.65 5.57 4.06 4.68 7.58
7 5.46 6.13 4.88 9.70 7.95 4.38 5.95 5.86 4.38 4.16 5.93 9.65 7.97 6.14 5.85 7.82 5.53 4.17 4.91 7.82

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8 5.64 6.21 4.98 9.89 8.06 4.62 6.08 6.07 4.52 4.22 5.85 9.80 8.08 6.47 6.19 7.86 5.84 4.28 4.95 7.91
9 5.30 5.70 4.50 9.90 7.80 4.20 5.70 5.50 4.30 4.60 5.80 10.00 8.40 6.00 5.60 7.70 5.20 3.90 4.50 7.60
10 5.86 6.12 4.91 9.54 7.91 4.98 5.93 5.93 4.58 4.24 5.85 9.50 7.87 6.12 5.82 7.65 6.14 4.42 5.03 7.57
11 4.92 5.65 4.42 9.67 7.78 4.66 5.57 5.77 4.05 3.82 5.32 9.65 7.51 6.73 6.75 7.25 5.46 3.93 4.36 6.97
12 5.40 5.89 4.80 9.89 7.94 4.22 5.83 5.70 4.34 4.04 5.92 9.84 8.00 6.12 5.79 8.06 5.49 4.17 4.89 7.80
13 6.29 6.51 5.48 9.36 7.80 5.48 6.54 6.27 4.86 4.49 5.99 9.05 7.95 6.29 5.02 7.60 6.54 4.78 5.06 7.63
14 5.65 6.24 5.04 9.79 8.05 4.54 6.04 6.05 4.49 4.39 5.99 9.77 8.03 6.31 6.07 7.82 5.73 4.42 5.01 7.76
15 5.45 6.05 6.05 10.15 8.15 4.55 5.85 6.25 4.65 5.09 6.14 11.69 9.31 6.35 7.03 7.96 7.10 4.61 5.61 7.67
16 5.55 6.05 4.84 9.76 7.70 4.44 5.82 5.98 4.40 4.25 5.81 9.86 7.90 6.12 6.09 7.77 5.82 4.39 4.88 7.76
17 5.42 6.81 4.78 9.73 7.76 5.14 6.11 5.83 4.23 6.10 5.81 9.90 7.85 5.92 7.27 7.30 5.33 4.15 4.91 7.51
18 5.46 6.10 4.73 9.47 7.85 4.32 5.90 5.78 4.30 4.11 5.91 9.56 7.76 6.13 5.81 7.58 5.57 4.16 4.80 7.51
19 4.95 5.68 4.37 9.85 4.13 4.12 5.54 5.33 3.78 3.75 5.66 9.95 7.70 5.75 5.66 7.56 5.18 3.81 4.55 7.21
20 5.51 6.12 4.84 9.67 8.07 4.45 6.16 6.07 4.54 4.40 6.11 9.75 8.10 6.42 6.20 8.04 5.89 4.60 5.28 8.09
21 5.40 6.01 4.70 10.23 7.84 4.75 5.75 5.78 4.25 4.06 5.74 9.95 7.75 6.60 6.90 7.69 7.45 4.27 4.68 7.14
22 5.40 6.00 4.80 9.74 7.82 4.40 5.80 5.70 4.40 4.06 5.83 9.76 7.86 6.06 5.70 7.91 5.40 4.06 4.78 8.01
23 5.78 6.30 5.03 9.88 8.18 4.46 6.10 6.05 4.48 4.30 6.00 9.89 8.00 6.23 6.33 8.05 5.70 4.33 4.94 7.75
24 5.11 5.74 4.32 9.57 7.52 4.21 5.39 5.08 4.24 3.65 5.44 9.63 7.60 5.86 5.45 7.57 5.58 3.79 4.50 7.53
25 5.47 5.97 4.73 9.72 7.84 4.31 5.83 5.76 4.32 4.15 5.88 9.65 7.85 6.02 5.78 7.85 5.51 4.18 4.77 7.88
26 5.59 5.96 5.03 9.62 7.95 4.55 5.74 6.25 4.47 4.19 5.65 9.53 8.00 5.92 5.62 7.99 5.46 4.10 4.79 7.90
27 5.46 6.11 4.91 9.66 7.84 4.57 5.95 5.88 4.39 4.21 5.96 9.76 7.90 6.13 5.96 7.67 5.51 4.24 4.88 7.70
28 6.25 6.45 5.20 9.55 7.90 4.65 6.15 6.20 4.65 4.60 6.10 9.65 7.95 6.45 6.15 7.85 5.80 4.50 5.50 7.85
29 5.25 5.85 4.66 9.91 7.78 4.44 5.75 5.62 4.37 4.02 5.67 9.89 7.82 5.85 5.80 7.86 5.30 4.01 4.65 7.86
30 5.45 6.05 4.81 9.79 7.97 4.82 5.91 5.94 4.79 4.16 5.90 9.78 7.98 6.07 5.92 7.82 5.48 4.16 4.84 7.89
31 5.46 5.98 4.81 9.69 7.88 4.63 5.95 6.00 4.41 4.24 5.88 9.66 7.87 6.17 6.08 7.69 6.00 4.29 4.84 7.60
32 5.42 6.02 4.78 9.71 7.95 4.74 5.84 5.81 4.72 4.10 5.86 9.68 7.95 6.06 5.81 7.77 5.40 4.06 4.79 7.74
33 5.45 5.96 4.69 9.52 7.75 4.36 4.33 5.77 4.27 4.12 5.75 9.54 7.80 6.00 5.80 7.68 5.50 4.15 4.61 7.65
34 5.44 6.02 4.78 9.60 7.99 5.25 5.82 6.54 4.69 4.32 5.73 9.57 7.83 6.17 6.57 7.62 5.63 4.55 4.94 7.91
35 5.52 6.07 4.90 9.69 8.05 4.42 5.93 5.90 4.41 4.21 5.88 9.67 8.03 6.12 5.91 7.91 5.52 4.22 4.86 7.91
36 5.54 6.02 6.25 9.92 7.99 5.05 5.99 6.00 4.90 4.12 4.87 9.91 7.94 6.28 6.06 7.80 5.70 4.15 4.80 7.61
37 5.42 6.11 4.82 9.65 7.97 4.69 6.10 5.78 4.62 4.06 5.97 9.75 7.94 6.13 5.81 7.74 5.51 4.09 4.90 7.77
38 5.50 6.10 4.90 9.70 7.90 4.80 5.90 5.90 4.80 4.20 5.90 9.70 7.90 6.10 5.90 7.90 5.50 4.20 4.90 7.90
39 5.63 6.14 4.94 9.76 8.02 4.39 5.91 6.01 4.40 4.22 5.94 9.69 7.93 6.05 5.97 7.83 5.56 4.22 4.84 7.90
40 5.40 6.06 4.83 9.60 7.89 4.51 5.90 5.71 4.36 4.06 5.87 9.68 7.95 5.98 5.69 7.84 5.46 4.06 4.78 7.88
41 5.16 5.96 4.73 9.68 7.88 4.73 5.79 5.55 4.69 3.91 5.78 9.66 7.86 5.97 5.50 7.73 5.19 3.95 4.75 7.72
42 5.58 6.07 4.82 9.93 8.01 4.42 5.84 5.97 4.33 4.17 5.77 9.78 7.96 6.20 5.97 7.76 5.78 4.28 4.80 7.78
43 5.50 6.10 4.90 10.00 8.00 4.70 5.90 5.80 4.70 4.10 5.90 10.00 8.00 6.00 5.80 8.00 5.50 4.10 4.80 8.00
44 5.45 5.96 4.81 9.72 7.92 4.39 5.83 5.95 4.29 4.19 5.81 9.74 7.85 6.11 6.07 7.79 5.52 4.15 4.75 7.76
45 7.08 6.60 5.18 10.14 7.44 5.73 6.13 6.20 5.18 4.63 5.42 9.97 6.90 6.98 6.96 7.13 7.07 4.90 5.11 6.83
46 5.57 6.55 4.87 9.72 7.38 4.78 5.95 6.34 7.80 4.14 5.88 9.67 7.91 6.06 5.56 7.74 5.44 4.19 4.84 7.73
47 5.59 6.22 5.05 9.79 8.07 4.55 6.08 5.82 4.44 4.25 5.95 9.69 8.08 6.45 6.11 7.78 5.76 4.36 4.98 7.91
48 5.55 6.09 4.90 9.66 7.98 4.50 5.96 5.95 4.44 4.22 5.89 9.66 7.99 6.22 6.02 7.84 5.99 4.41 4.99 7.76
49 5.51 6.04 4.80 9.60 7.91 4.80 5.92 5.72 4.78 4.01 5.82 9.61 7.87 6.19 5.70 7.67 5.62 4.10 4.84 7.68
50 5.22 5.81 4.60 9.64 7.70 4.68 5.68 5.60 4.67 4.00 5.68 9.65 7.76 5.91 5.65 7.80 5.33 4.04 4.66 7.80
51 5.70 6.22 5.03 9.63 8.04 4.51 6.05 6.09 4.50 4.81 6.04 9.65 8.01 6.29 6.16 7.92 5.77 4.90 5.11 7.81
52 5.62 6.17 4.98 9.69 7.96 4.42 5.98 5.90 4.43 4.22 5.95 9.66 7.98 6.15 5.91 7.74 5.61 4.25 4.96 7.76
53 5.83 6.17 4.90 9.32 7.19 5.26 5.93 6.29 4.70 5.13 6.38 9.50 7.90 6.42 6.36 7.74 6.29 7.73 4.86 7.40
 KALRA: JOURNAL O F AOAC INTERNATIONAL VOL. 78, No. 2,1995 317

