SOLUTION_MASTER_SPECIES # Required master species H H3O+ -1. H 1.008 H(0) H2 0.0 H H(1) H3O+ -1. 0.0 E e- 0.0 0.0 0.0 O H2O 0.0 O 16.00 O(0) O2 0.0 O O(-2) H2O 0.0 0.0 # Other master species 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 Cl Cl- 0.0 Cl 35.453 # Elements with isotopes C CO2 0 HCO3 12.0111 C(4) CO2 0 HCO3 [13C] [13C]O2 0 13 13 [13C](4) [13C]O2 0 13 [14C] [14C]O2 0 14 14 [14C](4) [14C]O2 0 14 [18O] H2[18O] 0 18 18 D D2O 0 2 2 T HTO 0 3 3 S SO4-2 0.0 SO4 31.972 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 N(-3) NH4+ 0.0 N ISOTOPES H -isotope D permil 155.76e-6 # VSMOW (Clark and Fritz, 1997) -isotope T TU 1e-18 # Solomon and Cook, in eds, Cook and Herczeg, 2000 # 1 THO in 10^18 H2O # -isotope T pCi/L 3.125e-18 # 1e-18/3.2 = T/mol H2O C -isotope [13C] permil 0.0111802 # VPDB, Vienna Pee Dee Belemnite # Chang and Li, 1990, Chinese Science Bulletin -isotope [14C] pmc 1.175887709e-12 # Mole fraction of 14C in Modern Carbon # 13.56 Modern Carbon dpm (Kalin, in eds, Cook and Herczeg, 2000) C(4) -isotope [13C](4) permil 0.0111802 # VPDB, Vienna Pee Dee Belemnite # Chang and Li, 1990, Chinese Science Bulletin -isotope [14C](4) pmc 1.175887709e-12 # Mole fraction of 14C in Modern Carbon # 13.56 Modern Carbon dpm (Kalin, in eds, Cook and Herczeg, 2000) # 14C calculation # # lambda = ln(2)/(5730 yrs * 3.15576e7 sec/yr) # mole/g carbon = -(dn/dt)/lambda = 0.226 dps / 3.8332476e-12 / 6.022136736e23 # mole C/g C NBS Oxalic Acid with 13C = -19.3: 0.08325783313 # mole 14C/mol Modern Carbon mol/g carbon/ (mole C/g C) = 1.175887709e-12 # # -isotope [13C](-4) permil 0.0111802 # ? # ? O -isotope [18O] permil 2005.2e-6 # VSMOW (Clark and Fritz, 1997) ISOTOPE_RATIOS R(13C)_Calcite [13C] R(18O)_Calcite [18O] R(13C)_CO2(g) [13C] R(18O)_CO2(g) [18O] R(13C)_CO2(aq) [13C] R(18O)_CO2(aq) [18O] R(13C)_HCO3- [13C] R(D)_HCO3- D R(18O)_HCO3- [18O] R(13C)_CO3-2 [13C] R(18O)_CO3-2 [18O] R(18O)_H2O(l) [18O] R(D)_H2O(l) D R(D)_OH- D R(18O)_OH- [18O] R(D)_H3O+ D R(18O)_H3O+ [18O] R(18O)_H2O(g) [18O] R(D)_H2O(g) D R(D) D R(T) T R(18O) [18O] R(13C) [13C] R(14C) [14C] ISOTOPE_ALPHAS Alpha_18O_CO2(aq)/CO2(g) Log_alpha_18O_CO2(aq)/CO2(g) Alpha_13C_CO2(aq)/CO2(g) Log_alpha_13C_CO2(aq)/CO2(g) Alpha_18O_CO2(aq)/H2O(l) Log_alpha_18O_CO2(aq)/H2O(l) Alpha_D_H2O(l)/H2O(g) Log_alpha_D_H2O(l)/H2O(g) Alpha_18O_H2O(l)/H2O(g) Log_alpha_18O_H2O(l)/H2O(g) Alpha_18O_H3O+/H2O(l) Log_alpha_18O_H3O+/H2O(l) Alpha_D_H3O+/H2O(l) Log_alpha_D_H3O+/H2O(l) Alpha_18O_OH-/H2O(l) Log_alpha_18O_OH-/H2O(l) Alpha_D_OH-/H2O(l) Log_alpha_D_OH-/H2O(l) Alpha_13C_CO3-2/CO2(aq) Log_alpha_13C_CO3-2/CO2(aq) Alpha_18O_CO3-2/CO2(aq) Log_alpha_18O_CO3-2/CO2(aq) Alpha_13C_HCO3-/CO2(aq) Log_alpha_13C_HCO3-/CO2(aq) Alpha_18O_HCO3-/CO2(aq) Log_alpha_18O_HCO3-/CO2(aq) Alpha_D_HCO3-/H2O(l) Log_alpha_D_HCO3-/H2O(l) Alpha_13C_CO2(aq)/Calcite Log_alpha_13C_CO2(aq)/Calcite Alpha_18O_CO2(aq)/Calcite Log_alpha_18O_CO2(aq)/Calcite NAMED_EXPRESSIONS # # H2O fractionation factors # Log_alpha_D_H2O(l)/H2O(g) # 1000ln(alpha(25C)) = 76.4 # 0-100 C -ln_alpha1000 52.612 0.0 -76.248e3 0.0 24.844e6 Log_alpha_T_H2O(l)/H2O(g) # 1000ln(alpha(25C)) = 152.7 # 0-100 C -ln_alpha1000 105.224 0.0 -152.496e3 0.0 49.688e6 Log_alpha_18O_H2O(l)/H2O(g) # 1000ln(alpha(25C)) = 9.3 # 0-100 C -ln_alpha1000 -2.0667 0.0 -0.4156e3 0.0 1.137e6 # # OH- fractionation factors # Log_alpha_D_OH-/H2O(l) # 1000ln(alpha(25C)) = -1435 # 13.5 C -ln_alpha1000 -1435.0 Log_alpha_T_OH-/H2O(l) # 1000ln(alpha(25C)) = -2870 # 13.5 C -ln_alpha1000 -2870.0 Log_alpha_18O_OH-/H2O(l) # 1000ln(alpha(25C)) = -37.8 # 25 C -ln_alpha1000 -37.777 # # H3O- fractionation factors # Log_alpha_D_H3O+/H2O(l) # 1000ln(alpha(25C)) = 40.8 # 13.5 C -ln_alpha1000 40.82 Log_alpha_T_H3O+/H2O(l) # 1000ln(alpha(25C)) = 81.6 # 13.5 C -ln_alpha1000 81.64 Log_alpha_18O_H3O+/H2O(l) # 1000ln(alpha(25C)) = 22.9 # 25 C -ln_alpha1000 22.86 # # CO2 fractionation factors # Log_alpha_18O_CO2(aq)/H2O(l) # 1000ln(alpha(25C)) = 41.2 # 0-100 C -ln_alpha1000 -21.9285 0.0 19.43596e3 0.0 -0.181115e6 Log_alpha_18O_CO2(aq)/CO2(g) # 1000ln(alpha(25C)) = 1.07 # 0-60 C -ln_alpha1000 -1.9585 0.0 1.44176e3 0.0 -0.160515e6 # Fit from Vogel and others, 1970 data in Friedman and O'Neill Log_alpha_13C_CO2(aq)/CO2(g) # 1000ln(alpha(25C)) = -0.8 # 0-100 C -ln_alpha1000 -0.91 0.0 0.0 0.0 0.0063e6 Log_alpha_14C_CO2(aq)/CO2(g) # 1000ln(alpha(25C)) = -1.7 # 0-100 C -ln_alpha1000 -1.82 0.0 0.0 0.0 0.0126e6 # # HCO3 fractionation factors # Log_alpha_D_HCO3-/H2O(l) -ln_alpha1000 0.0 Log_alpha_T_HCO3-/H2O(l) -ln_alpha1000 0.0 Log_alpha_18O_HCO3-/CO2(aq) -ln_alpha1000 0.0 Log_alpha_13C_HCO3-/CO2(aq) # 1000ln(alpha(25C)) = 8.7 # 0-100 C -ln_alpha1000 -3.63 0.0 0.0 0.0 1.0927e6 Log_alpha_14C_HCO3-/CO2(aq) # 1000ln(alpha(25C)) = 17.3 # 0-100 C -ln_alpha1000 -7.26 0.0 0.0 0.0 2.1854e6 # # CO3 fractionation factors # Log_alpha_18O_CO3-2/CO2(aq) -ln_alpha1000 0.0 Log_alpha_13C_CO3-2/CO2(aq) # 1000ln(alpha(25C)) = 7.2 # 0-100 C -ln_alpha1000 -2.49 0.0 0.0 0.0 0.8637e6 Log_alpha_14C_CO3-2/CO2(aq) # 1000ln(alpha(25C)) = 14.5 # 0-100 C -ln_alpha1000 -4.98 0.0 0.0 0.0 1.7274e6 # # CO2-Calcite fractionation factors # Log_alpha_18O_CO2(aq)/Calcite # 1000ln(alpha(25C)) = 13.6 # 0-100 C -ln_alpha1000 -4.7383 0.0 12.05276e3 0.0 -1.963915e6 Log_alpha_13C_CO2(aq)/Calcite # 1000ln(alpha(25C)) = -10.6 # 0-100 C -ln_alpha1000 2.72 0.0 0.0 0.0 -1.1877e6 Log_alpha_14C_CO2(aq)/Calcite # 1000ln(alpha(25C)) = -21.3 # 0-100 C -ln_alpha1000 5.44 0.0 0.0 0.0 -2.3754e6 Log_QQ_18O_HCO3_1 -log_k -.36178e-02 Log_QQ_18O_HCO3_2 -log_k 0.46989 Log_QQ_18O_HCO3_3 -log_k 1.4205 # # Selected equilibrium_constants # Log_KH_H2O(g) H2O(g) = H2O(l) log_k 1.51 delta_h -44.03 kJ Log_K_water 2H2O = OH- + H3O+ log_k -14.000 delta_h 13.362 kcal -analytic -283.971 -0.05069842 13323.0 102.24447 -1119669.0 Log_KH_CO2(g) CO2(g) = CO2(aq) log_k -1.468 delta_h -4.776 kcal -analytic 108.3865 0.01985076 -6919.53 -40.45154 669365.0 Log_K_HCO3- # 2H2O + CO2(aq) = HCO3- + H3O+ log_k -6.352 delta_h 2.177 kcal -analytic -356.3094 -0.06092 21834.37 126.8339 -1684915 Log_K_CO3-2 3H2O + CO2(aq) = CO3-2 + 2H3O+ log_k -16.681 delta_h 5.738 kcal -analytic -464.1965 -0.09344813 26986.16 165.75951 -2248628.9 Log_K_calcite CaCO3 + 2H3O+ = Ca+2 + 3H2O + CO2 log_k 8.201 delta_h -8.035 kcal -analytic 292.29 0.015455 -24146.841 -94.16451 2248628.9 NAMED_EXPRESSIONS # # Ion pair log Ks # Log_K_CaCO3 log_k 3.224 delta_h 3.545 kcal -analytic -1228.732 -0.299440 35512.75 485.818 Log_K_CaHCO3+ # log_k 11.435 # delta_h -0.871 kcal # -analytic 1317.0071 0.34546894 -39916.84 -517.70761 563713.9 log_k 1.106 delta_h 2.69 kcal -analytic 1209.12 0.31294 -34765.05 -478.782 0 Log_K_MgCO3 log_k 2.98 delta_h 2.713 kcal -analytic 0.9910 0.00667 Log_K_MgHCO3+ # log_k 11.399 # delta_h -2.771 kcal # -analytic 48.6721 0.03252849 -2614.335 -18.00263 563713.9 log_k 1.07 delta_h 0.79 kcal -analytic -59.215 0 2537.455 20.92298 0 Log_K_NaCO3- log_k 1.270 delta_h 8.910 kcal Log_K_NaHCO3 log_k -0.25 Log_K_CaOH+ log_k -12.780 Log_K_MgOH+ log_k -11.440 delta_h 15.952 kcal Log_K_NaOH log_k -14.180 Log_K_KOH log_k -14.460 # # Ion pair fractionation factors # Log_alpha_D_CaHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_T_CaHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_13C_CaHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_14C_CaHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_18O_CaHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_13C_CaCO3/CO3-2 -ln_alpha1000 0.0 Log_alpha_14C_CaCO3/CO3-2 -ln_alpha1000 0.0 Log_alpha_18O_CaCO3/CO3-2 -ln_alpha1000 0.0 Log_alpha_D_CaOH+/OH- -ln_alpha1000 0.0 Log_alpha_T_CaOH+/OH- -ln_alpha1000 0.0 Log_alpha_18O_CaOH+/OH- -ln_alpha1000 0.0 Log_alpha_D_MgHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_T_MgHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_13C_MgHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_14C_MgHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_18O_MgHCO3+/HCO3- -ln_alpha1000 0.0 Log_alpha_13C_MgCO3/CO3-2 -ln_alpha1000 0.0 Log_alpha_14C_MgCO3/CO3-2 -ln_alpha1000 0.0 Log_alpha_18O_MgCO3/CO3-2 -ln_alpha1000 0.0 Log_alpha_D_MgOH+/OH- -ln_alpha1000 0.0 Log_alpha_T_MgOH+/OH- -ln_alpha1000 0.0 Log_alpha_18O_MgOH+/OH- -ln_alpha1000 0.0 Log_alpha_D_NaHCO3/HCO3- -ln_alpha1000 0.0 Log_alpha_T_NaHCO3/HCO3- -ln_alpha1000 0.0 Log_alpha_13C_NaHCO3/HCO3- -ln_alpha1000 0.0 Log_alpha_14C_NaHCO3/HCO3- -ln_alpha1000 0.0 Log_alpha_18O_NaHCO3/HCO3- -ln_alpha1000 0.0 Log_alpha_13C_NaCO3-/CO3-2 -ln_alpha1000 0.0 Log_alpha_14C_NaCO3-/CO3-2 -ln_alpha1000 0.0 Log_alpha_18O_NaCO3-/CO3-2 -ln_alpha1000 0.0 Log_alpha_D_NaOH/OH- -ln_alpha1000 0.0 Log_alpha_T_NaOH/OH- -ln_alpha1000 0.0 Log_alpha_18O_NaOH/OH- -ln_alpha1000 0.0 Log_alpha_D_KOH/OH- -ln_alpha1000 0.0 Log_alpha_T_KOH/OH- -ln_alpha1000 0.0 Log_alpha_18O_KOH/OH- -ln_alpha1000 0.0 SOLUTION_SPECIES H3O+ = H3O+ log_k 0.000 -gamma 9.0000 0.0000 e- = e- log_k 0.000 Ca+2 = Ca+2 log_k 0.000 -gamma 5.0000 0.1650 Mg+2 = Mg+2 log_k 0.000 -gamma 5.5000 0.2000 Na+ = Na+ log_k 0.000 -gamma 4.0000 0.0750 K+ = K+ log_k 0.000 -gamma 3.5000 0.0150 Cl- = Cl- log_k 0.000 -gamma 3.5000 0.0150 SO4-2 = SO4-2 log_k 0.000 -gamma 5.0000 -0.0400 NO3- = NO3- log_k 0.000 -gamma 3.0000 0.0000 H2O = H2O log_k 0.000 6 H2O = O2 + 4 H3O+ + 4 e- log_k -86.08 delta_h 134.79 kcal 2 H3O+ + 2 e- = H2 + 2H2O log_k -3.15 delta_h -1.759 kcal SOLUTION_SPECIES Ca+2 + SO4-2 = CaSO4 log_k 2.300 delta_h 1.650 kcal Ca+2 + HSO4- = CaHSO4+ log_k 1.08 Mg+2 + SO4-2 = MgSO4 log_k 2.370 delta_h 4.550 kcal Na+ + SO4-2 = NaSO4- log_k 0.700 delta_h 1.120 kcal K+ + SO4-2 = KSO4- log_k 0.850 delta_h 2.250 kcal -analytical 3.106 0.0 -673.6 SOLUTION_SPECIES H2O = H2O log_k 0 H2[18O] = H2[18O] -activity_water log_k 0 CO2 = CO2 log_k 0 [13C]O2 = [13C]O2 log_k 0 D2O = D2O -activity_water log_k 0 HTO = HTO -activity_water log_k 0 [14C]O2 = [14C]O2 log_k 0 # Water species D2O + H2[18O] = D2[18O] + H2O log_k 0.0 -activity_water 0.5H2O + 0.5D2O = HDO log_k 0.301029995663 # log10(2) -activity_water 0.5H2[18O] + 0.5D2[18O] = HD[18O] log_k 0.301029995663 # log10(2) -activity_water HTO + HDO = DTO + H2O log_k -0.301029995663 # -log10(2) -activity_water HTO + H2[18O] = HT[18O] + H2O log_k 0.0 -activity_water # CO2 reactions 0.5CO2 + 0.5C[18O]2 = CO[18O] log_k 0.301029995663 # log10(2) [13C]O2 + C[18O]2 = [13C][18O]2 + CO2 log_k 0.0 0.5[13C]O2 + 0.5[13C][18O]2 = [13C]O[18O] log_k 0.301029995663 # log10(2) [14C]O2 + C[18O]2 = [14C][18O]2 + CO2 log_k 0.0 0.5[14C]O2 + 0.5[14C][18O]2 = [14C]O[18O] log_k 0.301029995663 # log10(2) CO2 + 2H2[18O] = C[18O]2 + 2H2O -add_logk Log_alpha_18O_CO2(aq)/H2O(l) 2.0 # Hydroxide 2H2O = OH- + H3O+ -add_logk Log_K_water 1.0 -gamma 3.5000 0.0000 H2O + HDO = OD- + H3O+ log_k -0.301029995663 # -log10(2) -add_logk Log_K_water 1.0 -add_logk Log_alpha_D_OH-/H2O(l) 1.0 -gamma 3.5000 0.0000 H2O + H2[18O] = [18O]H- + H3O+ -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_OH-/H2O(l) 1.0 -gamma 3.5000 0.0000 H2O + HD[18O] = [18O]D- + H3O+ log_k -0.301029995663 # -log10(2) -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_OH-/H2O(l) 1.0 -add_logk Log_alpha_D_OH-/H2O(l) 1.0 -gamma 3.5000 0.0000 H2O + HTO = OT- + H3O+ log_k -0.301029995663 # -log10(2) -add_logk Log_K_water 1.0 -add_logk Log_alpha_T_OH-/H2O(l) 1.0 -gamma 3.5000 0.0000 H2O + HT[18O] = [18O]T- + H3O+ log_k -0.301029995663 # -log10(2) -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_OH-/H2O(l) 1.0 -add_logk Log_alpha_T_OH-/H2O(l) 1.0 -gamma 3.5000 0.0000 # Hydronium H2O + HDO = H2DO+ + OH- log_k 0.176091259055 # log10(1.5) -add_logk Log_K_water 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 1.0 -gamma 9.0000 0.0000 H2O + D2O = HD2O+ + OH- log_k 0.477121254719 # log10(3) -add_logk Log_K_water 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 2.0 -gamma 9.0000 0.0000 3HDO = D3O+ + OH- + H2O log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_water 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 3.0 -gamma 9.0000 0.0000 H2O + H2[18O] = H3[18O]+ + OH- -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_H3O+/H2O(l) 1.0 -gamma 9.0000 0.0000 HD[18O] + H2O = H2D[18O]+ + OH- log_k 0.176091259055 # log10(1.5) -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_H3O+/H2O(l) 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 1.0 -gamma 9.0000 0.0000 D2[18O] + H2O = HD2[18O]+ + OH- log_k 0.477121254719 # log10(3) -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_H3O+/H2O(l) 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 2.0 -gamma 9.0000 0.0000 H2[18O] + 3HDO = D3[18O]+ + OH- + 2H2O log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_H3O+/H2O(l) 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 3.0 -gamma 9.0000 0.0000 H2O + HTO = H2TO+ + OH- log_k 0.176091259055 # log10(1.5) -add_logk Log_K_water 1.0 -add_logk Log_alpha_T_H3O+/H2O(l) 1.0 -gamma 9.0000 0.0000 HT[18O] + H2O = H2T[18O]+ + OH- log_k 0.176091259055 # log10(1.5) -add_logk Log_K_water 1.0 -add_logk Log_alpha_18O_H3O+/H2O(l) 1.0 -add_logk Log_alpha_T_H3O+/H2O(l) 1.0 -gamma 9.0000 0.0000 DTO + H2O = HDTO+ + OH- log_k -0.124939 # log10(0.75) -add_logk Log_K_water 