Published 1982

10 Soluble Salts·

J. D. RHOADES
U. S. Salinity Laboratory
Riverside, California

10-1 INTRODUCTION

The term soluble salts, as applied to soils, refers to major dissolved inorgan-
ic solutes. Soil salinity is described and characterized in terms of the concen-
trations (or, occasionally, the content) of soluble salts. The management
and need for reclamation of saline soils are evaluated from measurements
of such concentrations.
Ideally, it would be desirable to know the individual solute concentra-
tions in the soil water over the entire range of field water contents and to
obtain this information immediately in the field, without need for collection
of soil samples or laboratory analyses. No practical methods are available at
present to permit such determinations, although determinations of total
salinity can be made in situ using electrical signals from various types of
sensors (Rhoades, 1978, 1984). Such determinations are valuable for sur-
vey, monitoring, and irrigation and drainage needs, even though they give
a measure of only total soluble salt concentration. Such methods are, in
many cases, supplanting the need for more conventional analytical proce-
dures.
Soluble salts in soils can be determined or estimated from measure-
ments made (i) on aqueous extracts of soil samples, (ii) on samples of soil
water itself obtained from the soil, (iii) in soil using buried porous salinity
sensors that imbibe and equilibrate with soil water, and (iv) in soil (or soil
pastes) using four-electrode probes or electromagnetic (EM) systems. The
appropriate method of measuring soil salinity must be selected for the
specific condition and purpose. If only a measure of total soluble electrolyte
level is needed, salinity sensors, EM, or four-probe devices are recommended.
To monitor soil water salinity as the soil dries between irrigations, the salinity
sensor is recommended. When determination of a particular solute is
needed, then either collection and extraction of soil samples or collection of
water samples is required. Collection of water samples is more convenient
for monitoring needs but is limited to relatively wet soil conditions. Soil
sample extracts give relative comparisons only, since the soils are adjusted
to unnaturally high water contents during extraction. A combination of the
1 Contribution from the U.S. Salinity Laboratory, USDA-ARS, Riverside, CA 92501.
Copyright 1982 © ASA-SSSA, 677 S. Segoe Rd., Madison, WI 53711, USA. Methods oj Soil
Analysis, Part 2. Chemical and Microbiological Properties-Agronomy Monograph no. 9
(2nd Edition).
167
168 SOLUBLE SALTS

various methods minimizes need for sample collection and chemical analy-
sis, especially when monitoring salinity changes with time and characteriz-
ing large field or project situations. For the latter, use of EM and four-
probe techniques are recommended with supplemental use of the other
methods as needed. Only methods for obtaining aqueous extracts of soil
samples are dealt with in this section.
The following sections describe methods for determining soluble salts
in water and soils using various methods and procedures for obtaining
aqueous extracts of soil samples.

10-2 SATURATION EXTRACT AND OTHER

AQUEOUS EXTRACTS

10-2.1 Principles

For some needs, knowing the composition of solutes in soil water at

field water contents is desirable. However, present methods of obtaining
soil water samples at usual field water contents are not practical for routine
purposes. Thus, soil solution extracts often must be made at higher than
normal water contents. Because the absolute and relative amounts of vari-
ous solutes are influenced by the soil/water ratio at which the extract is
made (Reitemeier, 1946), the ratio must be standardized to obtain results
that can be applied and interpreted universally. Soil salinity is convention-
ally defined and measured on aqueous extracts of saturated soil pastes (U .S.
Salinity Laboratory Staff, 1954). This soil/water ratio is used because it is
the lowest reproducible ratio for which enough extract for analysis can be
readily removed from the soil with pressure or vacuum and because it is
often related in a predictable manner to field soil water contents. For these
reasons, crop tolerance to salinity is often related to the electrical conduc-
tivity, or total electrolyte concentration, of the saturation extract (U. S.
Salinity Laboratory, 1954).
Other extraction ratios, 1:1, 1:5, etc., are easier to use than that of
saturation, but they are not so well related to field soil water contents.
Errors from peptization, hydrolysis, cation exchange, and mineral dissolu-
tion also become greater for such extracts. As a compromise, Sonnevelt and
van den Ende (1971) recommended a 1:2 volume extract. When relative
changes rather than absolute solute concentrations are monitored, these
wider extraction ratios may be used to advantage.
Once soil extract samples are obtained, laboratory chemical analyses
are carried out to determine the electrical conductivity of the extract (ae)
and the concentrations of major solutes (section 10-3).

