SOLUTION_MASTER_SPECIES # #element species alk gfw_formula element_gfw # Urea Urea 0 1 1 H H+ -1.0 H 1.008 H(0) H2 0.0 H H(1) H+ -1.0 0.0 E e- 0.0 0.0 0.0 O H2O 0.0 O 16.0 O(0) O2 0.0 O O(-2) H2O 0.0 0.0 Ca Ca+2 0.0 Ca 40.08 Mg Mg+2 0.0 Mg 24.312 Na Na+ 0.0 Na 22.9898 K K+ 0.0 K 39.102 Fe Fe+2 0.0 Fe 55.847 Fe(+2) Fe+2 0.0 Fe Fe(+3) Fe+3 -2.0 Fe Mn Mn+2 0.0 Mn 54.938 Mn(+2) Mn+2 0.0 Mn Mn(+3) Mn+3 0.0 Mn Al Al+3 0.0 Al 26.9815 Ba Ba+2 0.0 Ba 137.34 Sr Sr+2 0.0 Sr 87.62 Si H4SiO4 0.0 SiO2 28.0843 Cl Cl- 0.0 Cl 35.453 C CO3-2 2.0 HCO3 12.0111 C(+4) CO3-2 2.0 HCO3 C(-4) CH4 0.0 CH4 Alkalinity CO3-2 1.0 Ca0.5(CO3)0.5 50.05 S SO4-2 0.0 SO4 32.064 S(6) SO4-2 0.0 SO4 S(-2) HS- 1.0 S N NO3- 0.0 N 14.0067 N(+5) NO3- 0.0 N N(+3) NO2- 0.0 N N(0) N2 0.0 N Amm AmmH+ 0.0 AmmH 17.0 B H3BO3 0.0 B 10.81 P PO4-3 2.0 P 30.9738 F F- 0.0 F 18.9984 Li Li+ 0.0 Li 6.939 Br Br- 0.0 Br 79.904 Zn Zn+2 0.0 Zn 65.37 Cd Cd+2 0.0 Cd 112.4 Pb Pb+2 0.0 Pb 207.19 Cu Cu+2 0.0 Cu 63.546 Cu(+2) Cu+2 0.0 Cu Cu(+1) Cu+1 0.0 Cu SOLUTION_SPECIES Urea = Urea log_k 0 H+ = H+ log_k 0.0 -gamma 9.0 0.0 e- = e- log_k 0.0 H2O = H2O log_k 0.0 Ca+2 = Ca+2 log_k 0.0 -gamma 5.0 0.1650 Mg+2 = Mg+2 log_k 0.0 -gamma 5.5 0.20 Na+ = Na+ log_k 0.0 -gamma 4.0 0.075 K+ = K+ log_k 0.0 -gamma 3.5 0.015 Fe+2 = Fe+2 log_k 0.0 -gamma 6.0 0.0 Mn+2 = Mn+2 log_k 0.0 -gamma 6.0 0.0 Al+3 = Al+3 log_k 0.0 -gamma 9.0 0.0 Ba+2 = Ba+2 log_k 0.0 -gamma 5.0 0.0 Sr+2 = Sr+2 log_k 0.0 -gamma 5.260 0.121 H4SiO4 = H4SiO4 log_k 0.0 Cl- = Cl- log_k 0.0 -gamma 3.5 0.015 CO3-2 = CO3-2 log_k 0.0 -gamma 5.4 0.0 SO4-2 = SO4-2 log_k 0.0 -gamma 5.0 -0.04 NO3- = NO3- log_k 0.0 -gamma 3.0 0.0 AmmH+ = AmmH+ log_k 0.0 -gamma 2.5 0.0 H3BO3 = H3BO3 log_k 0.0 PO4-3 = PO4-3 log_k 0.0 -gamma 4.0 0.0 F- = F- log_k 0.0 -gamma 3.5 0.0 Li+ = Li+ log_k 0.0 -gamma 6.0 0.0 Br- = Br- log_k 0.0 -gamma 3.0 0.0 Zn+2 = Zn+2 log_k 0.0 -gamma 5.0 0.0 Cd+2 = Cd+2 log_k 0.0 Pb+2 = Pb+2 log_k 0.0 Cu+2 = Cu+2 log_k 0.0 -gamma 6.0 0.0 H2O = OH- + H+ log_k -14.0 delta_h 13.362 kcal -analytic -283.971 -0.05069842 13323.0 102.24447 -1119669.0 -gamma 3.5 0.0 2 H2O = O2 + 4 H+ + 4 e- log_k -86.08 delta_h 134.79 kcal 2 H+ + 2 e- = H2 log_k -3.15 delta_h -1.759 CO3-2 + H+ = HCO3- log_k 10.329 delta_h -3.561 kcal -analytic 107.8871 0.03252849 -5151.79 -38.92561 563713.9 -gamma 5.4 0.0 CO3-2 + 2 H+ = CO2 + H2O log_k 16.681 delta_h -5.738 kcal -analytic 464.1965 0.09344813 -26986.16 -165.75951 2248628.9 CO3-2 + 10 H+ + 8 e- = CH4 + 3 H2O log_k 41.071 delta_h -61.039 kcal SO4-2 + H+ = HSO4- log_k 1.988 delta_h 3.85 kcal -analytic -56.889 0.006473 2307.9 19.8858 0.0 HS- = S-2 + H+ log_k -12.918 delta_h 12.1 kcal -gamma 5.0 0.0 SO4-2 + 9 H+ + 8 e- = HS- + 4 H2O log_k 33.65 delta_h -60.140 kcal -gamma 3.5 0.0 HS- + H+ = H2S log_k 6.994 delta_h -5.30 kcal NO3- + 2 H+ + 2 e- = NO2- + H2O log_k 28.570 delta_h -43.760 kcal -gamma 3.0 0.0 2 NO3- + 12 H+ + 10 e- = N2 + 6 H2O log_k 207.08 delta_h -312.130 kcal AmmH+ = Amm + H+ log_k -9.252 delta_h 12.48 kcal #NO3- + 10 H+ + 8 e- = AmmH+ + 3 H2O # log_k 119.077 # delta_h -187.055 kcal # -gamma 2.5 0.0 AmmH+ + SO4-2 = AmmHSO4- log_k 1.11 H3BO3 = H2BO3- + H+ log_k -9.24 delta_h 3.224 kcal H3BO3 + F- = BF(OH)3- log_k -0.4 delta_h 1.850 kcal H3BO3 + 2 F- + H+ = BF2(OH)2- + H2O log_k 7.63 delta_h 1.618 kcal H3BO3 + 2 H+ + 3 F- = BF3OH- + 2 H2O log_k 13.67 delta_h -1.614 kcal H3BO3 + 3 H+ + 4 F- = BF4- + 3 H2O log_k 20.28 delta_h -1.846 kcal PO4-3 + H+ = HPO4-2 log_k 12.346 delta_h -3.530 kcal -gamma 4.0 0.0 PO4-3 + 2 H+ = H2PO4- log_k 19.553 delta_h -4.520 kcal -gamma 4.5 0.0 H+ + F- = HF log_k 3.18 delta_h 3.18 kcal -analytic -2.033 0.012645 429.01 H+ + 2 F- = HF2- log_k 3.76 delta_h 4.550 kcal Ca+2 + H2O = CaOH+ + H+ log_k -12.78 Ca+2 + CO3-2 = CaCO3 log_k 3.224 delta_h 3.545 kcal -analytic -1228.732 -0.299440 35512.75 485.818 Ca+2 + CO3-2 + H+ = CaHCO3+ log_k 11.435 delta_h -0.871 kcal -analytic 1317.0071 0.34546894 -39916.84 -517.70761 563713.9 -gamma 5.4 0.0 Ca+2 + SO4-2 = CaSO4 log_k 2.3 delta_h 1.650 kcal Ca+2 + PO4-3 = CaPO4- log_k 6.459 delta_h 3.10 kcal Ca+2 + HPO4-2 = CaHPO4 log_k 2.739 delta_h 3.3 kcal Ca+2 + H2PO4- = CaH2PO4+ log_k 1.408 delta_h 3.4 kcal Ca+2 + F- = CaF+ log_k 0.94 delta_h 4.120 kcal Mg+2 + H2O = MgOH+ + H+ log_k -11.44 delta_h 15.952 kcal Mg+2 + CO3-2 = MgCO3 log_k 2.98 delta_h 2.713 kcal -analytic 0.9910 0.00667 Mg+2 + H+ + CO3-2 = MgHCO3+ log_k 11.399 delta_h -2.771 kcal -analytic 48.6721 0.03252849 -2614.335 -18.00263 563713.9 Mg+2 + SO4-2 = MgSO4 log_k 2.37 delta_h 4.550 kcal Mg+2 + PO4-3 = MgPO4- log_k 6.589 delta_h 3.10 kcal Mg+2 + HPO4-2 = MgHPO4 log_k 2.87 delta_h 3.3 kcal Mg+2 + H2PO4- = MgH2PO4+ log_k 1.513 delta_h 3.4 kcal Mg+2 + F- = MgF+ log_k 1.82 delta_h 3.20 kcal Na+ + H2O = NaOH + H+ log_k -14.18 Na+ + CO3-2 = NaCO3- log_k 1.27 delta_h 8.910 kcal Na+ + HCO3- = NaHCO3 log_k -0.25 Na+ + SO4-2 = NaSO4- log_k 0.7 delta_h 1.120 kcal Na+ + HPO4-2 = NaHPO4- log_k 0.29 Na+ + F- = NaF log_k -0.24 K+ + H2O = KOH + H+ log_k -14.46 K+ + SO4-2 = KSO4- log_k 0.85 delta_h 2.250 kcal K+ + HPO4-2 = KHPO4- log_k 0.29 Fe+2 + H2O = FeOH+ + H+ log_k -9.5 delta_h 13.20 kcal Fe+2 + Cl- = FeCl+ log_k 0.14 Fe+2 + CO3-2 = FeCO3 log_k 4.38 Fe+2 + HCO3- = FeHCO3+ log_k 2.0 Fe+2 + SO4-2 = FeSO4 log_k 2.25 delta_h 3.230 kcal Fe+2 + HSO4- = FeHSO4+ log_k 1.08 Fe+2 + 2HS- = Fe(HS)2 log_k 8.95 Fe+2 + 3HS- = Fe(HS)3- log_k 10.987 Fe+2 + HPO4-2 = FeHPO4 log_k 3.6 Fe+2 + H2PO4- = FeH2PO4+ log_k 2.7 Fe+2 + F- = FeF+ log_k 1.0 Fe+2 = Fe+3 + e- log_k -13.02 delta_h 9.680 kcal -gamma 9.0 0.0 Fe+3 + H2O = FeOH+2 + H+ log_k -2.19 delta_h 10.4 kcal Fe+3 + 2 H2O = Fe(OH)2+ + 2 H+ log_k -5.67 delta_h 17.1 kcal Fe+3 + 3 H2O = Fe(OH)3 + 3 H+ log_k -12.56 delta_h 24.8 kcal Fe+3 + 4 H2O = Fe(OH)4- + 4 H+ log_k -21.6 delta_h 31.9 kcal 2 Fe+3 + 2 H2O = Fe2(OH)2+4 + 2 H+ log_k -2.95 delta_h 13.5 kcal 3 Fe+3 + 4 H2O = Fe3(OH)4+5 + 4 H+ log_k -6.3 delta_h 14.3 kcal Fe+3 + Cl- = FeCl+2 log_k 1.48 delta_h 5.6 kcal Fe+3 + 2 Cl- = FeCl2+ log_k 2.13 Fe+3 + 3 Cl- = FeCl3 log_k 1.13 Fe+3 + SO4-2 = FeSO4+ log_k 4.04 delta_h 3.91 kcal Fe+3 + HSO4- = FeHSO4+2 log_k 2.48 Fe+3 + 2 SO4-2 = Fe(SO4)2- log_k 5.38 delta_h 4.60 kcal Fe+3 + HPO4-2 = FeHPO4+ log_k 5.43 delta_h 5.76 kcal Fe+3 + H2PO4- = FeH2PO4+2 log_k 5.43 Fe+3 + F- = FeF+2 log_k 6.2 delta_h 2.7 kcal Fe+3 + 2 F- = FeF2+ log_k 10.8 delta_h 4.8 kcal Fe+3 + 3 F- = FeF3 