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WATEQF - A FORTRAN IV VERSION OF WATEQ,A COMPUTER PROGRAM FOR CALCULATING CHEMICALEQUILIBRIUM OF NATURAL WATERS
U. S. GEOLOGICAL SURVEY
Water-Resources Investigations 76-13
BIBLIOGRAPHIC DATA SHEET
1. Report No. 2-
4. Title and SubtitleWATEQF: A FORTRAN IV Version of WATEQ, a Computer Program for Calculating Chemical Equilibrium of Natural Waters
7. Author(s)L. Niel Plummer, Blair F. Jones, and Alfred H. Truesdell
9. Performing Organization Name and Address
U.S. Geological Survey Water Resources Division 12201 Sunrise Valley Drive Reston, VA. 22092
12. Sponsoring Organization Name and Address
U.S. Geological Survey Water Resources Division 12201 Sunrise Valley Drive Reston, VA. 22092
3. Recipient's Accession No.
5. Report Date
September. 19766.
8. Performing Organization Reot.No- USGS/WRD/WRI-
10. Project/Task/Work Unit No.
11. Contract/Grant No.
13. Type of Report & Period Covered
Final14.
15. Supplementary Notes
16. Abstracts
WATEQF is a FORTRAN IV computer program that models the thermodynamic speciation of inorganic ions and complex species in solution for a given water analysis. The original version (WATEQ) was written in 1973 by A. H. Truesdell and B. F. Jones in Programming Language/one (PL/1). With but a few exceptions, the thermochemical data, speciation, activity coefficients, and general calculation procedure of WATEQF is identical to the PL/1 version. This report notes the differences between WATEQF and WATEQ, demonstrates how to set up the input data to execute WATEQF, provides a test case for comparison, and makes available a listing of WATEQF.
17. Key Words and Document Analysis. 17a. Descriptors
* * * *Computer models, Equilibrium, Aqueous solutions, Stability, water chemistry, saturation
I7b. Identifiers /Open-Ended Terms
17c. COSATI Field/Group
18. Availability Statement
No Restriction on Distribution
19.. Security Class (This Report)
UNCLASSIFIED20. Security Class (This
PageUNCLASSIFIED
21. No. of Pages
22. Price
FORM NTis-35 (REV. 1O-73) ENDORSED BY ANSI AND UNESCO. THIS FORM MAY BE REPRODUCED USCOMM-DC B265-P74
WATEQF - A FORTRAN IV VERSION OF WATEQ,A COMPUTER PROGRAM FOR CALCULATING CHEMICALEQUILIBRIUM OF NATURAL WATERS
By L. Niel Plummer, Blair F. Jones, and Alfred H. Truesdell
U. S. GEOLOGICAL SURVEY
Water-Resources Investigations 76-13
September 1976
UNITED STATES DEPARTMENT OF THE INTERIOR Thomas S. Kleppe, Secretary
GEOLOGICAL SURVEY V. E. McKelvey, Director
For additional information write to:
U.S. Geological SurveyNational CenterOffice of Regional Hydrologist, MS 432Reston, Virginia 22092
Requests, at cost, for the card deck listed in Attachment B should be directed to: Ralph N. Eicher, Chief, Office of Teleprocessing, MS 805, National Center, U.S. Geological Survey, Reston, Virginia 22092.
CONTENTS
Page
Abstract——————————————————————————————————— 1
Introduction————————————————————————————————— 2
Differences between WATEQF and WATEQ—————————————— 2
Input—————————————————————————————————————— 3
Description of Input Variables—————————————————— 4
Description of Optional Input —————————————————— 7Type 1 Optional Input ————————————————————— 7Type 2 Optional Input ————————————————————— 7
Oxidation - Reduction Options —————————————————— 9
Output ————————————————————————————————————— 10
References—————————————————————————————————— 11
ii
TABLES and ATTACHMENTS
Page
Table 1. Revised Thermochemical Data——————————————————— 12 Data Sources for Table 1 ———————————————————— 14 Footnotes to Table 1 ——————————————————————— 14
Attachment A. Test Case, Data, and Computed Results——————— 16 List of Data Cards for Test Case—————————— 16 Data———————————————————————————————— 17 Computed Results of Test Case————————————— 21
Attachment B. Program Listing———————————————————————— 27
Attachment C. Equilibrium Reactions Considered by WATEQF——— 51
iii
ABSTRACT
WATEQF is a FORTRAN IV computer program that models the thermodynamic speciation of inorganic ions and complex species in solution for a given water analysis. The original version (WATEQ) was written in 1973 by A. H. Truesdell and B. F. Jones in Programming Language/one (PL/1). With but a few exceptions, the thermochemical data, speciation, activity coefficients, and general calculation procedure of WATEQF is identical to the PL/1 version. This report notes the differences between WATEQF and WATEQ, demonstrates how to set up the input data to execute WATEQF, provides a test case for comparison, and makes available a listing of WATEQF.
-1-
INTRODUCTION
WATEQF is a FORTRAN IV computer program that models the thermodynamic speciation of inorganic ions and complex species in solution for a given water analysis. The original version (WATEQ) was written by Truesdell and Jones (1973) in Programming Language/one (PL/1). With but a few exceptions, the thermochemical data, speciation, activity coefficients, and general calculation procedure of WATEQF is identical to the PL/1 version. For discussion of the program theory and original source of most of the thermo- chemical data, see Truesdell and Jones (1974). It is the purpose of this report to note the differences between WATEQF and WATEQ, demonstrate how to set up the input data to execute WATEQF, provide a test case for com parison (Attachment A), and make available a listing of WATEQF (Attachment B). This report also provides a list of all equilibrium reactions that are considered (Attachment C).
DIFFERENCES BETWEEN WATEQF AND WATEQ
1. In addition to the 100 aqueous species used in the WATEQ aqueous model, WATEQF includes 14 species of manganese and computes saturation data for 21 manganese minerals. See Table 1 for the thermochemical data used.
2. All reference to maximum and minimum estimates of log K used by WATEQ have been omitted in WATEQF.
3. In addition to calculating pe from dissolved oxygen and Eh, pe can also be set by the dissolved oxygen relation of Sato (1960) and by the S0= / S= ratio.
4. The carbon-bearing species are computed from either titration alkalinity, carbonate alkalinity, or total carbon in solution.
5. An option has been added that allows calculation of activity coefficients of charged ion pairs from either the Debye-Hlickle equation or the Davies equation.
6. Thermodynamic data used in the program can be changed through the use of optional input cards.
7. Various print options are provided to limit the amount of printed output.
8. WATEQF now consists of a main program and 5 subroutines, PREP, SET, MODEL, PRINT, and SAT. PREP reads the water data, converts the units of concentration to molality, and calculates all temperature dependent data at the temperature of the water
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sample. SET initalizes values of individual species for the iterative Mass Action - Mass Balance loop. MODEL ealculates activity coefficients and solves Mass Action and Mass Balance equations for the species considered. PRINT prints the results calculated from the aqueous model, and SAT calculates and prints the thermodynamic saturation state of the water with respect to the various minerals considered by the program.
9. The method of convergence on Mass Balance for anions has beenchanged to a more accurate and rapid convergence method, essentially identical to the method used by Truesdell and Jones (1974) for Mass Balance on cations.
10. The aqueous model will not be solved on analyses if pH is outside the interval 3.0 - 11.0, or if there is greater than 30 percent error in charge balance. This procedure is useful in screening data for punching and/or errors in the analysis. The procedure can be ignored, however, with the appropriate option specified in the input.
11. There are several changes in the aqueous model over those of Truesdell and Jones (1973) as shown in Table 1 and Attachment B, although none results in major differences between the calculations of WATEQ and WATEQF for most natural waters. The choice of speciation, thermodynamic data, and activity coefficients used by WATEQF are in a continuous process of revision, as better data become available. The responsibility for final selection of constants used in WATEQF rests with the user.
INPUT
The data matrix of species considered and thermochemical constants is read initially, either from disk or cards. The format of the data matrix is summarized as follows:
Variables Format
(NSPEC(I), Z(I), GFW(I), DHA(I), 1=1,115) (5X, A8, 2X, 12, 3X,F10.4, IX, F4.1)
(NREACT(I), DH(I), LOGKTO(I), 1=1,193) (5X, A8, 2X, 2F10.4)
Following input of the data matrix, data cards for one or more water analyses are read. Each water analysis requires 5 cards (4 data cards followed by a blank card). WATEQF can receive additional data on option cards that fit into the data stream between card 4 and the blank card (5),
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The required input for each water analysis is summarized as follows;
Card
1
2
Variables
TITL
Format
20A4
TEMP, PH, EHM, EHMC, (5(F6.0,1X), EMFZ, DENS, DOX, FLAG, 2F5.0, IX, 911, CORALK, PECALC, IGO, 213) (PRT(I), 1=1,4) IDAVES, ISPEC, IMIN
CUNITS(I) (1=1,2,3,4, (6E12.5,8X) 5,6)
CUNITS(I) (1=7,35,8,45, (6E12.5,8X) 88,62)
•—————Optional input appears here-
Blank card
Comments
Title
See description below
Ca,Mg,Na,K,Cl,SO^ (in order)
HCO~,SiO? ,Fe,P04 ,
SR, F (in order)
Required to note end of data for a particular analysis
DESCRIPTION OF INPUT VARIABLES
NSPEC(I) Names of the species
Z(I) Charge of the species
GFW(I) Gram formula wt. of ith species
DHA(I) Debye-Huckel a parameter for ith species
NREACT(I) Name of ith reaction
DH(I) AH° for ith reaction (Kcal/mole)
LOGKTO(I) Log K for the ith reaction at 25°C
TITL General description, identifying information, etc
TEMP Temperature in degrees C.
pH Negative log of the activity of hydrogen ion.
EHM "True" Eh of solution to which no temperature correction will be made (volts)
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EHMC Electical potential (volts) of the Eh cell with a calomel reference electrode.
EMFZ Electrical potential (volts) of the Eh cell with calomel reference in Zobell's solution.
3 DENS Solution density (g/cm ). If not known, read 1.0.
DOX Dissolved oxygen content (mg/1).
FLAG Signal for units of input concentrations (CUNITS). l=meq/l, 2=mg/l, 3=ppm, 4=molality.
CORALK Carbon signal. Set to zero (or blank) if the alkalinity has not been corrected for silica, boron, etc. CORALK=1 if this correction has been made. Normally, one would report alkalinity as HCO- (and CO- if detected) and set CORALK to zero. To input total carbon rather than alkalinity, set CORALK to 2. Total C02 can then be input as HCO~, or, * if desired, as the individual species of HCO~, CO* and H2C03 . H2CO* and CO^ are read on an optional "CONC" card.
(H 0CO~ denotes H0CO° + C00 ). £• j £. j Zaq
PECALC Signal for pe calculation. If PECALC =0, pe is set to 100 and oxidation-reduction is ignored. =1 computes pe from Eh, =2 computes pe from dissolved oxygen, =3 computes pe from dissolved oxygen using the Sato (1960) relation, =4 computes pe from SO^ / S= .
IGO =0 or blank, if desired to have the data checked for possible input error or analytical error. pH must be greater than 3 and less than 11 and the analysis must have less than 30% error in charge balance. =1 if this check is not desired.
PRT(I),1=1,4 Signals which when set to some non-zero value (say 1) omit
print of: 1=1, thermochemical data table; 1=2, mass balance convergence iterations; 1=3, ion ratios; 1=4, mineral saturation calculations. To obtain the above printout, leave the appropriate value of PRT(I) blank or zero.
IDAVES Signal used to indicate desired method of calculation of activity coefficients, y., of charged ion pairs. If 1, the Davies equation,
-A Z. x/I~ log y.= ———-————— - 0.31
+
is used. If zero, or blank, the Debye-Hiickel equation,
—5—
logi + •t VT
is used. A and B are constants that depend on the dielectric constant, density and temperature of the solvent, Z. is the charge on the ion, I is ionic strength (1= 1/2 £. m. Z^, where
. is the molality of the ith ion) , and a . is the "ion size" parameter. As a general rule, the Davies equation is probably accurate to ionic strengths less than 0.5 and the Debye-Hiickel equation is more accurate at ionic strength less than 0.1 (Stumm and Morgan, 1970) . Activity coefficients of Ca+ , Mg , Na+, K+ , Cl~, S0= C0«, and HCO" are always calculated from the extended Debye- Huckel equations of Truesdell and Jones (1974).
ISPEC Number, of species desired in output (if less than totalnumber possible for the given water analysis) . Leave ISPEC blank or zero to obtain output for all possible species for the defined system. If ISPEC is greater than zero, ISPEC values of KSPEC (species index numbers) must be read (Type 1 optional input; see below).
IMIN Number of minerals for which saturation data are required (if less than the total possible) . Leave IMIN blank (or zero) to obtain saturation data on all possible minerals for the defined system. If IMIN is greater than zero, IMIN values of KMIN (mineral reaction index numbers) must be read (Type 1 optional input; see below).
Total concentration (units of FLAG) of Calcium (1), Magnesium (2) , Sodium (3) , Potassium (4) , Chloride (5) , Sulfate (6) , Carbon, as HCO~ (7), Silica, as Si09 , (35) Iron (8), Phosphate,
3- as PO, (45) , Strontium (88) , and Fluoride (62) , where thenumbers in parentheses are the appropriate species index numbers in the program. To enter other species, use Type 2 optional input cards (see below) .
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DESCRIPTION OF OPTIONAL INPUT
Additional input is optional and must appear between cards 4 and 5. Two types of optional input cards are used, Type 1 and Type 2. If used, Type 1 optional input cards must precede Type 2 optional input cards. »
Type 1 Optional Input
These cards are used to limit the number of species or minerals in the output. Omit these cards to obtain the complete calculated results for the given water analysis. To specify individual species for which output is desired, read ISPEC values of KSPEC(I),
Variable Format
(KSPEC(I), 1=1, ISPEC) (1615)
where KSPEC(I) is the index number of the ith species for which output is desired. Species index numbers are listed in the data tables of Attachment A. To specify individual minerals for which saturation data is desired, read IMIN values of KMIN(I),
Variable Format
(KMIN(I), 1=1, IMIN) (1615)
where KMIN(I) is the index number of the ith mineral reaction for which saturation output is desired. Mineral index numbers are listed in the data tables of Attachment A. If values of both KSPEC(I) and KMIN(I) are entered, KSPEC(I) must be read before KMIN(I).
Type 2 Optional Input
Type 2 optional input cards are used to (1) enter the total concen trations of species not included on cards 3 and 4 ("CONC" card(s)); (2) change the convergence tests on mass balance for anion species ("EROR" card); (3) change AH° ("DELH" card(s)); (4) change log K at 25°C ("TABL" card(s)); or, (5) change existing analytical expressions for logK(T), or enter new analytical expressions for reactions previously defined by the Van't Hoff equation ("LOCK" card(s)). It is possible to use none, 1,2,3,4. or all 5 cases of type 2 optional input in a single data set, providing the sequencing is 1., "CONC", 2., "EROR", 3., "DELH", 4., "TABL",5.. "LOCK". The form of type 2 optional input cards is
Variable Format
(WORD,(INT(I),VAL(I), 1=1,5)) (A4,1X,5(I3,E12.5))
-7-
where WORD is "CONC", "EROR", "DELH", "TABL", or "LOCK". The meaning of INT(I) and VAL(I) is described below for each value of WORD.
"CONC" enters concentration (units of FLAG) of constituents not on card 3 and 4. INT(I) = 17 (H2S), 18 (CO.), 39 (NH4), 51 <A1), 81(Li), 85 (N03), 86 (H2C03), 87 (B), 90 (Ba), 98 (Br), and 101 (Mh). VAL (I) is the concentration of the INT(I) constituent.
"EROR" overrides pre-set mass balance convergence constraints on anions. Pre-set values of EROR1-EROR5 are 0.001 (0.1 percent error in mass balance). EROR1-EROR5 are entered on the "EROR" card as VAL (1) - VAL (5). In the order l=carbon, 2=sulfate, 3=fluoride, 4=phosphate, 5=chloride. Values of INT(I) are not used.
"DELH" overrides values of the standard delta enthalpy of reaction(25 degrees C) used in computing the temperature dependence of equilibriumconstants from the Van't Hoff equation. INT(I) is the index numberof the ith reaction (see Attachment A) for which DH(I) is to be changedand VAL(I) is the appropriate new value of DH(INT(I)).
"TABL" overrides values of LOGKTO(INT(I)) (log K of reaction at 25 degrees C used in computing the temperature dependence of equilibrium constants from the Van't Hoff equation). INT(I) is the index number of the ith reaction (see Attachment B) for which LOGKTO is to be changed and VAL(I) is the appropriate new value of LOGKTO(I).
"LOCK" overrides existing analytical expressions for log K as a function of T (degree K), or enters as many as 35 new, previously undefined analytical expressions for log K (T degrees K).The form of the analytical expression must be
Log KT(INT(I)) = A + BT + C/T + DT2 + E/T2 }
where T is temperature in degree K and A,B,C,D, and E are fit parameters (may be zero or blank). INT(l) is the index number of reaction (see Attachment A) and INT(2)-INT(5) are ignored. VAL(1)=A, VAL(2)=B, VAL(3)=C, VAL(4)=D, VAL(5)=E.
Values of A,B,C,D, and E for analytical expressions pre-set in the program are listed in the data tables of Attachment A. Note that the analytical expression for reaction (26) is further modified in the program (see card B1600 of Attachment B). If any of the cards, "EROR", "DELH", "TABL", "LOCK", are used in a particular water data set, calculations for that data set and all subsequent data sets will use the new input values. The last card in each water analysis data set must be blank, whether option cards are used or not.
-8-
OXIDATION-REDUCTION OPTIONS
There are several possible options that result from choosing appro priate values of EHM, EHMC, DOX, EMFZ, and PECALC. To specify Eh directly, the desired value should be read as EHM (in volts). This value of Eh will not be corrected for temperature. If the redox potential with Calomel reference was measured in the field and it is desired to correct that measurement for temperature, the measured value should be read as EHMC (in volts). EHM must then be greater than 9.0. Any value of EHMC less than 9.0 is then considered real and a temperature-corrected Eh (EHM) is computed. If no Eh was measured, EHMC and EHM should be greater than 9.0. If the Eh-Calomel of a standard Zobell's solution was measured in the field, read the value as EMFZ (in volts) and EHMC will be corrected. If EMFZ is greater than 9.0, EHMC will be corrected for temperature only (provided EHMC is less than 9.0).
Oxidation-reduction equations used in calculating the distribution of species are written in terms of pe. pe can be computed from Eh, dis^- solved oxygen, or SO? / S=. If PECALC =1, pe is calculated from Eh. If PECALC =2, pe is computed from dissolved oxygen. If PECALC = 3, pe is computed from dissolved oxygen using the relation of Sato (1960). If PECALC = 4, pe is computed from SO" / S= (provided SO^ and total H2S are entered). If PECALC = 0, redox relations are ignored. If pe is to be computed from dissolved oxygen, a real value of DOX must be read, and to calculate pe from Eh requires either a real value of EHM or EHMC to be read.
Six possible examples of redox options are tabulated and discussed below:
EHM EHMC EMFZ DOX PECALC
1)2)
3)
4)
5)
6)
< 9
< 9
> 9
> 9
> 9
blank
> 9
> 9
< 9
< 9
< 9
blank
> 9
> 9
> 9
> 9k
< 9
blank
blank
> 0.0
blank
> 0.0
blank
blank
1
2
1
2
1
0or >9 or >9 or >9
-9-
1) Eh is to be used without correction and pe is to be computed from Eh.
2) Same as 1) but pe is computed from dissolved oxygen.
3) Eh was measured in the field and it is desired to correct that measurement for temperature. The Eh of standard Zobell's solution was not measured, pe is to be computed from Eh.
4) Same as 3) but pe is to be computed from dissolved oxygen.
5) Eh was measured in the field as well as the Eh of standard Zobell's solution, pe is to be computed from Eh.
6) No information on oxidation-reduction is available, and redox relations are to be ignored, (pe is set to 100)
Other possible options should be obvious from these examples.