10-2.2 Reagent

1. Sodium hexametaphosphate [(NaP0 3)6] solutions, 0.1070: Dissolve 0.1 g

of (NaP0 3)6 in water, and dilute the solution to 100 ml.
10-2 SATURATION EXTRACT AND AQUEOUS EXTRACTS 169

10-2.3 Procedure

10-2.3.1 SATURATION EXTRACT

Weigh 200 to 400 g of air-dry soil of known water content into a plastic
container having a snaptight lid. Weigh the container plus contents. Add
distilled water to the soil with stirring until it is nearly saturated. Allow the
mixture to stand covered for several hours to permit the soil to imbibe the
water, and then add more water to achieve a uniformly saturated soil-water
paste. At this point, which is generally reproducible to within ± 5070, the
soil paste glistens as it reflects light, flows slightly when the container is
tipped, slides freely and cleanly off a spatula, and consolidates easily by
tapping or jarring the container after a trench is formed in the paste with the
side of the spatula. After mbdng, allow the sample to stand (preferably
overnight, but at least 4 hours), and then recheck the criteria for saturation.
Free water should not collect on the soil surface, nor should the paste stiffen
markedly or lose its glisten. If the paste is too wet, add additional dry soil to
the paste mixture. Upon attainment of saturation, reweigh the container
plus contents. Record the increase in weight, which is the amount of water
added. Calculate the saturation water percentage from the weight of oven-
dry soil and the sum of the weights of water added and that initially present
in the air-dry sample. After allowing the saturated soil paste to stand 4 or
more hours, transfer it to a Buchner or Richards (1949) filter funnel fitted
with highly retentive filter paper. Apply vacuum, and collect the filtrate in a
test tube or bottle. If the initial filtrate is turbid, refilter or discard it.
Terminate the filtration when air begins to pass through the filter. Add 1
drop of 0.1 0J0 (NaP0 3)6 solution for each 25 mt of extract.

10-2.3.2 EXTRACTS AT SOIL/WATER RATIOS OF 1:1 AND 1:5

Weigh a sample of air-dry soil of appropriate size, and transfer it to a
flask or bottle. Add the required amount of distilled water, stopper the con-
tainer, and shake it in a mechanical shaker for 1 hour. If a mechanical
shaker is not available, shake the container vigorOUSlY by hand for 1 min at
least 4 times at 30-min intervals. Filter the suspension using highly retentivt:
filter paper. (Discard or refilter the initial filtrate if it is turbid.) Add 0.1 0J0
(NaP0 3)6 solution at the rate of 1 drop125 ml of extract.

10-2.4 Comments

The weight of soil required will depend on the number and kind of de-
terminations to be made on the extract, the analytical methods employed,
and the salt content of the soil. In general, from one fourth to one third of
the water in saturated soil pastes can be removed by vacuum filtration.
Soil samples should not be oven-dried before extracting for determina-
tion of soluble salts, because heating to 105°C converts at least a part of the
gypsum (CaS0 40 2H 2 0) to plaster of paris (CaS04 0 1/2H2 0). The latter
hydrate has a higher solubility in water than does the former.
170 SOLUBLE SALTS