Table 3. Collaborative study results for pH measurements of mineral soils using alternative II
Sample

Lab. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

1 3.76 7.49 7.47 4.49 7.48 4.53 4.36 5.32 5.64 4.48 5.64 4.44 4.44 5.77 5.33 5.80 9.08 7.56 3.75 9.10
2 3.59 7.41 7.50 4.41 7.45 4.30 4.28 5.07 5.44 4.52 5.40 4.28 4.20 5.46 5.10 5.52 9.35 7.48 3.64 9.35
3 3.50 7.60 7.60 4.25 7.60 4.25 4.25 5.15 5.45 4.20 5.45 4.25 4.20 5.60 5.15 5.60 9.35 7.60 3.50 9.35
4 3.61 7.44 7.42 4.34 7.45 4.32 4.37 5.03 5.29 4.24 5.36 4.35 4.25 5.51 5.06 5.51 9.53 7.44 3.59 9.46
5 3.73 7.13 7.25 4.85 7.33 4.43 4.35 4.91 5.35 4.44 5.40 4.37 4.22 5.48 5.01 5.58 8.76 7.28 3.93 8.74
6 3.38 7.26 7.41 4.49 7.25 4.29 4.26 5.05 5.35 4.22 5.38 4.32 4.26 5.51 5.13 5.54 9.09 7.56 3.70 9.05
7 3.62 7.58 7.55 4.33 7.56 4.33 4.28 5.09 5.41 4.30 5.43 4.28 4.27 5.57 5.13 5.58 9.26 7.53 3.68 9.24