OUTPUT
The output of WATEQF consists of a table of data constants used in the calculations (printed once). The output for each water analysis lists the title card and tabulates most of the input data. At the end of each iteration through the equilibria equations, the difference between the computed and analytical anion species is tabulated so that convergence progress can be followed. When convergence on the aqueous model has been obtained, various parameters that describe the solution are printed. Some of these are ionic strength, activity of water, comparison of com puted and analytical charge balance, pH, pe, temperature, P n , Pn , totalLU2 2 dissolved solids, and others. The concentration of each aqueous species(value greater than zero) is printed as ppm, molality, and activity, and log values, as well as ionic activity coefficients and their logs. Mole ratios and log activity ratios are computed and tabulated. The activity product of 101 minerals and their saturation index, AG and logK are printed. Saturation output for minerals in which the activity of an ith species in the reaction is zero are omitted from the tabulation. Parts of the output can be deleted with appropriate values of PRT(I), as des cribed above, and by use of the ISPEC and IMIN options.
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REFERENCES CITED
Garrels, R. M., and Christ, C. L., 1965, Solutions, Minerals, andEquilibria. Harper and Row, 450 p.
Earned, H. S., and Davis, R., Jr., 1943, The ionization constant ofcarbonic acid in water and the solubility of carbon dioxide inwater and aqueous salt solutions from 0 to 50°: Am. Chem. Soc.Jour., v. 65, p. 2030-2037.
Earned, H. S., and Scholes, S. R., Jr., 1941, The ionization constantof HCO~ from 0 to 50°: Am. Chem. Soc. Jour., v. 63, p. 1706-1709.
Hem, J. D., 1963, Chemical Equilibria and Rates of Manganese Oxidation.U.S. Geological Survey Water-Supply Paper 1667-A.
Jacobson, R. L., and Langmuir, D., 1974, Dissociation constants ofcalcite and CaHCO* from 0 to 50°C: Geochim. et Cosmochim. Acta,v. 38, p. 301-3187
Langmuir, D., 1969, The Gibbs free energies of substances in the systemFe-02-H20-C02 at 25°C: U.S. Geol. Survey Prof. Paper 650-B, p.
B180-B184. Latimer, W. M., 1952, The oxidation states of the elements and their
potentials in aqueous solutions. Prentice-Hall, Incl., 392 p. McGee, K. A., and Hostetler, P. B., 1975, Studies in the system MgO-
Si02-C02-H20 (IV): The stability of MgOH+ from 10° to 90°C.
Amer. Jour. Science, v. 275, p. 304-317. Nordstorn, D. K., and Jenne, E. A., 1976, Fluorite Solubility equilibria
in selected geothermal waters. Geochim. Cosmochim. Acta (in press), Reardon, E. J., and Langmuir, D., 1974, Thermodynamic properties of
the ions pairs MgCO? and CaCO° from 10 to 50°C: Amer. Jour. Sci.,v. 274, p. 599-612.
Robie, R. A., and Waldbaum, D. R., 1968, Thermodynamic Properties ofMinerals and Related Substances at 298.15°K(25.0°C) and oneatmosphere (1.013 Bars) Pressure and at higher temperatures. U.S.Geological Survey Bulletin 1259, 256 p.
Sato, Motaki, 1960, Oxidation of sulfide ore bodies. Econ. Geology,v. 55, p. 928-961, 1202-1231.
Siebert. R. M., 1974, The Stability of MgHC03 and MgCO° from 10°C to90 C. Ph.D. dissertation, Univ. of Missouri.
Stumm, Werner, and Morgan, J. J., 1970, Aquatic Chemistry. Wiley-Inter- science. 583 p.
Truesdell, A. H., and B. F. Jones, 1973. WATEQ, a computer program forcalculating chemical equilibria on natural waters. Nat. Tech. Info.Serv. P.B. 220464.
Truesdell, A. H., and Jones, B. F., 1974, WATEQ, a computer program forcalculating chemical equilibria on natural waters. U.S. Geol.Survey Jour. Research, v. 2, p. 233-248.
Wagman, D. D., Evans, W. H., Parker, V. B., Halow, I., Bailey, S. M.,and Schumm, R. H., 1969, NBS Tech. Note 270-4. Selected Values ofChemical Thermodynamic Properties, Tables for elements 35 through53 in the standard order of arrangement. 152 p.
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Table 1: Revised Thermochemical Data
I
10
13
25
31
33
36
63
69
74
75
78
79
80
149
158
159
160
161
162
163
164
165
166
167
NREACT
SIDERITE
CALCITE
KMGOH
KNAHPO
KKHPO
KH2C03
FLUOR
KHC03
KMGC03
KMGHC03
KCAHC03
KCAC03
KCAF+
BLANK
KMN 3+
KMNCL+
KMNCL2
KMNCL3-
KMNOH+
KMN(OH) 3
KMNF+
KMNS04
KMNN03,2
KMNHC03+
Source
1
23/
3
4
4
54/
6
74/
8
9
2
10
11
12
13
14
14
14
14
14
14
15
14
16
AH LogK 25 Cr
-10.55
0.0 0.23
0.0 0.29
-10.50
4.12 0.94
25.760 -25.507
0.0 0/607
0.0 0.041
0.0 -0.305
0.0 3.449
0.0 7.782
0.0 0.850
3.700 1.708
-0.396 0.059
0.0 1.716
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Analytical Expression for log K(T K)
13.543 - 0.0401T - 3000./T
0.684 + 0.0051T
-14.8435 + 0.032786T + 3404.71/T
-6.4980 + 0.02379T +2902.39/T
0.991 + 0.00667T
2.319 -.011056T + 2.29812xlO~5T2
-2.95 + .0133T
-27.393 + 4114/T + .05617T
OPTIONAL FORM NO. toMAY issa EDITIONGSA F?MR («i CFH) loi-it.e
UNITED STATES GOVERNMENT
MemorandumTO The Record DATE: April 21, 1977
FROM L. Niel Plummer
SUBJECT: Summary of Errors, changes and revision of WATEQF
1. Reaction 91 log K25 = +40.64 , AH° = -65.44. write up. Program is correct, however.
is wrong in
2. Table errors on AH£ and log K25 for reaction 90. Correct AH£ = 4.9104. Correct log K25 = 1.9869. Analytical expression which is currently used in the program is correct.
3. Summation of mass balance on anions now preceeds anion loop. Listing shows summation within anion loop. Printed mass balance in sea water test case in WRI 76-13 are eroneous owing to improper loca tion of summation.
4. CaF was enormously summed into COpTOT* See card E320.
5. If Fe or Mn are specified without redox information, the program will now set PE to zero, print a message stating that such has occurred, and continue calculation. Previously, the program would fail on iteration. With this change, the program will not fail but, of course, one should always supply desired redox information whenever iron and/or manganese are specified.
6. A new option for units of input concentration has been added. Millimoles per liter (1000 x M) may be input. For this case, FLAG is set to zero.
7. In correcting titratlon alkalinity for non-carbonate alkalinity, a new option (CORALK = 3) has been added which considers all possible non-carbonate alkalinity species. This is similar to CORALK = 0 which considers only the major non-carbonate alkalinity species.
8. The values of EPM are now correctly calculated from PPM rather than molality.
&SOIO-IOt)
Buy U.S. Savings Bonds JUcgtlarly on the Payroll Savings Plan
9. Prints have been added to show:
a) FLAG, CORALK, PECALC, IDAVES options
b) charge balance in Meq/kg HpO
c) total alkalinity in Meq/kg H20
d) carbonate alkalinity in Meq/kg H«0
10. It is now possible to override an existing analytical expression with a Van't Hoff relation for the temperature dependence of equilibrium constants. This is done internally whenever an optional DELH or TABL card is used for a pre-existing analytical expression.
11. The minimum number of iterations required to solve the aqueous model within the mass balance limits has been changed from 5 to 2.
12. Corrections to WRI 76-13
a) Page 54, line 69 should read: CO^" + H+ = HCO^
b) Page 57, line 127 should read: Li + + S0^"= LiSO~
13. Other changes have been made to improve the efficiency of the program which may be found by comparison of a current listing with that in WRI 76-13.
V
L. Niel Plummer Hydro!ogist
OPTIONAL FORM NO. 10MAY 1»82 EDITIONGSA FPMR (41 CFR) IOI-M.C
UNITED STATES GOVERNMENT
TO
FROM
Users of WATEQF - A FORTRAN IV version of WATEQ: DATE: A Computer Program for Calculating Chemical Equilibria of Natural Waters
May 17, 1977
L. Niel Plummer, WRN, NR
SUBJECT: change of resident disk for WATEQF and TABLES, and program revision.
Due to a recent upgrading of on-line disk facilities in the Northeastern Region, it has been necessary to move the-program WATEQF and data TABLES , from the on-line disk CCD907 to CCDS08. To use WATEQF off a Reston disk after May 17, 1977, your control language should be changed to indicate the new location of the program and data file (CCD808).
The following control cards will now execute the program:
/*RELAY PUNCH RE2//...(JOB CARD).../*ROUTE PRINT REMOTEXX/ / EXEC PGM=WATEQF, REGION= 11 OK//STEPLIB DD UNIT=3330,VOL=SER=CCD808,DISP=SHR,DSN=BFJONES.PGMLIB//FT05F001 DD DDNAME=SYSIN//FT06F001 DD SYSOUT=A//FT07F001 DD SYSOUT=B//FT09F001 DD UNIT=3330,VOL=SER=CCD808,DISP=SHR,// DSN=BFJONES.TABLES.WATEQF//SYSIN DD *
Insert Water Analyses Here // $$$
In addition a revision of WATEQF has recently been completed. The more important changes are summarized on the attached memo dated April 21, 1977. You may obtain current listings or card decks of WATEQF by using one of the attached utility routines.
If you have any questions or problems, feel free to contact me.
L. Niel Plummer Hydro!ogist
Attachment
i i Buy U.S. Savings Bonds Regularly on the Payroll Savings Plan
NREACT Source AH° LogK 25°C Analytical Expression for log K(T K)
168 KMN04-
169 KMN04—
170 BLANK
171 KHMN02--
172 MANGANO
173 PYROLUST
174 BIRNSITE
175 NUSTITE
176 BIXBYITE
177 HAUSMITE
178 MNOH2
179 MNOH3
180 MANGANIT
181 RHODOCHR
182 BLANK
183 MNCL2
184 MNCL2,1W
185 MNCL2,2W
186 MNCL2,4W
187 TEPHRITE
188 RHODONIT
189 MNS CRN
190 MNS04
191 MN2S04,3
192 MN3P04,2
193 MNHP04
14
14
12
17
18
18
19
19
18
18
19
17
19
18
12
18
14
14
14
18
18
17
14
17
17
14
r
176.620
150.020
0.0
-24.025
-29.180
0.0
0.0
-15.245
-80.140
4.100
20.090
0.0
-2.079
-17.622
-7.175
1.710
17.380
-40.060
-21.885
-5.790
-15.480
-39.060
2.120
0.0
-127.824
-118.440
-34.440
17.938
15.861
18.091
17.504
-0.611
61.540
-12.912
-35.644
-0.238
-10.539
8.760
5.522
3.974
2.710
23.122
9.522
3.800
2.669
-5.711
-23.827
-12.947
-13-
Data sources for Table 1
1. Langmuir (1969).2. Jacobson and Langmuir (1974).3. McGee and Hostetler (1975).4. Estimated using the pH and composition of NBS buffers
(6.86 and 7.41), and charge balance.5. Earned and Davis (1943).6. E. A. Jenne (1975), oral communication to B. F. Jones.7. Earned and Scholes (1941).8. Siebert (1974).9. Fit to the data of Siebert (1974).
10. Reardon and Langmuir (1974).11. Nordstrom and Jenne (1976).12. Not presently used „13. AG°, AH° Mn , Wagman, £t. al, (1969). AG°, AH° Mn , Latimer (1952)
14. Wagman, et. al. (1969).15. AG°, Hem (1963), AH° Wagman, ^t. al, (1969).
16. Hem (1963).17. Latimer (1952).18. Robie and Waldbaum (1968).19. Garrels and Christ (1965).
Footnotes to Table 1
No attempt has been made for internal consistency of thermodynamic data in WATEQF. Responsibility for selection of thermodynamic data rests with the user. The revised thermodynamic data o£ Table 1 do not reflect the forth coming revision of U.S. Geological Survey Bulletin 1259 which may have profound effects on the thermodynamic data for Aluminium.
'The ion pairs Na2CO° and Na2SO° are no longer used in WATEQF. The
CaF ion pair has been added to the model.
3/This analytical expression for the calcite equilibrium constantassumes that the ion pair CaHCOJT is present in the aqueous model.
i -^ If CaHCO is deleted from the model via an optional LOCK card (by
setting log KCaHCQ+ to, for example, to -30.), log Kcalcite should
by changed to 13.8/0 - 0.04035T - 305.9./T, as recommended by Jacobson and Langmuir (1974).
-14-
4/Reactions 36 and 63 have been changed from dissociation (in WATEQ)to association in WATEQF. For the most part, all ion pair reactions are written as association in WATEQF, that is, most ion pair equilibria show the pair as a product. All mineral equilibria are written with the solid as reactant. See Attachment C for details of all reactions in WATEQF.
-15-
Attachment A: Test case, data, and computed results
(VJoo
o n ^ •CM rH
~* oin <a-f- <*rH * *~ r-t •
O
x n o CD^L. (^ ** 2^°°
CO **•
O O (VI
•«-» « (VIW UJ O O O ^ O • (VI O
o o 0*0J-l • O* O •o _j m o r-< o^ <[ O GO •M o • ro o in •-«-rt »-« ~+ 00 O
co 2: ••o t? o ui o
oc r- o GOit ^^ C> i""*
O" O • • ••P cr • r^ o o r-CO UJ O* vC
>H jp
^ UJ --H CO nr OQ C^ CD• O
JC O
Q. • o r»-
LL (VI • (VIO •-• ^ o
(VI Ocr o o • oJ rvi o o >— • •< ccJK r-« O
•^ IT! 0s« o nUJ » • • VI U> IV O O O
CVi ^ ^ ^ Z.*• •-* o o v
O O X
-16-
< oiftoooo-*ooooo-*oooo-*ir»inooooo-*inoooooooooinoin-*-*-*o«o.*o«o o «
to ooo oo H-o(*> (M < « « <« « O « •*~ -* O x «•>•*•*•* m t~ o of) x o « •* ro o •* o o o c\i o <*) •* f> -* ro ro < -* a •*> o -*
<*> xxoa. o _i _i x o «j o ««-• «-i _ixooo_iO(MOO oruouo -* o oo
_IOUbJUlUIUJUlUiniUJUIZOO(9OOO-«l*>(MX
I »- II < Ii a i
IOOOOOOOOO
omowm-<«-«nj't>
o —• "• <* «M inX ^ -» r O • •
i (MI x <\j o iru.rrvjrooj — ~<o in •«•
-17-
I M
00 I
50 51 52 53
54 55 56 57 58
59
60 61 62 63 64 65
66 67 68
69 70 71 72 73 74 75 76 77 78 79 80 61 82 63 84 85 86 87 68 89 90 91
92 93 94 95 96 97 98 99 100
101
102
103
104
105
106
107
108
109
110
CHLC
PAL
CMT
GI8CRS
BOEHM
PYRCPH
PHILIP
ERICN
CLINOP
HORCEN
NAhCOL
TRONA
NATRON
THRNAT
FLLCR
PONTCA
HALITE
THEKAR
PIRABI
WACKIT
KHCC3
KNAC03
KNAHC03
KNAS04
KKSC4
KH6C03
KMGHC03
KPGS04
KCACH
KCAHC03
KCAC03
KCAF*
KALCH
KALCH2
KALCH4
KALF
KALF2
KALF3
KALF4
KALS04
KASC42
KHSC4
KH2SC
KH2S
KHS
KOXV
KCH4
HYXAPT
FLOAPT
CHAL
CMAGAOI
CRISTO
SILGEL
QUARTZ
KFECH2
KFECH3
KFECH4
KFECH2
VIVIAN
MAGNET
HENA
TIMAGhEM
54,7600
29.8200
14,4700
11.9050
0.0
0.0
0.0
0.0
0.0
3.7200
-18,0000
15.7450
•2.8020
1.5300
58,3730
0.9180
-0,5720
18,9870
0,0
-3.6040
8.9110
0.0
1.1000
3.0820
2.7100
1.0770
1.2700
1.1900
5.4100
4.0230
4.1200
1.9900
0.0
-9.3200
0.0
20.0000
2.5000
0.0
2.2900
3.0700
H-
' '
* a * Qft
^ V'V A" ' V
-S'
•»G,*400
5.2990
12.1000
34.1570
-57.4350
17,2250
19.6950
4.6150
0.0
5.5000
4.4400
6.2200
0.0
0.0
0.0
28,5650
0.0
•40.6600
-30.8450
0.0
-90.6100
-85.3200
-32.7700
-33.4100
-42.4300
-19.8600
0.0
0.0
0.0
-0.5480
-0.7950
-1.3110
0.1250
•10.5000
•45.0000
1.5620
-0.1790
-1.1130
-4,6310
10,3300*
1,2680
-0,2500
0,7200
0.8470*
2.9600*
1.0660*
2.2380
1.4000
1.0150*
3.1530*
0.9400
8.9980
18,2350
33.9380
7.0100
12.7500
17.0200
19.7200
3.2000
5.1000
-2-^45*0*
/.""?
40.6440
-6,9420*
-12.9180
-20.7600
30^7410
-59.3500
-66.7900
-3.5230
-14.3000
-3.5860
-3.0170
-4.0050
-20.1730
-26,5710
-34.8940
-20.5700
-36.0000
-9.5650
-4,0070
6.3700
50 51 52 53 54 55
56 57 5fl
59 60 61 62
63 64 65 66 67 6fl
69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 ea 89 90 91 92 93 94 95 9f 97 9* 99 100
101
102
103
104
105
106
107
108
109
110
NAHP04
AL ALOH
AL(OH)2
AL(OH)4
ALF
ALF2
ALF3
ALF4
ALSO*
AL(S04)2
KHP04
F HS04
H FEH2P04
H2S CALC
HS S BLANK
P02
PCH4
AH20
PGHP04
CAHP04
CAP04
CAM2P04
FE(OH)2
FE(OH)3
FE(OM)4
FE(OH)2
LI LIOM
LIS04
NH4CALC
N03
H2C03
B TOT
SR SHOH
BA BAOH
NH4S04
HCL
NACL
KCL
H2S04
BLANK
BRFEH2P04
FEHP04
PNPN CNCL
HNCL2
PNCL3
MNOH
HN(OM)3
HNF
HNS04
MN(N03)2
-13 2 1
-12 1 0
-11
• • • •
0 -1 -2 0 0 0 0 0 0 -1 1 1 0 -1 0 1 0 -1 1 -I 0 0 2 1 2 1-10 0 0 0 0 -1 2 0 2 3 1 0
-11
-11 0 0
5.4
9.0
5.4
5.4
4.5
5.4
5.4
0.0
4.5
4.5
4.5
5.4
3.5
4.5
9.0
5.4
0.0
3.5
5.0
0.0
0.0
0.0
0.0
0.0
0.0
5.4
5.4
5.4
0.0
5.4
0.0
6.0
0.0
5.0
2.5
3.0
0.0
0.0
5.0
5.0
5.0
5.0
5.0
0.0
0.0
0.0
0.0
0.0
4.0
5.4
0.0
6.0
9.0
5.0
0.0
5.0
5.0
5.0
5.0
0.0
0*0
118.9692
26.9815
43.9889
60.9962
95.0110
45.9799
64,9783
83.9767
102.9751
123.0431
219.1047
135.0814
18.9984
97.0696
1.0080
152.8340
34.0799
33.0720
32.0640
1.0000
31.9988
16.0430
18.0153
120.2914
136.0594
135.0514
137.0673
89.8616
106.8689
123.8762
89.8616
6.9390
23.9464
103.0006
18.0386
62.0049
62.0253
10.8100
87,6200
104.6274
137.3400
154,3474
114.1002
36.4610
58.4428
74.5550
98.0775
1.0000
79,9090
152.8340
151.8200
54,9400
54,9400
90,3970
125*8540
161.3110
71.8480
105.9640
73.9400
151.0060
178*9560
Ill
112
113
11
4115
11
6117
118
119
120
121
12
21
23
124
125
12
6127
128
12
91
30
131
13
21
33
134
135
13
61
37
138
139
140
141
14
2143
144
145
14
6'
147
14
81
49
150
151
152
153
154
15
5156
15
71
58
159
160
161
16
2163
164
165
166
167
168
16
9170
171
GO
ET
HG
RE
EN
AF
EO
3A
AN
MT
EP
YR
ITE
MO
MBF
MONT
ABH
UN
TIT
EG
HE
GIT
EFE
SFPT
KF
EH
2P
KC
AP
04
KC
AJ-
2PK
VG
P04
KM
GH
2PKL
ICH
KLIS
04
KN
H4R
LA U
K O
NK
SR
CH
KB
AC
HK
NH
4SO
KH
CL
KK
AC
LK
KC
LK
H2
S0
4K
02
S
AT
OK
C02
KF
EH
PO
KF
EH
P*
ALO
3A
PR
EH
NT
ST
RC
NT
CE
LES
TB
AR
ITE
tuIT
t-E
RIT
ST
RE
NG
ITLE
ON
BLA
NK
NE
SG
UE
AH
TIN
K 0
2A
QKM S
EP
P
TD
IAS
PM
AIR
KT
KF
E»-
P2
KC
N
3*
KV
KC
L*
KM
NC
L2K
HN
CL3-
KM
KO
*K
HN
(O
H)3
KM
NF
*K
MN
S04
KM
NK
03»2
KM
NK
T03*
KM
NC
4-
KM
NC
4--
8LA
KK
KM
HK
O?