In determinations of extract water contents when a low ratio of soil to

water is used, it is desirable to correct for the water content of the air-dry
soil. For example, an air-dry sample containing 2"70 water on an oven-dry
basis can be adjusted to a soil/water ratio of 1: 1 by adding 98 ml of water to
102 g of air-dry soil. At soil/water ratios of 1:5 or greater, no correction is
ordinarily made for water in the air-dry sample.
Special precautions should be taken in preparing a saturated soil paste
with peat and muck soils or very fine or very coarse-textured soils. If possi-
ble, peat and muck soils should not be allowed to dry following collection
because their saturation water content changes. Peat and muck, especially if
coarse or woody, require an overnight imbibition period to obtain a definite
endpoint for the saturation point. After the first wetting, pastes of these
soils usually stiffen upon standing. Adding water and remixing then give a
mixture that usually retains the characteristics of a saturated paste. With
fine-textured soils, enough water should be added immediately, with a mini-
mum of mixing, to bring the sample nearly to saturation. This minimizes
the formation of clumps of soil during stirring, speeds the mixing process,
and helps attain a more definite endpoint. Care should also be taken not to
overwet coarse-textured soils. The presence of free water on the surface of
the paste after standing is a very important indication of oversaturation in
the case of coarse-textured soils. Even small amounts of free water can lead
to appreciable errors in saturation paste water contents for these materials.
Sodium hexametaphosphate is added to the extract to prevent the pre-
cipitation of CaC0 3 from the extract upon standing. The quantity of
(NaP0 3)6 solution added increases the Na concentration - 0.5 ppm, or 0.02
meq/liter, which is inconsequential compared with the possible loss of
CaC0 3 • Alternatively, a subsample of the extract could be immediately
diluted twofold and used for the Ca and alkalinity determinations.
Alternative methods of preparing the saturated soil paste have been de-
scribed by Longenecker and Lyerly (1964), who proposed wetting the soil
sample on a capillary saturation table, Beatty and Loveday (1974) and
Loveday (1972), who recommended predetermining the amount of water at
saturation on a separate soil sample using a capillary wetting technique, and
Allison (1973), who recommended slowly adding soil to water (oversatura-
tion method). Similar results are obtained with these methods. The choice
of method is primarily one of personal preference.
Thymol can be added to the paste to minimize the effect of microbial
activity on saturation extract composition during equilibration (Carlson et
aI., 1971).
The extracts should be stored at -4°C until analyzed.

10-3 SOLUBLE CONSTITUENTS IN SOIL WATERS AND

AQUEOUS EXTRACTS

The major solutes of interest found in soil waters and aqueous extracts
of salt-affected soils are Ca 2+, Mg2+, Na+, K+, CO/-, HC0 3 -, S04 2-, CI-,
N0 3 -, and H 3 B0 3 • There are many satisfactory analytical methods for de-
10-3 SOLUBLE CONSTITUENTS 171

termining these solutes. These methods range from wholly automated to

manual. The choice of which to use is usually determined by the number of
samples being processed and the availability of analysts, automated equip-
ment, or both. The methods described here are those in common use in
laboratories having typical modern but not fully automated instrumenta-
tion. Methodology more suited to laboratories without such conveniences
was given previously by Bower and Wilcox (1965).

10-3.1 Sequence of Analyses

Alkalinity and pH determinations should be made immediately on

fresh extracts or on the solutions treated with hexametaphosphate. Next,
electrical conductivity, a, should be determined; it is a useful means of esti-
mating total salt concentration (meq/liter == 10 a, in deci-Siemens per
meter, dS/m). The cations can be determined in any sequence. After any
three of the four major cations have been determined, the appropriate
aliquot for the remaining cation can be estimated by deducting the sum of
the three concentrations, in milliequivalents per liter, from 10 a, in deci-
Siemens per meter. Among the anions, N0 3 - and Cl- determinations are
normally made after alkalinity since they are simpler to measure than SO/-.
After that, SO/- is determined; the appropriate aliquot is estimated from
the difference between (Ca 2 + + Mg2+ + Na+ + K+) and (alkalinity + N0 3 -
+ Cn. Finally, B is determined. Concentration of this solute is negligible
compared with that of the major cations and anions, but it is still extremely
important because of its pronounced toxicity even in small concentrations
to many plants.

10-3.2 pH and Alkalinity

10-3.2.1 APPARATUS
1. Automatic potentiometric titrator.
2. Single probe combination pH electrode.

10-3.2.2 REAGENTS
1. Standard buffer solutions, pH 4.00 and 7.00.
2. Standard hydrochloric acid (HCI), approximately 0.0200N.