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8 3.58 7.33 7.37 4.34 7.34 4.28 4.31 4.98 5.26 4.22 5.36 4.32 4.28 5.36 4.99 5.36 9.29 7.53 3.52 9.27
9 3.50 7.40 7.50 4.30 7.10 4.20 3.80 4.80 5.10 4.00 5.40 3.80 3.80 5.20 4.80 5.30 7.00 7.40 3.60 9.71
10 3.73 7.28 7.39 4.83 7.39 4.42 4.34 5.11 5.40 4.39 5.44 4.33 4.34 5.60 5.20 5.69 9.09 7.47 3.78 9.03
11 3.66 6.82 7.22 4.39 6.70 4.41 4.43 5.02 5.36 4.34 5.38 4.32 4.23 5.48 5.10 5.48 8.61 7.67 3.69 9.24
12 3.34 7.15 7.36 4.15 7.41 4.16 4.18 4.84 4.99 3.93 5.09 4.20 3.97 5.26 4.89 5.40 9.44 7.43 3.65 9.43
13 3.59 7.35 7.49 4.52 7.42 4.35 4.24 4.91 5.49 4.72 5.44 4.26 4.26 5.49 5.12 5.53 9.14 7.45 3.96 9.19
14 3.78 7.62 7.59 4.46 7.71 4.42 4.42 5.26 5.60 4.40 5.54 4.46 4.49 5.67 5.26 5.68 9.41 7.64 3.78 9.42
15 4.66 7.59 7.88 4.74 7.78 4.50 4.55 5.20 5.62 4.37 5.64 4.63 4.70 6.05 5.47 5.74 9.47 7.70 3.70 9.39
16 3.98 7.49 7.60 4.63 7.57 4.60 4.59 5.32 5.59 4.56 5.59 4.57 4.51 5.71 5.34 5.74 9.32 7.66 4.08 9.37
17 3.34 6.92 7.09 4.59 6.98 4.31 4.17 4.95 5.31 4.18 5.29 4.17 4.16 5.42 4.99 5.44 9.29 7.82 3.87 9.14
18 3.55 7.34 7.42 4.36 7.44 4.38 4.29 5.10 5.46 4.27 5.46 4.18 4.25 5.66 5.12 5.70 9.28 7.46 3.57 9.32
19 3.45 7.11 7.42 4.32 6.95 4.31 4.26 5.05 5.44 4.21 5.41 4.26 4.21 5.55 5.11 5.58 9.36 7.61 3.56 9.25
20 3.69 7.23 7.34 4.46 7.33 4.46 4.44 5.27 5.52 4.47 5.51 4.47 4.44 5.72 5.40 5.75 8.93 7.50 3.97 8.93
21 3.59 7.53 7.60 4.59 7.50 4.50 4.35 4.99 5.50 4.29 5.25 4.39 4.29 5.59 5.20 5.60 9.45 7.53 3.73 9.20
22 3.49 7.51 7.53 4.35 7.57 4.26 4.23 5.09 5.39 4.31 5.40 4.25 4.23 5.56 5.04 5.56 9.40 7.55 3.48 9.42
23 3.66 7.50 7.57 4.46 7.40 4.50 4.42 5.22 5.54 4.37 5.53 4.45 4.46 5.70 5.35 5.75 9.49 7.65 3.93 9.53
24 3.24 7.33 7.35 4.22 7.33 4.18 4.13 4.90 5.10 4.20 4.93 4.30 4.19 5.22 4.90 5.28 9.32 7.23 3.56 8.91
25 3.66 7.45 7.48 4.27 7.46 4.25 4.25 5.09 5.35 4.23 5.36 4.25 4.24 5.51 5.08 5.50 9.20 7.47 3.65 9.24
26 3.67 6.74 6.96 4.46 6.80 4.27 4.28 5.06 5.33 4.40 5.55 4.53 4.42 5.65 5.18 5.59 9.28 7.62 3.68 9.09
27 3.54 7.35 7.31 4.30 7.36 4.26 4.36 5.06 5.38 4.25 5.40 4.38 4.27 5.49 5.11 5.58 9.16 7.34 3.66 9.22
28 3.65 7.20 7.15 4.25 7.20 4.30 4.30 5.05 5.30 5.00 5.55 4.25 5.00 5.50 5.05 5.50 8.80 7.20 3.75 8.70
29 3.63 7.49 7.46 4.31 7.42 4.23 4.26 5.09 5.33 4.25 5.34 4.29 4.24 5.50 5.06 5.51 9.52 7.51 3.73 9.47
30 3.61 7.57 7.61 4.41 7.57 4.34 4.36 5.19 5.46 4.58 5.45 4.37 4.58 5.62 5.13 5.61 9.44 7.65 3.74 9.46
31 3.58 7.31 7.46 4.35 7.37 4.31 4.30 5.13 5.39 4.30 5.39 4.31 4.33 5.56 5.14 5.59 9.25 7.47 3.71 9.29
32 3.58 7.58 7.53 4.30 7.57 4.27 4.24 5.06 5.38 4.50 5.38 4.24 4.47 5.52 5.04 5.51 9.31 7.53 3.55 9.31
33 3.51 7.47 7.44 4.53 7.48 4.26 4.27 5.07 5.38 4.25 5.42 4.30 4.22 5.52 5.08 5.54 9.26 7.45 3.95 9.28
34 3.56 7.26 7.32 4.38 7.26 4.24 4.29 5.02 5.26 4.21 5.26 4.36 4.24 5.45 5.07 5.43 9.14 7.49 4.69 9.10
35 3.62 7.48 7.48 4.29 7.52 4.33 4.30 5.12 5.43 4.29 5.41 4.29 4.29 5.55 5.16 5.59 9.22 7.57 3.64 9.24
36 3.82 7.41 7.47 4.58 7.45 4.53 4.39 5.08 5.37 4.63 5.36 4.40 4.55 5.53 5.11 5.84 9.29 7.56 3.75 9.29
37 3.51 7.45 7.47 4.23 7.46 4.21 4.20 5.04 5.39 4.37 5.35 4.23 4.36 5.47 5.02 5.52 9.21 7.47 3.50 9.19
38 3.60 7.60 7.60 4.20 7.60 4.20 4.40 5.10 5.40 4.50 5.40 4.40 4.50 5.50 5.10 5.50 9.30 7.60 3.80 9.30
39 3.55 7.39 7.39 4.21 7.44 4.23 4.26 5.05 5.29 4.21 5.28 4.17 4.13 5.44 5.02 5.42 9.11 7.36 3.52 9.17
40 3.56 7.58 7.52 4.35 7.58 4.29 4.28 5.08 5.42 4.27 5.43 4.29 4.25 5.54 5.08 5.54 9.27 7.52 3.72 9.29
41 3.51 7.52 7.53 4.30 7.53 4.29 4.26 5.03 5.38 4.53 5.38 4.23 4.53 5.55 5.04 5.56 9.30 7.54 3.52 9.32
42 3.64 7.41 7.52 4.45 7.42 4.30 4.27 5.04 5.35 4.23 5.34 4.35 4.24 5.48 5.09 5.53 9.42 7.59 4.25 9.35
43 3.40 7.60 7.70 4.30 7.60 4.20 4.10 5.00 5.30 4.40 5.30 4.10 4.40 5.50 5.00 5.50 9.70 7.60 3.60 9.70
44 3.54 7.34 7.43 4.20 7.35 4.21 4.20 5.00 5.30 4.19 5.29 4.21 4.12 5.42 5.02 5.34 9.28 7.42 3.33 9.27
45 3.72 6.37 6.61 4.73 6.40 4.67 4.22 4.79 5.20 4.28 5.17 4.34 4.21 5.28 5.08 5.37 9.20 7.59 3.69 9.40
46 3.69 5.18 7.58 4.61 6.84 5.05 4.37 4.76 5.70 4.65 5.48 4.37 4.63 5.12 5.18 5.61 9.28 7.57 3.79 9.26
47 3.69 7.64 7.57 4.51 7.58 4.45 4.35 5.20 5.60 4.36 5.62 4.30 4.39 5.73 5.22 5.69 9.26 7.62 3.81 9.30
48 3.63 7.55 7.55 4.49 7.55 4.39 4.37 5.13 5.47 4.32 5.44 4.37 4.30 5.55 5.14 5.56 9.29 7.58 4.04 9.29
49 3.60 7.49 7.40 4.45 7.49 4.27 4.21 5.02 5.36 4.41 5.39 4.21 4.41 5.58 5.01 5.50 9.30 7.38 3.81 9.37
50 3.51 7.42 7.48 4.33 7.44 4.27 4.40 4.97 5.30 4.48 5.32 4.26 4.50 5.49 5.01 5.48 9.28 7.49 3.54 9.28
51 4.04 7.64 7.62 4.60 7.67 4.53 4.51 5.30 5.55 4.41 5.54 4.51 4.40 5.68 5.28 5.68 9.34 7.62 4.31 9.32
52 3.61 7.60 7.58 4.31 7.61 4.31 4.30 5.13 5.46 4.26 5.51 4.31 4.27 5.58 5.13 5.60 9.28 7.60 3.68 9.28
53 3.60 7.18 7.27 5.34 7.38 4.54 4.42 5.20 5.40 4.44 5.36 4.47 4.31 4.45 5.16 5.47 8.96 7.42 5.22 8.95
318 KALRA: JOURNAL O F AOAC INTERNATIONAL VOL. 78, No. 2,1995

Table 4. Collaborative study results for pH measurements of saline-sodic soils3

Sample
Lab. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

1 7.47 7.59 4.98 4.35 7.67 5.95 5.50 4.90 7.76 6.17 9.36 5.94 9.47 4.28 6.10 4.12 5.48 4.34 5.60 5.64
2 7.66 7.46 4.81 4.26 7.80 5.75 5.44 4.78 7.68 5.89 9.75 5.79 9.71 4.41 5.92 3.96 5.40 4.23 5.40 5.42
3 7.45 7.40 4.60 4.15 7.60 5.70 5.15 4.60 7.60 5.80 9.25 5.65 9.15 3.70 5.80 3.70 5.20 4.10 5.35 5.35
4 7.52 7.63 4.87 4.11 7.76 5.80 5.64 4.70 7.79 6.02 9.76 5.66 9.80 4.23 5.89 4.12 5.49 4.07 5.46 5.36
5 7.56 7.57 5.16 4.46 7.76 5.76 5.54 4.70 7.79 5.96 9.27 5.74 9.20 4.04 5.90 3.93 5.40 4.23 5.37 5.38
6 7.33 7.40 4.54 4.11 7.45 5.55 5.16 4.51 7.47 5.76 9.47 5.64 9.48 3.89 5.75 3.91 5.23 4.17 5.27 5.23
7 7.54 7.57 4.84 4.31 7.78 5.80 5.39 4.81 7.79 6.00 9.46 5.82 9.46 4.21 6.00 4.05 5.37 4.31 5.56 5.56

