Designation: D 4328 – 97

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Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Practice for

Calculation of Supersaturation of Barium Sulfate, Strontium
Sulfate, and Calcium Sulfate Dihydrate (Gypsum) in
Brackish Water, Seawater, and Brines1
This standard is issued under the fixed designation D 4328; 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 D 3986 Test Method for Barium in Brines, Seawater, and

1.1 This practice covers the calculation of supersaturation of Brackish Water by Direct-Current Argon Plasma Atomic
barium sulfate, strontium sulfate, and calcium sulfate dihydrate Emission Spectroscopy3
(gypsum) in brackish water, seawater, and brines in which
3. Terminology
barium, strontium, and calcium ions either coexist or exist
individually in solution in the presence of sulfate ions. 3.1 Definitions: For definitions of terms used in this prac-
1.2 This practice is not applicable for calculating calcium tice, refer to Terminology D 1129.
sulfate dihydrate supersaturation if the temperatures of saline 4. Significance and Use
waters under investigation exceed 95°C. At temperatures above
95°C, hemianhydrate and anhydrite would be major insoluble 4.1 This practice covers the mathematical calculation of the
forms. supersaturation of three principal sulfate scaling compounds
1.3 This standard does not purport to address all of the found in industrial operations. Application of this standard
safety concerns, if any, associated with its use. It is the practice to the prediction of scale formation in a given system,
responsibility of the user of this standard to establish appro- however, requires experience. The calculations tell the user if
priate safety and health practices and determine the applica- a water, or mixture of waters, is in a scaling mode. Whether or
bility of regulatory limitations prior to use. not scale will in fact form, how quickly it will form, where it
will form, in what quantities, and what composition are subject
2. Referenced Documents to factors beyond the scope of this practice. However, based on
2.1 ASTM Standards: how supersaturated a given water or mixture of waters is, an
D 511 Test Methods for Calcium and Magnesium in Water2 objective evaluation of the relative likelihood of scale forma-
D 512 Test Methods for Chloride Ion in Water tion can be made.
D 513 Test Methods for Total and Dissolved Carbon Diox- NOTE 1—There are several personal computer (PC) type programs that
ide in Water2 are both available commercially and publicly that will perform these
D 516 Test Method for Sulfate Ion in Water2 calculations.
D 1129 Terminology Relating to Water2
5. Procedure
D 1192 Specification for Equipment for Sampling Water
and Steam in Closed Conduits2 5.1 Collect water samples for compositional analysis in
D 3352 Test Method for Strontium Ion in Brackish Water, accordance with Practices D 3370 and Specification D 1192.
Seawater, and Brines3 5.2 Determine the calcium and magnesium concentrations
D 3370 Practices for Sampling Water from Closed Con- in accordance with Test Methods D 511.
duits2 5.3 Determine the barium concentration in accordance with
D 3561 Test Method for Lithium, Potassium, and Sodium Test Methods D 3651 or D 3986.
Ions in Brackish Water, Seawater, and Brines by Atomic 5.4 Determine the strontium concentration in accordance
Absorption Spectrophotometry3 with Test Method D 3352.
D 3651 Test Method for Barium in Brackish Water, Seawa- 5.5 Determine sodium and potassium concentrations in
ter, and Brines3 accordance with Test Method D 3561.
5.6 Determine sulfate ion concentration in accordance with
1
This practice is under the jurisdiction of ASTM Committee D-19 on Water and Test Method D 516.
is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents in 5.7 Determine chloride ion concentration in accordance
Water. with Test Methods D 512.
Current edition approved Dec. 10, 1997. Published December 1998. Originally
published as D 4328–84. Last previous edition D 4328–84 (1993)e1.
5.8 Determine carbonate and bicarbonate ion concentrations
2
Annual Book of ASTM Standards, Vol 11.01. in accordance with Test Methods D 513.
3
Annual Book of ASTM Standards, Vol 11.02.