log_k 14.0 delta_h 5.4 kcal Mn+2 + H2O = MnOH+ + H+ log_k -10.59 delta_h 14.40 kcal Mn+2 + Cl- = MnCl+ log_k 0.61 Mn+2 + 2 Cl- = MnCl2 log_k 0.25 Mn+2 + 3 Cl- = MnCl3- log_k -0.31 Mn+2 + CO3-2 = MnCO3 log_k 4.9 Mn+2 + HCO3- = MnHCO3+ log_k 1.95 Mn+2 + SO4-2 = MnSO4 log_k 2.25 delta_h 3.370 kcal Mn+2 + 2 NO3- = Mn(NO3)2 log_k 0.6 delta_h -0.396 kcal Mn+2 + F- = MnF+ log_k 0.84 Mn+2 = Mn+3 + e- log_k -25.51 delta_h 25.80 kcal Al+3 + H2O = AlOH+2 + H+ log_k -5.0 delta_h 11.49 kcal -analytic -38.253 0.0 -656.27 14.327 Al+3 + 2 H2O = Al(OH)2+ + 2 H+ log_k -10.1 delta_h 26.90 kcal -analytic 88.50 0.0 -9391.6 -27.121 Al+3 + 3 H2O = Al(OH)3 + 3 H+ log_k -16.9 delta_h 39.89 kcal -analytic 226.374 0.0 -18247.8 -73.597 Al+3 + 4 H2O = Al(OH)4- + 4 H+ log_k -22.7 delta_h 42.30 kcal -analytic 51.578 0.0 -11168.9 -14.865 Al+3 + SO4-2 = AlSO4+ log_k 3.5 delta_h 2.29 kcal Al+3 + 2SO4-2 = Al(SO4)2- log_k 5.0 delta_h 3.11 kcal Al+3 + HSO4- = AlHSO4+2 log_k 0.46 Al+3 + F- = AlF+2 log_k 7.0 delta_h 1.060 kcal Al+3 + 2 F- = AlF2+ log_k 12.7 delta_h 1.980 kcal Al+3 + 3 F- = AlF3 log_k 16.8 delta_h 2.160 kcal Al+3 + 4 F- = AlF4- log_k 19.4 delta_h 2.20 kcal Al+3 + 5 F- = AlF5-2 log_k 20.6 delta_h 1.840 kcal Al+3 + 6 F- = AlF6-3 log_k 20.6 delta_h -1.670 kcal H4SiO4 = H3SiO4- + H+ log_k -9.83 delta_h 6.12 kcal -analytic -302.3724 -0.050698 15669.69 108.18466 -1119669.0 H4SiO4 = H2SiO4-2 + 2 H+ log_k -23.0 delta_h 17.6 kcal -analytic -294.0184 -0.072650 11204.49 108.18466 -1119669.0 H4SiO4 + 4 H+ + 6 F- = SiF6-2 + 4 H2O log_k 30.18 delta_h -16.260 kcal Ba+2 + H2O = BaOH+ + H+ log_k -13.47 Ba+2 + CO3-2 = BaCO3 log_k 2.71 delta_h 3.55 kcal -analytic 0.113 0.008721 Ba+2 + HCO3- = BaHCO3+ log_k 0.982 delta_h 5.56 kcal -analytical -3.0938 0.013669 0.0 0.0 0.0 Ba+2 + SO4-2 = BaSO4 log_k 2.7 Sr+2 + H2O = SrOH+ + H+ log_k -13.29 -gamma 5.0 0.0 Sr+2 + CO3-2 + H+ = SrHCO3+ log_k 11.509 delta_h 2.489 kcal -analytic 104.6391 0.04739549 -5151.79 -38.92561 563713.9 -gamma 5.4 0.0 Sr+2 + CO3-2 = SrCO3 log_k 2.81 delta_h 5.22 kcal -analytic -1.019 0.012826 Sr+2 + SO4-2 = SrSO4 log_k 2.29 delta_h 2.08 kcal Li+ + H2O = LiOH + H+ log_k -13.64 Li+ + SO4-2 = LiSO4- log_k 0.64 Cu+2 + e- = Cu+ log_k 2.72 delta_h 1.65 kcal -gamma 2.5 0.0 Cu+2 + H2O = CuOH+ + H+ log_k -8.0 -gamma 4.0 0.0 Cu+2 + 2 H2O = Cu(OH)2 + 2 H+ log_k -13.68 Cu+2 + 3 H2O = Cu(OH)3- + 3 H+ log_k -26.9 Cu+2 + 4 H2O = Cu(OH)4-2 + 4 H+ log_k -39.6 Cu+2 + SO4-2 = CuSO4 log_k 2.31 delta_h 1.220 kcal Zn+2 + H2O = ZnOH+ + H+ log_k -8.96 delta_h 13.4 kcal Zn+2 + 2 H2O = Zn(OH)2 + 2 H+ log_k -16.9 Zn+2 + 3 H2O = Zn(OH)3- + 3 H+ log_k -28.4 Zn+2 + 4 H2O = Zn(OH)4-2 + 4 H+ log_k -41.2 Zn+2 + Cl- = ZnCl+ log_k 0.43 delta_h 7.79 kcal Zn+2 + 2 Cl- = ZnCl2 log_k 0.45 delta_h 8.5 kcal Zn+2 + 3Cl- = ZnCl3- log_k 0.5 delta_h 9.56 kcal Zn+2 + 4Cl- = ZnCl4-2 log_k 0.2 delta_h 10.96 kcal Zn+2 + CO3-2 = ZnCO3 log_k 5.3 Zn+2 + 2CO3-2 = Zn(CO3)2-2 log_k 9.63 Zn+2 + HCO3- = ZnHCO3+ log_k 2.1 Zn+2 + SO4-2 = ZnSO4 log_k 2.37 delta_h 1.36 kcal Zn+2 + 2SO4-2 = Zn(SO4)2-2 log_k 3.28 Cd+2 + H2O = CdOH+ + H+ log_k -10.08 delta_h 13.1 kcal Cd+2 + 2 H2O = Cd(OH)2 + 2 H+ log_k -20.35 Cd+2 + 3 H2O = Cd(OH)3- + 3 H+ log_k -33.3 Cd+2 + 4 H2O = Cd(OH)4-2 + 4 H+ log_k -47.35 Cd+2 + Cl- = CdCl+ log_k 1.98 delta_h 0.59 kcal Cd+2 + 2 Cl- = CdCl2 log_k 2.6 delta_h 1.24 kcal Cd+2 + 3 Cl- = CdCl3- log_k 2.4 delta_h 3.9 kcal Cd+2 + CO3-2 = CdCO3 log_k 2.9 Cd+2 + 2CO3-2 = Cd(CO3)2-2 log_k 6.4 Cd+2 + HCO3- = CdHCO3+ log_k 1.5 Cd+2 + SO4-2 = CdSO4 log_k 2.46 delta_h 1.08 kcal Cd+2 + 2SO4-2 = Cd(SO4)2-2 log_k 3.5 Pb+2 + H2O = PbOH+ + H+ log_k -7.71 Pb+2 + 2 H2O = Pb(OH)2 + 2 H+ log_k -17.12 Pb+2 + 3 H2O = Pb(OH)3- + 3 H+ log_k -28.06 Pb+2 + 4 H2O = Pb(OH)4-2 + 4 H+ log_k -39.7 2 Pb+2 + H2O = Pb2OH+3 + H+ log_k -6.36 Pb+2 + Cl- = PbCl+ log_k 1.6 delta_h 4.38 kcal Pb+2 + 2 Cl- = PbCl2 log_k 1.8 delta_h 1.08 kcal Pb+2 + 3 Cl- = PbCl3- log_k 1.7 delta_h 2.17 kcal Pb+2 + 4 Cl- = PbCl4-2 log_k 1.38 delta_h 3.53 kcal Pb+2 + CO3-2 = PbCO3 log_k 7.24 Pb+2 + 2 CO3-2 = Pb(CO3)2-2 log_k 10.64 Pb+2 + HCO3- = PbHCO3+ log_k 2.9 Pb+2 + SO4-2 = PbSO4 log_k 2.75 Pb+2 + 2 SO4-2 = Pb(SO4)2-2 log_k 3.47 Pb+2 + NO3- = PbNO3+ log_k 1.17 PHASES Urea_degradation Urea=Urea log_k 0 delta_h 0 kcal Calcite CaCO3 = CO3-2 + Ca+2 log_k -8.48 delta_h -2.297 kcal -analytic -171.9065 -0.077993 2839.319 71.595 Aragonite CaCO3 = CO3-2 + Ca+2 log_k -8.336 delta_h -2.589 kcal -analytic -171.9773 -0.077993 2903.293 71.595 Dolomite(dis) CaMg(CO3)2 = Ca+2 + Mg+2 + 2 CO3-2 log_k -17.09 delta_h -9.436 kcal Siderite FeCO3 = Fe+2 + CO3-2 log_k -10.89 delta_h -2.480 kcal Rhodochrosite MnCO3 = Mn+2 + CO3-2 log_k -11.13 delta_h -1.430 kcal Strontianite SrCO3 = Sr+2 + CO3-2 log_k -9.271 delta_h -0.400 kcal -analytic 155.0305 0.0 -7239.594 -56.58638 Witherite BaCO3 = Ba+2 + CO3-2 log_k -8.562 delta_h 0.703 kcal -analytic 607.642 0.121098 -20011.25 -236.4948 Gypsum CaSO4:2H2O = Ca+2 + SO4-2 + 2 H2O log_k -4.58 delta_h -0.109 kcal -analytic 68.2401 0.0 -3221.51 -25.0627 Anhydrite CaSO4 = Ca+2 + SO4-2 log_k -4.36 delta_h -1.710 kcal -analytic 197.52 0.0 -8669.8 -69.835 Celestite SrSO4 = Sr+2 + SO4-2 log_k -6.63 delta_h -1.037 kcal -analytic -14805.9622 -2.4660924 756968.533 5436.3588 -40553604.0 Barite BaSO4 = Ba+2 + SO4-2 log_k -9.97 delta_h 6.35 kcal -analytic 136.035 0.0 -7680.41 -48.595 Hydroxyapatite Ca5(PO4)3OH + 4 H+ = H2O + 3 HPO4-2 + 5 Ca+2 log_k -3.421 delta_h -36.155 kcal Fluorite CaF2 = Ca+2 + 2 F- log_k -10.6 delta_h 4.69 kcal -analytic 66.348 0.0 -4298.2 -25.271 SiO2(a) SiO2 + 2 H2O = H4SiO4 log_k -2.71 delta_h 3.340 kcal -analytic -0.26 0.0 -731.0 Chalcedony SiO2 + 2 H2O = H4SiO4 log_k -3.55 delta_h 4.720 kcal -analytic -0.09 0.0 -1032.0 Quartz SiO2 + 2 H2O = H4SiO4 log_k -3.98 delta_h 5.990 kcal # -analytic 0.41 0.0 -1309.0 # Better for St.Paul: -analytic 1.8810 -0.00203 -1560.0 Gibbsite Al(OH)3 + 3 H+ = Al+3 + 3 H2O log_k 8.11 delta_h -22.800 kcal Al(OH)3(a) Al(OH)3 + 3 H+ = Al+3 + 3 H2O log_k 10.8 delta_h -26.500 kcal Kaolinite Al2Si2O5(OH)4 + 6 H+ = H2O + 2 H4SiO4 + 2 Al+3 log_k 7.435 delta_h -35.300 kcal Albite NaAlSi3O8 + 8 H2O = Na+ + Al(OH)4- + 3 H4SiO4 log_k -18.002 delta_h 25.896 kcal Anorthite CaAl2Si2O8 + 8 H2O = Ca+2 + 2 Al(OH)4- + 2 H4SiO4 log_k -19.714 delta_h 11.580 kcal K-feldspar KAlSi3O8 + 8 H2O = K+ + Al(OH)4- + 3 H4SiO4 log_k -20.573 delta_h 30.820 kcal K-mica