1.0 -add_logk Log_alpha_D_H3O+/H2O(l) 1.0 -add_logk Log_alpha_T_H3O+/H2O(l) 1.0 -gamma 9.0000 0.0000 # HCO3- species CO2 + 2H2O = HCO3- + H3O+ -add_logk Log_K_HCO3- 1.0 CO[18O] + 2H2O = HCO2[18O]- + H3O+ -log_k 0.176091259055 # log10(1.5) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 C[18O]2 + 2H2O = HCO[18O]2- + H3O+ -log_k 0.477121254719 # log10(3) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 2.0 -add_logk Log_QQ_18O_HCO3_2 1.0 2H2O + 3CO[18O] = HC[18O]3- + H3O+ + 2CO2 -log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 3.0 -add_logk Log_QQ_18O_HCO3_3 1.0 [13C]O2 + 2H2O = H[13C]O3- + H3O+ -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 [13C]O[18O] + 2H2O = H[13C]O2[18O]- + H3O+ -log_k 0.176091259055 # log10(1.5) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 [13C][18O]2 + 2H2O = H[13C]O[18O]2- + H3O+ -log_k 0.477121254719 # log10(3) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 2.0 -add_logk Log_QQ_18O_HCO3_2 1.0 2H2O + 3CO[18O] + [13C]O2 = H[13C][18O]3- + H3O+ + 3CO2 -log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 3.0 -add_logk Log_QQ_18O_HCO3_3 1.0 [14C]O2 + 2H2O = H[14C]O3- + H3O+ -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 [14C]O[18O] + 2H2O = H[14C]O2[18O]- + H3O+ -log_k 0.176091259055 # log10(1.5) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 [14C][18O]2 + 2H2O = H[14C]O[18O]2- + H3O+ -log_k 0.477121254719 # log10(3) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 2.0 -add_logk Log_QQ_18O_HCO3_2 1.0 2H2O + 3CO[18O] + [14C]O2 = H[14C][18O]3- + H3O+ + 3CO2 -log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 3.0 -add_logk Log_QQ_18O_HCO3_3 1.0 CO2 + H2O + HDO = DCO3- + H3O+ -log_k -0.301029995663 # -log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 CO[18O] + H2O + HDO = DCO2[18O]- + H3O+ -log_k -0.124938736682 # log10(0.75) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 C[18O]2 + H2O + HDO = DCO[18O]2- + H3O+ -log_k 0.176091259055 # log10(1.5) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 2.0 -add_logk Log_QQ_18O_HCO3_2 1.0 H2O + HDO + 3CO[18O] = DC[18O]3- + H3O+ + 2CO2 -log_k -1.204119982655 # -4*log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 3.0 -add_logk Log_QQ_18O_HCO3_3 1.0 [13C]O2 + H2O + HDO = D[13C]O3- + H3O+ -log_k -0.301029995663 # -log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 [13C]O[18O] + H2O + HDO = D[13C]O2[18O]- + H3O+ -log_k -0.124938736682 # log10(0.75) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 [13C][18O]2 + H2O + HDO = D[13C]O[18O]2- + H3O+ -log_k 0.176091259055 # log10(1.5) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 2.0 -add_logk Log_QQ_18O_HCO3_2 1.0 H2O + HDO + 3CO[18O] + [13C]O2 = D[13C][18O]3- + H3O+ + 3CO2 -log_k -1.204119982655 # -4*log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 3.0 -add_logk Log_QQ_18O_HCO3_3 1.0 [14C]O2 + H2O + HDO = D[14C]O3- + H3O+ -log_k -0.301029995663 # -log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 [14C]O[18O] + H2O + HDO = D[14C]O2[18O]- + H3O+ -log_k -0.124938736682 # log10(0.75) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 [14C][18O]2 + H2O + HDO = D[14C]O[18O]2- + H3O+ -log_k 0.176091259055 # log10(1.5) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 2.0 -add_logk Log_QQ_18O_HCO3_2 1.0 H2O + HDO + 3CO[18O] + [14C]O2 = D[14C][18O]3- + H3O+ + 3CO2 -log_k -1.204119982655 # -4*log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_D_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_14C_HCO3-/CO2(aq) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 3.0 -add_logk Log_QQ_18O_HCO3_3 1.0 CO2 + H2O + HTO = TCO3- + H3O+ -log_k -0.301029995663 # -log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_T_HCO3-/H2O(l) 1.0 CO[18O] + H2O + HTO = TCO2[18O]- + H3O+ -log_k -0.124938736682 # log10(0.75) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_T_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_18O_HCO3-/CO2(aq) 1.0 -add_logk Log_QQ_18O_HCO3_1 1.0 [13C]O2 + H2O + HTO = T[13C]O3- + H3O+ -log_k -0.301029995663 # -log10(2) -add_logk Log_K_HCO3- 1.0 -add_logk Log_alpha_T_HCO3-/H2O(l) 1.0 -add_logk Log_alpha_13C_HCO3-/CO2(aq) 1.0 # CO3-2 species CO2 + 3H2O = CO3-2 + 2H3O+ -add_logk Log_K_CO3-2 1.0 CO[18O] + 3H2O = CO2[18O]-2 + 2H3O+ log_k 0.176091259055 # log10(1.5) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 1.0 C[18O]2 + 3H2O = CO[18O]2-2 + 2H3O+ log_k 0.477121254719 # log10(3) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 2.0 3CO[18O] + 3H2O = C[18O]3-2 + 2H3O+ + 2CO2 log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 3.0 [13C]O2 + 3H2O = [13C]O3-2 + 2H3O+ -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_13C_CO3-2/CO2(aq) 1.0 [13C]O[18O] + 3H2O = [13C]O2[18O]-2 + 2H3O+ log_k 0.176091259055 # log10(1.5) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_13C_CO3-2/CO2(aq) 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 1.0 [13C][18O]2 + 3H2O = [13C]O[18O]2-2 + 2H3O+ log_k 0.477121254719 # log10(3) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_13C_CO3-2/CO2(aq) 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 2.0 3H2O + 3CO[18O] + [13C]O2 = [13C][18O]3-2 + 2H3O+ + 3CO2 log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_13C_CO3-2/CO2(aq) 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 3.0 [14C]O2 + 3H2O = [14C]O3-2 + 2H3O+ -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_14C_CO3-2/CO2(aq) 1.0 [14C]O[18O] + 3H2O = [14C]O2[18O]-2 + 2H3O+ log_k 0.176091259055 # log10(1.5) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_14C_CO3-2/CO2(aq) 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 1.0 [14C][18O]2 + 3H2O = [14C]O[18O]2-2 + 2H3O+ log_k 0.477121254719 # log10(3) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_14C_CO3-2/CO2(aq) 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 2.0 3H2O + 3CO[18O] + [14C]O2 = [14C][18O]3-2 + 2H3O+ + 3CO2 log_k -0.903089986991 # -3*log10(2) -add_logk Log_K_CO3-2 1.0 -add_logk Log_alpha_14C_CO3-2/CO2(aq) 1.0 -add_logk Log_alpha_18O_CO3-2/CO2(aq) 3.0 PHASES # Water gas-liquid H2O(g) H2O = H2O -add_logk Log_KH_H2O(g) 1.0 HDO(g) HDO = HDO -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_D_H2O(l)/H2O(g) 1.0 D2O(g) D2O = D2O -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_D_H2O(l)/H2O(g) 2.0 H2[18O](g) H2[18O] = H2[18O] -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_18O_H2O(l)/H2O(g) 1.0 HD[18O](g) HD[18O] = HD[18O] -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_18O_H2O(l)/H2O(g) 1.0 -add_logk Log_alpha_D_H2O(l)/H2O(g) 1.0 