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8 7.42 7.61 5.02 4.16 7.58 5.98 5.70 4.88 7.64 6.20 9.47 5.99 9.52 4.32 5.94 4.05 5.52 4.31 5.21 5.19
9 7.65 7.67 4.84 4.20 7.63 5.82 5.42 5.05 7.79 6.08 9.65 5.90 9.78 5.30 6.17 4.09 5.13 4.20 5.20 5.30
10 7.31 7.47 4.87 4.33 7.48 5.81 5.38 4.79 7.56 6.01 9.21 7.07 9.36 4.31 5.78 4.04 5.26 4.31 5.48 5.51
11 7.14 7.48 4.52 4.27 7.31 5.61 5.16 4.41 7.17 6.45 9.34 5.51 9.26 4.16 5.67 3.90 5.24 4.15 5.01 5.12
12 7.47 7.70 4.66 4.25 7.62 5.65 5.41 4.67 7.68 5.87 9.62 5.64 9.61 3.99 5.87 3.97 5.39 4.27 5.45 5.49
13 7.49 7.58 4.90 4.34 7.65 5.79 5.44 4.82 7.90 6.00 9.49 5.79 9.39 4.06 6.16 4.03 5.47 4.37 5.60 5.60
14 7.54 7.57 4.95 4.44 7.70 5.81 5.53 4.85 7.75 5.99 9.52 5.87 9.59 4.68 6.61 4.17 5.58 4.44 5.68 5.65
15 7.66 7.59 4.90 4.43 7.62 5.88 5.36 4.75 7.43 5.90 9.16 5.80 9.20 4.06 5.86 3.92 5.32 4.29 5.45 5.53
16 7.56 7.65 4.95 4.49 7.66 5.91 5.65 4.90 7.82 6.14 9.64 6.11 9.63 4.24 6.00 4.20 5.55 4.50 5.62 5.65
17 7.35 7.49 5.22 4.53 7.82 5.92 5.72 5.02 7.79 6.27 9.44 6.48 9.32 6.27 6.50 5.54 5.60 4.61 5.68 5.75
18 7.38 7.43 4.85 4.28 7.58 5.87 5.45 4.85 7.61 6.11 9.52 6.10 9.64 4.14 6.11 4.02 5.45 4.30 5.56 5.55
19 7.62 7.68 4.61 4.21 7.33 5.64 5.13 4.39 7.45 5.75 9.98 5.59 9.82 4.22 5.68 3.67 5.08 4.17 4.97 4.99
20 7.33 7.37 4.69 4.31 7.47 5.73 5.33 4.74 7.51 5.92 9.12 5.92 9.21 4.43 5.95 4.03 5.49 4.40 5.54 5.52
21 7.38 7.35 5.92 4.55 7.28 5.95 5.42 5.35 4.59 7.59 9.48 5.98 9.57 5.14 5.91 4.08 5.38 4.24 5.39 5.35
22 7.78 7.59 4.62 4.29 7.72 5.78 5.42 4.75 7.77 5.99 9.67 5.78 9.63 4.00 5.95 3.95 5.43 4.26 5.50 5.52
23 7.85 7.51 5.04 4.42 7.56 5.92 5.44 4.89 7.59 6.18 9.53 5.92 9.50 4.38 5.86 4.13 5.43 4.34 5.58 5.60
24 7.45 7.52 4.35 4.16 7.48 5.66 5.60 4.31 7.54 5.98 9.69 5.76 9.71 4.33 5.84 3.88 5.13 4.14 5.25 5.28
26 6.70 6.71 4.31 4.22 6.77 5.32 5.12 4.23 6.77 5.36 9.09 5.23 9.10 3.53 5.34 3.75 5.27 4.06 4.95 4.87
27 7.48 7.50 4.67 4.23 7.74 5.80 5.44 4.65 7.70 5.94 9.26 5.70 9.22 3.92 5.95 3.90 5.36 4.20 5.47 5.14
28 7.30 7.00 4.70 4.10 7.05 5.50 5.20 4.70 7.30 5.70 8.20 6.00 8.65 4.30 5.70 4.00 5.25 4.25 5.45 5.50
29 7.60 7.60 4.70 4.02 7.74 5.61 5.45 4.72 7.77 5.92 9.73 5.81 9.70 4.45 5.90 4.01 5.45 4.36 5.48 5.47
30 7.60 7.60 4.78 4.54 7.78 5.78 5.55 4.76 7.77 5.92 9.55 5.81 9.57 4.15 5.91 4.03 5.49 4.55 5.50 5.49
31 7.30 7.52 4.79 4.26 7.41 5.63 5.43 4.61 7.39 5.95 9.43 5.69 9.41 4.35 5.78 4.03 5.39 4.19 5.38 5.40
32 7.53 7.55 4.80 4.62 7.82 5.78 5.50 4.78 7.74 6.03 9.56 5.76 9.51 4.40 5.99 4.04 5.42 4.53 5.55 5.52
33 7.33 7.35 5.54 4.40 7.60 5.63 5.25 4.60 7.54 5.92 9.31 5.80 9.29 5.23 5.92 4.05 5.32 4.25 5.45 5.41
34 7.38 7.50 5.93 4.59 7.50 6.16 5.14 4.67 7.48 6.56 9.03 6.48 9.08 3.99 6.08 4.20 5.35 4.19 5.67 5.42
35 7.65 7.61 5.05 4.33 7.90 5.86 5.40 4.78 7.89 6.07 9.51 6.02 9.54 4.53 6.07 4.05 5.58 4.35 5.72 5.74
36 7.63 7.66 5.03 4.68 7.60 5.81 5.65 4.82 7.61 6.02 9.65 5.95 9.69 4.24 6.07 4.23 5.51 4.63 5.47 5.51
37 7.54 7.53 4.57 4.61 7.75 5.80 5.34 4.78 7.66 5.96 9.45 5.81 9.42 3.88 5.97 3.88 5.34 4.66 5.46 5.42
38 7.50 7.50 4.70 4.50 7.70 5.80 5.40 4.70 7.80 6.00 9.50 5.80 9.50 3.90 6.00 3.90 5.30 4.50 5.50 5.50
39 7.64 7.60 4.74 4.24 7.73 5.71 5.41 4.79 7.76 5.97 9.60 5.69 9.64 4.04 5.94 4.00 5.45 4.29 5.54 5.55
40 7.51 7.51 4.75 4.32 7.70 5.85 5.41 4.86 7.70 6.08 9.49 5.85 9.49 4.12 6.08 3.95 5.40 4.39 5.57 5.59
41 7.61 7.61 4.76 4.63 7.77 5.83 5.39 4.76 7.80 6.00 9.60 5.82 9.65 3.97 6.04 3.96 5.33 4.63 5.46 5.50
42 7.62 7.66 4.89 4.36 7.76 5.87 5.58 4.78 7.79 6.04 9.60 5.91 9.63 4.09 6.01 4.05 5.46 4.31 5.57 5.60
43 7.70 7.70 4.70 4.50 7.80 5.70 5.30 4.70 7.90 6.00 9.90 5.70 10.00 4.10 5.90 3.90 5.30 4.60 5.50 5.50
44 7.45 7.42 4.58 4.16 7.59 5.61 5.29 4.56 7.58 5.78 9.29 5.64 9.39 3.92 5.85 3.88 5.31 4.17 5.36 5.40
45 6.98 7.67 5.09 4.41 6.94 5.93 5.86 4.91 7.90 6.13 9.89 5.98 10.02 4.35 5.72 4.16 5.38 4.29 5.67 5.53
46 7.31 7.56 4.92 4.74 7.79 5.87 5.43 4.82 8.15 6.03 9.64 5.89 9.75 4.07 5.95 4.07 5.42 4.73 5.60 5.63
47 7.55 7.65 4.97 4.41 7.85 6.07 5.69 5.06 7.87 6.30 9.43 6.09 9.46 5.04 6.11 4.26 5.63 4.45 5.72 5.68
48 7.47 7.50 4.83 4.30 7.60 5.73 5.43 4.77 7.59 5.88 9.31 5.78 9.38 4.45 5.78 3.78 5.16 4.05 5.35 5.33
49 7.59 7.59 4.78 4.63 7.72 5.79 5.39 4.74 7.72 6.00 9.52 5.80 9.52 4.02 5.99 3.98 5.40 4.61 5.46 5.49
51 7.72 7.67 5.25 4.49 7.85 5.92 5.51 4.79 7.83 6.04 9.61 6.23 9.44 4.81 6.15 4.11 5.49 4.24 5.57 5.54
52 7.68 7.74 4.88 4.30 7.90 5.84 5.46 4.85 7.90 6.10 9.71 5.93 9.64 4.04 6.10 4.01 5.46 4.30 5.60 5.57
53 7.64 7.58 5.84 4.50 7.61 6.12 6.16 4.91 7.54 5.98 9.10 5.83 9.24 5.43 5.91 4.83 6.02 4.59 5.82 5.64

Results not provided by Laboratories 25 and 50.