--
25
.55
50
o.o
•*0
.06
2.4
80
01
1.3
00
00
.00
.0-2
5.7
60
00
.00
.00.0
3.1
000
3.4
000
3.1
00
03.4
000
4.8
320
0.0
•187.0
550
39
.61
00
1.1
500
1.7
50
00
.01
8.6
30
00
.00
.00
.00
.0•5
.00
00
0.0
0.0
12
.99
00
10
.39
00
2.3
610
•1.0
54
06
.14
10
6.9
50
0•2
.03
00
90
.07
00
0.0
•4.5
51
00.4
980
33
.45
70
13
.34
50
0.0
•15
.40
50
26
.14
00
0.0
25
.76
00
0.0
0.0
0.0
0.0
0.0
0.0
3.7
00
0•0
.39
60
0.0
17
6.6
20
01
50
.02
00
0.0
0.0
•41
.20
00
•63.1
900
4.8
65
0•8
4.2
400
•lfl.4
600
•34
.97
00
-29
.78
00
-30
.51
00
-17
.97
00
•3.9
15
02.7
000
6.4
59
01
.40
80
6.5
69
01
.51
30
0.2
00
00
.64
00
11
9.0
77
0•3
1.9
60
00
.82
00
0.6
400
1.1
10
0•6
.10
00
•1.6
02
0-1
.58
50
•1.0
00
0•1
1.3
850
•1.4
52
03
.60
00
-7.6
13
0-3
1.6
100
•11.5
200
•11
.41
00
-5.9
740
•9.7
56
0•1
3.3
200
•26.4
000
•69
.57
00
0.0
•5.2
11
0•1
8.4
00
0-2
1.4
95
0-1
3.9
98
0-3
7.2
120
-35
.06
00
-26
.62
00
-7.5
83
0-2
5.5
07
00.6
070
0.0
41
0-0
.30
50
3.4
49
07
.78
PO
0.8
50
01.7
080
0.0
590
1.7
160
-12
7.8
24
0-1
18
.44
00
0.0
-34
.44
00
lu 112
PN04
113
VN04
114
BLANK
115
HMN02
1 S.O
•1
3.0
•2
5.0
0 0.0
•1
S.O
115.9590
116.9400
118.9400
1.0000
87.9480
172
K-ANGAMO
173
PYRCLUST
17*
HIRf^SITE
175
NUSTITE
176
8IXEVITE
177
HAUSflTE
178
MNOH2
179
MNOH3
180
MANGANIT
181
RHOCOCHR
182
BLANK
183
HNCL2
184
HNCL2.1W
185
MNCL2.2*
186
MNCL2t4*
187
TEPHRITE
188
RHOCONIT
189
MNS GRN
190
MNSC4
191
fN2S04»3
192
MM3P04»2
193
*NHP04
-24.0250
-29,1800
0.0
0.0
-15.2450
-80.1400
4.1000
20.0900
0.0
-2.0790
0.0
-17.6220
-7.1750
1.7100
17.3800
-40*0600
-21.8B50
-5.7900
-15.4800
-39.0600
2.1200
0.0
17.9380
15.8610
18.0910
17.5040
-0.6110
61.5400
-12.9120
-35.6440
-0.2380
-10.5390
0.0
8.7600
5.5220
3.9740
2*7100
23.1220
9.5220
3.8000
2*6690
-5.7110
-23.8270
-12*9470
••••
• DENOTES TH
AT AN ANALYTICAL EXPRESSION FOR KT
HAS BEEN USED
SUMMARY OF
ANALYTICAL EXPRESSIONS OF TH
E FORM
LOG K
* A*B«T*C/T*0»T»«2*E/T««2
O
II
NREACT
13
CALCITE
14
KH3SI04
15
KH2SI04
25
KPGOH
26
KH3B03
27
KNH3
36
KH2C03
69
KHCC3
73
KKSC4
74
KPGC03
75
KMGHC03
78
KCAK03
79
KCAC03
90
KHSC4
92
KH2S
13.5430
6.3680
39.4780
0.6840
28.6059
0.6322
-14.8435
-6.4980
3.1060
0.9910
2.3190
-2*9500
-27.3930
-5.3505
11.1700
•0.0
40
1>
0.0
16
3•0
.06
59
0.0
05
10
.01
21
-0.0
01
20.0
328
0.0
238
0.0
0.0
067
•0.0
11
10.0
133
0.0
562
0.0
183
•0.0
23
9
-3000.0
000
-3405.8
999
-12355.0
977
0.0
1573.2
100
-2835.7
598
34
04
.71
00
29
02
.38
99
-673.5
999
0.0
0.0
0.0
4114.0
000
55
7.2
46
1-3
279.0
000
0.0 o.o
0.0
0.0
0.0
0.0 o.o
0.0
0.0
0.0
2.2
961E
-05
0.0 o.o
0.0 o.o
0.0
0.0
0.0
0*0
0.0
0.0
0.0
0*0
0.0
0.0
0.0
0.0
0*0
0.0
0.0
SEA WATER OF P.K.RREtaER
FROM CHEMICAL OCEANOGRAPHY (1975)
INITIAL SOLUTION
TEMPERATURE *
25.00 DEGREES C
PH *
6.200
••••• OXIDATION -
REDUCTION •••••
ANALYTICAL EP^CAT »
608.205
ANALYTICAL EPMAN
606.626
DISSOLVED OXYGEN *
0.0
MG/L
EH MEASURED talTH
CALOMEL *
9.9000 VOLTS
MEASURED EH OF
ZOBELL SOLUTION *
9.9000 VOLTS
CORRECTED EH •
0.4000 VOLTS
PE COMPUTED FROM CORRECTED EH «
6.761
••• TOTAL CONCENTRATIONS OF
INPUT SPECIES ••
•
I N3SPECIES
TOTAL
MOLALITY
LOG TOTAL
MOLALITY
TOTAL
MG/LITRE
CA MG NA K CL SO*
HC03
SI02 TOT
FE P04
SR F AL LI N03
B TOT
BA BR MN
2 2 1 1-1 -2 -1
0 2-32
-13 1
-1 0 2
-1 2
1.033261E-02
5.333470E-02
4.708921E-01
9.768441E-03
5.489001E-01
2.834IS54E-02
2.311902E-03
7.143362E-05
3.599738E-08
2.010951E-06
9.177571E-05
6.878075E-05
7.*50825E-08
2.607451E-05
3.2*2?36E-06
4.126553E-04
1.463773E-08
8.427915E-04
3.659167E-09
•1.9
85
8•1
.27
30
•0.3
271
•2.0
102
•0.2
605
•1.5
475
•2.6
360
•4.1
461
•7.4
437
•5.6
966
•4.0
37
3•4
.16
25
•7.1
278
•4.5
A3
6•5
.4B
92
•3.3
842
•7.8
345
•3.0
743
•8.4
36
6
4.119998E 02
1.290000E 03
1.077000E 04
3.799998E 02
1.936000E 04
2.709000E 03
1.403400E 02
4.269999E 00
2.000000E-03
1.899999E-01
7.S99999E 00
1.299998E 00
2.000000E-03
1.799999E-01
1.999999E-01
4.439999E 00
2.000000E-03
6.699998E 01
2.000000E-04
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Attachment B: Program Listing
•««« PROGRAM WATECF «««« A FORTRAN IV VERSION OF WATEQ
REVISED FROM PL1 VERSION OF TRUESDELL AND JONES. NIEL PLUMMER, SUMMER 1972. LATEST REVISION ALGUSTt 1976.
«««« DESCRIPTION CF INPUT - 5 CARDS ARE REQUIRED •*••CARD 1 TITLEt JCB DESCRIPTION. (20A4)CARD 2 TEMP,PH,EHM,EHMCtEHMZ,DENS,DOX,FLAG,CORALK,PECALC,IGO,
(PRTU) ,1 = 1,4) , IDA VES, I SPEC, IMIN(5(F6.0,IX),2F5.0,IX,911*213)
TEMP....TEMPERATURE IN DEGREES CPH......NEGATIVE LOG ACTIVITY H*EHM... .PREFERRED EH ...SEE OPTIONSEHMC. .MEASURED EH ... SEE OPTIONSFMFZ. .MEASURED EH OF ZOBELL SOLUTIONDENS. .DENSITY OF SOLUTION (G/CC)DOX.. .DISSOLVED OXYGEN (MG/L)FLAG. .SIGNAL FOR UMTS OF INPUT CONCENTRATION.
l=MEQ/Lt 2»MG/L, 3=PPM, 4=MOLALITY, 0 - *"" '••>'"-,'/.'-•/ ,^~3«)CORALK..=0 IF ALKALINITY HAS NOT BEEN CORRECTED FOR BORON CETC.
=1 IF THE CORRECTION HAS BEEN MADE. =2 IF TOTAL C02 IS INPUT RATHER THAN ALKALINITY, -3 cor-tv^ ».v: A^ r*w.< ^-ov^^c ̂ :CAU«.T v
PECALC..=0 WILL SET PE TO 100, =1 COMPUTES PE FROM FH» ' *2 COMPUTES PE FROM DOX(THEORETICAL). = 3 COMPUTES PE FROM THE SATO RELATION, = 4 COMPUTES PE FROM S— - SO*—.
IGO..=0,OR BLANK, IF DESIRED TO HAVE DATA CHECKED FOR INPUT ERROR. PH MUST BE GREATER THAN 3 AND LESS THAN lit AND THE ANALYSIS MUST HAVE LESS THAN 30% ERROR IN CHARGE BALANCE. =1 IF THIS CHECK IS NOT TO BE MADE.
(PRT(I),1=1,4), CAN BE SET TO 1 TO DELETE PRINT OFTHERMOCHEMICAL DATA,MASS BALANCE CONVERGENCE ITERATIONS,
RATIOS OF IONS. AND MINERAL SATURATION, RESPECTIVELY. PRTU) SHOULD BE SET.TO ZERO OR BLANK TO OBTAIN THE RESPECTIVE PRINT.
IDAVES..=1, ACTIVITY COEFFICIENTS OF CHARGED ION PAIRS ARECALCULATED FRCM THE DAVIES EQUATION. =0 (OR BLANK), ACTIVITY COEFFICIENTS CF CHARGED ION PAIRS ARE CALCULATED FROM THF DEBYE-HUCKEL EQUATION, IDAVES HAS NO EFFECT ON GAMMA(l)- GAMMA(7), AND GAMMAU8).
ISPEC.. = NUMBER OF SPECIES DESIRED IN OUTPUTUF LESS THAN TOTAL POSSIBLE), TO OBTAIN OUTPUT OF MOLALITY, ACTIVITY, ETC, OF ALL POSSIBLE SPECIES FOR THE DEFINED SYSTEM, LEAVE ISPEC BLANK (OR ZERO, IF ISPEC GT. ZERO, ISPEC VALUES OF KSPEC (SPECIES INDEX NUMBER) MUST BE READ (SEE BELOW). IF ISPEC = BLANK (ZERO), OMIT KSPEC CARD(S).
IMIN.. = NUMBER OF MINERALS FOR WHICH SATURATION OUTPUT IS DESIRED (IF LESS THAN TOTAL POSSIBLE). TO OBTAIN SATURATION DATA ON ALL POSSIBLE MINERALS FOR THE DEFINED SYSTEM, LEAVE IMIN BLANK (OR ZERO), IF IMIN GT. ZERO, IMIN VALUES OF KMIN (MINERAL INDEX NUMBER) MUST BE READ (SEE BELOW). IF IMIN a BLANK (OR ZERO, OMIT KMIN CARDS(S).
CARD 3 CA MG NA K CL S04 (6 <E 12'.5 ) ,8X ) CARD 4 HC03 SIC2 FE P04 SR F (6(E12.5),8X)
... OPTIONAL CARDS OF TYPE 1 APPEAR HERE ...
... OPTIONAL CARDS OF TYPE 2 APPEAR HERE .. CARD 5 BLANK CARD (DENOTES END OF DATA FOR A PARTICULAR
WATER ANALYSIS.)
....DESCRIPTION OF OPTIONAL INPUT....ALL OPTIONAL INPUT MUST APPEAR BETWEEN CARDS 4 AND 5.
AAAAAAAAAA
AA
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1020304050607080SO100110120130140150160170160ISOPOO?102202302402502602702602SO3003103203303403503603703603SO4004104204304404504604704604SO~
5005105205305405505605705805SO600610
-27-
c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c
TYPE 1 CARDS MUST PRECEEO TYPE 2 CARDS.
*•*•*«***•«***•*«•****»****TYPE 1 OPTIONAL INPUT CARDS***************************(KSPEC(I)»Isl,ISPEC) (1615) KSPEC(I) IS THE INDEX NUMBER OF THE
ITH SELECTED SPECIES FOR WHICH OUTPUT IS DESIRED. OMIT CARDIF ISPEC * BLANK (OR ZERO).
(KMIN(I)»I=1»IMIN) (1615) KMIN(I) IS THE INDEX NUMBER OF THEITH SELECTED MNERAL FOR WHICH SATURATION OUTPUT IS DESIRED.OMIT CARD IF IMIN * BLANK (OR ZERO).
NCTE THAT IF BOTH KSPEC AND KMIN ARE READt KSPEC (I) MUST BE READ PEFORE KMIN(I).
***************************TYPE 2 OPTIONAL INPUT CARDS***************************WCRCt(INT(I)tVAL(I),I=ltS) (A4,1X»5(I3»E12.5)) WORD a »CONC»» »EROR»t »DELH»» »TABL»» OR'LCGK*.
•CONC'..ENTERS CONCENTRATION (UNITS OF FLAG) OF CONSTITUENTS NOT ON CARDS 3 AND 4. INT(I) = 17(H2S)»16(C03)t39(NH4)»5l(AL)t 81(LI)*85(NC3)t66(H2CC3)f87(B)t90(BA)t98(BR)tAND 101 (MN). VALd) IS THE CONCENTRATION OF THE INT(I) CONSTITUENT.
»EROR»..OVERRIDES PRE-SET MASS BALANCE CONVERGENCE CONSTRAINTS ON ANIONS. PER-SET VALUES OF EROR1-EROR5 ARE 0.001(0.1% ERROR IN MASS BALANCE). EROR1-EROR5 ARE ENTERED ON THE »EROR» CARD AS VALd)-VAL(S) . IN THE ORDER 1=CARBON, 2«SULFATEt 3»FLUORIDEt 4*PHOSPHATE» 5=CHLORIOE. VALUES OF INT(I) ARE NOT USED.
»DELH»..OVERRIDES VALUES OF THE STANDARD DELTA ENTHALPY OF REACTION (2b DEG. C) LSED IN COMPUTING THE TEMPERATURE DEPENDENCE OF ECUILIBRIUM CONSTANTS FROM THE VANT HOFF EQUATION. IMT(I) IS THE INDEX NUMBER OF THE ITH REACTION FOR WHICH OH(I) IS TO BE CHANGED AND VAL(I) IS THE APPPRIATE NEW VALUE OF DH(INT(D).
•TABL'..OVERRIDES VALLES OF LOGKTO(INT(I)) (LOG K OF REACTION AT 25 DEG. C USED IN COMPUTING THE TEMPERATURE DEPENDENCE OF EQUILIBRIUM CONSTANTS FROM THE VANT HOFF EQUATION). INT(I) ISTHE INDEX NUMBER OF THE ITH REACTION FOR WHICH LOGKTO is TO BECHANGED AND VAL(I) IS THE APPROPRIATE NEW VALUE OF. LOGKTO(I).
»LOGK»..OVERRIDES EXISTING ANALYTICAL EXPRESSIONS FOR LOG K AS A FUNCTION OF T(DEG.K), OR ENTERS NEWt PREVIOUSLY UNDEFINED ANALYTICAL EXPRESSIONS FOR LOG K(T DEG.K). THE FORM OF THE ANALYTICAL EXPRESSION MUST BE
LOG KT(INTd) )=A*B«T*C/T*D*T»»2*E/T«»2WHERE T IS TEMPERATURE IN DEG. K» AND AtB.C»D« AND E ARE FIT PARAMETERS (MAY BE ZERO OR BLANK). INT(1) IS THE INDEX NUMBER OF REACTION AND INT (2)-INT (5) ARE IGNORED. VAL(1)=A»VAL(2)=B» VAL(3)=C»VAL(4)=D»VAL(5)=E.
IF ANY OF THE CAROSt »EROR»•»DELH«,»TABL»t»LOGK» • ARE USED IN A PARTICULAR WATER DATA SETi CALCULATIONS FOR THAT DATA SET AND ALL SLBSEQUENT DATA SETS WILL USE THE NEW INPUT VALUES. TH^E ORDER CF TYPE 2 OPTIONAL INPUT CARDS IS »CONC»•»EROR»•»DELH»t»TABL»tAND •LOGK»» IF ALL 5 ARE USED. THE LAST CARD IN EACH WATER ANALYSIS DATA SET MUST BE BLANK* WHETHER OPTION CARDS ARE USED OR NOT.