D2[18O](g) D2[18O] = D2[18O] -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_18O_H2O(l)/H2O(g) 1.0 -add_logk Log_alpha_D_H2O(l)/H2O(g) 2.0 HTO(g) HTO = HTO -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_T_H2O(l)/H2O(g) 1.0 HT[18O](g) HT[18O] = HT[18O] -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_18O_H2O(l)/H2O(g) 1.0 -add_logk Log_alpha_T_H2O(l)/H2O(g) 1.0 DTO(g) DTO = DTO -add_logk Log_KH_H2O(g) 1.0 -add_logk Log_alpha_D_H2O(l)/H2O(g) 1.0 -add_logk Log_alpha_T_H2O(l)/H2O(g) 1.0 # CO2 CO2(g) CO2 = CO2 -add_logk Log_KH_CO2(g) 1.0 CO[18O](g) CO[18O] = CO[18O] -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_18O_CO2(aq)/CO2(g) 1.0 C[18O]2(g) C[18O]2 = C[18O]2 -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_18O_CO2(aq)/CO2(g) 2.0 [13C]O2(g) [13C]O2 = [13C]O2 -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_13C_CO2(aq)/CO2(g) 1.0 [13C]O[18O](g) [13C]O[18O] = [13C]O[18O] -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_13C_CO2(aq)/CO2(g) 1.0 -add_logk Log_alpha_18O_CO2(aq)/CO2(g) 1.0 [13C][18O]2(g) [13C][18O]2 = [13C][18O]2 -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_13C_CO2(aq)/CO2(g) 1.0 -add_logk Log_alpha_18O_CO2(aq)/CO2(g) 2.0 [14C]O2(g) [14C]O2 = [14C]O2 -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_14C_CO2(aq)/CO2(g) 1.0 [14C]O[18O](g) [14C]O[18O] = [14C]O[18O] -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_14C_CO2(aq)/CO2(g) 1.0 -add_logk Log_alpha_18O_CO2(aq)/CO2(g) 1.0 [14C][18O]2(g) [14C][18O]2 = [14C][18O]2 -add_logk Log_KH_CO2(g) 1.0 -add_logk Log_alpha_14C_CO2(aq)/CO2(g) 1.0 -add_logk Log_alpha_18O_CO2(aq)/CO2(g) 2.0 # Calcite Calcite CaCO3 + 2H3O+ = Ca+2 + CO2 + 3H2O -add_logk Log_K_calcite 1.0 CaCO2[18O] CaCO2[18O] + 2H3O+ = Ca+2 + 3H2O + CO[18O] log_k -0.176091259055 # -log10(1.5) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 1.0 CaCO[18O]2 CaCO[18O]2 + 2H3O+ = Ca+2 + 3H2O + C[18O]2 log_k -0.477121254719 # -log10(3) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 2.0 CaC[18O]3 CaC[18O]3 + 2CO2 + 2H3O+ = Ca+2 + 3H2O + 3CO[18O] log_k 0.903089986991 # 3*log10(2) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 3.0 Ca[13C]O3 Ca[13C]O3 + 2H3O+ = Ca+2 + 3H2O + [13C]O2 -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_13C_CO2(aq)/Calcite 1.0 Ca[13C]O2[18O] Ca[13C]O2[18O] + 2H3O+ = Ca+2 + 3H2O + [13C]O[18O] log_k -0.176091259055 # -log10(1.5) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_13C_CO2(aq)/Calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 1.0 Ca[13C]O[18O]2 Ca[13C]O[18O]2 + 2H3O+ = Ca+2 + 3H2O + [13C][18O]2 log_k -0.477121254719 # -log10(3) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_13C_CO2(aq)/Calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 2.0 Ca[13C][18O]3 Ca[13C][18O]3 + 3CO2 + 2H3O+ = Ca+2 + 3H2O + 3CO[18O] + [13C]O2 log_k 0.903089986991 # 3*log10(2) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_13C_CO2(aq)/Calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 3.0 Ca[14C]O3 Ca[14C]O3 + 2H3O+ = Ca+2 + 3H2O + [14C]O2 -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_14C_CO2(aq)/Calcite 1.0 Ca[14C]O2[18O] Ca[14C]O2[18O] + 2H3O+ = Ca+2 + 3H2O + [14C]O[18O] log_k -0.176091259055 # -log10(1.5) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_14C_CO2(aq)/Calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 1.0 Ca[14C]O[18O]2 Ca[14C]O[18O]2 + 2H3O+ = Ca+2 + 3H2O + [14C][18O]2 log_k -0.477121254719 # -log10(3) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_14C_CO2(aq)/Calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 2.0 Ca[14C][18O]3 Ca[14C][18O]3 + 3CO2 + 2H3O+ = Ca+2 + 3H2O + 3CO[18O] + [14C]O2 log_k 0.903089986991 # 3*log10(2) -add_logk Log_K_calcite 1.0 -add_logk Log_alpha_14C_CO2(aq)/Calcite 1.0 -add_logk Log_alpha_18O_CO2(aq)/Calcite 3.0 SOLUTION_SPECIES Ca+2 + HCO3- = CaHCO3+ -add_logk Log_K_CaHCO3+ -gamma 5.4000 0.0000 Ca+2 + HCO2[18O]- = CaHCO2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + HCO[18O]2- = CaHCO[18O]2+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 -gamma 5.4000 0.0000 Ca+2 + HC[18O]3- = CaHC[18O]3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 -gamma 5.4000 0.0000 Ca+2 + H[13C]O3- = CaH[13C]O3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + H[13C]O2[18O]- = CaH[13C]O2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + H[13C]O[18O]2- = CaH[13C]O[18O]2+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 -gamma 5.4000 0.0000 Ca+2 + H[13C][18O]3- = CaH[13C][18O]3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 -gamma 5.4000 0.0000 Ca+2 + H[14C]O3- = CaH[14C]O3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + H[14C]O2[18O]- = CaH[14C]O2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + H[14C]O[18O]2- = CaH[14C]O[18O]2+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 -gamma 5.4000 0.0000 Ca+2 + H[14C][18O]3- = CaH[14C][18O]3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 -gamma 5.4000 0.0000 Ca+2 + DCO3- = CaDCO3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + DCO2[18O]- = CaDCO2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + DCO[18O]2- = CaDCO[18O]2+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 -gamma 5.4000 0.0000 Ca+2 + DC[18O]3- = CaDC[18O]3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 -gamma 5.4000 0.0000 Ca+2 + D[13C]O3- = CaD[13C]O3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + D[13C]O2[18O]- = CaD[13C]O2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + D[13C]O[18O]2- = CaD[13C]O[18O]2+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 -gamma 5.4000 0.0000 Ca+2 + D[13C][18O]3- = CaD[13C][18O]3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 -gamma 5.4000 0.0000 Ca+2 + D[14C]O3- = CaD[14C]O3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + D[14C]O2[18O]- = CaD[14C]O2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + D[14C]O[18O]2- = CaD[14C]O[18O]2+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 -gamma 5.4000 0.0000 Ca+2 + D[14C][18O]3- = CaD[14C][18O]3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_D_CaHCO3+/HCO3- 1 -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 -gamma 5.4000 0.0000 Ca+2 + TCO3- = CaTCO3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 Ca+2 + TCO2[18O]- = CaTCO2[18O]+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 #Ca+2 + TCO[18O]2- = CaTCO[18O]2+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 # -gamma 5.4000 0.0000 #Ca+2 + TC[18O]3- = CaTC[18O]3+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 # -gamma 5.4000 0.0000 Ca+2 + T[13C]O3- = CaT[13C]O3+ -add_logk Log_K_CaHCO3+ -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 -gamma 5.4000 0.0000 #Ca+2 + T[13C]O2[18O]- = CaT[13C]O2[18O]+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 # -gamma 5.4000 0.0000 #Ca+2 + T[13C]O[18O]2- = CaT[13C]O[18O]2+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 # -gamma 5.4000 0.0000 #Ca+2 + T[13C][18O]3- = CaT[13C][18O]3+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_13C_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 # -gamma 5.4000 0.0000 #Ca+2 + T[14C]O3- = CaT[14C]O3+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 # -gamma 5.4000 0.0000 #Ca+2 + T[14C]O2[18O]- = CaT[14C]O2[18O]+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 1 # -gamma 5.4000 0.0000 #Ca+2 + T[14C]O[18O]2- = CaT[14C]O[18O]2+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 2 # -gamma 5.4000 0.0000 #Ca+2 + T[14C][18O]3- = CaT[14C][18O]3+ # -add_logk Log_K_CaHCO3+ # -add_logk Log_alpha_T_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_CaHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_CaHCO3+/HCO3- 3 # -gamma 5.4000 0.0000 Mg+2 + HCO3- = MgHCO3+ -add_logk Log_K_MgHCO3+ Mg+2 + HCO2[18O]- = MgHCO2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 Mg+2 + HCO[18O]2- = MgHCO[18O]2+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 Mg+2 + HC[18O]3- = MgHC[18O]3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + H[13C]O3- = MgH[13C]O3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 Mg+2 + H[13C]O2[18O]- = MgH[13C]O2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 Mg+2 + H[13C]O[18O]2- = MgH[13C]O[18O]2+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 Mg+2 + H[13C][18O]3- = MgH[13C][18O]3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + H[14C]O3- = MgH[14C]O3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 Mg+2 + H[14C]O2[18O]- = MgH[14C]O2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 Mg+2 + H[14C]O[18O]2- = MgH[14C]O[18O]2+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 Mg+2 + H[14C][18O]3- = MgH[14C][18O]3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + DCO3- = MgDCO3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 Mg+2 + DCO2[18O]- = MgDCO2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 Mg+2 + DCO[18O]2- = MgDCO[18O]2+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 Mg+2 + DC[18O]3- = MgDC[18O]3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + D[13C]O3- = MgD[13C]O3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 Mg+2 + D[13C]O2[18O]- = MgD[13C]O2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 Mg+2 + D[13C]O[18O]2- = MgD[13C]O[18O]2+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 Mg+2 + D[13C][18O]3- = MgD[13C][18O]3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + D[14C]O3- = MgD[14C]O3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 Mg+2 + D[14C]O2[18O]- = MgD[14C]O2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 Mg+2 + D[14C]O[18O]2- = MgD[14C]O[18O]2+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 Mg+2 + D[14C][18O]3- = MgD[14C][18O]3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_D_MgHCO3+/HCO3- 1 -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + TCO3- = MgTCO3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 Mg+2 + TCO2[18O]- = MgTCO2[18O]+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 #Mg+2 + TCO[18O]2- = MgTCO[18O]2+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 #Mg+2 + TC[18O]3- = MgTC[18O]3+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Mg+2 + T[13C]O3- = MgT[13C]O3+ -add_logk Log_K_MgHCO3+ -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 #Mg+2 + T[13C]O2[18O]- = MgT[13C]O2[18O]+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 #Mg+2 + T[13C]O[18O]2- = MgT[13C]O[18O]2+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 #Mg+2 + T[13C][18O]3- = MgT[13C][18O]3+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_13C_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 #Mg+2 + T[14C]O3- = MgT[14C]O3+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 #Mg+2 + T[14C]O2[18O]- = MgT[14C]O2[18O]+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 1 #Mg+2 + T[14C]O[18O]2- = MgT[14C]O[18O]2+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 2 #Mg+2 + T[14C][18O]3- = MgT[14C][18O]3+ # -add_logk Log_K_MgHCO3+ # -add_logk Log_alpha_T_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_14C_MgHCO3+/HCO3- 1 # -add_logk Log_alpha_18O_MgHCO3+/HCO3- 3 Na+ + HCO3- = NaHCO3 -add_logk Log_K_NaHCO3 Na+ + HCO2[18O]- = NaHCO2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 Na+ + HCO[18O]2- = NaHCO[18O]2 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 Na+ + HC[18O]3- = NaHC[18O]3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + H[13C]O3- = NaH[13C]O3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 Na+ + H[13C]O2[18O]- = NaH[13C]O2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 Na+ + H[13C]O[18O]2- = NaH[13C]O[18O]2 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 Na+ + H[13C][18O]3- = NaH[13C][18O]3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + H[14C]O3- = NaH[14C]O3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 Na+ + H[14C]O2[18O]- = NaH[14C]O2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 Na+ + H[14C]O[18O]2- = NaH[14C]O[18O]2 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 Na+ + H[14C][18O]3- = NaH[14C][18O]3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + DCO3- = NaDCO3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 Na+ + DCO2[18O]- = NaDCO2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 Na+ + DCO[18O]2- = NaDCO[18O]2 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 Na+ + DC[18O]3- = NaDC[18O]3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + D[13C]O3- = NaD[13C]O3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 Na+ + D[13C]O2[18O]- = NaD[13C]O2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 Na+ + D[13C]O[18O]2- = NaD[13C]O[18O]2 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 Na+ + D[13C][18O]3- = NaD[13C][18O]3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + D[14C]O3- = NaD[14C]O3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 Na+ + D[14C]O2[18O]- = NaD[14C]O2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 Na+ + D[14C]O[18O]2- = NaD[14C]O[18O]2 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 Na+ + D[14C][18O]3- = NaD[14C][18O]3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_D_NaHCO3/HCO3- 1 -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + TCO3- = NaTCO3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_T_NaHCO3/HCO3- 