An American National Standard

Designation: D 4130 – 03

Standard Test Method for

Sulfate Ion in Brackish Water, Seawater, and Brines 1
This standard is issued under the fixed designation D 4130; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope* E 275 Practice for Describing and Measuring Performances

1.1 This test method covers the turbidimetric determination of Ultraviolet, Visible, and Near Infrared Spectrophotom-
of sulfate ion in brackish water, seawater, and brines. It has eters 4
been used successfully with synthetic brine grade waters;
3. Terminology
however, it is the user’s responsibility to ensure the validity of
this test method to other matrices. 3.1 Definitions—For definitions of terms used in this test
1.2 This test method is applicable to waters having an ionic method, refer to Terminology D 1129.
strength greater than 0.65 mol/L and a sulfate ion concentration 4. Summary of Test Method
greater than 25 mg/L. A concentration less than 25 mg/L sulfate
can be determined by using a standard addition method. 4.1 A sulfate ion is converted to a barium sulfate suspended
1.3 For brines having an ionic strength of less than 0.65 under controlled conditions. A glycerin-acid solution is added
mol/L, refer to Test Methods D 516. to acidify and stabilize the suspension. A calculated volume of
1.4 This standard does not purport to address all of the a NaCl solution is added to adjust the ionic strength to a set
safety concerns, if any, associated with its use. It is the value of 2 mol/L (Note 1). The turbidity resulting upon
responsibility of the user of this standard to establish appro- addition of barium chloride is determined by a photoelectric
priate safety and health practices and determine the applica- colorimeter and compared to a curve prepared from standard
bility of regulatory limitations prior to use. sulfate solutions.
NOTE 1—The ionic strength (IS) of the sample is calculated from the
2. Referenced Documents concentration of the major ion constituents (Na +, Ca 2+, Mg 2+, Cl −), (K +
2.1 ASTM Standards: and Sr 2+ if their concentration exceeds 2000 mg/L) as follows:
D 516 Test Methods for Sulfate Ion in Water 2 where:
D 1129 Terminology Relating to Water 2 IS, mol/L = 1/2 ( CiZi 2,
D 1192 Specification for Equipment for Sampling Water Ci = g/L ion i/molecular weight ion, i, and
and Steam in Closed Conduits 2 Zi = valence of ion i.
D 1193 Specification for Reagent Water 2
D 2777 Practice for Determination of Precision and Bias of 5. Significance and Use
Applicable Methods of Committee D-19 on Water 2 5.1 The determination of sulfate and other dissolved con-
D 3370 Practices for Sampling Water from Closed Con- stituents is important in identifying the source of brines
duits 2 produced during the drilling and production phases of crude oil
D 5810 Guide for Spiking into Aqueous Samples 2 or natural gas.
D 5847 Practice for Writing Quality Control Specifications
for Standard Test Methods for Water Analysis 3 6. Interferences
6.1 Suspended matter in the sample must be removed. Dark
1
colors that cannot be compensated for in the procedure
This test method is under the jurisdiction of ASTM Committee D19 on Water interfere with the measurement of suspended barium sulfate
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents
in Water. (BaSO4).
Current edition approved June 10, 2003. Published July 2003. Originally
approved in 1982. Last previous edition approved in 1999 as D 4130–99.
2
Annual Book of ASTM Standards, Vol 11.01.
3 4
Annual Book of ASTM Standards, Vol 11.02. Annual Book of ASTM Standards, Vol 03.06.