10-3.2.3 PROCEDURE
With electrode immersed in standard pH buffer, set the potentiometer
to the pH (7.00) of the first buffer solution. Rinse electrode, and repeat
calibration using the second pH buffer. Rinse electrode, immerse in 1 to 20
ml of sample solution (contained in a 50-ml plastic beaker along with a
microsize, Teflon-coated magnetic stirring bar), and initiate the automatic
titration operation using the full titration curve display mode. The initial
potential recorded on the strip chart gives the sample pH. The volumes of
titrant delivered to produce inflection points for C0 3 2 - and HC0 3 - are ob-
172 SOLUBLE SALTS

tained from the titration curve (pH vs. volume of standard acid delivered
from automatic burette).

10-3.2.4 CALCULA nONS

C0 3 2- in meq/liter = 2P N 1,OOO/aliq

where P is the number of milliliters of standard HCI of normality N to reach

the CO/- inflection point (pH = 8.3), and aliquot is the sample volume in
milliliters.

HC0 3 -inmeq/liter = (T - 2P)N1,OOO/aliquot

where T is the total number of milliliters of standard HCI of normality N to

reach the HC0 3 - inflection point (pH = 4.5), P is the number of milliliters
of standard HCI required to reach the CO/- inflection point, and aliquot is
the sample volume in milliliters. The blank is determined using CO/- free
distilled water.

10-3.3 Electrical Conductivity

For this determination, use a direct readout from a temperature com-

pensating conductivity meter.

10-3.3.1 APPARATUS
1. Conductivity meter.
2. Conductivity flow cell with automatic temperature compensation.
3. Vacuum line and suction flask.

10-3.3.2 REAGENT
1. Standard potassium chloride (KCI) solutions, 0.010 and 0.100N:
For O.01ON solution (1.412 dS/m at 25°C) dissolve 0.7456 g of KCI in
distilled water, and add water to make 1 liter at 25°C. For 0.100N solu-
tion (12.900 dS/m at 25°C), use 7.456 g ofKCl.

10-3.3.3 PROCEDURE
Rinse and fill the conductivity cell with standard KCI solution. Adjust
the conductivity meter to read the standard conductivity. Rinse and fill the
cell with the soil extract or water sample, and read the (J, corrected to 25°C,
directly from the digital display.

10-3.3.4 COMMENTS
Because of marked differences in the equivalent weights, equivalent
conductivities, and proportions of major solutes in soil extracts and water
samples, the relationships between (J and salt concentration or between (J
10-3 SOLUBLE CONSTITUENTS 173

and osmotic pressure are only approximate. They are still quite useful, how-
ever. These relationships are:
1) Total cation (or anion concentration), meq/liter == 10 x a, in dS/m.
2) Salt concentration, mg/liter == 640 x a, in dS/m.
3) Osmotic pressure, bars at 25°C == 0.39 x a, in dS/m.

10-3.4 Soluble Cations

Determine Ca2+, Mg2+, Na+, and K+ using an atomic absorption spec-

trometer or by methods outlined in sections 13-3.3.2 and 13-3.3.4 for K,
13-4.3.3 and 13-4.3.5 for Na, and 14-3.1 for Ca and Mg. If large numbers
of samples are to be routinely analyzed, it is extremely helpful to have this
unit equipped for automatic sample transport, sequencing, siphoning, read-
ing, and recording.

10-3.4.1 APPARATUS
1. Atomic absorption spectrometer.
2. Sampling and sequencing system.
3. Acetylene gas (C 2H 2), commercial grade.

10-3.4.2 REAGENTS
1. Suppressant solution for Ca2+ and Mg2+: Add 29.0 g of lanthanum oxide
(La 203), 250 ml of conc hydrochloric acid (HCI), and enough distilled
water to make up to 5OD-ml volume. Add sufficient to aliquot and
diluent (distilled water) to give 10070 (by volume) of this LaCl l solution
in the final solution.
2. Suppressant solution for Na+ and K+: Add 6.358 g of lithium chloride
(Liel) and make to 1 liter in distilled water (0.15N). Add enough to
aliquot, and diluent (distilled water) to give 10070 (by volume) of this
LiCI solution in the final solution.
3. Standard cation solutions: Ca2+ (0-0.4 meq/liter), Mg2+ (0-0.1 meq/
liter), Na+ (0-1.0 meq/liter), and K+ (0-0.1 meq/liter).