 KALRA: JOURNAL O F AOAC INTERNATIONAL VOL. 78, No. 2,1995 319

Table 5. Collaborative study results for pH measurements of organic soils

Sample

Lab. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

1 6.51 6.34 8.13 6.80 7.66 7.27 5.54 7.61 7.02 7.87 5.49 7.05 6.66 8.09 7.55 6.81 7.23 7.88 6.40 7.57
2 6.03 6.00 8.10 6.60 7.50 7.11 5.12 7.56 6.91 7.84 5.18 6.93 6.64 8.19 7.41 6.67 7.13 7.83 6.16 7.40
3 6.20 6.05 8.00 6.15 7.50 7.10 4.85 7.50 6.90 7.75 4.90 6.85 6.60 8.05 7.40 6.55 7.05 7.80 6.05 7.40
4 5.91 5.97 7.97 6.06 7.41 6.97 4.90 7.43 6.83 7.74 4.91 6.81 6.54 7.99 7.34 6.58 6.99 7.72 5.89 7.29
5 6.18 6.22 7.94 6.37 7.43 6.99 5.18 7.41 6.82 7.76 5.18 6.75 6.53 7.99 7.35 6.47 7.01 7.75 6.24 7.36
6 5.78 5.69 7.30 6.62 7.14 7.07 4.80 7.06 6.95 7.48 4.91 6.57 6.52 7.52 7.39 6.92 6.99 7.54 6.13 7.27
7 6.30 6.17 8.21 6.32 7.56 7.18 5.12 7.54 6.89 7.81 5.02 6.90 6.58 8.12 7.41 6.59 7.13 7.80 6.01 7.38

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8 6.13 5.96 8.06 6.47 7.48 7.28 5.19 7.50 7.11 7.91 5.16 6.72 6.63 8.08 7.49 6.97 7.26 7.83 6.31 7.42
9 5.60 5.50 7.60 5.80 7.30 6.50 4.30 7.10 6.60 7.60 4.80 6.30 6.30 7.90 7.20 6.40 6.60 7.40 6.00 7.10
10 6.23 6.14 7.97 6.45 7.23 7.22 5.16 7.44 6.92 7.72 5.26 6.69 6.57 7.85 7.38 6.68 7.12 7.59 6.49 7.36
11 5.24 5.25 7.10 6.60 6.37 6.75 4.63 6.55 6.76 6.93 4.43 5.64 6.60 6.54 6.88 6.66 6.50 6.64 5.22 6.67
12 6.26 6.19 8.18 6.35 7.54 7.19 5.18 7.56 6.99 7.72 5.16 6.97 6.63 8.39 7.43 6.58 7.08 7.81 6.12 7.39
13 5.82 5.59 7.57 5.79 7.32 6.85 4.54 7.30 6.67 7.52 4.54 6.63 6.45 7.63 7.28 6.49 6.81 7.53 5.62 7.25
14 6.45 6.25 8.34 6.33 7.68 7.32 5.25 7.63 7.07 7.88 5.28 7.03 6.76 8.25 7.56 6.74 7.16 7.88 6.31 7.54
15 6.38 6.23 8.20 6.40 7.61 7.25 5.25 7.60 6.97 7.95 5.29 6.80 6.70 8.18 7.48 6.62 7.16 7.96 6.64 7.50
16 6.39 6.17 8.11 6.37 7.64 7.28 5.18 7.58 7.08 7.90 5.17 6.95 6.76 8.10 7.54 6.84 7.24 7.91 6.20 7.56
17 6.54 6.26 7.93 6.44 7.56 7.06 5.17 7.36 6.99 7.76 5.46 6.96 6.68 7.95 7.49 6.77 7.07 7.64 6.30 7.46
18 6.37 6.14 7.87 6.29 7.51 7.08 5.09 7.54 6.86 7.73 5.06 6.99 6.67 8.06 7.41 6.61 7.08 7.73 6.16 7.39
19 5.48 5.44 7.41 6.35 7.33 7.00 5.51 7.28 6.82 7.61 4.49 6.52 6.41 7.55 7.34 6.74 6.86 7.67 5.81 7.28
20 6.14 6.07 8.05 6.28 7.49 7.10 4.96 7.49 6.88 7.77 4.96 6.85 6.56 8.06 7.39 6.63 7.06 7.76 6.02 7.38
21 5.70 5.87 5.97 6.12 7.27 7.14 5.30 7.02 6.78 7.59 5.43 6.35 6.41 7.30 7.32 6.89 7.07 7.44 7.12 7.25
22 6.32 6.14 8.35 6.42 7.59 7.21 5.14 7.52 7.01 7.92 5.12 6.96 6.63 8.36 7.38 6.63 7.10 7.79 6.14 7.38
23 5.99 6.02 7.44 6.55 7.33 7.18 5.32 7.34 6.94 7.82 5.32 6.78 6.67 7.99 7.48 6.87 7.24 7.88 6.35 7.39
24 5.69 5.61 7.60 5.76 7.22 6.86 4.52 7.22 6.67 7.52 4.55 6.58 6.39 7.69 7.11 6.44 6.86 7.54 5.85 7.17
25 6.15 6.00 8.08 6.20 7.54 7.17 4.98 7.53 6.89 7.74 4.96 6.88 6.59 8.04 7.41 6.59 7.06 7.77 6.04 7.38
26 5.18 5.08 6.96 5.70 6.66 6.33 4.84 6.77 6.35 7.12 4.09 5.86 5.75 7.12 6.81 6.23 6.52 6.95 5.64 6.70
27 6.30 6.06 8.06 6.23 7.45 7.07 5.10 7.52 6.85 7.75 5.08 6.84 6.57 8.03 7.38 6.54 7.02 7.74 6.02 7.33
28 6.20 6.05 7.60 6.15 7.15 6.90 5.15 7.15 6.70 7.40 5.10 6.70 6.40 7.70 7.10 6.45 6.80 7.40 6.10 7.10
29 5.78 6.56 7.80 5.85 7.40 6.89 4.60 7.44 6.72 7.77 4.60 6.70 6.46 7.98 7.34 6.42 6.86 7.69 5.75 7.34
30 6.29 6.12 8.18 6.35 7.53 7.16 5.09 7.51 6.95 7.94 5.12 6.90 6.61 8.20 7.42 6.62 7.15 7.97 6.14 7.40
31 6.02 5.85 7.88 6.08 7.38 7.00 5.06 7.49 6.86 7.71 5.05 6.81 6.63 7.94 7.42 6.71 7.05 7.70 6.08 7.35
32 6.21 6.04 8.09 6.31 7.52 7.09 5.00 7.51 6.89 7.90 5.05 6.88 6.60 8.12 7.40 6.62 7.11 7.85 6.09 7.41
33 6.02 6.00 7.99 6.22 7.46 7.12 4.87 7.46 6.96 7.76 4.93 6.87 6.64 8.05 7.42 6.72 7.11 7.76 6.06 7.40
34 6.15 5.99 8.01 6.30 7.46 7.07 5.10 7.49 7.77 5.15 7.03 7.04 6.76 8.07 7.36 6.84 7.09 7.74 6.18 7.35
35 6.23 6.09 8.20 6.30 7.56 7.19 5.08 7.58 6.97 7.91 5.12 6.88 6.65 8.22 7.45 6.69 7.16 7.85 6.18 7.44
36 6.10 6.01 8.10 6.31 7.53 7.77 4.98 7.50 7.00 7.94 5.14 6.88 6.63 8.16 7.43 6.72 7.16 7.95 6.18 7.41
37 6.28 6.17 8.13 6.33 7.47 7.02 5.02 7.45 6.85 7.79 5.01 6.83 6.62 8.11 7.40 6.57 7.05 7.84 6.10 7.34
38 6.30 6.20 8.20 6.30 7.60 7.20 5.10 7.60 7.00 8.00 5.10 7.00 6.70 8.20 7.40 6.70 7.20 8.00 6.20 7.40
39 6.84 6.31 8.28 6.74 7.60 7.31 5.23 7.56 7.05 7.86 5.23 6.93 6.67 8.20 7.44 6.68 7.14 7.84 6.17 7.43
40 6.29 6.10 8.15 6.27 7.57 7.13 5.01 7.57 6.96 7.81 5.04 6.94 6.64 8.15 7.46 6.62 7.05 7.83 6.10 7.44
41 6.11 5.94 8.06 6.16 7.50 7.06 4.95 7.51 6.83 7.89 4.95 6.85 6.58 8.08 7.40 6.57 7.06 7.89 5.97 7.42
42 6.35 6.08 8.10 6.32 7.67 7.25 4.99 7.64 7.02 7.89 5.05 6.95 6.69 8.09 7.51 6.73 7.20 7.90 6.19 7.49
43 6.20 6.00 8.10 6.20 7.60 7.10 5.10 7.60 6.90 8.10 5.10 6.90 6.50 8.40 7.40 6.50 7.10 8.10 6.00 7.50
44 6.35 6.06 8.14 6.52 7.42 7.17 5.28 7.38 6.91 7.78 5.14 6.70 6.56 8.12 7.37 6.65 7.08 7.79 6.22 7.31
45 6.63 6.38 6.92 6.83 6.93 6.78 5.45 6.84 6.86 7.75 5.24 6.59 6.43 8.23 7.42 6.57 6.90 7.80 6.29 7.41
46 6.25 6.04 8.11 6.51 7.62 7.36 5.08 7.59 6.96 7.95 5.17 6.77 6.61 8.14 7.48 6.65 7.11 7.91 6.07 7.40
47 6.43 6.28 8.22 6.50 7.64 7.21 5.26 7.68 7.09 7.94 5.25 7.06 6.75 8.30 7.56 6.74 7.22 7.93 6.29 7.49
48 6.34 6.20 8.19 6.42 7.56 7.23 5.22 7.53 7.00 7.86 5.24 6.94 6.66 8.20 7.43 6.69 7.11 7.84 6.26 7.41
49 6.38 6.10 8.00 6.38 7.48 7.04 5.10 7.41 6.88 7.82 5.18 6.83 6.52 7.98 7.41 6.59 7.01 7.82 6.10 7.40
50 6.12 6.04 8.17 6.23 7.52 7.09 5.02 7.51 6.91 7.93 5.02 6.87 6.58 8.13 7.38 6.61 7.06 7.93 6.08 7.38
51 6.53 6.36 8.22 6.57 7.66 7.23 5.50 7.64 7.03 7.88 5.53 7.00 6.72 8.24 7.52 6.74 7.20 7.88 6.37 7.49
52 6.40 6.20 8.30 6.37 7.60 7.22 5.19 7.61 6.97 7.88 5.19 6.90 6.62 8.27 7.51 6.74 7.15 7.80 6.26 7.46
53 6.27 6.23 7.92 6.60 7.46 7.14 5.41 7.39 7.02 7.64 5.15 6.88 6.75 7.88 7.45 6.95 7.03 7.64 6.06 7.00
320 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995