*A Summary of Changes section appears at the end of this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 4130 – 03
7. Apparatus 100 mL with water. Adjust the temperature of these solutions to
7.1 Photometer—A filter photometer or a spectrophotom- 25 6 2°C. These solutions will contain 1.0, 2.0, 3.0, 4.0, 5.0,
eter for measurements between 400 to 450 nm, the preferable 6.0, 8.0, and 10.0 mg of sulfate ion, respectively.
wavelength being 425 nm. The cell for the instrument must 10.2 Follow the procedure as given in 11.6-11.8. Prepare a
have a light path of 20 6 2 mm and hold a volume of 25 mL. calibration curve showing sulfate ion content in milligrams on
Filter photometers, spectrophotometers, and photometric prac- the linear axis with the corresponding percent transmittance
tices prescribed in this test method shall conform to Practice (%T) reading of the photometer on the logarithmic axis of a
E 275. one cycle semilogarithmic graph paper (Note 2).
NOTE 2—The plot of concentration versus %T is not linear but shows a
8. Reagents slight s curvature. A separate calibration curve must be prepared for each
8.1 Purity of Reagents—Reagent grade chemicals shall be photometer and a new curve must be prepared if it is necessary to change
used in all tests. Unless otherwise indicated, it is intended that the photo cell, lamp, filter, or if any other alterations of the instrument or
reagents are made. Check the curve with each series of tests by running
all reagents shall conform to the specifications of the commit-
two or more solutions of known sulfate concentrations.
tee on Analytical Reagents of the American Chemical Society,
where such specifications are available. 5 Other grades may be 11. Procedure
used, providing it is first ascertained that the reagent is of
11.1 Filter the sample through a 0.45-µm membrane filter.
sufficiently high purity to permit its use without lessening the
This is necessary to remove nucleating particles.
accuracy of the determination.
11.2 Pipet a volume of filtered sample not to exceed 50 mL
8.2 Purity of Water—Unless otherwise indicated, reference
and 10 mg SO42- into a 100-mL graduated mixing cylinder. The
to water shall be understood to mean reagent water conforming
ionic strength (IS) of the sample when diluted to 100 must not
to Specification D 1193, Type I. Other reagent water types may
exceed 2.00 mol/L.
be used provided it is first ascertained that the water is of
11.3 Add 5 mL of glycerin-acid solution.
sufficiently high purity to permit its use without adversely
11.4 Add by a graduated pipet or a buret a volume of
affecting the precision and bias of the test method. Type III
sodium chloride solution (5 mol) calculated as follows:
water was specified at the time of round robin testing of this
test method. In addition, reagent water used for this test method mL NaCl 5 ~200 2 ~V 3 IS!/5
shall be sulfate-free.
8.3 Barium Chloride—Crystals of barium chloride V = volume of sample, and
(BaCL2·2H2O) screened to 20 to 70 mesh. IS = ionic strength of sample as calculated in Note 1, 4.1.
8.4 Glycerin-Acid Solution—Mix 250 mL of glycerin and 11.5 Dilute with water to 100 mL, mix well, and adjust the
50 mL of hydrochloric acid (HCl, sp gr 1.19) and dilute to 500 temperature to 25 6 2°C.
mL with water.
8.5 Sodium Chloride Solution (5 mol)—Dissolve 584.4 g of NOTE 3—The temperature of the solution in the mixing cylinder during
sodium chloride (NaCl) containing less than 0.001% SO4 in the development and measurement of the turbidity must be within 2°C of
the temperature of the standards when the calibration was performed. A
about 1800 mL of water and dilute to 2 L with water.
higher temperature will result in a positive error, a lower temperature in a
8.6 Sulfate Solution, Standard (1 mL = 1.00 mg SO4 = )— negative error.
Dissolve 1.479 g of anhydrous sodium sulfate, (Na2SO4), in
water and dilute to 1 L in a volumetric flask. 11.6 Pipet a 25-mL aliquot of the sample solution into a
sample cell and place it in the cell compartment. Set the
9. Sampling photometer to 100 % T (transmittance) with the wavelength set
9.1 Collect the sample in accordance with the applicable at 425 nm or blue filter in place.
ASTM standard as follows: Specification D 1192 or Practices 11.7 Add 0.3 6 0.01 g of BaCl2·2H2O crystals to the 75 mL
D 3370. remaining in the mixing cylinder, stopper, set a timer for 5 min,
9.2 Preserve the samples with high purity hydrochloric acid and mix for 30 s by inverting and righting the cylinder 15
to a pH of two or less immediately at the time of collection (2 times.
mL/L). NOTE 4—It is important the mixing be performed at a constant rate and
duplicated in all determinations.
10. Calibration
11.8 Just before 5 min has expired, check the blank setting.
10.1 Prepare standards by adding 1.0, 2.0, 3.0, 4.0, 5.0, 6.0,
Adjust to 100 %T if drifting has occurred. Replace the blank
8.0, and 10.0 mL of sulfate standard solution (1 mL = 1.00 mg
with the sample cell and measure turbidity at 5 min. If the % T
SO4 = ) to separate 100 mL graduated mixing cylinders. Add
is greater than 80 % or less than 30 % T, the determination
5.0 mL of glycerin-acid solution and 40.0 mL of sodium
with a smaller or larger sample volume providing the restric-
chloride solution (5 mol) to each of the cylinders and dilute to
tions in step 11.2 are not violated.
NOTE 5—The most reproducible section of the calibration curve is from
5
Reagent Chemicals, American Chemical Society Specifications, Am. Chemical 80 to 30 % T. Very low concentrations of sulfate ion can be determined by
Soc., Washington, DC. For suggestions on the testing of reagents not listed by the adding 3 mL of sulfate standard (1 mL = 1.00 mg SO42-) before diluting
American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH to 100 mL in step 11.5 and then subtracting the 3 mg SO42- from the final
Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia. results.