1 Na+ + TCO2[18O]- = NaTCO2[18O] -add_logk Log_K_NaHCO3 -add_logk Log_alpha_T_NaHCO3/HCO3- 1 -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 #Na+ + TCO[18O]2- = NaTCO[18O]2 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 #Na+ + TC[18O]3- = NaTC[18O]3 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Na+ + T[13C]O3- = NaT[13C]O3 -add_logk Log_K_NaHCO3 -add_logk Log_alpha_T_NaHCO3/HCO3- 1 -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 #Na+ + T[13C]O2[18O]- = NaT[13C]O2[18O] # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 #Na+ + T[13C]O[18O]2- = NaT[13C]O[18O]2 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 #Na+ + T[13C][18O]3- = NaT[13C][18O]3 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_13C_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 #Na+ + T[14C]O3- = NaT[14C]O3 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 #Na+ + T[14C]O2[18O]- = NaT[14C]O2[18O] # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 1 #Na+ + T[14C]O[18O]2- = NaT[14C]O[18O]2 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 2 #Na+ + T[14C][18O]3- = NaT[14C][18O]3 # -add_logk Log_K_NaHCO3 # -add_logk Log_alpha_T_NaHCO3/HCO3- 1 # -add_logk Log_alpha_14C_NaHCO3/HCO3- 1 # -add_logk Log_alpha_18O_NaHCO3/HCO3- 3 Ca+2 + CO3-2 = CaCO3 -add_logk Log_K_CaCO3 Ca+2 + CO2[18O]-2 = CaCO2[18O] -add_logk Log_K_CaCO3 -add_logk Log_alpha_18O_CaCO3/CO3-2 1 Ca+2 + CO[18O]2-2 = CaCO[18O]2 -add_logk Log_K_CaCO3 -add_logk Log_alpha_18O_CaCO3/CO3-2 2 Ca+2 + C[18O]3-2 = CaC[18O]3 -add_logk Log_K_CaCO3 -add_logk Log_alpha_18O_CaCO3/CO3-2 3 Ca+2 + [13C]O3-2 = Ca[13C]O3 -add_logk Log_K_CaCO3 -add_logk Log_alpha_13C_CaCO3/CO3-2 1 Ca+2 + [13C]O2[18O]-2 = Ca[13C]O2[18O] -add_logk Log_K_CaCO3 -add_logk Log_alpha_13C_CaCO3/CO3-2 1 -add_logk Log_alpha_18O_CaCO3/CO3-2 1 Ca+2 + [13C]O[18O]2-2 = Ca[13C]O[18O]2 -add_logk Log_K_CaCO3 -add_logk Log_alpha_13C_CaCO3/CO3-2 1 -add_logk Log_alpha_18O_CaCO3/CO3-2 2 Ca+2 + [13C][18O]3-2 = Ca[13C][18O]3 -add_logk Log_K_CaCO3 -add_logk Log_alpha_13C_CaCO3/CO3-2 1 -add_logk Log_alpha_18O_CaCO3/CO3-2 3 Ca+2 + [14C]O3-2 = Ca[14C]O3 -add_logk Log_K_CaCO3 -add_logk Log_alpha_14C_CaCO3/CO3-2 1 Ca+2 + [14C]O2[18O]-2 = Ca[14C]O2[18O] -add_logk Log_K_CaCO3 -add_logk Log_alpha_14C_CaCO3/CO3-2 1 -add_logk Log_alpha_18O_CaCO3/CO3-2 1 Ca+2 + [14C]O[18O]2-2 = Ca[14C]O[18O]2 -add_logk Log_K_CaCO3 -add_logk Log_alpha_14C_CaCO3/CO3-2 1 -add_logk Log_alpha_18O_CaCO3/CO3-2 2 Ca+2 + [14C][18O]3-2 = Ca[14C][18O]3 -add_logk Log_K_CaCO3 -add_logk Log_alpha_14C_CaCO3/CO3-2 1 -add_logk Log_alpha_18O_CaCO3/CO3-2 3 Mg+2 + CO3-2 = MgCO3 -add_logk Log_K_MgCO3 Mg+2 + CO2[18O]-2 = MgCO2[18O] -add_logk Log_K_MgCO3 -add_logk Log_alpha_18O_MgCO3/CO3-2 1 Mg+2 + CO[18O]2-2 = MgCO[18O]2 -add_logk Log_K_MgCO3 -add_logk Log_alpha_18O_MgCO3/CO3-2 2 Mg+2 + C[18O]3-2 = MgC[18O]3 -add_logk Log_K_MgCO3 -add_logk Log_alpha_18O_MgCO3/CO3-2 3 Mg+2 + [13C]O3-2 = Mg[13C]O3 -add_logk Log_K_MgCO3 -add_logk Log_alpha_13C_MgCO3/CO3-2 1 Mg+2 + [13C]O2[18O]-2 = Mg[13C]O2[18O] -add_logk Log_K_MgCO3 -add_logk Log_alpha_13C_MgCO3/CO3-2 1 -add_logk Log_alpha_18O_MgCO3/CO3-2 1 Mg+2 + [13C]O[18O]2-2 = Mg[13C]O[18O]2 -add_logk Log_K_MgCO3 -add_logk Log_alpha_13C_MgCO3/CO3-2 1 -add_logk Log_alpha_18O_MgCO3/CO3-2 2 Mg+2 + [13C][18O]3-2 = Mg[13C][18O]3 -add_logk Log_K_MgCO3 -add_logk Log_alpha_13C_MgCO3/CO3-2 1 -add_logk Log_alpha_18O_MgCO3/CO3-2 3 Mg+2 + [14C]O3-2 = Mg[14C]O3 -add_logk Log_K_MgCO3 -add_logk Log_alpha_14C_MgCO3/CO3-2 1 Mg+2 + [14C]O2[18O]-2 = Mg[14C]O2[18O] -add_logk Log_K_MgCO3 -add_logk Log_alpha_14C_MgCO3/CO3-2 1 -add_logk Log_alpha_18O_MgCO3/CO3-2 1 Mg+2 + [14C]O[18O]2-2 = Mg[14C]O[18O]2 -add_logk Log_K_MgCO3 -add_logk Log_alpha_14C_MgCO3/CO3-2 1 -add_logk Log_alpha_18O_MgCO3/CO3-2 2 Mg+2 + [14C][18O]3-2 = Mg[14C][18O]3 -add_logk Log_K_MgCO3 -add_logk Log_alpha_14C_MgCO3/CO3-2 1 -add_logk Log_alpha_18O_MgCO3/CO3-2 3 Na+ + CO3-2 = NaCO3- -add_logk Log_K_NaCO3- Na+ + CO2[18O]-2 = NaCO2[18O]- -add_logk Log_K_NaCO3- -add_logk Log_alpha_18O_NaCO3-/CO3-2 1 Na+ + CO[18O]2-2 = NaCO[18O]2- -add_logk Log_K_NaCO3- -add_logk Log_alpha_18O_NaCO3-/CO3-2 2 Na+ + C[18O]3-2 = NaC[18O]3- -add_logk Log_K_NaCO3- -add_logk Log_alpha_18O_NaCO3-/CO3-2 3 Na+ + [13C]O3-2 = Na[13C]O3- -add_logk Log_K_NaCO3- -add_logk Log_alpha_13C_NaCO3-/CO3-2 1 Na+ + [13C]O2[18O]-2 = Na[13C]O2[18O]- -add_logk Log_K_NaCO3- -add_logk Log_alpha_13C_NaCO3-/CO3-2 1 -add_logk Log_alpha_18O_NaCO3-/CO3-2 1 Na+ + [13C]O[18O]2-2 = Na[13C]O[18O]2- -add_logk Log_K_NaCO3- -add_logk Log_alpha_13C_NaCO3-/CO3-2 1 -add_logk Log_alpha_18O_NaCO3-/CO3-2 2 Na+ + [13C][18O]3-2 = Na[13C][18O]3- -add_logk Log_K_NaCO3- -add_logk Log_alpha_13C_NaCO3-/CO3-2 1 -add_logk Log_alpha_18O_NaCO3-/CO3-2 3 Na+ + [14C]O3-2 = Na[14C]O3- -add_logk Log_K_NaCO3- -add_logk Log_alpha_14C_NaCO3-/CO3-2 1 Na+ + [14C]O2[18O]-2 = Na[14C]O2[18O]- -add_logk Log_K_NaCO3- -add_logk Log_alpha_14C_NaCO3-/CO3-2 1 -add_logk Log_alpha_18O_NaCO3-/CO3-2 1 Na+ + [14C]O[18O]2-2 = Na[14C]O[18O]2- -add_logk Log_K_NaCO3- -add_logk Log_alpha_14C_NaCO3-/CO3-2 1 -add_logk Log_alpha_18O_NaCO3-/CO3-2 2 Na+ + [14C][18O]3-2 = Na[14C][18O]3- -add_logk Log_K_NaCO3- -add_logk Log_alpha_14C_NaCO3-/CO3-2 1 -add_logk Log_alpha_18O_NaCO3-/CO3-2 3 Ca+2 + OH- = CaOH+ -add_logk Log_K_CaOH+ Ca+2 + [18O]H- = Ca[18O]H+ -add_logk Log_K_CaOH+ -add_logk Log_alpha_18O_CaOH+/OH- 1 Ca+2 + OD- = CaOD+ -add_logk Log_K_CaOH+ -add_logk Log_alpha_D_CaOH+/OH- 1 Ca+2 + [18O]D- = Ca[18O]D+ -add_logk Log_K_CaOH+ -add_logk Log_alpha_D_CaOH+/OH- 1 -add_logk Log_alpha_18O_CaOH+/OH- 1 Ca+2 + OT- = CaOT+ -add_logk Log_K_CaOH+ -add_logk Log_alpha_T_CaOH+/OH- 1 Ca+2 + [18O]T- = Ca[18O]T+ -add_logk Log_K_CaOH+ -add_logk Log_alpha_T_CaOH+/OH- 1 -add_logk Log_alpha_18O_CaOH+/OH- 1 Mg+2 + OH- = MgOH+ -add_logk Log_K_MgOH+ Mg+2 + [18O]H- = Mg[18O]H+ -add_logk Log_K_MgOH+ -add_logk Log_alpha_18O_MgOH+/OH- 1 Mg+2 + OD- = MgOD+ -add_logk Log_K_MgOH+ -add_logk Log_alpha_D_MgOH+/OH- 1 Mg+2 + [18O]D- = Mg[18O]D+ -add_logk Log_K_MgOH+ -add_logk Log_alpha_D_MgOH+/OH- 1 -add_logk Log_alpha_18O_MgOH+/OH- 1 Mg+2 + OT- = MgOT+ -add_logk Log_K_MgOH+ -add_logk Log_alpha_T_MgOH+/OH- 1 Mg+2 + [18O]T- = Mg[18O]T+ -add_logk Log_K_MgOH+ -add_logk Log_alpha_T_MgOH+/OH- 1 -add_logk Log_alpha_18O_MgOH+/OH- 1 Na+ + OH- = NaOH -add_logk Log_K_NaOH Na+ + [18O]H- = Na[18O]H -add_logk Log_K_NaOH -add_logk Log_alpha_18O_NaOH/OH- 1 Na+ + OD- = NaOD -add_logk Log_K_NaOH -add_logk Log_alpha_D_NaOH/OH- 1 Na+ + [18O]D- = Na[18O]D -add_logk Log_K_NaOH -add_logk