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5.9 Determine the concentrations of all other major inor- Report BaSO4 supersaturation in molal terms of the weight
ganic constituents that may be present in the water under of BaSO4 per volume of water, mg/L.
investigation in accordance with appropriate test methods in BaSO4 supersaturation, mg/L

S D
Annual Book of ASTM Standards, Vols 11.01 and 11.02.
1000 3 D
5.10 Determine temperature and pressure of the water 5 BaSO4, ~molal2! 3 103 3 233 3 TDS 1 1000
system under investigation. 1000
6. Calculation of Ionic Strength
6.1 Calculate the ionic strength of the water under investi- where D 5 sample density.
gation as follows:
1
8. Calculation of Strontium Sulfate Supersaturation
µ 5 2(CiZi2 (1) (Refer to Appendix X1)
8.1 Calculate strontium sulfate solubility using the same
where: steps described for BaSO4(Section 7), but substituting the
µ 5 ionic strength, appropriate values for SrSO4 in Eq 2 (Refer to Appendix X3 or
Ci 5 molal concentration of each ion in solution, and Appendix X4).
Zi 5 charge number of ion, i.
NOTE 3—If barium sulfate supersaturation exists, the amount of sulfate
7. Calculation of Barium Sulfate Supersaturation (Refer available for strontium sulfate will be less by the amount of sulfate
to Appendix X1) equivalent to the calculated BaSO4 supersaturation.
7.1 Calculate barium sulfate solubility in the water under NOTE 4—If carbonate ions are present, strontium carbonate may
investigation, using the equation as follows: precipitate. The amount of strontium may then be corrected by that
required for strontium carbonate precipitation prior to the calculation of
S 5 ~=X 2 1 4K 2 X!/2 (2) SrSO4 solubility. (6) Practically speaking, however, due to the extremely
low solubility of SrCO3, this correction may usually be omitted.
where: 8.2 Calculate the amount of strontium sulfate moles per
S 5 solubility, moles of solute per kilogram of water kilogram water in the sample based on the lesser of the
corrected for the common ion effect, strontium or remaining sulfate ion concentration.
K 5 solubility product constant (molal) at the ionic
8.3 If the amount of SrSO4 in the sample (8.2) is less than
strength, temperature and pressure of the water under
its calculated solubility (8.1), the water in question is under-
investigation. For BaSO4 refer to Appendix X2, and
saturated with respect to SrSO4. If the amount of SrSO4 present
X 5 molal excess of soluble common ion.
is greater than its solubility, the water is supersaturated with
7.2 Calculate the amount of barium sulfate, moles per
respect to SrSO4. Calculate the amount of supersaturation,
kilogram of water, in the sample based on the lesser of the
moles per kilogram water by difference (Eq 3), or by substi-
barium or sulfate ion concentration.
tuting appropriate data in Eq 4 (Note 2).
7.3 If the amount of BaSO4 in the sample (7.2) is less than
8.3.1 Report SrSO4 supersaturation in terms of the weight of
its calculated solubility (7.1), the water in question is under-
SrSO4 per volume of water as follows:
saturated with respect to BaSO4. If the amount of BaSO4
present is greater than its solubility, the water is supersaturated SrSO4 supersaturation mg/L