2
 D 4130 – 03
TABLE 1 Determination of Precision and Bias TABLE 2 Composition of Synthetic Brine Samples
Amount Amount Statistically g/L
Added, Found, ST SO % Bias Significant (95 % Sample No.
1 2 3
mg/L mg/L confidence level)
NaCl 47.74 61.04 95.33
60.3 61.7 9.35 2.47 +2.32 no
CaCl2 27.22 40.85 54.47
86.3 83.9 6.98 2.45 −2.78 no
MgCl2 3.84 7.68 7.71
128.9 126.1 6.15 2.67 −2.17 no
SO4 = 0.0863 0.1289 0.0603

12. Calculation calibration standards. Alternately, the concentration of a mid-

12.1 Convert the photometer reading to mg SO42- by refer- range standard should fall within 615% of the known concen-
ring to the calibration curve. Calculate the sulfate ion concen- tration.
tration as follows: 14.2.3 If calibration cannot be verified, recalibrate the
Sulfate, mg/L 5 W 3 1000/V
instrument.
14.3 Initial Demonstration of Laboratory Capability
14.3.1 If a laboratory has not performed the test before, or if
W = milligram SO42- from the calibration curve, and there has been a major change in the measurement system, for
V = sample volume, mL. example, new analyst, new instrument, etc., a precision and
bias study must be performed to demonstrate laboratory
13. Precision and Bias 6 capability.
13.1 The overall and single-operator precision of this test 14.3.2 Analyze seven replicates of a standard solution
method within its designated range for brackish water, seawa- prepared from an Independent Reference Material containing a
ter, and brines varies with the quantity tested in accordance mid-range concentration of sulfate. The matrix and chemistry
with Table 1. of the solution should be equivalent to the solution used in the
13.2 These collaborative test data were obtained on syn- collaborative study. Each replicate must be taken through the
thetic brine waters. For other matrixes, these data may not complete analytical test method including any sample preser-
apply. It is the user’s responsibility to ensure the validity of this vation and pretreatment steps. The replicates may be inter-
test method for waters of untested matrices. spersed with samples.
13.3 The bias of the method determined in synthetic brine is 14.3.3 Calculate the mean and standard deviation of the
presented in Table 1. seven values and compare to the acceptable ranges of bias in
13.4 Precision and bias for this test method conforms to 13.1. This study should be repeated until the recoveries are
Practice D 2777-77, which was in place at the time of within the limits given in 13.1. If a concentration other than the
collaborative testing. Under the allowances made in 1.4 of D recommended concentration is used, refer to Practice D5847
2777-98, these precision and bias data do meet existing for information on applying the F test and t test in evaluating
requirements for interlaboratory studies of Committee D19 test the acceptability of the mean and standard deviation.
methods. 14.4 Laboratory Control Sample (LCS)
14.4.1 To ensure that the test method is in control, analyze
NOTE 6—The precision and bias estimates are based on an interlabo-
ratory study on three synthetic brine samples containing various amounts
a LCS containing a mid-range concentration of sulfate with
of sulfate and other inorganic compounds as shown in Table 2. One each batch or ten samples. If large numbers of samples are
analyst in five laboratories and two analysts in each of two laboratories analyzed in the batch, analyze the LCS after every ten samples.
performed single determinations on each of three days. Practice D 2777, The LCS must be taken through all of the steps of the analytical
was used in developing these precision and bias estimates. method including sample preservation and pretreatment. The
result obtained for the LCS shall fall within 615 % of the
14. Quality Control
known concentration.
14.1 In order to be certain that analytical values obtained 14.4.2 If the result is not within these limits, analysis of
using these test methods are valid and accurate within the samples is halted until the problem is corrected, and either all
confidence limits of the test, the following QC procedures must the samples in the batch must be reanalyzed, or the results must
be followed when analyzing sulfate. be qualified with an indication that they do not fall within the
14.2 Calibration and Calibration Verification performance criteria of the test method.
14.2.1 Analyze at least three working standards containing 14.5 Method Blank
concentrations of sulfate that bracket the expected sample 14.5.1 Analyze a reagent water test blank with each batch.
concentration prior to analysis of samples to calibrate the The concentration of sulfate found in the blank should be less
instrument. than 0.5 times the lowest calibration standard. If the concen-
14.2.2 Verify instrument calibration after standardization by tration of sulfate is found above this level, analysis of samples
analyzing a standard at the concentration of one of the is halted until the contamination is eliminated, and a blank
shows no contamination at or above this level, or the results
must be qualified with an indication that they do not fall within
6
Supporting data have been filed at ASTM International Headquarters and may the performance criteria of the test method.
be obtained by requesting Research Report RR: D19–1077. 14.6 Matrix Spike (MS)