Log_alpha_D_NaOH/OH- 1 -add_logk Log_alpha_18O_NaOH/OH- 1 Na+ + OT- = NaOT -add_logk Log_K_NaOH -add_logk Log_alpha_T_NaOH/OH- 1 Na+ + [18O]T- = Na[18O]T -add_logk Log_K_NaOH -add_logk Log_alpha_T_NaOH/OH- 1 -add_logk Log_alpha_18O_NaOH/OH- 1 K+ + OH- = KOH -add_logk Log_K_KOH K+ + [18O]H- = K[18O]H -add_logk Log_K_KOH -add_logk Log_alpha_18O_KOH/OH- 1 K+ + OD- = KOD -add_logk Log_K_KOH -add_logk Log_alpha_D_KOH/OH- 1 K+ + [18O]D- = K[18O]D -add_logk Log_K_KOH -add_logk Log_alpha_D_KOH/OH- 1 -add_logk Log_alpha_18O_KOH/OH- 1 K+ + OT- = KOT -add_logk Log_K_KOH -add_logk Log_alpha_T_KOH/OH- 1 K+ + [18O]T- = K[18O]T -add_logk Log_K_KOH -add_logk Log_alpha_T_KOH/OH- 1 -add_logk Log_alpha_18O_KOH/OH- 1 CALCULATE_VALUES R(13C)_CO2(aq) -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 100 30 total_13C = sum_species("[13C]{O,[18O]}2","[13C]") 40 total_12C = sum_species("C{O,[18O]}2","C") 50 if (total_12C <= 0) THEN GOTO 100 60 ratio = total_13C/total_12C 100 save ratio -end R(18O)_CO2(aq) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 if (TOT("C") <= 0) THEN GOTO 100 40 total_18O = sum_species("{C,[13C],[14C]}{O,[18O]}2","[18O]") 50 total_16O = sum_species("{C,[13C],[14C]}{O,[18O]}2","O") 60 if (total_16O <= 0) THEN GOTO 100 70 ratio = total_18O/total_16O 100 save ratio -end R(13C)_HCO3- -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 100 30 total_13C = sum_species("*{H,D,T}[13C]{O,[18O]}3*","[13C]") 40 total_12C = sum_species("*{H,D,T}C{O,[18O]}3*","C") 50 if (total_12C <= 0) THEN GOTO 100 60 ratio = total_13C/total_12C 100 save ratio -end R(D)_HCO3- -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 if (TOT("C") <= 0) THEN GOTO 100 40 total_D = sum_species("*D{C,[13C],[14C]}{O,[18O]}3*","D") 50 total_H = sum_species("*H{C,[13C],[14C]}{O,[18O]}3*","H") 60 if (total_H <= 0) THEN GOTO 100 70 ratio = total_D/total_H 100 save ratio -end R(18O)_HCO3- -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 if (TOT("C") <= 0) THEN GOTO 100 40 total_18O = sum_species("*{H,D,T}{C,[13C],[14C]}{O,[18O]}3*","[18O]") 50 total_16O = sum_species("*{H,D,T}{C,[13C],[14C]}{O,[18O]}3*","O") 60 if (total_16O <= 0) THEN GOTO 100 70 ratio = total_18O/total_16O 100 save ratio -end R(13C)_CO3-2 -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 100 30 total_13C = sum_species("*[13C]{O,[18O]}3*","[13C]") - sum_species("*{H,D,T}[13C]{O,[18O]}3*","[13C]") 40 total_12C = sum_species("*C{O,[18O]}3*","C") - sum_species("*{H,D,T}C{O,[18O]}3*","C") 50 if (total_12C <= 0) THEN GOTO 100 60 ratio = total_13C/total_12C 100 save ratio -end R(18O)_CO3-2 -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 if (TOT("C") <= 0) THEN GOTO 100 40 total_18O = sum_species("*{C,[13C],[14C]}{O,[18O]}3*","[18O]") - sum_species("*{H,D,T}{C,[13C],[14C]}{O,[18O]}3*","[18O]") 50 total_16O = sum_species("*{C,[13C],[14C]}{O,[18O]}3*","O") - sum_species("*{H,D,T}{C,[13C],[14C]}{O,[18O]}3*","O") 60 if (total_16O <= 0) THEN GOTO 100 70 ratio = total_18O/total_16O 100 save ratio -end R(18O)_H2O(l) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 total_18O = sum_species("{H,D,T}2{O,[18O]}","[18O]") 40 total_16O = sum_species("{H,D,T}2{O,[18O]}","O") 50 if (total_16O <= 0) THEN GOTO 100 60 ratio = total_18O/total_16O 100 save ratio -end R(D)_H2O(l) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("{H,D,T}2{O,[18O]}","D") 40 total_H = sum_species("{H,D,T}2{O,[18O]}","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_OH- -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("*{O,[18O]}D*","D") 40 total_H = sum_species("*{O,[18O]}H*","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(18O)_OH- -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 total_18O = sum_species("*[18O]{H,D,T}*","[18O]") 40 total_16O = sum_species("*O{H,D,T}*","O") 50 ratio = total_18O/total_16O 100 save ratio -end R(D)_H3O+ -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("{H,D,T}3{O,[18O]}+","D") 40 total_H = sum_species("{H,D,T}3{O,[18O]}+","H") 50 ratio = total_D/total_H 100 save ratio -end R(18O)_H3O+ -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 total_18O = sum_species("{H,D,T}3{O,[18O]}+","[18O]") 40 total_16O = sum_species("{H,D,T}3{O,[18O]}+","O") 50 ratio = total_18O/total_16O 100 save ratio -end R(18O)_H2O(g) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (GAS("H2O(g)") <= 0) THEN GOTO 1000 40 total_18O = SUM_GAS("{H,D,T}2[18O]", "[18O]") 50 total_O = SUM_GAS("{H,D,T}2O", "O") 60 if (total_O <= 0) THEN GOTO 1000 70 ratio = total_18O/total_O 1000 save ratio -end R(D)_H2O(g) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("H2O(g)") <= 0) THEN GOTO 1000 40 total_D = SUM_GAS("{H,D,T}2{O,[18O]}", "D") 50 total_H = SUM_GAS("{H,D,T}2{O,[18O]}", "H") 60 if (total_h <= 0) THEN GOTO 1000 70 ratio = total_D/total_H 1000 save ratio -end R(D) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = TOT("D") 40 total_H = TOT("H") 50 ratio = total_D/total_H 100 save ratio -end R(T) -start 10 ratio = -9999.999 20 if (TOT("T") <= 0) THEN GOTO 100 30 total_T = TOT("T") 40 total_water = MOL("H2O") 50 ratio = total_T/total_water 100 save ratio -end R(18O) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 total_18O = TOT("[18O]") 40 total_16O = TOT("O") 50 ratio = total_18O/total_16O 100 save ratio -end R(13C) -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 100 30 total_13C = TOT("[13C]") 40 total_12C = TOT("C") 50 ratio = total_13C/total_12C 100 save ratio -end R(14C) -start 10 ratio = -9999.999 20 if (TOT("[14C]") <= 0) THEN GOTO 100 30 total_14C = TOT("[14C]") 40 total_C = TOT("C") + TOT("[13C]") + TOT("[14C]") 50 ratio = total_14C/total_C 100 save ratio -end R(13C)_CO2(g) -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (GAS("CO2(g)") <= 0) THEN GOTO 1000 40 if (GAS("[13C]O2(g)") <= 0) THEN GOTO 1000 50 total_13C = SUM_GAS("[13C]{O,[18O]}2", "[13C]") 60 total_C = SUM_GAS("C{O,[18O]}2", "C") 70 if (total_C <= 0) THEN GOTO 1000 80 ratio = total_13C/total_C 1000 save ratio -end R(18O)_CO2(g) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (GAS("CO2(g)") <= 0) THEN GOTO 1000 40 total_18O = SUM_GAS("{C,[13C],[14C]}{O,[18O]}2", "[18O]") 50 total_O = SUM_GAS("{C,[13C],[14C]}{O,[18O]}2", "O") 60 if (total_O <= 0) THEN GOTO 1000 70 ratio = total_18O/total_O 1000 save ratio -end R(13C)_Calcite -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (S_S("Calcite") <= 0) THEN GOTO 1000 40 total_13C = SUM_S_S("Calcite", "[13C]") 50 total_C = SUM_S_S("Calcite", "C") 60 if (total_C <= 0) THEN GOTO 1000 70 ratio = total_13C/total_C 1000 save ratio -end