S D
with respect to BaSO4. Calculate the amount of supersaturation
as the difference between the two values: 1000 3 D
5 SrSO4, ~molal! 3 103 3 184 3 TDS
supersaturation 5 concentration 2 solubility
1000 1 1000
(3)
NOTE 2—Supersaturation may also be calculated directly from the
equation (1)4 9. Calculation of Calcium Sulfate Supersaturation (Refer
11 to Appendix X1)
~@Ba # 2 y!~@SO45# 2 y! 5 K (4)
9.1 Calculate calcium sulfate solubility using the same steps
where: described for BaSO4(Section 7), but substituting the appropri-
Ba++ 5concentration of barium, molal, ate values for CaSO4 in Eq 2 (Refer to Appendix X5).
SO45 5concentration of sulfate, molal, 9.2 Calculate the amount of calcium sulfate moles per
y 5excess (supersaturation) of BaSO4, molal, and kilogram in the sample based on the lesser of the calcium or
K 5solubility product constant (molal) of BaSO4 at remaining sulfate ion.
test conditions. 9.3 If the amount of CaSO4 in the sample (9.2) is less than
The value X may then be determined from the quadratic its calculated solubility (9.1), the water in question is under-
equation (see Appendix X1): saturated with respect to CaSO4. If the amount of CaSO4
2B 6 =B 2 2 4 AC present is greater than its solubility, the water is supersaturated
X 5 2A with respect to CaSO4. Calculate the amount of supersaturation
moles per kilogram by difference (Eq 3) or by substituting
appropriate data in Eq 4 (Note 2).
4
The boldfaced numbers in parentheses refer to a list of references at the end of 9.3.1 Report CaSO4 supersaturation in terms of the weight
this standard. of CaSO4·2H2O (gypsum) per volume of water after converting
2

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moles per data obtained above to mg/L as follows: 10. Keywords
CaSO·2H2O supersaturation, mg/L 10.1 barium sulfate; brines; calcium sulfate dihydrate;
5 CaSO4·2H2O2, moles/kg 3 172.17 3 103 3 D strontium sulfate

APPENDIXES

(Nonmandatory Information)

X1. SAMPLE CALCULATION OF BaSO4 SUPERSATURATION AT 95°C

Analysis of Water Ionic Strength

µ 5 1⁄2(,Z, 2
Component Ions mg/L moles per litre A molal A Concentration Z2
(Section 6)
Na 27 120 1.180 1.214 1 1.214
Ca 10 890 0.272 0.280 4 1.120
Mg 1679 0.69 0.071 4 0.284
Ba 6.4 0.000044 4.52 3 10−5 4 >0.001
Sr 444 0.00506 521.42 3 10−5 4 0.021
Cl 64 870 1.830 1.883 1 1.883
SO4 1210 0.012596 1296.14 3 10−5 4 0.052
HCO3 317 0.005 0.005 1 0.005
TDS 5 106 536 Total ionic strength 5 2.29
Density 5 1.078 g/ml KBaSOr at 95° (Appendix X1) 5 83.22 3 10−9

1000
Convert moles/L to molal 5 moles/L 3
TDS
~Sp gr 3 1000! 2 1000
1000
5 moles/L 3
1078 2 106.5
5 moles/L 3 1.029

X1.1 BaSO4 solubility (refer to 7.1) X1.4 Useful Information:

S 5 ~=X2 1 4K 2 X!/2
Equivalent Gravimetric Conversion
Mol Weight Weight Factors
Ba 137.33 68.66 Ba 3 1.6995 5 BaSO4
where: Ca 40.08 20.04 Ca 3 3.3967 5 CaSO4
X 5 molal excess of common ion (in this case SO4), Sr 87.62 43.81 Sr 3 2.0963 5 SrSO4
X 5 (1296.14 3 10 −5) − (4.52 3 10 −5) SO4 96.06 48.03
BaSO4 233.39 116.70 SO4 3 2.4296 5 BaSO4
5 1291.62 3 10 −5 CaSO4 136.14 68.07 SO4 3 1.4172 5 CaSO4
4K 5 4(83.22 3 10−9) 5 332.88 3 10 −9
, or CaSO4·2H2O 172.14 86.07 SO4 3 1.9121 5 SrSO4
3328.8 3 10 −10 SrSO4 183.68 91.84
S 5 @=~1291.62 3 10 25!2 1 ~3328.8 3 10 210!
X1.5 The amount of supersaturation (excess BaSO4) may
− (1291.62 3 10 −5)]/2
Solubility S 5 0.644 3 10− 5 molal also be calculated directly using the expression (Eq 4):
~@Ba11# 2 X! ~@SO4 5 # 2 X! 5 K BaSO4
X1.2 BaSO4 present (refer to 7.2):
X1.5.1 Using the molal values from the water analyis above
X1.2.1 Ba present 5 4.52 3 10 −5 molal
this becomes:
X1.2.2 SO4 present 5 1296.14 3 10 −5 molal
X1.2.3 Based on lower value (Ba), BaSO4 ~@4.52 3 10 25# 2 X! ~@1296.14 3 10 25# 2 X! 5 832.2 3 10 210
−
present 5 4.52 3 10 5 molal Multiplying: ~5858.55 3 10 210! 2 ~1300.66 3 10 25!