620630640660660670660690700710720730740750760770780790SCO610820830640850860670860890900910920930940950960970960990
10001010102010301040105010601070106010901100111011201130114011501160117011601190120012101220
-28-
INTEGER DtEtDCtRBIT,CORALKtZ(120)tPRT(4)INTEGER PECALCtPECKREAL HI (120) tKT(200) *LOGKT (200) tLOGKTO (200) tMNTOTtLH20tMU*NATOT tKT 10TtMGTOTtLITOT*NH4TOTtK*REAL »8NSPEC(120) tNHEACT(200)CCMMON MI»KT»LOGKT«LOGKTOtKW»D«EtDD«CtRtT*F*TEMp»A»B«PEtPEStPEDCtP lESATOtPECKfPECALCtPH.TENMPEfTENPHt ALFA (120) tGAMMA ( 120) t AP (200) *XLA 2LFA(120)*ZtCUMTS(120) *ANALMI ( 120) *NSPEC.NREACT *GFW ( 120) »OHA ( 120 ) • 3DM200) *AH20»LH20»ERORltF-ROR2tERO«3tEROR4»EROR5*EHMtDENS*OOXtXLM( 4120) *ITER*RBIT*ClSAVEtCCRALK»MU*LCHEK(200) *C02TIT • ANALCO tSITOT tCAT 50T f MGTOT»KTOTtNATCT,S04TOTtFETOTtPTOT»ALTCT*FTOT*BTOTtLITOT,NH4TOT 6.SRTOTtBATOTtCLTOT«MNTOT*ICK»PRT.TITL(20)*EPMCAT*EPMAN,NEQU.ISPEC* 7K SPEC (120) tlMlN»KM!N(200) tTOSt IDAVESt IPRTDM15EM93IPRTsONEGU«15READ (9*50)READ (9*60)
10 CONTINUEREAD (5*70*ENCs40) TITL
20
(NSPEC(I)tZ(I>tGFU(I)tDHA(I)tI*ltD) (NREACT(I)•DH(I)»LOGKTO(I)«I*1«E)
30
40
50607060
CALL PREPIF (ICK.EQ.l) GO TO 10CALL SETCCNTINUECALL MODELIF (ITER.EQ.25) GC TO 30IF (HBIT.EQ.l) GO TO 20IF (ITER.LT.5) GO TO 20CALL PRINTIF (PRTU).NE.O) GO TO 10CALL SATGC TO 10
8010
PRINT GC TO STOP
FCRPAT (5XtAa«2X«I2«3X«F10.4«lX,F4.1)FORMAT (5X«A8«2Xt2F10«4)FCRKAT (20A4)FCRMAT (10X,'CONVERGENCE DID NOT OCCUR WITHIN 200 ITERATIONS* CALC1ULATION TEHMINATEC»t///) END SUBROUTINE PREPINTEGER D»E»DD»ReiT,coRALK.z(i20),WORD,CARD(6)tFLAG»pRT(4)»siGN(2)INTEGER PECALC.PECKDIMENSION INT(5)» VAL(S)« INPT(22)» GRAMSU20). IEQU(50), COEF(5*2100)* V(120)REAL MI(120).KT(200)»LOGKT(200)»LOGKTO(200)*MNTOTtLH20»MU*NATOT*KT 10T»MGTOT»LITOTtNH4TOT»K*PEAL *8NSPEC(120),NREACT(200)COMMON MI»KT.LOGKT»LOGKTOtKhi»DfEtDD,C*RfT»F*TEMP.A,B»PEtPESfPEDC«P 1FSATO*PECK»PECALC*PHtTENMPEtTENPH*ALFA(120)tGAMMA(120)*AP(200)*XLA 2LFA(120)tZtCUMTS(120)tANALMl(120).NSPEC.NREACT»GFW(120)«DHA(120)• 30H(200)•AH20«LH20«ERORl«EROR2«EROR3tEROR4«EROR5tEHMtDENStDOX«XLM ( 4120)*ITERtRBIT»ClSAVE*CCRALK»MU.LCHEK(200)*C02TIT,ANALCO.SI TOT.CAT 50T»MGTOT,KTOT»NATCT,S04TOT.FETOT»PTOT,ALTOT»FTOT.BTOTfLITOT,NH4TOT 6tSRTOT»BATOTtCLTOT»MNTOT»ICK.PRT»TITL(20)»EPMCATtEPMAN,NEQU,I SPECf 7KSPEC(120)fIMIN»KMIN(200)*TDS*IDAVES*IPRT
BRBBBBR
BBRBBBRBB
1?301240125012601?70L28012901300131013201330134013501360137013601390140014101420143014401450146014701460145015001510152015301540155015601570156015SO16001610162016301640165016601670
102030405060708090100110120130140150160
-29-
DATA CARD/»CONC»«»EROR«»»DELH»»»TABL«»»LOGK«»» «/»SlGN/» •»•«•/ R 170DAT* IEQU/13*14,15»25»26»27t36,69,73»74*'75»78*79»90»92*35*0/ R 180DATA COEF/60*0«0»13.543»-0.0401*-3000.«2«0.0*6.368*-0.016346*-3405 R 19 °1.9»2«0.0 *39.478»-0.065927*-l2355.1*47*0.0*0.684,0.0051295.3*0.0*28 R 2002.6059*0.012078•1573.21*2*0.0*0.6322»-0.001225»-2835.76»42*0.»-14.8 R ?1034351+ 0.032786•*3404.71 * 162*0.»-6.498»*0.02379,*2902.39*17*0.0*3.10 8 22046*0.0•-673.6*2*0.0*0.991*0.00667*3*0.0*2.319*-.Oil056*0.0*2.29812E P 2305-05* 11*0.0»-2.95.0.0133*3*0.0.-27.393»0.05617*4114.0*52*0.0.-5.350 R ?4065*0.0183412*557.2461,7*0.0.11.l7»-0.02386»-3279.0*542*0.O/ R 250DATA INPT/1*2»3,4,5»6»7»35»8*45,88*62*17,18*39*51*81»85,87*90*98,1 p ?60101/ H 270O2.302585092 B ?60F*23.0603 B 290PM.98719E-03 B 300ERORl'.OOl R 310EROR2=.001 R 320EROR3=.001 R 330EROR4=.001 R 340ERORbs.OOl R 350ICKrQ B 360PEDOslOO.O R 370PESATO&100. R 360PES*100.0 R 3SODC 10 I=1»D R 400CtNlTS(I)=0.0 B 410ALFA(I)sO.O R 420MI(I)=0.0 R 430XLMI(I)=0.0 R 440IF (Z(I).EQ.O) V(I)sl.O R 450IF (Z(I).EQ.O) 60 TO 10 R 460IF (Z(I).LT.O) V(I)r-1.0*Z(I) R 470IF (Z(I).GT.O) V(I)sl.O*Z(I) R 460
10 CONTINUE R 490PECKsO R 500PRINT 560 R 510READ 570, TEMP*PH,EHW,EHMC*EMFZ«DENS»DOX,FLAG*CORALK,PECALCfIGO,(P R 5201RT(I)»I=1.4)*IDAVES*ISPEC.I*IN R 530IF (IPRT.EQ.l) PRTUJsl B 540IF (PRT(l).NE.O) GO TO 70 B 550PRINT 580 R 5.60DC 30 1=1*0 B 570ISIG=SIGN(1) B 560DC 20 J=1»NEQL R 5SOIF (I.EO.IEQU(J)) ISIG=SIGN(2) B 600
20 CONTINUE B 610PRINT 590* I»NREACT(I)*DH(I),LOGKTO(I)*ISIG»I*NSPEC(I)»Z(I),DHA(I) B 620
l*GFta(I) B 63030 CONTINUE B 640
DC=D*1 B 650DC 50 I=DD.E B 660ISIG=SIGN(1) B 670DC 40 J=1»NEOL R 660IF (I.EQ.IEQU(J)) ISIG=SIGN(3) B 690
40 CONTINUE B 700PRINT 600. I*KREACT(I)»DH(I),LOGKTO(I)*ISIG R 710
50 CONTINUE B 720PRINT 510 B 730DC 60 I=1»NEQL R 740PRINT 520. lEQUm.NREACTJlEQUd) ) tCOEF (ItlEOU (I) ) ,COEF (2. IEOU (I) ) R 7501*COEF(3*IEQU(I)),COEF(4»IEOU(I))*COEF(5*1EOU(I)) R 760
€0 CONTINUE B 770
-30-
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so
100
no
120
130
140
150
160170
ieo
ISO
CONTINUEIPRT»1PRIM 610» TITLREAD 620* (CUMTSdNPT(I) ) .1 = 1.13)IF USPEC.GT.O) READ 530* (KSPEC(I).1=1.ISPEC)IF (I^IN.GT.O) READ 530. (KHIN (I) , 1 = 1,READ 630* WORD.(INT(I).VAL(I).1=1.5)IF (WORD.NE.CAROUM GO TO 100OC 90 1=1.5IF (IMU).EQ.O) GO TO 90CLNlTSdNT(I) )=VAL(I)CONTINUE<?C TO 80CONTINUEIF (WORO.NE.CARDC2)) GO TO 110EROR1=VAL(1)Efif)R2=VAL<2>EROR3-VALC3)FROR4*VAL<4)FROR5=VAL<5)READ 630* WOPC. (IM(I) ,VAL(I) .1 = 1.5)IF (*ORD.NE.CARO<3)) GO TO 130DC 120 1=1.5IF UNT(I).EG.O) GO TO 120Dh(lNT(I))=VAL(I)PRINT 640. IM(I) ,NRF.ACT(INT(I) ) ,VAL(I)CONTINUEREAD 630. WORD. (IM(I) »VAL(I) .1 = 1.5)GC TO 110IF (WORD.NE.CARDU)) GO TO 150OC 140 1=1.5IF (IMd).EQ.O) GO TO 140LCGKTO(INT(I))=VAL(I)PRINT 650* INT(I) .NREACT(INTd) ) .VALd)CONTINUEREAD 630, WORD, (INTd) ,VALd) .1 = 1.5)GO TO 130CONTINUE
VANT HOFF EQUATION FOR EFFECT OF T ON K
TsTEMP*273.16C1=(298.16-T)/<296.16«T«C«R)DC 170 I»ltELCGKT <I)=LOGKTO(I)-DH{I)«C1LCHEMI)=0IF (LOGKTd).LT.-77.0.OR.LOGKTCD.GT.75.0) LCHEK(I)=1IF (LCHEK(I).EO.l) GO TO 160KT(I)=10.««LOGKT(I)CONTINUECONTINUE
T ON KANALYTICAL EXPRESSIONS FOR EFFECT OFIF (WORD.KE.CARDC5)) GO TO 220IF (INT(I).EQ.O) GO TO 210OC 190 1=1.5CCEFd.lNT(l) )=VALd)CONTINUE
780 7SO 800 810 820 830 840 850 860 870 860 890 900 910 920 930 940 950 960 970 980 990
R 1000 R 1010 R 1020 R 1030 B 1040 R 1050 R 1060 R 1070 R 1080 8 1090 R 1100 R 1110 R 1120 B 1130 R 1140 B 1150 B 1160 B 1170 R 1180 B 1190 B 1200 B 1?10 B 1?20 B 1230 B 1240 B 1?50 B 1260 B 1270 B 1260 B 1290 B 1300 B 1310 B 1320 B 1330 B 1340 B 1350 B 1360 B 1370 B 1360
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I£Q*0DC 200 I*1*NEGUIF (lEQU(I).EC.IKT(l)) IEQ=1
200 CONTINUEIF (IEQ.EO.O) N£QL«NEQU*1IF (IEQ.EO.O) IEQL<NEQU)«INT(nPRIM 660. INT(l)fNREACT(INT(l)>tCOEFUtIKT(l>)tCOEF(2tINT(l))
lF(3tINT(l)>fCCEF(4tINTU))tCOEF(5tINT(l» 210 CONTINUE
READ 630* WORCt(INT(I)fVAL(I)tI*lt5)GC TO 180
220 CONTINUEIF (WORD.EQ.CA«D<6)) GO TO 230PMNT 540READ 630* WORC. (INT(I) ,VAI_(I) »I = 1»5)GC TO 220
230 CONTINUEDC 240 I«1»NECULCGKT <IEQU(I))=COEF(11IEOU <I))*COEF(2• IEQU(I))«T*COEF(3,IEQU(I 1*COEF<4,1EQU(I))«T«T*CCEF(5,IEQU(I))/(T«T)
2*0 CONTINUELCGKT<26)=LOGKT(26)*ALOG10<KW)-13.2258«ALCG10(T)DC 250 I=1.NECUKT(IEOUd) >»1E1«<»(LOGKT(IEQU(I) ) )
250 CONTINUE
ANALYZED MOLALITY GO TO 270
CALCULATION OFIF (FLAG.NE.l)DC 260 I = 1»DCLNlTS(I)sCUNlTS(I)«GFW(I)/VU>
260 CONTINUEFLAG=2
270 CONTINUEIF (FLAG.NE.2) GO TO 290DC 280 I=1»DCLNITS(I)=CUNITS(I)/DEN5
280 CONTINUEFLAG=3
290 CONTINUEIF (FLAG.NE.3) GO TO 320ClsO.ODC 300 I=1»DCUC1+CUNITSJI)
300 CONTINUEDC 310 1=1.0C1SAVE=C1Hl(I)s(CUMITS(I)/(1.0E*03*GFW(I)))«(1.O/(1.0-1.OE-06«C1) )IF (MI(I).GT.0.0) XLMI(I)=ALOG10(MI(I))GRAMS(I)aCUNITS(I)«DENS
310 CONTINUEGC TO 350
320 CONTINUEClsO.OIF (FLAG.NE.4) GO TO 480DC 330 1=1.DWI(I)=CUNITS(I)ClsCl*Ml(I)«GFW(I)«1000./DENSIF (MI(I).GT.0.0) XLMI(I)=ALOG10(MI (I))
330 CONTINUEC1SAVE*C1
R B R R R R
• COE R R R R R P R R R R R R
M/T R R R B R R R R B R R R R R R R B R B RR R R R B B B B R R R B B B B R B R R B B R B
13SO 1400 1410 1420 1430 1440 1450 1460 1470
1490150015101520153015401550156015701580155016001610162016301640165016601670166016901700171017201730174017501760177017601790IflOO1810182018301840185018601870I860189019001910192019301940195019601970I9601990
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340350
360
370380
350400
410420
DC 340 1*1,0GPANS(I)aNl (I)«1000,»GFKI)»DENS»< 1.0-1,OE-06«C1 SAVE)CONTINUECONTINUETCSsO.ODC 36U I«1.DANALMI(I)«MI(I)TCS»TOS*GRAMS(I)CONTINUEEPMCAT=0.0EPMAN«0*0
CALCULATION OF CATION-AMON BALANCEDO 380 1=1,0IF (Z(I).GT.O) GO TO 370EFM/»N=EPMAN-Z (I) »M (I)GC TO 380EFMCAT»EPNCAT*Z(I)»MI(I)CCNTINUEEPMCATsEPPCATMOOO.EPMAN=EPMAN«1000.
CALCULATION OF EH FROM FIELD DATAIF (EHM.LT.9.0) GC TO 420IF (EMFZ.GT.9.0) GO TO 390Cl=0.429*2.4E-03«(25.OrTEMP)-EMFZGC TO 400Cl=0.244*8.6E-04«(25.0-TEMP)CCNTINUEIF (EHMC.LT.9.0) GO TO 410GC TO 420
lOO. PEEH=100.