KAl3Si3O10(OH)2 + 10 H+ = K+ + 3 Al+3 + 3 H4SiO4 log_k 12.703 delta_h -59.376 kcal Chlorite(14A) Mg5Al2Si3O10(OH)8 + 16H+ = 5Mg+2 + 2Al+3 + 3H4SiO4 + 6H2O log_k 68.38 delta_h -151.494 kcal Ca-Montmorillonite Ca0.165Al2.33Si3.67O10(OH)2 + 12 H2O = 0.165Ca+2 + 2.33 Al(OH)4- + 3.67 H4SiO4 + 2 H+ log_k -45.027 delta_h 58.373 kcal Talc Mg3Si4O10(OH)2 + 4 H2O + 6 H+ = 3 Mg+2 + 4 H4SiO4 log_k 21.399 delta_h -46.352 kcal Illite K0.6Mg0.25Al2.3Si3.5O10(OH)2 + 11.2H2O = 0.6K+ + 0.25Mg+2 + 2.3Al(OH)4- + 3.5H4SiO4 + 1.2H+ log_k -40.267 delta_h 54.684 kcal Chrysotile Mg3Si2O5(OH)4 + 6 H+ = H2O + 2 H4SiO4 + 3 Mg+2 log_k 32.2 delta_h -46.800 kcal -analytic 13.248 0.0 10217.1 -6.1894 Sepiolite Mg2Si3O7.5OH:3H2O + 4 H+ + 0.5H2O = 2 Mg+2 + 3 H4SiO4 log_k 15.760 delta_h -10.700 kcal Sepiolite(d) Mg2Si3O7.5OH:3H2O + 4 H+ + 0.5H2O = 2 Mg+2 + 3 H4SiO4 log_k 18.66 Hematite Fe2O3 + 6 H+ = 2 Fe+3 + 3 H2O log_k -4.008 delta_h -30.845 kcal Goethite FeOOH + 3 H+ = Fe+3 + 2 H2O log_k -1.0 Fe(OH)3(a) Fe(OH)3 + 3 H+ = Fe+3 + 3 H2O log_k 4.891 Pyrite FeS2 + 2 H+ + 2 e- = Fe+2 + 2 HS- log_k -18.479 delta_h 11.300 kcal FeS(ppt) FeS + H+ = Fe+2 + HS- log_k -3.915 Mackinawite FeS + H+ = Fe+2 + HS- log_k -4.648 Sulfur S + 2H+ + 2e- = H2S log_k 4.882 delta_h -9.5 kcal Vivianite Fe3(PO4)2:8H2O = 3 Fe+2 + 2 PO4-3 + 8 H2O log_k -36.0 Pyrolusite # H2O added for surface calc's MnO2:H2O + 4 H+ + 2 e- = Mn+2 + 3 H2O log_k 41.38 delta_h -65.110 kcal Hausmannite Mn3O4 + 8 H+ + 2 e- = 3 Mn+2 + 4 H2O log_k 61.03 delta_h -100.640 kcal Manganite MnOOH + 3 H+ + e- = Mn+2 + 2 H2O log_k 25.34 Pyrochroite Mn(OH)2 + 2 H+ = Mn+2 + 2 H2O log_k 15.2 CO2(g) CO2 = CO2 log_k -1.468 delta_h -4.776 kcal -analytic 108.3865 0.01985076 -6919.53 -40.45154 669365.0 # Gases from LLNL.dat... O2(g) O2 = O2 log_k -2.8983 -analytic -7.5001 7.8981e-003 0.0 0.0 2.0027e+005 H2(g) H2 + 0.5 O2 = H2O log_k 43.0016 -analytic -1.1609e+001 -3.7580e-003 1.5068e+004 2.4198e+000 -7.0997e+004 N2(g) N2 = N2 log_k -3.1864 -analytic -58.453 1.81800E-03 3199 17.909 -27460 H2S(g) H2S = H+ + HS- log_k -7.9759 -analytic -9.7354e+001 -3.1576e-002 1.8285e+003 3.7440e+001 2.8560e+001 CH4(g) CH4 = CH4 log_k -2.8502 -analytic -2.4027e+001 4.7146e-003 3.7227e+002 6.4264e+000 2.3362e+005 Amm(g) Amm = Amm log_k 1.7966 -analytic -1.8758e+001 3.3670e-004 2.5113e+003 4.8619e+000 3.9192e+001 Melanterite FeSO4:7H2O = 7 H2O + Fe+2 + SO4-2 log_k -2.209 delta_h 4.910 kcal -analytic 1.447 -0.004153 0.0 0.0 -214949.0 Alunite KAl3(SO4)2(OH)6 + 6 H+ = K+ + 3 Al+3 + 2 SO4-2 + 6H2O log_k -1.4 delta_h -50.250 kcal Jarosite-K KFe3(SO4)2(OH)6 + 6 H+ = 3 Fe+3 + 6 H2O + K+ + 2 SO4-2 log_k -9.21 delta_h -31.280 kcal Zn(OH)2(e) Zn(OH)2 + 2 H+ = Zn+2 + 2 H2O log_k 11.5 Smithsonite ZnCO3 = Zn+2 + CO3-2 log_k -10.0 delta_h -4.36 kcal Sphalerite ZnS + H+ = Zn+2 + HS- log_k -11.618 delta_h 8.250 kcal Willemite 289 Zn2SiO4 + 4H+ = 2Zn+2 + H4SiO4 log_k 15.33 delta_h -33.37 kcal Cd(OH)2 Cd(OH)2 + 2 H+ = Cd+2 + 2 H2O log_k 13.65 Otavite 315 CdCO3 = Cd+2 + CO3-2 log_k -12.1 delta_h -0.019 kcal CdSiO3 328 CdSiO3 + H2O + 2H+ = Cd+2 + H4SiO4 log_k 9.06 delta_h -16.63 kcal CdSO4 329 CdSO4 = Cd+2 + SO4-2 log_k -0.1 delta_h -14.74 kcal Cerrusite 365 