All laboratories informed us that all 80 bags containing test Agricultural Related Materials); and the following collabora-
samples were received intact. All 53 laboratories were familiar tors:
with soil-to-liquid suspension methods. Five laboratories indi- Donna Collins, W.M. Ward Technical Services Laboratory,
cated that they did not have any experience with the saturated Manitoba Environment, Winnipeg, MB, Canada
paste method. Clive Dawson, B.C. Ministry of Forests, Research Labora-
Most of the participants used a combination electrode, while tory, Victoria, BC, Canada
some used a glass electrode and a calomel reference electrode. Brian Douglas, P.E.I. Soil and Feed Testing Laboratory,
Two laboratories reported that it was difficult to obtain a stable Charlottetown, PEI, Canada
reading when using the method for mineral soils (due to lack Brian G. Drought, Soil Science & Agricultural Engineering,
of a significant amount of supernatant hquid), while the Agriculture Canada, Research Station, Summerland, BC, Can-
method for saline-sodic soils gave stable readings. Ten labora- ada
tories found it necessary to tilt beakers when measuring pH by Lloyd Hodgins, Saskatchewan Soil Testing Laboratory,

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the method for mineral soils in order to cover the junction of University of Saskatchewan, Saskatoon, SK, Canada
the combination electrode by the supernatant liquid. Increasing P.M. Kelly, Chemical and Geological Laboratories, Cal-
the amount of soil to 20 g and the volume of water or CaCl2 gary, AB, Canada
solution to 20 mL would have eliminated that problem.
John Konwicki, Department of Soil Science, Faculty of Ag-
One laboratory reported that readings from the method for riculture and Forestry, University of Alberta, Edmonton, AB,
organic soils were less stable than from the methods for mineral Canada
and saline-sodic soils. When using the saline-sodic soils Grant Kowalenko, Agriculture Canada, Research Station,
method, most of the collaborators took readings 1 h after pre- Agassiz, BC, Canada
paring the saturated paste. One laboratory reported that there Ian Murchison, Agriculture Canada, Research Station,
was no difference in the readings taken at 1,1.5, or 2 h after the
Brandon, MB, Canada
preparation of saturated paste.
Anne Neary, Ministry of Environment, Dorset, ON, Canada
There are no potential hazards in handling reagents, sam- Randy Neumann, and John Ashworth, Norwest Laborato-
ples, or buffer solutions. None of the participating laboratories ries, Edmonton, AB, Canada
provided any comments regarding the safety aspects of the col- Rosalind Olive, Soil and Plant Testing Laboratory, Univer-
laboratively studied methods. sity of New Brunswick, Hugh John Hemming Forestry Centre,
Fredericton, NB, Canada
Recommendation Liz Pastorek, and Jane Trash, Laboratory Services Branch,
Ministry of Environment, Rexdale, ON, Canada
On the basis of the results of this study it is recommended Terry Peel, Econotech Services Ltd., New Westminster, BC,
that the methods for measurement of pH of mineral, saline-so- Canada
dic, and organic soils be adopted first action. Jo Ramakers, Great Lakes Forestry Centre, Canadian Forest
Service, Sault Ste. Marie, ON, Canada
Acknowledgments Vernon Rodd, Nappan Experimental Farm, Nappan, NS,
Canada
Rod Schultz, and Gerry Lutwick, Alberta Environment,
The Associate Referee is grateful to the Soil Science Society
Lethbridge, AB, Canada
of America (SSS A) and the AOAC INTERNATIONAL for the
Regis Simard, Agriculture Canada, Research Station,
opportunity to coordinate this study. Thanks are also due to the
Sainte-Foy, PQ, Canada
Canadian Forest Service for its cooperation. I thank the follow-
Sen Tran, and Pierre Audesse, MAPAQ, Soils Service,
ing individuals for their assistance at different stages of the
study, whose help and cooperation have been of vital impor- Sainte-Foy, PQ, Canada
tance to this collaborative study: AOAC Methods and Safety Donald Trenholm, Newfoundland Forestry Centre, Cana-
Committees; Nat B. Dellavalle; Editors of Agronomy News and dian Forest Service, St. John's, NF, Canada
The Referee; Thomas L. Jensen and Charles L. Focht (Succeed- Evelyn Turcotte, Petawawa National Forestry Institute, Ca-
ing General Referees for Nutrients in Soils); J. Benton Jones, nadian Forest Service, Chalk River, ON, Canada
Jr; Fred Kaisaki; John J. Mortvedt (Chairman) and other mem- Ann Van Niekerk, Pacific Forestry Centre, Canadian Forest
bers of the SSSA S889 Committee: Joan K. Bartz (also SSSA Service, Victoria, BC, Canada
liaison to AOAC INTERNATIONAL), Boyd G. Ellis, Ellis G. Joel Villanueva, and P.N. Vrjan, Alpha Laboratories, Inc.,
Knox, Ted R. Peck, and Dean E. Wesley; Daniel H. Mowrey Don Mills, ON, Canada
(Committee Statistician); Julie Norman and Lucyna Kurtyka Chang Wang, Centre for Land and Biological Resources
(Succeeding Methods Program Coordinators); D.G. Maynard; Research, Central Experimental Farm, Ottawa, ON, Canada
John Shuya; Sheldon Radford; Joe Crumbaugh; SSSA Re- Paul Yeung, Alberta Environmental Centre, Vegreville, AB,
viewers: S.J. Donohue, Mark A. Flock, Gordon V. Johnson, Canada
John L. Kovar, and Dean E. Wesley; Harold C. Thompson, Jr H.P. Agrawal, Department of Soil Science and Agricultural
(Chairman of the Methods Committee on Feeds, Fertilizers and Chemistry, Banaras Hindu University, Varanasi, India
 KALRA: JOURNAL O F AOAC INTERNATIONAL VOL. 78, No. 2,1995 321