X1.3 Amount of BaSO4 supersaturation (refer to 7.3)

X 1 X2 5 832.2 3 10 210
X1.3.1 BaSO4 present based on Ba+ + 5 4.52 3 10− 5 molal
X1.3.2 Calculated BaSO4 solubility, S 5 0.64 3 10 −5 mo- Combining: X2 2 ~1300.66 3 10 25! X 1 5026.35 3 10210 5 0
lal
X1.3.3 BaSO4 excess; i.e. supersaturation 5 3.88 3 10 −5 X1.5.2 Substituting the above coefficients of X in the
molal; or 8.8 mg/L of sample quadratic equation:

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2 b 6 =b2 2 4 ac and solving, X 5 3.88 3 10 −5

molal; or 8.8 mg/L of
X 5 2a sample.

X2. SOLUBILITY DATA FOR BaSO4·NaCl·H2O SYSTEMS (2)

Solution Solubility Product Constant, K (Molal)

Ionic Strength,
µ 25°C 35°C 50°C 65°C 80°C 95°C

0.1 1.54 3 10 −9
2.00 3 10 −9
2.70 3 10 −9
3.34 3 10 −9
3.76 3 10 3.97 3 10−9
0.2 2.70 3.36 4.76 5.93 7.06 7.74
0.4 4.49 5.63 7.92 10.61 13.69 16.13
0.6 6.08 7.74 11.03 15.38 20.45 24.97
0.8 7.74 9.60 13.69 20.16 26.57 33.49
1.0 9.22 11.24 16.38 24.02 32.76 42.02
1.5 12.54 15.38 22.20 32.40 44.94 62.00
2.0 15.63 19.04 27.23 39.60 56.17 78.96
2.5 18.23 21.90 31.33 44.94 63.50 93.64
3.0 20.74 24.65 34.97 49.73 70.23 107.57
3.5 23.41 27.56 38.81 53.82 76.73 120.41
4.0 25.92 30.63 42.44 58.08 82.94 132.50
4.5 28.56 34.23 45.80 63.00 89.40 144.40

X3. SOLUBILITY PRODUCT DATA FOR SrSO42·NaCl·H2O SYSTEMS (3)

Solution Ionic A Solubility Product Constant, K (Molal)

Strength, µ 40°C (104°F) 71°C (160°F)
0.1 0.250 3 10−5 0.160 3 10−5
0.2 0.390 0.250
0.3 0.505 0.345
0.4 0.617 0.440
0.5 0.723 0.518
0.75 1.02 0.785
1.0 1.26 1.04
1.25 1.48 1.25
1.5 1.68 1.41
1.75 1.86 1.57
2.0 2.00 1.68
2.25 2.09 1.76
2.5 2.14 1.81
2.75 2.16 1.84
3.0 2.17 1.86
3.25 2.19 1.87
3.50 2.20 1.88
A
The above table may be used to interpolate the solubility product (K) for SrSO4 in brines at 0 psig. The interpolated values can be substituted in Eq 2 (Section 6) for
estimating the solubility (S) of SrSO4. For more precise K values at temperatures up to 300°F (149°C) and pressures up to 3000 psig add SI unit, refer to Appendix X4.