PbCO3 = Pb+2 + CO3-2 log_k -13.13 delta_h 4.86 kcal Anglesite 384 PbSO4 = Pb+2 + SO4-2 log_k -7.79 delta_h 2.15 kcal Pb(OH)2 389 Pb(OH)2 + 2H+ = Pb+2 + 2H2O log_k 8.15 delta_h -13.99 kcal EXCHANGE_MASTER_SPECIES X X- EXCHANGE_SPECIES X- = X- log_k 0.0 Na+ + X- = NaX log_k 0.0 -gamma 4.0 0.075 K+ + X- = KX log_k 0.7 -gamma 3.5 0.015 delta_h -4.3 # Jardine & Sparks, 1984 Li+ + X- = LiX log_k -0.08 -gamma 6.0 0.0 delta_h 1.4 # Merriam & Thomas, 1956 # !!!!! # H+ + X- = HX # log_k 1.0 # -gamma 9.0 0.0 AmmH+ + X- = AmmHX log_k 0.6 -gamma 2.5 0.0 delta_h -2.4 # Laudelout et al., 1968 Ca+2 + 2X- = CaX2 log_k 0.8 -gamma 5.0 0.165 delta_h 7.2 # Van Bladel & Gheyl, 1980 Mg+2 + 2X- = MgX2 log_k 0.6 -gamma 5.5 0.2 delta_h 7.4 # Laudelout et al., 1968 Sr+2 + 2X- = SrX2 log_k 0.91 -gamma 5.26 0.121 delta_h 5.5 # Laudelout et al., 1968 Ba+2 + 2X- = BaX2 log_k 0.91 -gamma 5.0 0.0 delta_h 4.5 # Laudelout et al., 1968 Mn+2 + 2X- = MnX2 log_k 0.52 -gamma 6.0 0.0 Fe+2 + 2X- = FeX2 log_k 0.44 -gamma 6.0 0.0 Cu+2 + 2X- = CuX2 log_k 0.6 -gamma 6.0 0.0 Zn+2 + 2X- = ZnX2 log_k 0.8 -gamma 5.0 0.0 Cd+2 + 2X- = CdX2 log_k 0.8 Pb+2 + 2X- = PbX2 log_k 1.05 Al+3 + 3X- = AlX3 log_k 0.41 -gamma 9.0 0.0 AlOH+2 + 2X- = AlOHX2 log_k 0.89 -gamma 0.0 0.0 SURFACE_MASTER_SPECIES Hfo_s Hfo_sOH Hfo_w Hfo_wOH SURFACE_SPECIES # All surface data from # Dzombak and Morel, 1990 # # # Acid-base data from table 5.7 # # strong binding site--Hfo_s, Hfo_sOH = Hfo_sOH log_k 0.0 Hfo_sOH + H+ = Hfo_sOH2+ log_k 7.29 # = pKa1,int Hfo_sOH = Hfo_sO- + H+ log_k -8.93 # = -pKa2,int # weak binding site--Hfo_w Hfo_wOH = Hfo_wOH log_k 0.0 Hfo_wOH + H+ = Hfo_wOH2+ log_k 7.29 # = pKa1,int Hfo_wOH = Hfo_wO- + H+ log_k -8.93 # = -pKa2,int ############################################### # CATIONS # ############################################### # # Cations from table 10.1 or 10.5 # # Calcium Hfo_sOH + Ca+2 = Hfo_sOHCa+2 log_k 4.97 Hfo_wOH + Ca+2 = Hfo_wOCa+ + H+ log_k -5.85 # Strontium Hfo_sOH + Sr+2 = Hfo_sOHSr+2 log_k 5.01 Hfo_wOH + Sr+2 = Hfo_wOSr+ + H+ log_k -6.58 Hfo_wOH + Sr+2 + H2O = Hfo_wOSrOH + 2H+ log_k -17.6 # Barium Hfo_sOH + Ba+2 = Hfo_sOHBa+2 log_k 5.46 Hfo_wOH + Ba+2 = Hfo_wOBa+ + H+ log_k -7.2 # table 10.5 # # Cations from table 10.2 # # Cadmium Hfo_sOH + Cd+2 = Hfo_sOCd+ + H+ log_k 0.47 Hfo_wOH + Cd+2 = Hfo_wOCd+ + H+ log_k -2.91 # Zinc Hfo_sOH + Zn+2 = Hfo_sOZn+ + H+ log_k 0.99 Hfo_wOH + Zn+2 = Hfo_wOZn+ + H+ log_k -1.99 # Copper Hfo_sOH + Cu+2 = Hfo_sOCu+ + H+ log_k 2.89 Hfo_wOH + Cu+2 = Hfo_wOCu+ + H+ log_k 0.6 # table 10.5 # Lead Hfo_sOH + Pb+2 = Hfo_sOPb+ + H+ log_k 4.65 Hfo_wOH + Pb+2 = Hfo_wOPb+ + H+ log_k 0.3 # table 10.5 # # Derived constants table 10.5 # # Magnesium Hfo_wOH + Mg+2 = Hfo_wOMg+ + H+ log_k -4.6 # Manganese Hfo_sOH + Mn+2 = Hfo_sOMn+ + H+ log_k -0.4 # table 10.5 Hfo_wOH + Mn+2 = Hfo_wOMn+ + H+ log_k -3.5 # table 10.5 # Iron, strong site: Appelo, Van der Weiden, Tournassat & Charlet, subm. Hfo_sOH + Fe+2 = Hfo_sOFe+ + H+ log_k -0.95 # Iron, weak site: Liger et al., GCA 63, 2939, re-optimized for D&M Hfo_wOH + Fe+2 = Hfo_wOFe+ + H+ log_k -2.98 Hfo_wOH + Fe+2 + H2O = Hfo_wOFeOH + 2H+ log_k -11.55 ############################################### # ANIONS # ############################################### # # Anions from table 10.6 # # Phosphate Hfo_wOH + PO4-3 + 3H+ = Hfo_wH2PO4 + H2O log_k 31.29 Hfo_wOH + PO4-3 + 2H+ = Hfo_wHPO4- + H2O log_k 25.39 Hfo_wOH + PO4-3 + H+ = Hfo_wPO4-2 + H2O log_k 17.72 # # Anions from table 10.7 # # Borate Hfo_wOH + H3BO3 = Hfo_wH2BO3 + H2O log_k 0.62 # # Anions from table 10.8 # # Sulfate Hfo_wOH + SO4-2 + H+ = Hfo_wSO4- + H2O log_k 7.78 Hfo_wOH + SO4-2 = Hfo_wOHSO4-2 log_k 0.79 # # Derived constants table 10.10 # Hfo_wOH + F- + H+ = Hfo_wF + H2O log_k 8.7 Hfo_wOH + F- = Hfo_wOHF- log_k 1.6 # # Carbonate: Van Geen et al., 1994 reoptimized for D&M model # Hfo_wOH + CO3-2 + H+ = Hfo_wCO3- + H2O log_k 12.56 Hfo_wOH + CO3-2 + 2H+= Hfo_wHCO3 + H2O log_k 20.62 RATES ####### # Example of quartz kinetic rates block: #KINETICS #Quartz #-m0 158.8 # 90 % Qu #-parms 23.13 1.5 #-step 3.1536e8 in 10 #-tol 1e-12 # Rate definition: Quartz -start #1 rem Specific rate k from Rimstidt and Barnes, 1980, GCA 44,1683 #2 rem k = 10^-13.7 mol/m2/s (25 C), Ea = 90 kJ/mol #2 rem sp. rate * parm(2) due to salts (Dove and Rimstidt, MSA Rev. 29, 259) #4 rem parm(1) = A (m2) recalc's to mol/s #5 rem parm(2) salt correction: (1 + 1.5 * c_Na (mM)), < 35 10 dif_temp = 1/TK - 1/298 20 pk_w = 13.7 + 4700.4 * dif_temp 40 moles = parm(1) * parm(2) * (m/m0)^0.67 * 10^-pk_w * (1 - SR("Quartz")) # Integrate... 50 save moles * time -end ########### #K-feldspar ########### # Example of KINETICS data block for K-feldspar rate: # KINETICS 1 # K-feldspar # -m0 2.16 # 10% K-fsp, 0.1 mm cubes # -m 1.94 # -parms 1.36e4 0.1 K-feldspar -start #1 rem specific rate from Sverdrup, 1990, in kmol/m2/s #2 rem parm(1) = 10 * (A/V, 1/dm) (recalc's sp. rate to mol/kgw) #3 rem parm(2) = corrects for field rate relative to lab rate #4 rem temp corr: from p. 162. E (kJ/mol) / R / 2.303 = H in H*(1/T-1/298) 10 dif_temp = 1/TK - 1/298 20 pk_H = 12.5 + 3134 * dif_temp 30 pk_w = 15.3 + 1838 * dif_temp 40 pk_OH = 14.2 + 3134 * dif_temp 50 pk_CO2 = 14.6 + 1677 * dif_temp #60 pk_org = 13.9 + 1254 * dif_temp # rate increase with DOC 70 rate = 10^-pk_H * ACT("H+")^0.5 + 10^-pk_w + 10^-pk_OH * ACT("OH-")^0.3 71 rate = rate + 10^-pk_CO2 * (10^SI("CO2(g)"))^0.6 #72 rate = rate + 10^-pk_org * TOT("DOC")^0.4 80 moles = parm(1) * parm(2) * rate * (1 - SR("K-feldspar")) * time 81 rem decrease rate on precipitation 90 if SR("K-feldspar") > 1 then moles = moles * 0.1 100 save moles -end ########### #Albite ########### # Example of KINETICS data block for Albite rate: # KINETICS 1 # Albite # -m0 0.43 # 2% Albite, 0.1 mm cubes # -parms 2.72e3 0.1 Albite -start #1 rem specific rate from Sverdrup, 1990, in kmol/m2/s #2 rem parm(1) = 10 * (A/V, 1/dm) (recalc's sp. rate to mol/kgw) #3 rem parm(2) = corrects for field rate relative to lab rate #4 rem temp corr: from p. 162. E (kJ/mol) / R / 2.303 = H in H*(1/T-1/298) 10 dif_temp = 1/TK - 1/298 20 pk_H = 12.5 + 3359 * dif_temp 30 pk_w = 14.8 + 2648 * dif_temp 40 pk_OH = 13.7 + 3359 * dif_temp #41 rem ^12.9 in Sverdrup, but larger than for oligoclase... 