10-3.4.3 PROCEDURE
Adjust the atomic absorption spectrometer controls and settings for
the cation to be run as recommended by the manufacturer. Set the atomic
absorption spectrometer readout to read the upper and lower standard solu-
tions. Then initiate transport/readout system, which automatically posi-
tions a sequence of samples, siphons and aspirates the samples in the air-
acetylene flame, and reads and records (as a digital printout) the concen-
tration of the cation in the aspirated solution. Standard solutions are in-
serted into the sampling rack every 20 samples to ensure stability of instru-
ment calibration during the automated run. Two-hundred samples can be
processed per hour without attendance after the automatic sample pro-
cessing system is initiated. Alternatively, the same sequence of operations
can be performed by hand.
174 SOLUBLE SALTS

10-3.4.4 CALCULATIONS
Concentration of cations in original sample in meq/liter
= (atomic absorption spectrometer readout, meq/liter in aspirated sample)

x (Analytical dilution factor).

With Ca, the dilution factor must include the 1: 1 predilution made at sam-
pling time to prevent precipitation of CaCO J during storage, if appropriate.

10-3.5 Chloride

Determine Cl- in solution by electro metric titration with silver or al-

ternative procedures outlined in section 26-3. Silver ions are automatically
generated coulometrically, and the endpoint is indicated amperometrically
(elapsed time is indicated to the nearest 0.1 sec). Since the rate of Ag+ gener-
ation is constant, the amount of Cl- precipitated is proportional to time.
The proportionality between duration of titration and concentration is
established using standard Cl- solutions and a blank.

10-3.5.1 APPARATUS
1. Automatic coulometric/amperometric Cl- titrator (section 26-3.5).

10-3.5.2 REAGENT
1. Nitric acid-acetic acid/polyvinyl alcohol (PV A): Dissolve 1.8 g of
powdered PYA in 100 ml of demineralized water with heating and stir-
ring, cool to room temperature. Add 6.4 ml of cone nitric acid (HNO J)
and 100 ml of glacial acetic acid to a I-liter volumetric flask containing
600 ml of demineralized water, and mix thoroughly. Add the cooled
PVA solution to the nitric acid-acetic acid solution, mix, cool, and make
to volume with demineralized water. Store this nitric acid-acetic acid/
PVA reagent in a tightly stoppered container at room temperature. This
reagent is stable for at least 12 months.

10-3.5.3 PROCEDURE
Add 4 ml of nitric acid-acetic acid/PVA reagent together with a sam-
ple aliquot ( < 3 ml) to a titration vial. Position vial in titrator, immersing
electrode assembly into the solution. Zero the timer, and initiate automatic
titration at low, medium, or high current setting. Note the titration times of
blank, standards, and samples.

10-3.5.4 CALCULATION
Cl- in meq/liter
= (K)(Titration time of sample minus titration time of blank)/ aliquot

where K is a standardization factor and aliquot is sample size in ml.

10-3 SOLUBLE CONSTITUENTS 175

K = (Volume of Cl- standard in ml)(Conc of Cl- standard in meq/liter)/

(Titration time of standard minus blank).

10-3.6 Nitrate

Determine N0 3 - concentration using a specific ion electrode (section

33-6) or alternative procedures (section 33-7). Its concentration is primarily
used to allow for a check on cation/anion balance, because N0 3- seldom is
an appreciable fraction of the anions in saline waters. It is an important
contaminant in return flows from many irrigated areas and an indicator of
poor fertility management.

10-3.6.1 APPARATUS
1. Electrometer.
2. Specific N0 3 - selective electrode.
3. Calomel reference electrode.

10-3.6.2 REAGENT
1. Standard nitrate (N0 3 -) solutions: 0.01, 0.10, 1.00, 10.0, and 100 in
meq/liter.

10-3.6.3 PROCEDURE
Prepare electrode according to manufacturers directions. Place elec-
trodes in 5 to 10 ml of sample or standard solution, and record millivolt
readings. Determine concentration of N0 3 - in sample by comparison with
standard curve.