R.S. Singh, Central Research Laboratory, Udai Pratap Col- W Shaw Reid, CU Nutrient Analysis Laboratory, Cornell
lege, Varanasi, India University, Department of Soil, Crops and Atmosperic Sci-
Zev Gerstl, Agricultural Research Organization, The Vol- ences, Ithaca, NY
cani Center, Institute of Soils & Water, Bet Dagan, Israel Janet Sorrels, Agrico Agronomic Services Laboratory,
Earl Allen, Department of Agronomy, Oklahoma State Uni- Washington Court House, OH
versity, Stillwater, OK M. Ray Tucker, North Carolina Department of Agriculture,
Vernon W. Case, University of Kentucky, Soil Testing Raleigh, NC
Laboratory, Lexington, KY Darryl D. Warncke, MSU Soil Testing Laboratory, Michi-
gan State University, East Lansing, MI
Sherry M. Combs, University of Wisconsin, Department of
Maurice E. Watson, Research Extension Analytical Labora-
Soil Science, Madison, WI
tory, Ohio State University, Wooster, OH
Joe Denning, University of Nebraska, Lincoln, NE
Larry Wikoff, Minn. Valley Testing Laboratory, Grand

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S.J. Donohue, Soil Testing Laboratory, Virginia Tech,
Forks, ND
Blacksburg, VA
Mark A. Rock, Brookside Farms Laboratory Association, References
Inc., New Knoxville, OH
James B. Friedericks, Servi-Tech Laboratory, Hastings, NE (1) McLean, E.O. (1982) in Methods of Soil Analysis, Part 2,
Gary J. Gascho, Coastal Plain Experiment Station, Univer- Agron. 9, A.L. Page, R.H. Miller, & D.R. Keeney (Eds), Am.
sity of Georgia, Department of Agronomy, Tifton, GA Soc. Agron., Madison, WI, pp. 199-224
Bryan Hopkins, Agronomy Department, Kansas State Uni- (2) Schofield, R.K., & Taylor, A.W. (1955) Soil Sci. Soc. Am.
versity, Manhattan, KS Proc. 19,164-167
Donald Horneck, Central Analytical Laboratory, Oregon (3) Diagnosis and Improvement of Saline and Alkali Soils
(1954), L.A. Richards (Ed.), Agriculture Handbook 60, U.S.
State University, Corvallis, OR
Dept of Agriculture, Washington, DC, p. 84
Robert A. Isaac, Agriculture Services Laboratories, Soil, (4) Robbins, C.W., & Wiegand, C.L. (1990) in Agricultural Sa-
Plant & Water Analyses Laboratory, University of Georgia, linity, Assessment, and Management, K.K. Tanji (Ed.), ASCE
Athens, GA Manuals and Reports No. 71, Am. Soc. Civil Eng., New
John Kovar, Agronomy Department, Louisiana State Uni- York, NY, pp. 201-219
versity, Baton Rouge, LA (5) Kalra, Y.P., & Maynard, D.G. (1991) Methods Manual for
Robert O. Miller, Department of Land, Soil, and Water, Uni- Forest Soil and Plant Analysis, Forestry Canada, Northwest
versity of California, Davis, CA Region, Northern Forestry Centre, Edmonton, AB, Canada,
Robert Munter, Soil Testing Laboratory, University of Min- Inf. Rep. NOR-X-319
(6) Guidelines for Collaborative Study Procedure to Validate
nesota, St. Paul, MN
Characteristics of a Method of Analysis, (1989) J. Assoc. Off.
Mike Neville, Milwaukee Metropolitan Sewerage District,
Anal. Chem. 72, 694-704
Milwaukee, WI (7) Handbook for AOAC members (1989), AOAC, Arlington, VA
Charles B. Nolan, Conagra Frozen Foods Analytical Labo- (8) Youden, W.J., & Steiner, E.H. (1975) Statistical Manual of
ratory, Batesville, AR the AOAC, AOAC, Arlington, VA
Wayne Pask, Office of Indiana State Chemists, Purdue Uni- (9) Pleijsier, L.K. (1986) The Laboratory Methods and Data Ex-
versity, West Lafayette, IN change Programme, Interim Report on the Exchange Round
Ted R. Peck and Marilyn Sullivan, University of Illinois, 86-1, International Soil Reference and Information Centre,
Agronomy Department, Urbana, IL Wageningen, The Netherlands
322 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995

Appendix: Descriptions of Soils Used in the Collaborative Study

for pH Measurements8
Halii Series subangular blocky structure; neutral (pH 7.0 in KCl); abrupt
smooth boundary.
Classification: Clayey, ferritic, isothermic Typic Gibbsihumox. Oa2—9-13"—Black (7.5YR 2/0) broken face very dark
Location: Island of Kauai, Hawaii, University of Hawaii brown (7.5YR 2/2) rubbed sapric material; about 5% fiber, a
Wailua Experiment Station, Wailua, Kauai, edge of experimen- trace rubbed; weak medium granular structure; neutral (pH 7.0
tal maize field, approximately 270 m northwest of Station of- in KCl); abrupt smooth boundary.

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fice and approximately 35 m east of dirt road along western Oa3—13-24"—Dark reddish brown (5YR 3/2) broken face
portion of ridge: latitude 22°04'17"N, longitude 159°24'03"W. dark reddish brown (5YR 2/2) rubbed sapric material; about
Vegetation: Grassy area adjacent to experimental maize 15% fiber, less than 5% rubbed; massive, breaking to thick
field; Kaimi clover (Desmodium canum), Hilograss (Paspalum platy fragments; neutral (pH 7.0 in KCl); abrupt smooth
conjugatum), Dallisgrass (Paspalum dilatatum), and rattail- boundary.
grass (Sporobolus africanus). Oa4—24-32"—Black (5YR 2/1) broken face and rubbed
Climate: Mean annual rainfall, 2500 mm, mean annual tem- sapric material; about 10% fiber, a trace rubbed; massive; few
perature, 20°C. woody fragments; neutral (pH 7.0 in KCl); clear wavy bound-
Parent material: Residuum from melilite nepheline basalt. ary.
Physiography: Gently sloping upland ridge. Oa5—32-48"—Dark reddish brown (5 YR 2/2) broken face
Relief. Convex side slope of ridge. black (5YR 2/1) rubbed sapric material about 20% fiber, less
Slope: 3%. than 10% rubbed; massive, breaking to thick platy fragments;
Permeability: Moderately rapid. neutral (pH 7.0 in KCl); abrupt smooth boundary.
Drainage: Well drained.
Moisture: Moist. Houston
Described by: H. Ikawa.
Collected by: H. Ikawa, J.R. Gordines, and K. Kagihara. Soil type: Houston Black clay, 1-3% slopes.
Date sampled: March 19,1981. Classification: Udic Pellusterts, fine montmorillonitic, thermic.
Remarks: Colors are for moist soil. Textures are "apparent Location: Bell County, TX; ca 2 miles south of Temple, in
field textures." native pasture in south part of the Blackland Research Center.
Ap—0-35 cm; dark brown (7.5YR 3/2) gravelly silty clay In microbasin.
loam; moderage very fine and fine subangular blocky struc- Date sampled: June 3, 1977, sampled in core hole 30 in. in
ture; friable, sticky, plastic, many very fine roots; many very diameter. Sampled by Robert N. Ramsey.
fine pores; lower portion of horizon has many iron concretions, Physiography: Gently sloping upland. The soil formed in
mostly ranging in size 1-2 mm, some as large as 1 cm; few Taylor Marl of the Upper Cretaceous period.
rock fragments, mostly 2-3 cm, occasionally 5-10 cm; very Sample numbers: National Soil Survey Laboratory (NSSL)
strongly acid (pH 5.0); abrupt smooth boundary. Tex-77-U27-2-l-2-3-4.
Pedon description: All 0-36 cm, very dark gray (10YR 3/1)
Houghton Series clay, black (10YR 2/1) moist; moderate fine subangular and
angular blocky structure; extremely hard, very firm; common
The Houghton series is a member of the euic, mesic family fine roots; few fragments of snail shells; calcareous, moder-
of Typic Medisaprists. The soil formes chiefly in herbaceous ately alkaline; clear wavy. NSSL-Tex-77-027-2-1 boundary.
organic deposits more than 51 in. thick. The surface 0-12 in.
layer is dominated by black highly decomposed organic mate- Laurentides
rial, subsurface 12-35 in. layer is dark reddish brown and black
highly decomposed organic material and the bottom layer is Location: Laurentides Provincial Park, latitude 47°16'00"
dark reddish brown highly decomposed organic material. The N, longitude 7 1°9'20"W.
soil is about neutral throughout. Altitude: 100 mM.S.L.
Type location: Clinton County, MI; 100 ft west of farm lane Landform: Rolling morainal.
at corner where lane turns north; SE14, SW!/4, SWW, Sec. 11, Slope: Upper slope, 5%.
Bath Township; on Michigan State University muck farm. Drainage: Well drained.
Typifying pedon: Houghton muck—cultivated. (Colors are Vegetation: Abies balsamea L., Betula papyrifera Marsh,
for moist soils unless otherwise stated.) Picea glauca Voss, Picea mariana BSP, Dryopteris spinulosa,
Oal—0-9"—Black (7.5YR 2/0) broken face and rubbed and Oxalis Montana.
sapric material; about 5% fiber, a trace rubbed; weak coarse Climate: Precipitation, 139 cm (47 cm from snowfall).
 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995 323