TEPPtPHtEPMCATfEPMAN
FEsPEEh
430
440
4SO
CCNTINUEPEEH=EHM/(C*R«T/F)IF (PECALC.EQ.O) PEIF (EHM.GE.9.0)PRINT 560PRINT 670PRINT 680tPRINT 690»IF (PECALC.EQ.l)PRINT 560PRINT 700DC 430 I=lt22IF (MI(INFT(I)).LE.0.0) GO TO 430PRINT 710, NSPEC(INPT(I))»Z(INPT(I)) IMS(INPTd))CCNTINUEPRINT 560PRINT 560IF (PRT(2).NE.O)PRINT 560PRINT 720CCNTINUE
(IGO.EQ.l) GO TO<PH.LT.3.0.0R.PH.GT.11«0) GO TO 490 s<(EPMCAT-EPMAN)/(l.*EPMCAT+£PHAN)
IF (ABS(DUM),GT,30.) 60 TO 490CCNTINUE
(IKPT (I) ) tXLHI (INPT (I) ) t€RA
IF IF
GO TO 440
450
R 2000 R 2010 R 2020 B 2030 B 2040 R 2050 R 2060 R 2070 R 2080 R 2090 R 2100 R 2110 R 2120 P 2130 B 2140 B 2150 B 2160 B 2170 R 2180 R 2190 R 2200 R 2210 B 2220 R 2230 R 2240 R 2250 B 2260 R 2270 R 2280 R 2250 B 2300 R 2310 R 2320 R 2330 B 2340 R 2350 R 2360 R 2370 B 2380 R 2390 R 2400 B 2410 B 2420 B 2430 B 2440 R 2450 B 2460 B 2470 B 2480 B 2450 B 2500 B 2510 B 2520 B 2530 B 2540 B 2550 B 2560 B 2570 B 2580 B 2550 B 2600
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TEMPERATURE EFFECTS ON CEBYE-HUCKEL SOLVENT CONSTANTSS1*374.11-TEMPS2sSl«*0.333333S3aSURT((1.0*0.1342489*52-3.946263E-03«S1)/<3.1975EO-.3151548EO«S2 1-1.203374E-3«S1*7.48908E-13«S1«*4))IF (T.LT.373.16) GO TO 460Cls5321EO/T*233.76EO-T«(T<M8.292E-7«T-1.417E-3)*.9297EO)GC TO 470
460 Cls87.74EO-TEMP«(TEMP»<1.4lE-6*TEMP-9.398E-4)*.4008EO) 470 CONTINUE
CUSQRT(C1«T)A»18246.0E02«S3/C1*«3P»50.29«S3/C1GC TO 500
480 PRINT 730TCKMGC TO 500
490 PRINT 550ICK*1
500 CONTINUEPETLRN
510 FORMAT <//,15X»•••«» DENOTES THAT AN ANALYTICAL EXPRESSION FOR KT H 1AS BEEN USED»»////,20X,»SUMMARY OF ANALYTICAL EXPRESSIONS OF THE F 20RM LOG K = A*B«T*C/T*D«T*«2*E/T«»2 l ///f23Xf»I NREACT A 3 B CD E»/)
520 FORMAT (22XtI3t2XtA8<3(IXtFl1,4),2(1X<1PE11.4))530 FORMAT (1615)540 FORMAT (/»10X,«MARKING—- INPUT ERROR. SEARCHING FOR BLANK CARD')550 FCPMAT {/, 10X t «EARNING——CHECK INPUT PH AND/OR CATION-AMON BALANC
IE ...CALCULATION TERMINATED')560 FORMAT (//)570 FORMAT (5(F6.0*IX)*2F5.0t1X*9I1t2I3)580 FORMAT (//,60X * ««-- « ,/,60Xt «DATA • f /,60X « «——— • t//t 18X t • I' t2Xt'NRE
UCT»»9Xf»DH»»8X,«LOGKTO»f37Xt«I»»2Xt«NSPEC»»6X,«Z».2Xi»CHA»,6X,»GF
590 FORMAT (1H *15X* 13t2X*A8t2(2XtF10,4)•Al*33Xt13»2XtA8«2XtI2*2X*F3.1
600
620630640
FORMAT FORMAT FORMAT FORMAT FORMAT
(1H tlSXtX3t2XtA8t2(2XtF10.4)»A1) (1H1*(5Xt20A4)*//) (6(E12.5)t8X) (A4tlX«5(I3«E12.5)) (5X»«NE* DATA
••« LOGKTO FOR REACTION »,I3flXtA8»» HAS BEE
••• LOGKT FOR REACTION
»,/,57Xt'INITIAL
•tI3t!XtA8«* = 'tlPE•iE11.4,»«T*«2') SCLUTXON«t/t57Xt» ——
••• DELTA H FOR REACTION i 9 I3tlXtA8t* HAS BEEIN CHANGED TO «»F9.4)
650 FORMAT <5X,«NE* DATAIN CHANGED TO »tF9.4)
660 FORMAT <5X.«NE* DATAlll,4t*••tE11.4t»«T*»
670 FORMAT (57X»»——-——1 ———————— ...i,///)
680 FORMAT (15X,•TEMPERATURE = «iF6.2t» DEGREES C PH = 'tF6,3<* 1ANALYTICAL EPMCAT s ».F8.3t» ANALYTICAL EPMAN = ».F8.3>//)
690 FORMAT (5X.•««••• OXIDATION - REDUCTION «••«•«.///.1IXt'DISSOLVED 10XYGEN s ».F6.3t» MG/L•»/»1IX.«EH MEASURED WITH CALOMEL = •tF7.4t«2 VOLTS'*/,11X,»MEASURED EH OF Z08ELL SOLUTION s »,F7.4,« VOLTS',/t 311X,'CORRECTED EH a «,F7.4,» VOLTS',/,1IX,»PE COMPUTED FROM COPREC 4TED L » »,F7,3,/)
700 FCRMAT f 40X,»»»» TOTAL CONCENTRATIONS OF INPUT SPECIES ««•«,//,50X
R 2610 B 2620 R 2630 R 2640 B 2650 B 2660 R 2670 B 2680 R 2690 R 2700 R 2710 R 2720 R 2730 R 2740 R 2750 R 2760 B 2770 B 2780 R 2790 R 2800 R 2810 R 2820 B 2830 R 2840 R 2850 fl 2860 R 2870 R 2860 R 2890 R 2900 R 2910 P 2920 R 2930 B 2940 8 2950 R 2960 R 2970 R 2980 B 2990 R 3000 R 3010 R 3020 R 3030 R 3040 R 3050 R 3060 R 3070 B 3080 B 3090 8 3100 R 3110 B 3120 B 3130 B 3140 R 3150 B 3160 B 3170 R 3180 B 3190 R 3200 R 3210
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1.'TOTAL••13X»«LOG TOTAL*»12X«'TOTAL*»/»33X,•SPECIES'»8X,«MOLALITY» 2»12X*»MOLALITY»tllXt»MG/LITRE»»/»33X»»-fc——— ••8X«»—————— ••12X«» 3——.——— ••1IX t • —————— • •/)
710 FORMAT UH t32X,A6»I3»3X»1PE13.6,8X,OPF9.4t8X,1PE13.6) 720 FCRHAT (50X«»««« CONVERGENCE ITERATIONS ••••«//t16Xt•ITERATION*t4X
lt»Sl-ANALC03»«6X»»S2-S04TOT»t8XttS3-FTOT»t9Xt»S4-PTOT»»9X,»S5-CLTO 2T»,X)
730 FORMAT <10Xt»INPUT ERROR——UNITS OF CONCENTRATION ARE NOT KNOfcNi't/ I//)ENDSUBROUTINE SETINTEGER DtEtDC»RBITtCORALKtZ<120)t*ORO»CARD<6)»FLAG«PHT(4) V SIGN(2)INTEGER PECALC»PECKDIMENSION INT(5)» VAL(5)» INPT(22)« GRAMS(120)t IEQU(50)t COEF(5.2 100)REAL MK120) tKT(200) tLOGKT(200) tLOGKTO(200) »MNTOTtLH20,KU.NATOT,KT 10T»*GTOTtLITOTtNH4TOTtKhREAL «8NSPEC(120)tNREACT(200)COMMON MItKTtLOGKTtLOGKTOtKMtDtEtOD«CtRtTtFtTEMPtAtB«PEtPEStPEDCtP lESATOtPECKtPECALCtPHtTENMPEtTENPHtALFA(120)tGAHMA(120)tAP(200).XLA 2LFAC120) t2tCUMTS(120) .ANALHK120) .NSPEC.NRfcACT.GFW (120) .DMA (120 ) » 3DM200)•AH?OtLH20*ERORl*EROR2tEROR3«EROR4*EROR5tEHM,OENSfDOXtXL^I( 4120)tITERtRBITfClSAVEtCGRALKt^UtLCHEK(200)tC02TITtANALCOtSITOTtCAT 5pTtKGTOTtKTOTtNATCTtS04TOTtFETOTtPTOTtALTOTtFTOTtBTOTtLITOTtNH4TOT 6iSRTOTtBATOTtCLTOTtMNTOTtICKtPRTtTITL(^0)»EPMCATtEPWAN,NEQUtISPECt 7KSPEC(120)tIHIN«KHIN(200)tTOStIDAVES.IPRT
INITIALIZE STARTING VALLES FOR ITERATIVE LOOP AH2C*1.0 DC 10 1 = 1.D GAMKA(I)=1.0
10 CONTINUECC2TIT*HI(7)*2.0»M(18)ANALCO=C02TITIF (CORALK.EQ.2) C02TIT=MI(7)*MI(18)+H(86)SITOT*MI(35)CATOT*MI(1)fGTOTsMI(2)NATOT=MI(3)KTOT=M(4)SC4TOT*PI(6)FETOTsMKS)PTOTsKI(45)PlOMCsPTOTALTOTsMKBl)FTOT*H1(62)BTOT=M1(87)LITCT*MI(81)Nh4TOT«MI(39)SRTOT*MI(88)BATOT=MI(90)CLTOT=MI(5)KNTOT=MI(101)Ml (35)=0.0MI(87)«0.0TENPH«10.«»PHALFA(64)slO.««(-PH)
CALCULATION OF ANION ACTIVITIES EXCEPT C02 AND P04 SPECIES
RBRBRRBBBBCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC
3?203?303?403250326032703?8032SO33003310
10203040506070eo90
100110120130140150160170ieo190200210220230240250260270280290300310320330340350360370380390400410420430440450460470480490500510
-35-
ALFA(5)«MI(5)«GAHHA(5) C 520ALFA(6)=MI(6)«GAMPA(6) C 530ALFA(62)=M (62)«GAHMA<62) C 540ALFA(85)sH(85)»GAMMA<85) C 550ALFA(98)*HI(98)«GANMA(98) C 560ALFA(27)»AH20«K*»7ENPH C 570MI(27)sALFA(27)/GAMMA(27) C 560KI(64)«UO/(7ENPH«GAMMA(64) ) C 590ALFA(63)=ALFA(6)«K7(90)/TENPH C 600HI(63)*ALFA(63)/GAMMA(63) C 610
C C 620C C 630C CC? SPECIES C 640
IF (CORALK.EQ.2) GO 70 20 C 650C1«2.0»TENPH/(GAM»A(18)«»KT<69) ) C 660.H(7)=C027I7/(1.+GAHMA(7)«C1) C 670C2=K7(36)/(TENPH«GAMMA(86)) C 680ALFA(7)=MI(7)«GAM»A(7) C 690MI(18)*Cl«ALFA(7)/2. C 700f-I(86)aC2«ALFA(7) C 710ALFAdS)^! (18)«GAMMA(18) C 720ALFA(86)=FI(86)«GAMMA(86) C 730GC 70 30 C 740
20 CCN7INUE C 750*I(7)=C02TIT/(1.0+GAMfA(7)»( (KT (36) / (TENPMGAPMA (86) ) ) *TENPH/(K7(6 C 76019)«GAMMA(18)))) C 770
(7)«GAM^A(7)«7ENPH/(GAMMA(18)«K7(69) ) C 780(7)«GAMNA(7)«KT(36)/(TENPH«GAMMA(86)) C 790
ALFA(7)=MI (7)«GAMM (7) C POOALFA(18)=H(ie)»GAMMA(18) C 810ALFA(86)sPI(86)«GAH»A(86) C ^20
30 CCN7INUE C 830C C 840C C 850C PHOSPHATE SPECIES C 860
*I(45)*PT07/(1.+ (K7(17)«GAMNA(45)/(GAMMA(48)«»TENPH«*2) )*<K7(16)«GA C 870l**A(45)/(TENPh«GA^A(47) ) ) ) C 880ALFA(45)=MI(45)«GAMMA(45) C 890ALFA(47)=K7(16)«ALFA(45)/7ENPH C 900MI(47)«ALFA(47)/GAMMA(47) C 910ALFA(48)=K7(17)«ALFA(45)/(TENPH««2) C 920f<I(48)*ALFA(4e)/GAMPA(48) C 930I7ER=0 C 940PE7URM C 950END C 960-SL6ROU7INE WODEL 0 10IN7EGER D«E»DD»RBI7«CORALK,Z(120)»LIS7(8),LIS71(5)fLIS72(18)«LIS73 0 20
1 (6)«PRT(4)«PECALC«PECK D 30PEAL ^1(120)«K7(200)«LOGK7(200)fLOGK70(200)«MN707fLH20V^UtNA7C7«K7 0 40107,PGTOT,LITOT»NH4T07tKW,MUHALF 0 50PEAL «8NSPEC(120)«NREAC7(200) 0 60DIMENSION NPAIR(5)t LlM(9)t L1K(9), L1C(9)« LlA(9)t L1ALK{9)« L2M( D 70
113)i L2K(13)» L2C(13)» L3M(7), L3K(7)t L3C(7)t L4W(14)t L4K(14) t L D 6024C(14)» L4A(14)» L5H(9)« L5K(9)t L5C(9) D 90
COMMON MItK7»LOGK7»LOGK70.KW»DtE»OD»C»R»7«F»7EMPtA»B»PE«PES«PEDC«P D 1001ESA70»PECKtPECALC»PH«7ENMPEt7ENPH,ALFA(120)»GAM*A(120)«AP(200),XLA D 1102LFAU20) t2«CUMTS(l20) «ANALHI (120) tNSPEC»NREAC7«GFW (120) «OHA(120) « D 1203DfM200)«AH20«LH20,ERORl«EROR2tEROR3»EROR4tEROR5«EHM,DENS,DOX«XLM < D 1304120)«IT£R«RBI7«ClSAVE«CORALKfHU«LCHEK(200),C02TI7«ANALCOtSI707«CA7 D 14050T,f6TOT»KTQT,NATCT»S0470T«FE70T,PTOT,AL70TtFTOT»BT07tLITOT,NH4T07 D 1506«S«T07,BATQT«CLTC7,WN70TtICKtPRT«TITL(20)tEPMCA7tEPMAN,NEQU»ISPEC» D 160
-36-
7KSPEC(120).IMIN,KMIN(200)»TDStIDAVES.IPRT 0 170DATA LIST/17,35,66.70,71,72,8A.87/ D 160DATA LISTl/42t43t44t50t94/ D 190DATA LIST2/8,9,10,11,12*13,15,16,28,33,34,65,77,78,79,80,100,99/ 0 ?00DATA LIST3/82,83,88,89,90,917 D, 210DATA L1M/7,21,22,30,31,42,43,86,111/,L1K/69,74,75,78,79,70,71,36,1 D 220167/,L1C/64,2,2»1,1,3,3,64,101/,L1A/18,18,7,7,18,18,7,7,7/,L1ALK/1. 0 23020,?.0,1.0,1.0,2.0,2.0,1,0,0,0,1.0/,L2H/15,23,32,34,44,46,59,60,63, 0 ?403e3,92,96,109/,L2K/5,76,24,9,72,73,88,89,90,127,l32»136,165/,L2C/8, n 25042,1»8,3,4,51,51,64,81,39,64,10l/,L3H/20,55,56,57,58,108,49/,L3K/?3 0 2605,e4,85,86,87,164,eO/»L3C/2,51,51,51,51,101,l/,L4M/13,40,41,47,46,5 0 27060,61,65,73,74,75,76,99,100/,L4K/140,124,125,16,17,31,33,121,34,35, n ?607122«l23,157,139/,L4C/8,2,2,64,64,3,4,8,2,l,l,l,8,8/»L4A/47,45,48,4 n 29085,45,47»47,48,47,47,45,48,48,47/,L5M/l6,?6,33,93,94,95,103,104,105 n 3009/,L5K/6,7,8,133,134,135,159,160,161/,L5C/e,8,8,64,3,4,101,101,101/ D 310S,NPAIR/9,13,7,14,S/ 0 320ITERalTER*! 0 330
C 0 340C D 350C CALCULATION OF TOTAL MOLALITY AND AH20 0 360
J«l 0 370Cl*0,0 0 380DC 20 1=1,D D 390IF (I.EQ.LIST(J)) 60 TO 10 D 400C1=C1*MI(I) D 410RC TO 20 D 420
10 J=J*1 0 43020 CONTINUE 0 440
AH2Csl.O-0.017«Cl 0 450L>2C«ALOG10<Ah20) 0 460IF (DOX.GT.0.0) PEDO=-<ALOG10(KT(152))*PH+0.5«LH20-0.25«ALOG1Q(DOX 0 470
1/32E3)) 0 480IF (OCX.GT.0.0) PESATO=-(ALOG10(KT(137))*PH*0.5»LH20-0.25«ALOG10CO 0 490
IOX/32E3)) D 500IF (PECALC.EQ.2) PE=PEOC 0 510IF CPECALC.EQ.3) PE=PESATO D 520
C D 530C 0 540C CALCULATION OF ACTIVITY COEFFICIENTS 0 550
ML»0.0 D 5600*1 0 570DC 40 1=1,0 D 580IF (I.EO.LIST(d)) GO TO 30 D 590Ml»HU*0.5«MI(I)«ZCI)«Z(I) D 600GC TO 40 D 610
30 J=J+1 D 62040 CCNTIKUE D 630
WIHALF=SQRT(MU D 640C1=-A«4EO«MUHALF D 650GAM*A(1)=1E1««(C1/(1EO + B«5EO»MUHALF)+0.165<»*U> D 660GAMVAC2)=1E1««(C1/(1EO*8«5.5«MUHALF)*0.2*KU) D 670GAMKAC3)=1E1««(-A«MUHALF/(1EO*B«4EO»MUHALF)+0.075«MU) D 680GAMyA<4)slEl»«(-A«MUHALF/(lEO+B«3.5«MUHALF)*0.015«MU) 0 690GAMPA(5)=GAMMA(4) D 700GAMVAC6)slEl»«(Cl/(lEO*B«5EO»MUHALF)-0.04«MU) 0 710DC 60 1=8,0 D 720IF (Z(I).EQ.O) GO TO 50 D 730IF (IDAVES.EO.l) GAMMA(I)»1E1«»C(-A»Z(I)»«2«MUHALF)/(1.0*MUHALF)-0 D 740
1.3«*U) D 750IF (IOAVES.EQ.1) GO TO 60 D 760GAMHA(I)»1E1»«<-A«MUHALF«Z(I)»»2/(1EO*DHA(I)»B»MUHALF)) D 770
-37-
GC TO 605060 CONTINUE
GAMI*Am*lEl««<-A«MUHALF«Zm**2/a£0<»OWA (7 )*8«WUHALF) ) GAMP AU8)*lEl««(-A«MUHALF«Z(18)**2/UEO*0*A(18)«e«WUHALF) ) GAMfA<86)*lEl««(fL«U70.01/T-.8798-*.0013935«T)**U<»MU«(28«ei/T-«210
18*,0003641*T))
SILFUR SPECIES ANC PF. CALCULATION F«0* SClaKT(92)*TENFH/GAMMA<67)C2*KT(92)«KT(93)«TENPH««2/GAM*A(68)MIU4)*HIU7)/<1EO*GAMMA<14)«MC1+C2))ALFA(14)s»I(14)*GAPHA(14)
WI(67)aALFA(14)«ClMl(68)*ALFA(14)«C2ALFA(67)*H(67)«GAMHA(67)ALFA(68)«*I (66)*GAMMA(66)C1«ALFA(6)«ALFA(14)IF (Cl.GT.0.0) GO TO 70GC TO 80
70 PES*0.125«ALOG10(KT(91) ) *0. 125«AL061Q (ALFA (6) )- 10(ALFA(14) )-0.5«LH20IF (PECALC.EQ.4) FEaPES
60 CONTINUEIF (PECALC.EQ.O.O.OR.PE.GE.100.) 60 TO 90TENKPEslO.»«(-PE)GC TO 100
90 TENKPEslO.««( 100 CCNTINUE
SILICA SPECIES C1*KT(14)«TENPH/GAMMA(25) C2=KT (15)«TENPH««2/GAf«MA (26) M(24)=SITOT/(1.0*GAMHA(24)«(C1*C2)
.25«PH-0«125*ALCG1
*I(25)=ALFA<24)«C1 VI (26)=ALFA(24)»C2 ALFA(25)=^I(25)*GAMMA(25)
M (26 ) «GAM|MA (26 )
PCRON SPECIESC1=GA*MA(36)«KT(26)«TENPH/GAMMA(37)VI(36)=BTOT/(1.0*C1)WI(37)=C1«MI(36)ALFA(36)=HI(36)«GAHHA(36)ALFA(37)=^I(37)«GAMHA(37)
NITROGEN SPECIESCUTENPH»KT(27)/GAMMA(38)C2=ALFA(6)*KT(132)/GAKMA(92)f«I(39)*NH4TOT/(lEO*GAVMA(39)«(Cl*C2)ALFA(39)«VI(39)«GAMMA(39)VI(3£)=ALFA(39)«C1ALFA(38)=MI(36)«GAMMA(36)
D00DD0DDDDnDD00D0000000Dn00000D0DD0000D0nD0DDD000D000000D00D0
780790800P10820830840850860870860H90900910920930940950960970960990100010101020103010401050106010701060109011001110112011301140115011601170116011901?0012101?201230124012501260127012601290130013101320133013401350136013701360
-38-
MAGNESIUM SPECIESMI(19)3ALFA(27)*KT(25)/GAMMA<19)MI(20)aALFA(62)«KT(23)/GAMMA(20)Ml(21)aALFA(18)«KT(74)/GAMMA(21)Ml(22)sALFA(7)»KT(75)/GAMMA(22)MI(23)*ALFA(6)«KT(76)/GAMMA(23)Ml(40)aALFA(45)«KT(124)/GAMMA(40)MI (41)«ALFA(48)*KT ( 125) /GAMMA (41 )MK73)*ALFA(47)«KT(34)/GAMMA(73)MI(2)=MGTOT/(1,0*GAMMA(2)»(MI(19)*MI(20)*>'I(21)*MI (22) (4
ALFA(2)sMI(2)«GAMMA(2)CUALFA(2)DC 110 1=19,23
ALFA(I)sMI(I)«GAMKA(I) 110 CONTINUE
MI(40)*C1«MI (40) ALFA(40)sMI(40)«GAMMA(40) MI(41)*C1«MI(41) ALFA(41)sMl (41)«GAMMA(41) MI (73)sCl«MI(73) ALFA(73)*MI(73)«GAMMA(73)