10-3.7 Sulfate

Determine SO/- in samples using one of two methods, depending on

amount of sample available and its estimated SO/- concentration (SO/- is
estimated initially from the difference between the sums of cations and
anions, excluding SO/-). Use the turbidimetric method whenever a sample
is expected to contain at least 5 meq/liter SO/-. When the concentration is
less, use the potentiometric titration method employing a Pb2+ selective elec-
trode or methods outlined in section 28-3.

10-3.7.1 TURBIDIMETRIC METHOD

Sulfate is converted to a BaSO. suspension under controlled condi-
tions. The resulting turbidity is determined by a spectrometer and compared
with a curve prepared from standard SO/- solutions (Standard Methods,
1980, p. 439-440).
10-3.7.1.1 Apparatus.
1. Absorption spectrometer.
2. Magnetic stirrer.
176 SOLUBLE SALTS

10-3.7.1.2 Reagents.
1. Barium chloride dihydrate (BaCI 2 02H 2 0) crystals, 20 to 30 mesh.
2. Conditioning reagent: Dissolve 7S g of sodium chloride (NaCl) in 27S ml
of water in a SOO-ml volumetric flask with magnetic stirring bar, add,
with stirring, 30 ml of cone hydrochloric acid (HCI), 100 ml of absolute
ethanol, and SO ml of glycerol. Rinse glycerol into flask. Continue stir-
ring until NaCl dissolves. Remove stirring bar and make to volume with
distilled water.
3. Standard sulfate (S04 2-) solutions, 0 to 1 meq/liter.
10-3.7.1.3 Procedure.
Remove suspended material from sample, if present, by filtration or
ultracentrifugation. Run a blank to correct for color interference and
residual suspended material. Dilute sample to obtain sample of < 1 meq
SO/-/liter. Transfer l00-ml aliquots of standards, blank, and diluted sam-
ples into 2S0-ml Erlenmeyer flasks. Add S.OO ml of conditioning reagent to
each flask with a S-ml automatic pipetter. Introduce a clean magnetic stir-
ring bar into the flask of the sample to be analyzed (read blank, standards
and then samples in that order). Place flask on magnetic stirrer preset at
constant speed (use fastest speed possible without splashing, but do not
change speed once runs are begun). While stirring, add, all at once, 0.2 g of
barium chloride crystals with a measuring spoon. Stir for exactly 60 sec,
then remove flask from stirrer. Read maximum absorbance with spec-
trometer set at 340 nm after 1 to 3 min. Construct standard curve and de-
termine concentration of SO.2- in final solution by comparison.
10-3.7.1.4 Calculations.
Concentration of SO/- in sample, meq/liter = (Analytical dilution factor)
x (Concentration of SO/- from standard curve).

10-3.7.2 POTENTIOMETRIC METHOD

Where the concentration in the sample is < S meq/liter, SO/- is de-
termined by titration with lead percolate, with the endpoint (presence of ex-
cess Pb 2+) detected potentiometrically using a Pb 2+-sensitive specific ion
electrode (Goertzen & Oster, 1972).
10-3.7.2.1 Apparatus.
1. Semiautomated potentiometric titrator.
2. Lead-sensitive specific ion electrode.
3. Calomel reference electrode.
10-3.7.2.2 Reagents.
1. Methanol, ASC grade.
2. Lead perchlorate [Pb(CI04)2], 0.002 and O.OOSN.
3. Sodium perchlorate (NaCI04), 0.100N.
10-3 SOLUBLE CONSTITUENTS 177

4. Sodium hydroxide (NaOH), 6N.

5. Perchloric acid (HCI0 4), 0.014N.
10-3.7.2.3 Procedure.
Transfer an aliquot containing about 0.004 meq of SO/- into a 50-ml
beaker. Add 0.6 ml of NaCI0 4 solution, and make to 5 ml with distilled
water. Add 11 ml of methanol, and adjust the pH to 4.3 to 4.4 with drop-
wise additions of either HCI0 4 or NaOH as needed using pH meter. Place
the magnetic stirring bar in beaker, insert electrodes (the millivolt reading
should be in the range - 240 to - 280), and titrate with standard Pb(CI0 4)2
solution using the automatic titration apparatus. Determine the equivalence
point from the inflection point of the titration curve.
10-3.7.2.4 Calculation.
SO/- in meq/liter = (V) (N)/aliquot

where V and N are volume in milliliters and normality of standard

Pb(CI0 4)2 used in titration to endpoint, respectively, and aliquot is the
sample volume in ml.
10-3.7.2.5 Comments.
The Pb electrode is subject to poisoning. If the potential reading is >
- 240 to - 280 mV, the electrode should be polished and cleaned.