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X4. Equation for Calculating SrSO4 Solubility (4)

X4.1 Experimental SrSO4 solubility data have been re- µ 5 solution ionic strength,
duced to the following regression equation for calculating the T 5 temperature,° K.
solubility product constant ( K) at various solution ionic X4.1.1 Coefficients of the above equation for R are as
strengths over a temperature range of 100 to 300°F (38 to follows:
149°C) and pressures up to 3000 psig. The equation is
adaptable to computer calculation which can then substitute the
value for K in Eq 2 (Section 6) for computing the solubility of A 5 0.266948 3 10 −3
SrSO4 at desired conditions. B 5 −244.828 3 10 −3
C 5 −0.191065 3 10 −3
Log KSrSO4 5 X/R
D 5 53.543 3 10 −6
where: E 5 −1.383 3 10 −12
X 5 1/T, F 5 1.103323 3 10−6
R 5 A+BX+Cµ1/2+Dµ+EZ2+FXZ+Gµ1/2Z, G 5 −0.509 3 10− 9
Z 5 pressure (psig),

X5. SOLUBILITY PRODUCT DATA FOR CaSO42·NaCl·H2O SYSTEMS (5)

Solution Ionic Solubility Product Constant, K (Molal)

Strength, µ 10°C 35°C 50°C 80°C
0 1.02 3 10−4 1.27 3 10−4 1.25 3 10−4 0.89 3 10−4
0.1 3.04 3.29 3.31 2.82
0.2 4.99 5.23 5.28 4.67
0.3 6.87 7.11 7.17 6.44
0.4 8.68 8.91 8.96 8.13
0.5 10.41 10.64 10.68 9.75
0.6 12.07 12.30 12.30 11.30
0.7 13.65 13.88 13.85 12.78
0.8 15.16 15.39 15.32 14.18
0.9 16.60 16.83 16.71 15.52
1.0 17.96 18.20 18.02 16.79
1.25 21.05 21.29 20.96 19.70
1.5 23.69 23.93 23.46 22.22
1.75 25.90 26.12 25.52 24.39
2.0 26.67 27.88 27.18 26.22
2.25 29.03 29.22 28.47 27.73
2.5 30.00 30.15 29.40 28.92
2.75 30.60 30.71 30.01 29.81
3.0 30.84 30.90 30.32 30.42
3.25 30.77 30.77 30.36 30.73
3.5 30.39 30.34 30.15 30.76
3.75 29.76 29.66 29.73 30.51
4.0 28.90 28.75 29.13 29.97
4.25 27.85 27.66 28.37 29.14
4.5 26.65 26.43 27.49 28.02
4.75 25.34 25.13 26.52 26.58
5.0 23.98 23.80 25.48 24.83

REFERENCES

(1) Ostroff, A. G., “Introduction To Oilfield Water Technology,” a NACE of Strontium Sulfate,” presented at NACE Middle East Oil Technical
publication, second edition, 1979. Conference and Exhibition, Bahrain, March 1981.
(2) Templeton, C. C., “Solubility of Barium Sulfate In Sodium Chloride (5) McDonald, Jr., J. P., Skillman, H. L., and Stiff, Jr., H. A., Paper No.
Solution From 25°C to 95°C,” J. Chem. and Engineering Data, 5 No. 906-14-I, “A Simple Accurate, Fast Method For Calculating Calcium
4, Oct. 1960, p. 514. Sulfate Solubility In Oilfield Brine,” presented at the Spring Meeting
(3) Goldberg, J. B., Jacques, D. F., and Whiteside, W. C., SPE 8874,
of the South Western District, API, Lubbock, TX, 1969.
“Strontium Sulfate Solubility and the Effects of Scale Inhibitors,”
presented at NACE Middle East Oil Technical Conference/79, Bahr- (6) Fletcher, G. E., French, T. R., and Collins, A. G.,“ A Method for
ain, March 9–12, 1979. Calculating Strontium Sulfate Solubility, U.S. Department of Energy
(4) Bourland, B. I., and Jacques, D. F. SPE 9625, “A Study of Solubility Publication DOE/BETC/BI-80/10, April 1981.

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