3
 D 4130 – 03
14.6.1 To check for interferences in the specific matrix results must be qualified with an indication that they do not fall
being tested, perform a MS on at least one sample from each within the performance criteria of the test method.
batch by spiking an aliquot of the sample with a known NOTE 7—Acceptable spike recoveries are dependent on the concentra-
concentration of sulfate and taking it through the analytical tion of the component of interest. See Test Method D 5810 for additional
method. information.
14.6.2 The spike concentration plus the background concen-
tration of sulfate must not exceed the high calibration standard. 14.7 Duplicate
The spike must produce a concentration in the spiked sample 14.7.1 To check the precision of sample analyses, analyze a
that is 2 to 5 times the analyte concentration in the unspiked sample in duplicate with each batch. If the concentration of the
sample, or 10 to 50 times the detection limit of the test method, analyte is less than five times the detection limit for the analyte,
whichever is greater. a matrix spike duplicate (MSD) should be used.
14.6.3 Calculate the percent recovery of the spike (P) using 14.7.2 Calculate the standard deviation of the duplicate
the following formula: values and compare to the precision in the collaborative study
using an F test. Refer to 6.4.4 of Practice D 5847 for
P 5 100 [A~Vs 1 V! – BVs# / CV information on applying the F test.
where 14.7.3 If the result exceeds the precision limit, the batch
must be reanalyzed or the results must be qualified with an
indication that they do not fall within the performance criteria
A = analyte concentration (mg/L) in spiked sample, of the test method.
B = analyte concentration (mg/L) in unspiked sample,
C = concentration (mg/L) of analyte in spiking solution, 14.8 Independent Reference Material (IRM)
Vs = volume (mL) of sample used, and 14.8.1 In order to verify the quantitative value produced by
V = volume (mL) added with spike. the test method, analyze an Independent Reference Material
14.6.4 The percent recovery of the spike shall fall within the (IRM) submitted as a regular sample (if practical) to the
limits, based on the analyte concentration, listed in Test laboratory at least once per quarter. The concentration of the
Method D 5810, Table 1. If the percent recovery is not within IRM should be in the concentration mid-range for the method
these limits, a matrix interference may be present in the sample chosen. The value obtained must fall within the control limits
selected for spiking. Under these circumstances, one of the established by the laboratory.
following remedies must be employed: the matrix interference
must be removed, all samples in the batch must be analyzed by 15. Keywords
a test method not affected by the matrix interference, or the 15.1 brackish; brine; seawater; sulfate

SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue
(D 4130 – 99) that may impact the use of this standard.

(1) Section 8.2 was modified. (3) Section 14 (Quality Control) was added to the test method.
(2) Section 13.4 was added.

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