10-3.8 Boron

Concentration of B in samples is determined by formation of the

colored boric acid-azomethine complex and spectrometry (John et aI.,
1975; section 25-5) or alternative methods outlined in Chapter 25.

10-3.8.1 APPARATUS
1. Automated spectrometric system: Use plastic containers. Do not use
borosilicate glassware.

10-3.8.2 REAGENTS
1. Buffer masking solution: Dissolve 250 g of ammonium acetate
(NH 4 0Ac) and 15 g of ethylenediaminetetraacetatic acid disodium salt
(EDT A disodium) in 400 ml of deionized distilled water, and slowly
adding 125 ml of glacial acetic acid.
2. Azomethine-H reagent: Dissolve 0.45 g of azomethine-H in 100 ml of
1070 L-ascorbic acid solution. Fresh reagent should be prepared each
week and stored in a refrigerator.
3. Stock solution: Dissolve 0.1143 g of boric acid (H 3 B0 3) in 1 liter of water
to obtain a stock solutiori of 20 ppm of B. Prepare standards containing
0.5 to 4 ppm B by diluting stock solution with water.
178 SOLUBLE SALTS

10-3.8.3 PROCEDURE
Pipette 1 ml of blank, standard solution, or sample into a 15-ml poly-
propylene tube, and then add 2 ml of buffer. Mix contents of tube with an
electrical stirrer. Add 2 ml of azomethine-H reagent. Stir thoroughly, and
allow to stand at room temperature for 30 min. Measure absorbance at 420
nm. Determine concentration of B in sample by comparison with standard
curve (0-4 ppm).

10-3.8.4 CALCULATION
Boron in ppm

= (Concentration read from standard curve)(Analytical dilution factor).

10-3.9 Accuracy of Analyses

Examine the analytical results to detect gross errors by looking for ex-
pected interrelationships among the constituent cations and anions. First
check water analyses for chemical balance (the sum of the equivalent con-
centration of cations in solution must equal the sum of the anions). Differ-
ences of 3 to 4010 are acceptable. Larger deviations indicate either a large
error in one or more of the determinations or the presence of some unde-
termined constituent, but a good balance is not conclusive evidence that
each of the determinations is accurate nor that all constituents have been de-
termined. Therefore, look for additional expected relations in the analyses.
For solutions having a values < 10 dS/m, check to see if the a, in deci-
Siemens per meter, multiplied by lOis approximately equal to the total
cation or anion concentration, in milliequivalents per liter. If CO l 2 - is pres-
ent in titratable amounts, the pH of the extract must be 2:= 8.3. The HCO l -
concentration of irrigation water seldom exceeds 10 meq/liter in the absence
of CO l 2 - but may exceed 20 meq/liter in drainage waters having pH's of 6 to
7.5. Compare sample results from a sequence of soil depths for presence of
a constituent deviating from profile trends. More extensive tests are de-
scribed in the Standard Methods/or the Examination 0/ Waste and Waste-
water (1980).
Some errors are practically unavoidable in analytical work. The
analyst's skill and judgment playa large part in controlling the extent of
such errors. The validity of the results must be evaluated after chemical
analyses are completed. The analytical methods described yield results of
moderate accuracy, probably with less error than the variation due to sam-
pling.

10-4 LITERATURE CITED

Allison, L. E. 1973. Oversaturation method for preparing saturation extracts for salinity ap-
praisal. Soil Sci. 116:65-69.
10-4 LITERATURE CITED 179

Beatty, H. J., and 1. Loveday. 1974. Soluble cations and anions. p. 108-117. In J. Loveday
(ed.) Methods for analysis of irrigated soils. Technical Communication no. 54, Common-
wealth Bureau of Soils, Commonwealth Agricultural Bureaus, Farmham Royal, Bucks,
England.
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