Parent material: Glacial till, loamy sand. Samples collected and profile described by: John M. Rob-
Classification: Orthic ferro-humic podzol (Canadian), Hu- bins, Jr, Richard D. Ford, SCS, and Tom Hallmark, IFAS, April
mic cryothod (American). 6,1978.
Laurentides: Ae (A2), 0-5 cm Gray (7.5YR 5/0 m), light Horizon: Al.
gray (7.5YR 7/0 d) loamy sand; single grain to weak fine Depth: 0-8 cm (0-3 in.).
subangular; firm in place, friable when removed; few fine and Description: Very dark gray (10YR 3/1 crushed) fine sand;
medium roots; abrupt, wavy to irregular boundary; 3-13 cm uncrushed colors have a salt and pepper appearance; weak fine
thick; pH 3.9. crumbs structure; very friable; matted with many fine and me-
Laurentides LFH: 8-0 cm Black (10YR 2/1 m), very dark dium roots; strongly acid; clear smooth boundary.
grayish-brown (10YR 3/1 d), semi-decomposed to well-de-
composed organic matter; fibrous to fine granular; abundant Peckb
fine and medium roots; abrupt, smooth boundary, 5-15 cm

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thick; pH 3.6. Peck 90-9: Flanagan SiCL that is classified as a fine, mont-
morillonitic, mesic Aquic Argiudoll that has a water pH of 6.1
Malbis Series was circulated as soil No. 90-9 in the Fall 1990 Split Soil Sam-
ple Study, as soil No. 91-4 in the Spring 1991, and as soil No.
Sample number: S76AL-003-l-(l-4). 91-7 in the Fall 1991 study. This soil came from afieldthat was
Representative profile: Malbis fine sandy loam. never limed and had not been fertilized with phosphorus or
Classification: Plinthic Paleudults; fine-loamy, siliceous, potassium for 4 years but was fertilized with nitrogen as the
thermic. field has grown corn since 1982.
Location: Gulf Coast Substation, Baldwin County, AL. Peck 90-10: Drummer SiCL that is classified as a fine silty,
Use of vegetation: Presently used as winter pasture. mixed, mesic, Typic Haplaquoll that has a water pH of 5.9 was
circulated as soil No. 90-10 in the Fall 1990 Split Soil Sample
Parent rock or regolith: Medium textured Coastal Plain
Study, as soil No. 91 -5 in the Spring 1991, and as soil No. 91 -10
sediments.
in the Fall 1991 study. This soil came from a research plot grass
Geomorphology, region: Lower Coastal Plain, MLRA-133.
border area that has not been fertilized or limed for at least
Position: Upland.
10 years.
Elevation: About 150 ft.
Peck 90-11: Harpster SiCL that is classified as a fine silty,
Drainage and permeability: Well drained and moderately mixed, mesic, Typic Calciaquoll that has a water pH of 7.8 was
permeable to ca 55 in. Moderately slowly permeable below. circulated as soil No. 90-11 in the Fall 1990 Split Soil Sample
Water table and duration: Water table at 55 in. when de- Study, as soil No. 91-1 in the Spring 1991, and as soil No. 91-8
scribed. in the Fall 1991 study. This soil came from the samefieldas the
Slope: Less than 1%. Flanagan SiCL previously described.
Effective rooting depth: About 50 in. Peck 90-12: Cisne SiL that is classified as afine,montmoril-
Sampled by: B.F. Hajek, R.L. Guthrie, D.E. Lewis, and L.F. lonitic, mesil Typic Albaqualf that has a water pH of 4.9 was
Ratliff. circulated as soil No. 90-12 in the Fall 1990 Split Soil Sample
Date sampled: December 17,1976. Study, as soil No. 91-3 in the Spring 1991, and as soil No. 91-11
Described by: R.L. Guthrie and D.E. Lewis. in the Fall 1991 study.
B21t—7-27 in.; yellowish brown (10YR 5/6) loam; weak
medium subangular blocky structure; friable; few fine roots; thin Saline soil (EC = 4.50 mS/cm)
patchy clayfilmson faces of peds; 5% medium ironstone concre-
tions; strongly acid; clear wavy boundary. (S76AL-003-1-2). U.S. Department of Agriculture—Soil Conservation Serv-
ice
Myaaka NSSL identification No.: 89P0110.
Soil survey No.: S88-JD-029-012-A.
Taxonomic class: Sandy, siliceous, hyperthermic Aerie Location: 227-15; 280'E and 1200' S of NW corner of sec-
Haplaquods. tion 15.
Location: Pardee County, FL; on a Range Cattle Experi- Classification: Fine silty, mixed, frigid Typic Natrixeralf.
ment Station, on an ARC pasture 74,1400 ft north of drainage Physiography: Rood plain.
canal and 100 west of Hwy 663, N E K NW14, Sec. 33, T. 35; Slope Characteristics: 001% south west facing undulating.
R24E. Elevation: 1502 mMSL.
Vegetation and use: Slash pine and saw palmetto. Used as Hydraulic conductivity: Moderately low.
pasture. Drainage class: Well drained.
Drainage and permeability: Poorly drained. Permeability is Erosion: Slight.
rapid in the surface layer and substratum and moderate or mod- Parent material: Alluvium material.
erately rapid in the subsoil. Described by: Michael Cook.
Parent material: Marine deposits of sandy materials. Date sampled: August 1988.
324 KALRA: JOURNAL OF AOAC INTERNATIONAL VOL. 78, No. 2,1995

Notes: Vegetation—greasewood.
Al—0-5 cm; dark brown (10YR 3/3) loam; pale brown
(10YR 6/3) dry; strong very fine platy structure; soft, very fri-
able, slightly sticky, slightly plastic; common very fine roots;
common very fine vesicular pores; 890941; slightly efferves-
cent; abrupt smooth boundary.

a
Provided by F. Kaisaki, except for Peck 90-9,90-10,90-11, and
90-12 samples.
Details received from T.R. Peck.

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