CALCIUM SPECIESMI(29)«ALFA(27)«KT(77)/GAMMA(29)MI(30)sAlFA(7)«KT(78)/GAMMA(30)MI(31)=ALFA(18)«KT(79)/GAMMA(31)MI (32)«ALFA(6)*KT(24)/GAMMA(32)MI (74)*ALFA(47)«KT(35)/GAMMA(74)Ml(76)sALFA(48)«KT(123)/GAMMA(76)Ml(75)sALFA(45)«KT(122)/GAMMA(75)Ml(49)sAlFA(62)«KT (80 ) /GAMMA (49)Ml(l)sCATOT/(1.0*GAMMA(l)«(FI(29)*Ml(30)*Ml(31)*Ml(32)*Ml(74)+MI(75)*NI (76)«MI(49M)C1=MI(1)«GAMMA(1)ALFA(1)=C1DC 120 1=29,32
120ALFA(I)=MI (CONTINUEMI (74)*C1«MI (74)ALFA(74)sMI(74)«GAMMA(74)Ml(75)sCl«MI (75)ALFA(75)=MI(75)«GAMMA(75)Ml(76)aCl«MI(76)ALFA(76)»MI(76)«GAMMA(76)MI (49)sCl«MI(49)ALFA(49)sMI (49)«GAMMA(49)
SODIUM SPECIESMl(42)sALFA(18)«KT(70)/GAMMA(42)MI(43)=ALFA(7)*KT(7l)/GAMMA(43)Ml (44)=ALFA(6)«KT (72)/GAMHA(44)MI(50)«ALFA(47)«KT(31)/GAMMA(50)MI(9*)sALFA(5)*KTU34)/GAMMA(94)MI(3)=NATOT/(1.0*GAMMA(3)*(MI (42)*MI (44)*MI(50)*MI(94)
0D00n000DnD00DDnDD00n0DDDn00Dn00DnD0DnnD00DD0n00D0D00000n00DD
13SO1400141014?01430144014501460147014PO14901500151015201530154015501560157015801590160016101620163016401650166016701680169017001710172017301740175017601770178017SO180018101*2018301P40185018601*701P80189019001910192019301940195019601970I9601990
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130
140
150
ALFA<3)*MH3)«GAMMA<3)CUALFAO)DC 130 I«lt5Ml<tISTl<I))sCl«MI<LlSTKI))ALFA(LIST1 (I))=MI(LIST1 (I) )«GAMMA(LIST1 (I) )CONTINUE
POTASSIUM SPECIESMI<46)»ALFA(6)»KT(73)/GAMMA<46)MI<61)*ALFA(47)»KT<33)/GAMMA(61)MI<95)*ALFA(5)«KT(135)/GAMMA<95)Ml(4)sKTOT/(1.0 + GAMMA(4)»(MH46)+MI<61)*MI(95))ALFA(4)sMl(4)"GAMMA(4)C1»ALFA<4)MI(46)sCl<»MI(46)ALFA(46)=MI(46)»GAMMA(46)MI(61)*C1«MJ(61)ALFA(61)=MI (61)"GAMMA(61)MI(95)sCl«MI<95)ALFA(95)=MI(95>»GAMMA(95)
ALUMINIUM SPECIESMI(52)»ALFA(27)»KT(fll)/GAMMA(52)Ml<53)sALFA(27)«n»2«KT(82)/GAMMA(53)MI(54)aALFA(27)««4«KT(83)/6AMMA(54)MI(55)«ALFA(62)«KT(84)/GAMMA(55)^I(56)=ALFA(62)««2»KT(85)/GAMHA(56)Ml(57)=ALFA(62)««3«KT(e6)/GAMMA(57)FI (58)=ALFA(62)«*4*KT(87)/GAMHA (58)MI (S9)=ALFA(6)»KT(88)/GAMMA(59)Ml(60)sALFA(6)»»2«KT(89)/GAMMA(60)
(54 (55)
ALFA (51)=* I (5D«GAMHA(51)C1=ALFA(51)DC 140 1=52*60
ALFA(I)=MI CONTINUE
IRON SPECIESIF (ABS(PE).LT. 20.0. AND. FETOT.GT. 0.0)GO TO 170
GO TO 150
MI (10)sKT(2)«AH20«TENPH/(TENMPE»GAMMA(10) ) MI (11)=KT(3)«AH20«TENPH/GAMMA(11)MI<12)eKT(4)«AH20««3«TENPH««3/GAMMA<12)MI (13)=KT(140)«ALFA(47)/(GAMMA(13)«TENMPE)MJ(15)=KT(5)«ALFA(6)/(TENMPE«GAMMA(15) >MI (16)eKT(6)»ALFA(5)/(TENMPE*GAMMA (16) )MI (28)=KT(7)*ALFA (5) »*2/ (TENMPE*GAMMA (28) )MI (33)e«T(8)»ALFA(5)«n»3/ (TENMPE*GAMMA (33) )MI (34)sKT(9)»ALFA(6)/GAMMA(34)MI(65)=KT(121)«ALFA(48)/GAMMA(65)MI (77)=KT(103)«(AH20«TENPH)««2/(TENMPE«GAMMA(77) )MI (78)=KT(104)»(AH20*TENPH)««3/(TENMPE*GA>'MA(78) )MI<79)=KT(105)«(AH20»TENPH)««4/(TENMPE<»GAMMA<79) )MI(80)=KT(106)«(AK20«TENPH)»»2/GAMMA(80)
0 0 0 0 D 0 0 0 0 0n o n n D o o DD00n D0 D 0nD D Dn0D
(56)*MI oD D D D D D 0 DnD D D 0 D 0 D 0 0 D D D D D D D D D
2000 2010 2020 2030 2040 2050 2060 2070 2060 2090 2100 2110 2120 2130 2140 2150 2)60 2170 2180 2190 2200 2210 2?20 2230 2240 2?50 2260 2270 ??80 2?90 2300 2310 2320 2330 2340 2350 2360 2370 2380 2390 2400 2410 2420 2430 2440 2450 2460 2470 2460 2490 2500 2510 2520 2530 2540 2550 2560 2570 2580 2590 2600
-40-
160
170
180
190
200
MI(99)«KT(157)«ALFA(48)/(TENMPE«GAMM.A(99MMI(100)«KT(139)«ALFA(47)/GAMMA(100)Ml(8)»FETOT/(1.0*<:AMMA(e)«(Ml(9)*MI(10)*MI(ll)*Ml(l2)*MI(13)*MI(15 1)*MI(16>*MI(28)*MI(33)*MI(34)*MI(65)*MI(77>*MI(78)*MI(79>*MI(80)*M 2I(100)*MI(99»)ALFA(8)sMK8)«GAMMA(8>C1*ACFA(8)DC 160 I=2tl8MI(LIST2(I»*C1«MI(LIST2(I)>ALFA (L IST2 ( I M =MI (LIST2 ( I >> -GAMMA (LIST2 ( I ) )CONTINUEGO TO 190CONTINUEDC 180 I=2»18MI(LIST2(I))=0.0CONTINUEALFA(8)sMl(8)«GAMMA(8)CONTINUE
MANGANESE SPECIES
IF (ABS(PE).LT.20.0.AND.MNTOT.GT.O.O) GO TO 200GO TO 240Ml(102>sKT(156)/(GAMMA(102)»TENMPE)MI (103>=KT(159)*MI (5) 'GAMMA (5) /GAMMA (103)MI (104)=KT(160)»MI(5)«»2«GAMMA(5)»*2/GAMMA<104)MI{1Q5)=KT(161)»MI(5)»»3*GAMMA(5)**3/GAMMA<105)MI (106)sKT(162)»MI (27)*GAMMA(27)/GAMMA (106)Ml(l07)sKT(163>«Ml(27)««3«GAMMA(27)«*3/G.AMMA(107)MI (108)sKT(164)«Ml (62)»GAMMA(62)/GAMMA(108)MI(109)=KT(165)*MI(6)«GAMMA(6)/GAMMA(109)MI(110)sKT(166)»MI(85)»«2*GAMMA(85)»*2/GAMMA(110)Ml(lll)sKT(l67)»MI(7)»GAM.MA(7)/GAMMA(lll)XMI112sLOGKT (168) *4»LH20- ( ALOG10 (GAMMA (112) )-8»PH-5«PE)IF (XMI112.LT.-50.) MI(H2)«0.0IF (XMIH2.LT.-50.) GO TO 210
210 CONTINUEXMI113=LOGKT(169)*4«LH2C-(ALOG10(GAMMA(113) )-8»PH-4»PE>IF (XMI113.LT.-50.) MK113)sO.OIF (XMI113.LT.-50.) GO TO 220MI(113)=10.»»XMI113
220 CONTINUEM I ( 1 15 > «KT ( 171 ) •Ah20»»2/ (GAMMA ( 1 15) * ALFA (64 ) «»3 )Ml(101)sMNTOT/(1.0*GAMMA(101)»(MI(102)*MI ( 1 03) *M I( 1 04 ) *M I ( 1 05 ) *M I ( 1106)*MI(107)*MI(108)*MI(109)+MI (110)*MI (111)*MI (H2)*MI(113)*MI (11 25)))ALFA(101)sM!(l01)«GAMMAUOl)C1=ALFA(101)DC 230 1=102.113Ml(I)sCl*MI(I)ALFA(I)sHI(I)«GAMMA(I)
230 CONTINUE
240
250
260
ALFA(115)sMI(115)«GAMMA(115)GO TO 26000 250 1=101.113MI(I)*0.0CONTINUEMI(115)«0.0CONTINUE
000DD000000000000DDn00D00DnD0D0000D0D00000nnnDD00D00D00000000
26102620263026402650266026702680269027002710272027302740.27502760277027602790280028102820283028402850286028702860289029002910292029302940295029602970296029903000301030203030304030503060307030603090310031103120313031403150316031703180319032003210
-41-
?70
260
290
300
310
320
330
340
CALCULATION OF P02 AND PCH4 IF UBS(PE).LT.19.0) GO TO 270 GC TO 260
ALFA(70)alO.<M»<4.0*Cl)CONTINUEIF (ABS(PE).LT. 19.0. AND. ALFAC7J.GT. 0.0) GC TO 290GC TO 300XLALFA(71)s<ALOG10<KT(95))-8.0*PE-9.0<»PH-3.0<»LH20*ALOG10<ALFA<7)IF (XLALFAC7D.LT.-78.) GO TO 300ALFA(71)=10.««XLALFA(71)CONTINUE
LITHIUM. STRONTIUM. BARIUP SPECIESC1«KT(126)*ALFA(27)/GAMMA(82)C2«KT(127)»ALFA<6)/GAWM.A<83)Ml(8l)sLITOT/<1.0*GAMMA<81)«<Cl+C2))ALFA(81)=PI (8I)«GAM.MA(81)Ml(82)sCl<»ALFA<ei)Ml(83)«C2«ALFA<enC1=KT(130)»ALFA(27)/GAMPA(89)MI <88)»SRTOT/(1.0+GAMMA(88)*C1)MI (89)sGAMMA(88)»Pl (88)«C1Ci«KTU31)«ALFA(27)/GAMM A (91)MI(90)«BATOT/<1.0*GAMMA<90)»C1)MI (91)sGAMMA(90)«M(90)«ClDC 310 I=l»6ALFA(LIST3(I))=MI(LIST3(I))»GAMMA(LIST3(I»CONTINUESl=0.052=0.053=0.0S«=0.055=0.0ANALCOsCOZTITMASS BALANCE CN CARBONIF (C02TIT.LE.O.O) GO TO 370ACT=KT (69) «ALFA (64)StMsQ.OSLM1=0.0N=NPAIR(1)DC 320 1 = 1. NMI(L1M(I))=KT(L1K(I))«ALFA(L1C(I) ) /GAHMA (L1K ( I ) )IF (LlA(l) .E0.7) M(L1M(I) )=MI (LIMd) )«ACTSIM,*SUM*MI (Ll^(I) )SIM.1 = SUM*L1ALK(1)«MI(L1M(IMCONTINUEIF (CORALK.NE.2) GO TO 340Ml (18)=ANALCO/ (1.0*GAHHA (18)«SUM)
DC 330 Isl.NMKLIH(I) )=MI(Llf(I))«ALFA(18)ALFA(L1M(I))=MI(L1M(I) ) «GAMMA (L1M ( I) )S1=S1*MI(L1M(I) )CONTINUESUS1+MK18)GC TO 370CONTINUE
0 3220 0 3?30 D 3240 0 3250 0 3260 D 3270 D 3260 n 3250 0 3300 0 3310 0 33?0 0 3330 0 3340 0 3350 0 3360 0 3370 0 3360 0 3350 0 3400 0 3410 0 3420 D 3430 0 3440 0 3450 0 3460 0 3470 0 3460 0 3490 0 3500 D 3510 0 3520 D 3530 0 3540 0 3550 0 3560 D 3570 0 3580 0 3590 0 3600 0 3610 D 3620 D 3630 0 3640 0 3650 D 3660 D 3670 D 3660 0 3690 D 3700 0 3710 0 3720 D 3730 0 3740 0 3750 D 3760 0 3770 D 3760 0 3790 D 3800 0 3610 D 3820
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IF (CORALK.EQ.l) GO TO 350ANALCOsC02TIT-MI(25)-2.0*Ml(26)-MI(27)-MI<37)-2.0»MI<45) 1<54)-MI<67)-2.0»MI(68)-MI<82)
350 CONTINUEMl(l8)sANALCO/(2.0*GAMMA(18)»SUMl)ALFA(18)=M I (18)"GAMMA(18)DC 360 I=1«NMI(L1M(I))=MI(L1M<I))»ALFA(18)ALFA(L1M(I))=MI(L1M(I))«GAMMA(L1M(I))SlsSl*LlALK(I)»MHLlM<I))
360 CONTINUESlsSl*2.0»MIU8)
370 CONTINUEMASS BALANCE ON SLLFATEIF (S04TOT.LE.O.O) 60 TO 410N*NPAIR(2)DC 380 I = ltNMKL2M<I))sKT(L2K(I))»ALFA(L2C(I))/GAMMAa2M(I) )
380 CONTINUEMI(15)*MI (15)/TENMPEMI(60)=MI(60)«4LFA(6)MI(96)=MI(96)«ALFA(64)9LMSMH60)DC 390 I=ltNSLM=SUM*MI(L2MI))
390 CONTINUEMI(6)sS04TOT/(1.0*GAMMA(6)«SUM)ALFA (6)sMI(6)«GAMPA(6)DC 400 I = ltNMI(L2M(I))sMI(L2MI))«ALFA(6)ALFA(L2M(I))=NI(L2M(I))«GAMMA (L2M (I))S2=S2*MI (L2M(I))
400 CONTINUES2=S2*MI(6)*MI(60)
410 CCNTIN'UE^ASS BALANCE ON FLUORIDETF (FTOT.LE.0.0) GO TO 450NsNPAlR(3)DC 420 I=ltNMI(L3M(I))=KT(L3K(I))»ALFA(L3C(I))/GAMMA«L3M (I))
420 CONTINUEMI(56)=MI(56)«ALFA(62)MI(57)sMI(57)«ALFA(6?)«ALFA{62)MI(58)=MI(58)«ALFA(62)*ALFA(62)*ALFA(62)SIM=MI(56)*2.0*MI(57)*3.0«MI(58)DC 430 IsltNStM=SUM*MI(L3M(I))
430 CONTINUEMI(62)=FTOT/(1,0*GAMMA(62)»SUM)ALFA(62)*MI(62)«GAMMA(62)DC 440 I=1»NMI (L3M(I))=MI(L3M(I))«ALFA(62)ALFA(L3M(I))=MI(L3M(I))«GAMMA(L3M(I))S3=S3*MI(L3M(I))
440 CONTINUES3=S3*MI(62)*MI(56)*2.0«MI(57)*3.0»MI(58)
450 CONTINUEMASS BALANCE ON PHOSPHATEIF (PTOT.LE.0.0) GO TO 490N*NPAIR(4>C1=KT(16)»ALFA(64)
0 3fl30•MI(47)-MI n 3840
D 3850 D 3860 n 3«70 D 3880 D 3890 0 3900 D 3910 D 3920 D 3930 D 3940 D 3950 D 3960 0 3970 D 3980 D 3990 D 4000 D 4010 D 4020 D 4030 D 4040 D 4050 D 4060 0 4070 D 4060 D 4090 H 4100n 41100 4120 D 4130 D 4140 D 4150 D 4160 D 4170 D 41PO 0 4190 D 4?00n 4?ioD 4220 D 4?30 D 4?40 D 4250 D 4260 D 4270 D 4280 D 4?90 D 4300 D 4310 D 4320 D 4330 D 4340 D 4350 0 4360 D 4370 D 4360 D 4390 D 4400 D 4410 D 4420 D 4430
-43-
460
470
480
490
500
510
520
530
C2aKTU7)«ALFA(64)«ALFA(64)DC 460 I«ltNMI (L4* ( I ) ) «KT (L4K ( I ) ) «ALFA (L4C ( I ) ) /GAMMA (L4P ( I ) )IF <L4A(I).EQ.47) M I (L4M ( I ) ) =MI (L4M ( I ) ) «C1IF (L4A(I).EQ.48) MI (L4M ( I ) ) *MI (L4M ( I ) ) «C2CONTINUE
540
MI (48)«HI (48)«ALFA (64)*I (99) *MI (99) /TENURESLM*0.0DC 470 I»1*NSCM»SUM*MI(L4M(I))CONTINUEMI(45)»PTOT/(1.0*GAMMA(45)»SUM)ALFA(45)»MI(45)*GAMMA(45)DC 480 I»1«NMI(L4M(I))sMI(L4M(I))«ALFA(45)ALFA (L4M ( I ) ) =M I (L4M ( I ) ) «GAMMA (L4M ( I ) )S4*S4+MI(L4M(I))CONTINUES4*S4+MI(45)CONTINUEMASS BALANCE ON CHLORIDEIF (CLTOT.LE.0.0) GO TO 530N»NPAIR(5)DC 500 1 = 1. NMI (L5M ( I ) ) =KT (L5K ( I ) ) «ALFA (L5C ( I ) ) /GAMMA (L5M ( I ) )CONTINUEMK16)»M.I(16)/TEM'PEMI (28)=MI (28)«»ALFA (5) /TENMPEMI(33)*MI(33)«ALFA(5)«ALFA(5)/TENMPEMK104)sHI(104)«ALFA(5)Ml(l05)aMK105)«ALFA(5)«ALFA(5)SCM=MI (28)*2.0«HI (33)*MI (104)*2.0«MI (105)00 510 1=1. N9LM=SUM+MHL5MI))CONTINUEMI(5)=CLTOT/<1.0*6AMMA(5)«SUM)ALFA(5)=MI(5)«GAMMA(5)DC 520 1=1. NMI(L5M(I))=MI(L5M(I))«ALFA(S)ALFA(L5M(I))sMKL5M(I))«GAMMA(L5M(I))S5=S5+MI(L5M(I))CONTINUES5=S5 + MI(5)+MI(28)+2.0*MI(33)*MI (104) *2.0«MI ( 105)CONTINUEALFA(85)*MI(85)*GAMMA(85)ALFA (98)=MI (98)«GAMMA (98)ALFA (27)=AH20«K!iK«TENPHMI(27)=ALFA(27)/GAMMA(27)MI(64)slEO/(TENPH«GAMMA(64) )TESTlsSl-ANALCOTEST2=S2-S04TCTTEST3=S3-FTOTTEST4=S4-PTOTTEST5=S5-CLTOTR6IT*0IF (S1.EQ.O.O«OR.ANALCO.LE.O.O) GO TO 540IF <ABS(TEST1).GT.EROR1«ANALCQ)GO TO 550ANAlCO=0.0
0 4440 0 4450 0 4460 0 4470 0 4480 0 4490 0 4500 0 4510 0 4520 n 4530 0 4540 0 4S50 0 4560 n 4570 0 4580 D 4590 0 4600 0 4610 0 4620 0 4630 0 4640 0 4650 0 4660 0 4670 D 4680 0 4690 0 4700 0 4710 0 4720 0 4730 0 4740 0 4750 0 4760 D 4770 0 4780 D 4790 0 4800 0 4810 0 4820 0 4830 H 4840 0 4850 0 4860 D 4870 0 4880 D 4890 D 4900 0 4910 n 4920 0 4930 0 4940 0 4950 0 4960 D 4970 0 4980 0 4990 0 5000 0 5010 0 5020 D 5030 D 5040
-44-
550 CONTINUEIF (S2.EQ.O.O) 60 TO 560IF <ABSUEST2).GT.EROR2«S04TOT) RBIT»1
560 CONTINUEIF (S3.EQ.O.OL) 60 TO 570IF <A8S<TEST3).6T.EROR3«FTOT) RBIT»1
570 CONTINUEIF (S4.EQ.O.O) 60 TO 580IF <ABSUEST4).6T.EROR4«PTOT) RBIT«1
5*0 CONTINUEIF (S5.EQ.O.O) 60 TO 590IF <ABS(TEST5).6T.EROR5«CLTOT) RBIT«1
590 CONTINUEIF (PRT(2) .NE.O) 60 TO 600PRINT 610t ITERfTESTltTEST2tTEST3tTEST4tTEST5
600 CONTINUERETURN
610 FORMAT (1H 1 19X v I3t5Xt5 <lPE13.6t3X) )FNDSUBROUTINE PRINTINTEGER DtEtDCtR8lTtCORALKtZ<120)tLIST4U04)»LIST5(8)tPRT<4)INTEGER PECALCtPECKREAL MIU20)tKT(200) tL06KT<200) tL06KTC<200) tMNTOTtLH20fMUtNATOTtKT 10TtMGTOTtLITOTtNH4TOTtKbtRATIOl<10) tRATI02<10)»RATIC3<8) tXLGAM(!20 2)REAL «8NSPEC<120) tNREACT<200)COMMON MItKTtLOGKTtLpGKTOtKVltOtEtDDtCtRtTtFtTEMPtAfBtPEtPESfPEDCtP IFSATOtPECKtPECALCtPHiTENMPEtTENPHtALFAUSO) tGAMMA(120) tAP(200) tXLA 2LFA<120)fZtCUMTS(120)fANALMl<120)»NSPECrtNREACTtGFW(120) tDHA(120)* 3DM200) tAH20»LH20*ERORltEROR2tEROR3tEROR^EROR5tEHMfOENS*DOXtXLMl( 4120 ) t ITERtRBITtCl SAVE tCCRALKtMUtLCHEK (200 )tC02TITtANALCCt SI TOT tCAT 50TfMGTOTtKTOTtNATCTtS04TOTtFETOTtPTOTtALTCTtFTOTt8TOTtLITOTtNH4TOT 6tSPTOTtBATOTtCLTOTtMNTOTtICKtPRTtTITL(20) tEPMCATtEPMANtNEQUt ISPECt 7KSPECU20) tIMINtKMlN(200) tTOSt IDAVESt IPRTDATA LIST4/lt2t3t4t64t5t6t7tl8t86t27t62t98tl9t23t22t21*20t29t32t30 It31»49t44t43t42t94t46t95t63t96t93t24t25t26tl4t67t68t8t9tl0tlltl2t7 27t78t79t80tl3tlOOt65t99tl5tl6t28t33t34tl01tl02tl06tl07tllltl09«110 3tl03tl04tl05«108tll?tll3tll5t51t52*53t54t55t56t57«58t59t60t45t47t4 4Bt40t73t4lt75t74t76t6lt50t36t37t85»38t39t92t81t82t83t88t89t90t91/DATA LIST5/lt2t3t4t51t8t6t7/CEPMANsO.OCEPMCTaO.O00 20 1*1.0IF (Z(I).GT.O) GO TO 10CEPMANaCEPMAN-Z ( I ) «MI { I )GO TO 20CEPMCTsCEPMCT*Z(I)«MI(I)CONTINUECEPMAN=CEPMAN«1000.CEPMCT«CEPMCT«1000.