50 pk_CO2 = 14.0 + 1677 * dif_temp #60 pk_org = 12.5 + 1254 * dif_temp # ...rate increase for DOC 70 rate = 10^-pk_H * ACT("H+")^0.5 + 10^-pk_w + 10^-pk_OH * ACT("OH-")^0.3 71 rate = rate + 10^-pk_CO2 * (10^SI("CO2(g)"))^0.6 #72 rate = rate + 10^-pk_org * TOT("DOC")^0.4 80 moles = parm(1) * parm(2) * rate * (1 - SR("Albite")) * time 81 rem decrease rate on precipitation 90 if SR("Albite") > 1 then moles = moles * 0.1 100 save moles -end ######## #Calcite ######## # Example of KINETICS data block for calcite rate: # KINETICS 1 # Calcite # -tol 1e-8 # -m0 3.e-3 # -m 3.e-3 # -parms 50 0.6 Calcite -start 1 rem parm(1) = A/V, 1/dm parm(2) = exponent for m/m0 10 si_cc = si("Calcite") 20 if (m <= 0 and si_cc < 0) then goto 200 30 k1 = 10^(0.198 - 444.0 / (273.16 + tc) ) 40 k2 = 10^(2.84 - 2177.0 / (273.16 + tc) ) 50 if tc <= 25 then k3 = 10^(-5.86 - 317.0 / (273.16 + tc) ) 60 if tc > 25 then k3 = 10^(-1.1 - 1737.0 / (273.16 + tc) ) 70 t = 1 80 if m0 > 0 then t = m/m0 90 if t = 0 then t = 1 100 moles = parm(1) * 0.1 * (t)^parm(2) 110 moles = moles * (k1 * act("H+") + k2 * act("CO2") + k3 * act("H2O")) 120 moles = moles * (1 - 10^(2/3*si_cc)) 130 moles = moles * time 140 if (moles > m) then moles = m 150 if (moles >= 0) then goto 200 160 temp = tot("Ca") 170 mc = tot("C(4)") 180 if mc < temp then temp = mc 190 if -moles > temp then moles = -temp 200 save moles -end ####### #Pyrite ####### # Example of KINETICS data block for pyrite rate: # KINETICS 1 # Pyrite # -tol 1e-8 # -m0 5.e-4 # -m 5.e-4 # -parms -5.0 0.1 .5 -0.11 Pyrite -start 1 rem parm(1) = log10(A/V, 1/dm) parm(2) = exp for (m/m0) 2 rem parm(3) = exp for O2 parm(4) = exp for H+ 10 if (m <= 0) then goto 200 20 if (si("Pyrite") >= 0) then goto 200 20 rate = -10.19 + parm(1) + parm(3)*lm("O2") + parm(4)*lm("H+") + parm(2)*log10(m/m0) 30 moles = 10^rate * time 40 if (moles > m) then moles = m 50 if (moles >= (mol("O2")/3.5)) then moles = mol("O2")/3.5 200 save moles -end ########## #Organic_C ########## # Example of KINETICS data block for Organic_C rate: # KINETICS 1 # Organic_C # -tol 1e-8 # # m in mol/kgw # -m0 5e-3 # -m 5e-3 Organic_C -start 10 if (m <= 0) then goto 200 20 mO2 = mol("O2") 30 mNO3 = tot("N(5)") 40 mSO4 = tot("S(6)") 50 rate = 1.57e-9*mO2/(2.94e-4 + mO2) + 1.67e-11*mNO3/(1.55e-4 + mNO3) 60 rate = rate + 1.e-13*mSO4/(1.e-4 + mSO4) 70 moles = rate * m * (m/m0) * time 80 if (moles > m) then moles = m 200 save moles -end ########### #Pyrolusite ########### # # Postma, D., Danish Technical University and # Appelo, C.A.J., GCA 64, in press. # # Example of KINETICS data block for Pyrolusite # KINETICS 1-12 # Pyrolusite # -tol 1.e-7 # -m0 0.1 # -m 0.1 Pyrolusite -start 5 if (m <= 0.0) then goto 200 7 sr_pl = sr("Pyrolusite") 9 if abs(1 - sr_pl) < 0.1 then goto 200 10 if (sr_pl > 1.0) then goto 100 #20 rem initially 1 mol Fe+2 = 0.5 mol pyrolusite. k*A/V = 1/time (3 cells) #22 rem time (3 cells) = 1.432e4. 1/time = 6.98e-5 30 Fe_t = tot("Fe(2)") 32 if Fe_t < 1.e-8 then goto 200 40 moles = 6.98e-5 * Fe_t * (m/m0)^0.67 * time * (1 - sr_pl) 50 if moles > Fe_t / 2 then moles = Fe_t / 2 70 if moles > m then moles = m 90 goto 200 100 Mn_t = tot("Mn") 110 moles = 2e-3 * 6.98e-5 * (1-sr_pl) * time 120 if moles <= -Mn_t then moles = -Mn_t 200 save moles -end END