1020
PC02»0.0IF (ALFA(86).6T.O«0) GO TO 30GO TO 40
30 PC02slO.»«(AL0610(ALFA(86) ) -2385. 73/T-1.5264E-?«T*14. 0184)XLPC02*ALOG10(PC02)
40 CONTINUEE»-PE*PE»C*R»T/FPRINT 110
0 5050 0 5060 0 5070 0 5060 0 5090 0 £100 0 5110 0 5120 0 5130 D 5140 D 5150 0 5160 D 5170 D 5160 D 5190 0 5?00 0 5?10 0 5220 0 5230 0 5240-
10203040506070eo90 100 110 120 130 HO 150 160 170ieoISO 200 210 220 ?30 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410
-45-
PRIM 110PRINT 120, AH20*EPMCAT.CEPMCT.PHtPCOH«£P«AN«CEP*AN.XLPCC2*ALFA(70)
l*EHl**PE*TEMP t ALFA(71),PES»Sl*PEDO*DENS*PESATO«MU*TDS PRIM 130t PEtEHPE PRINT 140 DLM=10.»«(-70) OC 50 1*1*0 CLNITS(I)*0.0IF (MI(I).LT.OUH) GO TO 50CLNITS(I)»MI(I)«1000.<»GFW(I)«(1.0-1«OE-06«C1SAVE) XLMI(I)=ALOG10(HI (I))XLALFA(I)=ALOG10(ALFA(I))XLGAM(I)=ALOG10(GAHMA(I))
50 CONTINUEOC 60 1-1*104IF (MI(LIST4(I)).LT.DU*) GO TO 80IF (ISPEC.EO.O) GC TO 7000 60 J=ltISPECTF (LIST4(I).EQ.KSPEC(J)) GO TO 70
60 CONTINUEGC TO 80
70 CONTINUEPRINT 150* LIST4(I)*NSPEC(LIST4(I))*2(LIST4(I)),CUNITS(LIST4 (I))*M IT(LIST4(I))tXLHI(LIST4(I))*ALFA(LIST4(I))«XLALFA(LIST*(I))«GA*WA (L 2ISTA(I)),XLGAN (LIST4(I) )
80 CONTINUEIF (PRT(3).NE.O) GO TO 100
CALCULATION OF HOLAR RATIOS AND LOG ACTIVITY PATIOS. DC 90 1=1*8IF (ANALMI(LIST5(I)).LT.IE-30) ANALMI(LISTS(I))=1E-30 IF (MI(LIST5(I))«LT.IE-30) Ml(LISTS(I))»1E-30 IF (MI(LIST5(I)).LT.IE-30) XLALFA(LISTS(I))=-30. RATI01(I)=ANAL»I(5)/ANALMI(LISTS(I)) RATI02(I)=MI(5)/"I(LISTS(I) )
50 CONTINUERAT 101 (9)=ANAL*I (D/ANAL^I (2) RATI01(10)=ANALKI(3)/ANALMI(4) RATI02(9)=MI(1)/*I(2) RATI02(10)*MI(3)/^I(4) RATI03(1)*XLALFA(1)*PH«2. RATI03(2)=XLALFA(2)*PH«2. RATI03(3)=XLALFA(3)*PH RATI03(4)=XLALFA(4)*PH RATI03(5)=XLALFA(51)*PH«3. RATI03(6)=XLALFA(8)*PH»2. PATI03(7)=XLALFA(1)-XLALFA(2) RATI03(8)=XLALFA(3)-XLALFA(4) PRINT 110PRINT 160, (RATI01(I),RATI02(I),RATI03(I)*I=1,6)«(«ATI01(I),PATI02 1(I)*I = 9,10).
100 CCNTINUE RETtKN
110 FORMAT (//)120 FCRPAT (//*46X*»*«««OESCRIPTION OF SOLUTION »«»•«,//*27Xi'ANALYTIC
1AL COMPUTED»*13X,»PH»,16X,'ACTIVITY H20 = •*F7.4»/*20X*'EPMCAT •» 2F5.3*3X,F9.3*10X,F6.3*14X*«PC02 a <•1PE13.6*/»20X*'EPMAN «,OPF9.3 3«3X*F9.3,30X*«LOG PC02 a •«F8.4,/»56X,»TEMPERATURE'•1IX*»P02 = ••!
FFEFFFFEFFFFFFEFEEFFEFEFFEFEEFEFEFEEEFFFFEFEFEEEFFEEEEEEEEFEF
4204304404504604704604 SO500510520530540,550560570580550600610620630640650660670650650700710720730740750760770780750POO610820P30840850860870880850900910920930940950960970980990100010101020
-46-
4PEl3.6./.20X,»Eh a « .OPF6.4.2X. »PE * • ,F.7.3» 11X.F6.2. • DEC C»*10X.5IPCH4 « »tlPEl3.6t/t20Xt»PE CALC S a • .E13.6.33X. «C02 TOT » ».E13.66./.20X.»PE CALC COXat ,£13.6. 10X. • IONIC STRENGTH* «9X« 'DENSITY = ».70FF8.4,/.20X.»PE SATO DCX*» • 1PE13.6, 10X.E13.6. 10X, »TOS a I OPF9.1,»8Me/L»»/)
130 FCRMAT (11X.MN COMPUTING THE DISTRIBUTION OF SPECIES* PE = ».F7.31.5X. 'EQUIVALENT Eh »• .F7.3. • VOLTS' »//)
140 FORMAT (X//.52X , »- — —— - —— ...... —— . —— i ,/,52X . 'DISTRlBUT ION OF S1PECIES»,/»52X,» ——————————————————— ».//,7X,»I».2X, 'SPECIES' ,10X2.»PPM»,11X.»MCLALITY»,8X,»LOG MQL» .6X, • ACTIVITYl ,8X, »LOG ACT».5X,»3ACT. COEFF.»,5X,»LOG A COF»,/)
150 FORMAT (1H ,5X.I3,1X,A8.I3.2X,1PE12.5.4X,E12.5,4X.OPF9.4,4X,1PE12.15.4X,OPF9.4,4X,1PE12.5,4X,OPF9.M
160 FCRMAT (//• 18X • »MOLE RATIOS FROM ANALYTICAL MCLALITY MOLE RATIOS1 FROM COMPUTED MOLALITY LOG ACTIVITY RATIOS' ,/• 18X» • ——————————
»CL/CA s »»!PE11.4»17Xf »CL/CA s 4.4,9X»»LOG CA/H2 s » , OPF9.4 , / ,25X » » CL/MG s • • 1PE1 1 «4« 17Xt *CL/MG 5 » •»E11.4t9X»»LCG MG/H2 = • »OPF9.4t/»25X, 'CL/NA » •»1PE11«4»17 6X»»CL/NA s »»E11.4f9X»»LOG NA/H1 a • , OPF9.4,/f 25Xf »CL/K a ».l 7PEll.4,17X»»CL/K s •»E11.4,9X,»LOG K/H1 s • ,OPF9.4t/ ,25X t »CL/A 81 « •»lPE11.4fl7X,«CL/AL » • ,E11 .4 ,9X t »LOG AL/H3 * »»OPF9,4,/» 925Xi»CL/FE « • 1 1PE11 .4 t!7Xt 'CL/FE = • ,E1 1.4,9X, 'LOG FE/H2 = •• SOFF9.4,/»25X»»CL/S04 a • . 1PE11.4, 17X, 'CL/SC4 s » ,E1 1 ,4,9X f »LOG C SA/MG « »tOPF9.4,/,25Xt»CL/HC03 a i , IPEll .4 • 17Xt 'CL/HC03 a i,E11.4, S9X,*LOG NA/K a * ,OPF9,4 •/•25X« *CA/MG a * • 1PE1 1 «4« 17X« *CA/MG a S '»E11.4,/,25X»'M/K a »,E11.4»17X, «NA/K : »,E11.4)FNDSLBROUTINE SATINTEGER D«EtDCtRBITfCORALKfZ(120) »LIST6(24) «PRT(4)INTEGER PECALCfPECKDIMENSION LIST7U01), LIST8(15)PEAL MK120) tKT(200) »LOGKT(200) »LOGKTO(200) »MNTOT»LH20tMU»NATOT»KT 10TfMGTOTiLITOTtNH4TOTtKViPEAL «8NSPEC(120) tNREACT(200)COMMON MIfKTtLOGKTtLOGKTOfKwtOtE»DDfC»RiT»FtTEMPf AfB»PF»PES»PEDCtP !ESATO»PECKtPECALC.PH»TENMPE»TENPH»ALFA(120) »GAMMA(120) tAP(200) »XLA 2LFA(120) »Z»CUMTS (120) tANALMl (120) »NSPF.C »KRF ACT .GFW ( 120 ) ,DHA(120) t 3DM200) *AH20«LH20tERORltEROR2*EROR3fEROR4«EROR5fEHM«OENStDOX*XLM ( 4120) »ITER»RBIT»ClSAVE.COHALK t MUtLCHEK(200) . C02TITt ANALCOtSITOT tCAT 50T,MGTOT,KTOTfNATCTfS04TOTiFETOTfPTOT»ALTOTtFTOT»BTOTtLITOT,NH4TOT 6tSRTOT,BATOT»CLTOT»MNTOT.ICKtPRTfTITL(20) .EPMCATtEPMANtNEQU. ISPECt 7KSPEC(120) tIM IN, KM IN (200) »TOS, IDAVES. IPRTDATA LIST6/lt 2»3 »4»5.6, 7 ,8,9,11, 18 .24,27,40 t 45 ,47,51 f 54,62*67 tflfi»9 10.101.102/DATA LIST7/4 0,4 1,1 4 1,5 1,43. 18, 11 4, 42, 22. 15 1.1 45, 49, 53. 20. 13, 144,98 1.50,21,30,57,100,29,12,56,113,120,97,63,28,52,111,112,119,19,65,48 2,109,118,39,96,46,47,44,129,148,68,99,110,11,108,64,116,117,58,67, 359,61,150,55,45,142,115,54,102,37,10,101,147,143,38,66,62,32,60,10 47»146,154f 155.156, 17?, 173*174 • 175, 176, 177 ,178, 179, 180 »18 It 183, 184 1 5 1 85. 186 • 1 87 » 188. 189, 190*191, 192 »193/DATA LIST8/ 107. 108. 109, 11 0.1 11. 11 2. 11 3. 114. 115. 119, 120. 173. 174. 175 1.177/
CALCULATION OF ION ACTIVITY PRODUCTS DC 20 1=1,24IF (ALFA(LIST6(I) ULT.l.E-40) GO TO ALFA(LIST6(I) )=ALCG10(ALFA(LIST6(I) ) GO TO 20
10 ALFA(LIST6(I))a.2E4
10
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a
AP(101)*AP(98)AP(102)sAP(98)IF (ABS(PE).LT.20.0) 60 TO 30GC TO 40
30 CONTINUEAP(107)«3EO*ALFA(8)*2EO«ALFA(45)*8EO»LH20AP(1G8)=3EO*ALFA(9)-2EO«PE*4EO«LH20+8EO*PHAP(109)«2EO*ALFA(9)*3EO«LH20*6EO«PHAP(110)=AP(109)AP(111)«ALFA(9)*3EO*ALFA(27)-LH20AP(112)«3EO*ALFA(8)+2EO«ALFA(24)+6EO«ALFA(27)-5EO«LH20AP (113)*ALFA(9)*3EO*(LH20*PH)AP (114)sAP(45)*3EO«(ALFA(8)-ALFA(2))AP(115)=ALFA(8)+2EO*(ALFA(67)*PE*PH)AP(119)=3EO*ALFA(8)+4EO*ALFA(67)+2EO*PE+4EO»PHAF(120)=AP(68)AP(173)«ALFA(102)*2«LH2C*4*PH+PEAP(174)sAP(173)AP(175)sAP(173)AP(177)s3*ALFA(101)+4«LH20*8*PH+2*PE60 TO 60
40 CONTINUEDC 50 I=lfl5JK«LIST8(I)AP (JK)=-6000.
50 CONTINUEPECK=1
6.0 CONTINUEAP(116)«.29«ALFA(2)*.23«ALFA(9)*1.58*ALFA(54)*3.93*ALFA(24)
120AP(117)=.45«ALFA(2)*.34«ALFA(9)+1.47*ALFA(54)*3.82«ALFA(24) 12C*.76»PHAP(118)=3EO«ALFA(2)*ALFA(1)*4EO*ALFA(18)AP(129)sALFA(l)*2EO«ALFA(54)*4EO»ALFA(24)-8EO*LH20AP (141)=AP(52)AP(142)s2EO*(ALFA(l)*ALFA(54)+PH)*3EO*ALFA(24)-8EO»LH20AF (143)=ALFA(88)*ALFA(18)AP (144)-ALFA(88)«ALFA(6)AP(145)=ALFA(90)*ALFA(6)AP (146)=ALFA (90)+ALFA(18)AP(147)=ALFA (9)*ALFA(45)*2EO»LH20AP (l48)s2EO«ALFA(l)+4EO«ALFA(54)*8EO»ALFA(24)-17EO*LH20AP(150)sALFA(2)*ALFA(18)*3EO*LH20AP(151)«2EO*ALFA(1)*ALFA(18)*2EO*ALFA(27)*3EO»LH20AP(172)sALFA(lOl)*LH20*2*PHAP(176)=2*ALFA(102)*3«LH20*6»PHAP(178)=ALFA(101)*2*ALFA(27)AP(179)=ALFA(102)*3»ALFA(27)AP(180)«ALFA(102)*2«LH2C*3«PHAP(181)sALFA(101)+ALFA(18)AP(183)=ALFA(101)*2*ALFA(b)AP(184)sAP(183)*LH20AP(185)SAP(183)«2«LH20AP(186)aAP(183)*4«LH20AP(187)«2«ALFA(101)*ALFA(24)+4*PHAP(188)s2*ALFA(101)*ALFA(24)*2*PH-LH20AP(189)sALFA(101)*ALFA(67)*PHAP(190)=ALFA(101)*ALFA(6)AP(191)s2*ALfA(102)*3«ALFA(6)AP(192)*3*ALFA(101)+2»ALFA(45)AP(193)«ALFA(101)*ALFA(47)
FFFFFFFFFFFFFFFFFFFFFFFFFFFF
10.«LH FF
9.2«LH FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF
95096097098099010001010102010301040105010601070108010901100111011201130114011501160117011801190120012101?2012301?401?5012601?701280129013001310132013301340135013601370138013901400141014201430144014501460147014801490150015101520153015401550
-49-
AP(154)sAP<37)AP(155)»AP(52)-LH20AP(156)*AP(129)-2«LH20PRIM 140PRIM 150DC 100 I«l,102IF (IMIN.EQ.O) 60 TO 60
DC 70 JMIF (LIST7(I) .EQ.KHIN(J) ) K*l
70 CONTINUEIF (K.EQ.l) GO TO 80GO TO 100
80 CONTINUEIF (AP(LIST7(I)).LT. -77.0. OR. AP(LIST7(I)).GT. 75.0) GO TO 90IF <LCHEK(LIST7(I)).EQ.1) GO TO 90OLMsAP(LIST7(I))-ALOG10(KT(LIST7(I)))IF (OUM.GT.75.) GC TO 90XlAPslO.**AP(LIST7(I) )RATsXlAP/KT<LIST7(I) )XLRAT»ALOG10(P'AT)DELGR=C«R«T*XL«ATPRINT 160 1 LIST7(I),NREACT(LIST7(I))»XIAP«KT(LIST7(I) ) , AP (LIST 7 ( I )
1) »LOGM(LIST7(I)),RAT»XLRAT,DELGRGC TO 100
90 IF (AP(LIST7(I) ).LT. -5000.0. OR. AP(LIST7(I)).GT. 5000.0) GO TO 100XLRAT*AP(LIST7(I))-LOGKT(LIST7(IMDELGR=C»R«T«XL«ATPRINT 170t LIST7(I) tNREACT(LIST7(IM tAP(LlST7(I))»LOGKT(LlST7(I) ) .
1XLRAT.DELGR 100 CONTINUE
IF (PECK. EQ.l. AND. PECALC.NE.O) GO TO 110GC TO 130
110 PRINT 180DC 120 1-1*15PRINT 190« NHEACT(LIST8(I) )
120 CONTINUE 130 CONTINUE
RETLHN
140 FCRKAT (//)150 FCRKAT (//«22X.«PHASE»t9X,«lAP»,10X«»KT»,8Xt»LOG lAP»t4X»»LOG KT»»
16X,»IAP/KT»«6X«»LCG IAP/KT » «5X » »DELGR» «/) 160 FORMAT (1H ,17X,I3«lXtA8,2(2X,lPE11.4) »2(2X,OPF9.4),2XtlPE11.4,2(2
1X,OPF10.5M170 FORMAT (1H » 1 7X , 13 « IX, A8 «28X«2 (F9.4«2X ) » 1 IX t2 (2X «F1 0 .5 ) ) ISO FCRKAT (///«20X,«FE IS GREATER THAN 20 OR LESS THAN -20 • ,/»20X » » AN
ID THE FOLLOWING MINERAL REACTIONS HAVE BEEN DISREGARDED',/) 190 FORMAT (1H ,20X,A6)
END
FFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF
1560157015801550160016101620163016401650166016701680169017001710172017301740175017601770178017901ROO1810182018301840185018601870I860189019001910192019301940195019601970I9601990200020102020203020402050
-50-
Attachment C: Equilibrium reactions considered by WATEQF
§CMi coo
EH
§
0 «, <
<C COP5 fi]M M
M W2 PM
CO
CO
<!adpHwM2
+XHM
,(U
+CM
1 0 <U (U
Pn
IICO+ 0
<U CMp^ aH +
CM CM
<U (U
CO CM-j- _f_
aw wS S
i ii ii i i ii i
+a
+
0 <U
PHIIo
CMa+
CM
<U PH
+aow
111 11
CO | |<U <U
1 a + <r CMo o +O CO rH (U (U U
PH PH (U
II IIII
O CMCM i <r ia o in
CM CO U
+ + +
CM CM CM
(U (U (U PH PH PH
a <ro o ^o co u[V] [V] [V]
&4 !^ S
1 1 11 1 11 1 1 1 1 11 1 1
, ,(U (U
+ +
+ CM o CO o <frH rH OO U CO (U (U (U
PH PH PH
II II II
1 1 CMrH rH I <JU 0 OCM CO CO
,+ + +CM CM CM+ + +
0) 0) 0) PH PH PH
CM CO^ hJ 00 0 CO[V] [V] [V]
[2 [2 [2
i ii ii i i ii i
CM1 COO U
CM
PH
II
COO
(U
wHM
SQM CO
(U4-J•H
(U
•H CO
CM1 CO0
CM
53llco
0 0
1?HM COW55O
ii
(U4-1•HCO (U
00
e
CJCM
CM+ 00
S
-f-
CM
0
II
CMx— \
CO00
IwHM2o)_30 Q
<u4J
1Oo
CM1 CO O 0
CM+ C0
0
II
coO 0
BMo(J
3
(U4-1 •HU
, — |
U
,a
0•HCO
COa
M
o•H CO
a
0MCOCO
3
1111
+CM
,
v V•H Cco m
CM ,ia "ii m" \ <»oo ^CO +
a Hi
0M <rto oCM pw
S S
iii ii
0 PM
CMaii
CO
oPM
+
+B
CM
^0PMCM
5
Ij1 11
CM'cT
CO
CM+ cO
0
II•s
oCO
HM
Q£-1a%
(U4J•HVI
>>,J3a
CM v£) CO v£) OO
-51-
NJ
I
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37
gypsum
bruc
ite
chry
soti
le
arag
onit
e
GYPS
UMCa
+2
+2.-2
BRUCITE
Mg(OH)
2 = Mg
+ 20
H
CHRYSOTL
5H20
=
3Mg+
260
H
ARAG
ONIT
CaC0
3 =
Ca+2
Mg+2 + F~
= MgF+
———
KCAS
04
Ca+2
+ SO
?2
= Ca
SO?
4 4
+2
+————
KMGOH
Mg
+ OH
= MgOH
————
KH3B03
H3B03 = H
+ H
2BO~
+
+
+2
forste
rite
FORSTRIT
Mg2Si04 + 4
H20
= 2M
g
diop
side
DIOPSIDE
CaMg
Si^O
, + 6
H20 -
Ca
2+
clinoens
tati
te
CLEN
STIT
MgSi03 + -3^0 - Mg
———
KNAHPO
Na+ + H
POT2=
Na
HPOT
4 4
trem
olit
e TR
EMOL
IT
Ca2Mg5Si
g022
(OH)
2 +
+
—
-2
__
—._
vvu
pn
v
-L
iiD
n
—
imi>
n^J
XX
lJr
\J
^
t L
L±
\J /
^
^
Xll
r w
/4
4
————
KMGHPO
Mg+2
+ HPO~2=
MgHP04
———
KCAHPO
Ca+2 + HP0
72= Ca
HPO?
4 4
————
KH2C
03
HCO~
+ H
= I^
CO*
i r\
40H
Mg
I o
40H
2Ca
20H
+25M
g+2
140H
sepiolite
+2SE
PIAL
IT
Mg0Si
.O_
C(OH)'3H00 + 4.5H00 »
2Mg
+ SH.SiO,
ZJ/.D
Z
Z
tftf
4 (OH)
u>
38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56
talc
hydr
omag
nesi
te
adularia
albite
anor
thit
e
analcime
muscovite
phlo
gopi
te
illi
te
kaol
init
e
halloysite
beid
elli
te
chlo
rite
al uni
te
gibbsite
boehmite
pyro
phyl
lite
phillipsite
erionite
TALC
HYDMAG
ADULAR
ALBITE
ANORTH
ANALCM
KMICA
PHLOG
ILLITE
KAOLIN
HALLOY
BEIDEL
CHLOR
ALUNIT
GIBC
RS
BOEHM
PYROPH
PHILIP
ERIO
N
Mg3Si401()(O
H)2 + 10H20 -
3Mg+Z + 4H4Si
04 + 60H
~
Mg5(C
03)4
(OH)
2' 4H
20 =
5Mg+2
+ 4C
O~2 + 20
H~ + 4H20
KAlSi3Og + 8H
20
= K+ + A1(OH)~ + 3H
4Si04
NaAlSi Og
+ 8H
20 = Na+ + A1(OH)~ + 3H
4Si04
CaAl
2Si
2Og + 8H
20 *
Ca+2 + 2A1(OH)~ + 2H
4Si
04
NaAlSi206»H
20 + 5H
20
- Na+ + A1(OH)~ + 2H
4Si
O
KAl3S
i30
10(O
H)2 + 12
H20
- K+ + 3A1(OH)~ + 3H
4Si04 + 2H+
KMg3AlSi30
1()(
OH)2 + 10
H20
= K+ + 3Mg+2 + A1(OH)~ + 3H
4Si04 + 60
H~1
10
J_
K 6Mg 25A1
2 3S
i3 50
10(O
H)2+11
.2H20 =
.6
K +.25Mg +2.3A1(OH)~+3.5H
4S10
4+1.
2H
Al Si 0
(OH)
+ 7H 0
= 2A
1(OH
)~ +
2H,S
iO,
+ 2H+
£
£*
,J
^
£•
^
"*T
Al2Si
205(O
H)4 + 7H
20 =
2A1(OH)~ + 2H
4Si04'
+ 2H+
(Na,
K,3sMg)
.33A12.
33Si
3.67
°10(OH)
2+12H20
= •33(Na,K,3sM
g)++2
.33A
l(OH
)~H-
3.67
H4Si
04+2H+
Mg5Al2S
i3010
(OH)
8 + 1
0H20 = 5Mg+
2 + 2
A1(O
H)4 + 3
H4Si
04 + 8
0H~
i i o
O
KA13(S
04
)2(O
H)6
= K + 3A
1 ° + 2S
O~ + 60H
A1(OH)
3 =
Al+3 + 30
H~
AIO(OH)
+ H
20 =
Al+3 + 30H~
jAl
2Si40
10(O
H)2 + 12H
20 =
2A1(
OH)4 + 4H4Si
04 + 2H
Na 5K 5
AlSi3Og
'H20 + 7H
20
= 0.5Na+ + 0.5K+ + A1(OH)
4 + 3H
4Si
04
NaAlSi3
509'3H20 + 6H
20 = Na+ + A1(OH)~ + 3.
5H4Si
04
I Ln
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 7«;
cli
no
pti
loli
te
CLI
NO
P
mo
rden
ite
MOR
DEN
nahcoli
te
NA
HCO
L
tro
na
TRO
NA
nat
ron
NATR
ON
therm
onatr
ite
THRN
AT
flu
ori
te
FLU
OR
Ca-
montm
ori
llonit
e M
ONTC
A
hali
te
HA
LITE
thenard
ite
THEN
AR
mir
ab
ilit
e
MIR
AB
I
mac
kin
awit
e M
ACK
IT
——
——
K
HC
03
——
——
K
NA
C03
—
— —
T
TN
TA
Hrm
— -
TfN
A<?
n4
JxiN
riQ
Wr
___ _
in^Q
nA—
—
JxIX
OU
H
——
——
K
MG
C03
——
T
^MPu
rni
(K,N
a)A
lSi5
012
«3.5
H20
+ 8
.5H
20 =
(K
,Na)
+
A1(
OH
)4
+ 5
H4S
i04
(Na,
K)A
lSi4
5°
11'3
H20
+ 8
H20
-
(Na,
K)+
+ A
1(O
H)~
+ 4
.5H
4Si0
4
NaH
C03
=
Na+
+ H
CO~
i o
NaH
C03
«Na2
C03
'2H
20 =
3N
a +
HC
03
+
C0~
+ 2
H20
i o
Na2
C03
'10H
20
= 2N
a +
C
O"
+ 1
0H20
• n
Na2
C03
«H20
=
2Na
+
C03
+
H20
CaF
2 =
Ca+
2 +
2F~
Ca
17A
12
33S
i3
67°1
0^°
H^2
+
12H
2°
= -1
7Ca+
2 +
2.3
3A1(
OH
)4
+
3.67
H4
Si0
4
NaC
l =
Na+
+ C
l~
+
2N
a0SO
. =
2Na
+
SO?
24
4 i 2
Na2
S04
«10H
20
= 2N
a +
S04
+
10H
20
+
-4-9
FeS
+
H
= F
e +
HS~
2 +
—CO
+
H
* H
CO~
+
2 —
Na
+ C
03
= N
aC03
Na+
+ H
CO~
= N
aHC
O°
+
-2M
a +
<?n
= N
fl^n
liel
~
ij
\J i
IN
ctO
vV,
4 4
+
-2K
-4-
cn
— vcn
T
O\J
,
—
JN.D
U.
4 4
-1-2
-2\x
~
i r>
f\ —
\X
r,r>
r\Q
Mg
+
C03
=
MgC
03
Mn
j- u
rn""
=
Mr»
urn
2H
76
----- -
77
—— —
79
—— —
80
—— —
81
———
flO
__
i _ .
Ln
84
—————
Ln
Of 88
———
89
———
90
— ——
91
— ——
92
—— —
93
———
QA
—————
KMGS04
KCAOH
KCAHC03
KCAC03
KCAF+
KALOH
KALO
H2
KALOH4
KALF
KALF
2
KALF
3
KALF
4
KALS04
KAS0
42
KHS0
4
KH2SC
KH2S
KHS
tfHYV
\t ~f-
Mg
Ca+2
Ca+2
Ca+2
Ca+2
Al+3
Al+3
Al+3
M+3
Al+3
Al+3
Al+3
Al+3
Al+3
H+ +
H2S
HS~
<
. sw
+ S0
4*
= MgSO°
+ OH"
=
CaOH+
+ HCO^
= CaHCO^
+ CO
^2
- Ca
CO°
+ F
~= CaF+
+ OH"
= A10H+2
+ 20
H~ = AKOH)^"
+ 40
H" =
A1(OH)
4
+ F
" = A1F+2
+ 2F"
= A1
F2
+ 3F"
= A1
F°
+ 4F
" - A1F~
+ soT2
- A
isot
4 4
soT2
- f
lsoT
4 4
+ 10
H+ + 8e~
= H,
H+ + H
S-
* H+ + S
"2
n =
. 9 ̂n
4- H
4- <
ON
I
95 96 97 98 99 100
101
102
103
104
105
106
107
108
109
110
111
112
113
hy
dro
xy
apat
ite
fluora
pati
te
chal
cedony
mag
adii
te
cri
sto
bali
te
sil
ica gel
quart
z
viv
ianit
e
mag
net
ite
hem
atit
e
mag
hem
ite
go
eth
ite
gre
enali
te
amor
phou
s F
e(O
H).
,
KCH
4
HY
XA
PT
FLU
APT
CHA
LC
MA
GA
DI
CR
ISTO
SIL
GE
L
QU
ART
Z
Jxj?
C"J
n.fc
T^Tp
rrf^T
j ^
KFE
OH
4
KFE
OH
2
VIV
IAN
MAG
NET
HEM
ATI
MAG
HEM
GO
ETH
GRE
ENA
FEO
H3A
HCO
~ +
8e~
+ 9
H+
-
CH4
+
3H20
Ca5
(P04
) ^(O
H)
+
3H20
-
5Ca+
2 +
3H
PO~'
Cac
CP
Q.K
F +
3H
00 -
5C
a+2
+
3HP0
72
+
5432
4
2 2
44
+
+
NaS
i70
1 ,.(
OH
)-«3
H90
+ H
+
9H
«0 =
N
a
C-f
<"\
-1
. *?
U
C\
—
II
C-I
rt
O-L
VJn
i^
&
fln\J
L
i, O
J.w
>2
2 44
2 2
44
c-i r
t >i>
*?
u r\
— ;
u
c-in
o^
.\jn
i^
^.n.
-\_/
=• n
, ox
*j,
2 2
44
+2
+
+
-F
e +
2H
20
= Fe
(OH
)2
+
2H
+e
+2
4-
Fe
+
3H20
=
Fe(
OH
)°
+
3H
+e~
1 2
j.F
e +
4H
20
= F
e(O
H)~
+
4H
+
e~
Fe+
2 +
2H
20
= F
e(O
H)°
+2
H+
+2
-3
Fe
(P0
4)2
»8H
20
= 3F
e +
2P
04
+ 8
HJ
+
+3Fe
0,
+
8H
-
3Fe
+ 4
H90
+ e
J
^
m*
, +
+
3F
e20
3 +
6H
=
2Fe
+
3H20
+
+3
Fe20
3 +
6H
-
2Fe
+
3H20
FeO
(OH
) +
H20
=
Fe+
3 +
30
H~ +2
Fe
^Si^
Og-
CO
H),
+
5H
«0 =
3F
e +
2H
oSi<
, , «
Fe(
OH
).
+ 3
H
= F
e +
3H
00
40H
30H
60H
114
115
116
anni
te
pyri
te
ANNI
TE
PYRITE
FeS.
10H20 = K+ + 3Fe+2 + A1(OH)~
60H
montmorillonite MO
NTBF
2H+ + 2e~
= Fe+2
+ 2HS
+ 10
.04H
20
0.28(H,Na,K)
+ + 0.
29Mg
+2 + 0.
23Fe+3 + 1.58 A1(OH)
+3.93
117
mont
mori
llon
ite
MONTAB
118
119
120
121
122
123
124
125
1 O
£J.
ZO
127
1 O
flJ.
ZO
129
130
131
1 79
hunti
te
HU
NTI
TE
gre
igit
e
GR
EGIT
E
amor
phou
s Fe
S FE
SPPT
__
__
__
__
in
jJT
IlO
P
__
__
__
_
KT
AP
nA
——
— —
— —
——
T
TP
AH
9P
——
——
——
K
MG
P04
Trv
roT
TO
'D
——
——
——
——
—
VT
TH
HJ\
.JL
J-U
n
_
__
__
__
tT
f T
Cn
A
__
___
__
__
IT
MW
AP
Lau
mon
tite
LA
UMON
_„ _ __
__
__
_
TfC
PH
H
TT
TJ
A f
\TJ
——
——
——
—
irM
wA
cn
CaM
g
Fe3S
FeS +2
Fe
x c Ca+
2u
d _ +2
l^a
L>
a +2M
g Z
+2M
gL
i+JL
l
Li
4-N
0~il
xx Q
CaA
l+2
<?r
ij*. +2
TD
ftU
a +
3(C
03)4
=
3Mg
4 +
4H
+ +
2e~
=
+
+2+
H
= Fe
+
HS
i TT
*D
^\
^ f ̂
\TI
T
rl2
rU4
—
i?et
l2,
-3
4- p
n =
Papn
• f\
J,
—
\j3il
. \J
.4
4_
-A*
XI
*D^\
™
" ^oX
I2
4
~ ^an
2.
o+
P
0~
° =
MgP
O~
I*
TJ
^/%
^
l^>
f/>
XJ
T
tirt-
cU.
— ng
n.2
+
nu
~
— T
^ nu
^U
tl
~
Lil
Utl
cn"~
—
T -i
QH"~
4^*
' '
—
JL1O
U, 4
+ 1
0H+
+ 8
e~
= N
0Si.
01 9
'4H
«0 +
81
Z
H
XZ
L
j.
nH~
— QT
-HH
T
uti
— oru
ri
+ O
H"
- Ba
OH
+
«i
cf\~
~
_
XTU
c?rC
~
=0.42(H,Na,K)~Vo.45Mg+2
+ 0.
34Fe+3 + 1.
47A1
(OH)
~
+2
-2
Ca Z + 4C
03
0.84H
3.82
Ca+2
+ 2A1(OH>
133
134
135
136
137
138
139
140
i
141
142
143
144
145
146
147
148
149
150
151
KHCL
KNAC
L
KKCL
KH2S04
K02SATO
KC02
KFEH
PO
KFEH
P+
amor
phou
s A1(OH)
3 AL
OH3A
H +
Cl
= HC
1'
prehnite
strontianite
cele
stit
e
bari
te
with
erit
e
strengite
leon
hard
ite
nesq
ueho
nite
arti
nite
Na K 2H
- Cl
Cl"
= Na
Cl°
KC1°
S0~2
0.5H
20
C02(
g)H20 =
H2C
O
Fe+2
+ HPO
T2 4
Fe+2
HPO
2
FeHPO? 4
FeHP
ot
+3Al(OH)
= Al
+
30H
SrC0
SrSO.
PREHNT
STRONT
CELE
ST
BARITE
WITH
ERIT
BaCO
STRE
NGIT
LEON
BLAN
K
NESQ
UE
ARTIN
Sr+2
C0
Sr+2
+
SO
BaSO.
= Ba
4+2
+ SO
~2 T2
4 2
Ba+2
2H2C
a+2 + 2
A1(OH)
Fe+3
= 2C
a+2
4A1(OH)
Mg+2
C0~2
2Mg+2
20H
VO
I
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
——
—
K02
AQ
sep
ioli
te
SEP
PT
dia
spo
ra
DIA
SP
wair
akit
e.
WA
IRK
T
——
—
KFE
HP2
——
—
KM
N3+
——
—
KM
NCL
+
——
—
KM
NCL
2
——
—
KM
NC
L3-
——
—
KMNO
H+
——
—
KM
N(O
H)3
——
—
KM
NF+
——
—
KM
NS0
4
WTH
TKT/
I o
O
KM
NH
C03
0.5
H2
H20
=
*2s
i
A10
0H
CaA
l,
Fe+
2
Mn+
2
vr +
2M
n
vr +
2M
n
vr +
2M
n
vr +
2M
n
vr +
2M
n
vr +
2M
n
vr
+2
Mn
0 =
0.2
50
2(a
q)
+ H
+
e
H+ +
OH
~
.07
,.(O
H).
3H90
+ 4
.5H
00 =
2M
g+2
+
3H,
O
/ • J
t*
A,
L
+ H
20
= A
l+3
+
30H
~
Si4
012
.2H
20 +
10
H20
=
Ca+
2 +
2A
1(O
H)
+ H
2P0;
-
FeH
2P0f +
e-
= M
n +
e
+ C
l~ -
MnC
l+
+
O ̂
1
turn
lkjTw
« f*
T £
\j±
, =
ru
iox
A
+ 3C
1~
= M
nCl"
+ O
H~
= M
nOH+
+ 30
H~
- M
n(O
H)~
+ F~
+ M
nF+
+ S0
7 =
MnS
O°
4 4
Mn+
2 +
2N
O~
= M
n(N
03)2
+2
- +
vr>%
i t3
r>r\
—
vr^u
rTt
JJHI
T
riL
«u«»
^
mir
HjL
/_3
3
40H
-LUO
169
170
171
172
173
174
i o 17
5
176
177
178
179
180
181
1R9
————
manganosite
pyrolusite
6, birnessite
nsut
ite
bixb
yite
hausmanite
pyro
chro
site
Mn(OH)
3
mang
anit
e
rhodochr
osit
e
KMN04—
BLAN
K
KHMN02--
MANG
ANO
PYRO
LUST
BIRNSITE
NUST
ITE
BIXBYITE
HAUSMITE
MNOH2
MNOH3
MANG
ANIT
HHODOCHR
ttT AMI?
jrm
i- ^n
«u =
jymu.
-r on
-r
2
4
Mn
+ 4H
00
= Mn
OT" + 8H
2
4
Mn+2 + 2H
?0 = HMnO~ + 3H+
£•
£
MnO + 2H+
- Mn
+2 + H
20
Mn02 +
4H+ +
e" =
Mn+3 +
21
Mn02 +
4H+ + e~ =
Mn+3 + 21
+
- +3
Mn02 + 4
H +
e = Mn
* 21
+
+3
Mn2°3 + ^H
= 2Mn
+ 3H
2°
Mn30
4 +
8H+ + 2e~
- 3Mn+2
-
Mn(O
H)2
= Mn
+2 +
20
H~
Mn(O
H)3
- Mn
+3 + 30H~
MnOOH +
3H+
- Mn
+3 -
2H20
MnC0
3 = Mn
+2 + G
O"
183
184
185
186
187
188
189
190
191
192
193
MnCl
+2
tephro
ite
rhodonite
MnS(gr
een)
MnSO,
Mn2(S04)3
MnCl
2 - Mn
+ 2C1
MNCL2
MNCL2,1W
MNCL
2,2W
MnCl
2.2H20
= Mn'" + 2C1
MNCL
2,4W
TEPHRITE
Mn+2 + 2C1
+2 Mn+2
+ 2C
1
4H+ -
2Mn+2
+2RHODONIT
MnSi03 + 2H
+ H
20 -
Mn
MNS
CRN
MnS + H+ =
Mn+2 + H
S"
MnSO
. - Mn+2 + SOT2
4 4
2Mh+3 + 3BO~
2MN
2S04
,3
MN3P04,2
3Mn+2
MnHP0
MNHP
04
MnHPO. - Mn+
2 + HPO
j2
4 4