R(18O)_Calcite -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (S_S("Calcite") <= 0) THEN GOTO 1000 40 total_18O = SUM_S_S("Calcite", "[18O]") 50 total_O = SUM_S_S("Calcite", "O") 60 if (total_O <= 0) THEN GOTO 1000 70 ratio = total_18O/total_O 1000 save ratio -end Alpha_18O_CO2(aq)/CO2(g) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (GAS("CO2(g)") <= 0) THEN GOTO 1000 40 if (GAS("CO[18O](g)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(18O)_CO2(aq)") 60 r2 = CALC_VALUE("R(18O)_CO2(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_13C_CO2(aq)/CO2(g) -start 10 alpha = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (GAS("CO2(g)") <= 0) THEN GOTO 1000 40 if (GAS("[13C]O2(g)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(13C)_CO2(aq)") 60 r2 = CALC_VALUE("R(13C)_CO2(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_CO2(aq)/H2O(l) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(18O)_CO2(aq)") 50 r2 = CALC_VALUE("R(18O)_H2O(l)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_H2O(l)/H2O(g) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("H2O(g)") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(D)_H2O(l)") 50 r2 = CALC_VALUE("R(D)_H2O(g)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_H2O(l)/H2O(g) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (GAS("H2O(g)") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(18O)_H2O(l)") 50 r2 = CALC_VALUE("R(18O)_H2O(g)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_H3O+/H2O(l) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 r1 = CALC_VALUE("R(18O)_H3O+") 40 r2 = CALC_VALUE("R(18O)_H2O(l)") 50 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_H3O+/H2O(l) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 r1 = CALC_VALUE("R(D)_H3O+") 40 r2 = CALC_VALUE("R(D)_H2O(l)") 50 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_OH-/H2O(l) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 r1 = CALC_VALUE("R(18O)_OH-") 40 r2 = CALC_VALUE("R(18O)_H2O(l)") 50 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_OH-/H2O(l) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 r1 = CALC_VALUE("R(D)_OH-") 40 r2 = CALC_VALUE("R(D)_H2O(l)") 50 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_13C_CO3-2/CO2(aq) -start 10 alpha = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(13C)_CO3-2") 50 r2 = CALC_VALUE("R(13C)_CO2(aq)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_CO3-2/CO2(aq) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(18O)_CO3-2") 50 r2 = CALC_VALUE("R(18O)_CO2(aq)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_13C_HCO3-/CO2(aq) -start 10 alpha = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(13C)_HCO3-") 50 r2 = CALC_VALUE("R(13C)_CO2(aq)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_HCO3-/CO2(aq) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(18O)_HCO3-") 50 r2 = CALC_VALUE("R(18O)_CO2(aq)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_HCO3-/H2O(l) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(D)_HCO3-") 50 r2 = CALC_VALUE("R(D)_H2O(l)") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_13C_CO2(aq)/Calcite -start 10 alpha = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (S_S("Calcite") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(13C)_CO2(aq)") 50 r2 = CALC_VALUE("R(13C)_Calcite") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_CO2(aq)/Calcite -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (S_S("Calcite") <= 0) THEN GOTO 1000 40 r1 = CALC_VALUE("R(18O)_CO2(aq)") 50 r2 = CALC_VALUE("R(18O)_Calcite") 60 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end # # Methane # SOLUTION_MASTER_SPECIES C(-4) CH4 0 CH4 [13C](-4) [13C]H4 0 [13C]H4 ISOTOPES C -isotope [13C](-4) permil 0.0111802 # VPDB, Vienna Pee Dee Belemnite ISOTOPE_RATIOS R(13C)_CH4(aq) [13C] R(13C)_CH4(g) [13C] R(D)_CH4(aq) D R(D)_CH4(g) D ISOTOPE_ALPHAS Alpha_13C_CH4(aq)/CH4(g) Log_alpha_13C_CH4(aq)/CH4(g) Alpha_D_CH4(aq)/CH4(g) Log_alpha_D_CH4(aq)/CH4(g) Alpha_13C_CH4(aq)/CO3-2 Log_alpha_13C_CH4(aq)/CO3-2 Alpha_D_CH4(aq)/H3O+ Log_alpha_D_CH4(aq)/H3O+ CALCULATE_VALUES R(13C)_CH4(aq) -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 100 30 total_13C = sum_species("{C,[13C]}{H,D}4","[13C]") 40 total_C = sum_species("{C,[13C]}{H,D}4","C") 50 if (total_C <= 0) THEN GOTO 100 60 ratio = total_13C/total_C 100 save ratio -end R(13C)_CH4(g) -start 10 ratio = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (GAS("CH4(g)") <= 0) THEN GOTO 1000 40 total_13C = SUM_GAS("{C,[13C]}{H,D,T}4", "[13C]") 50 total_C = SUM_GAS("{C,[13C]}{H,D,T}4", "C") 60 if (total_C <= 0) THEN GOTO 1000 70 ratio = total_13C/total_C 1000 save ratio -end R(D)_CH4(aq) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("{C,[13C]}{H,D}4","D") 40 total_H = sum_species("{C,[13C]}{H,D}4","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_CH4(g) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("CH4(g)") <= 0) THEN GOTO 1000 40 total_D = SUM_GAS("{C,[13C]}{H,D,T}4", "D") 50 total_H = SUM_GAS("{C,[13C]}{H,D,T}4", "H") 60 if (total_H <= 0) THEN GOTO 1000 70 ratio = total_D/total_H 1000 save ratio -end Alpha_13C_CH4(aq)/CH4(g) -start 10 alpha = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (GAS("CH4(g)") <= 0) THEN GOTO 1000 40 if (GAS("[13C]H4(g)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(13C)_CH4(aq)") 60 r2 = CALC_VALUE("R(13C)_CH4(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_CH4(aq)/CH4(g) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("CH4(g)") <= 0) THEN GOTO 1000 40 if (GAS("CH3D(g)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(D)_CH4(aq)") 60 r2 = CALC_VALUE("R(D)_CH4(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_13C_CH4(aq)/CO3-2 -start 10 alpha = -9999.999 20 if (TOT("[13C]") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(13C)_CH4(aq)") 60 r2 = CALC_VALUE("R(13C)_CO3-2") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_CH4(aq)/H3O+ -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (TOT("C") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(D)_CH4(aq)") 60 r2 = CALC_VALUE("R(D)_H3O+") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end NAMED_EXPRESSIONS Log_KH_CH4(g) CH4 = CH4 log_k -2.860 delta_h -3.373 kcal Log_K_CH4 CO3-2 + 10 H3O+ + 8 e- = CH4 + 13 H2O log_k 41.071 delta_h -61.039 kcal Log_alpha_13C_CH4(aq)/CH4(g) -ln_alpha1000 0.0 Log_alpha_D_CH4(aq)/CH4(g) -ln_alpha1000 0.0 Log_alpha_13C_CH4(aq)/CO3-2 -ln_alpha1000 0.0 Log_alpha_D_CH4(aq)/H3O+ -ln_alpha1000 0.0 SOLUTION_SPECIES CO3-2 + 10 H3O+ + 8 e- = CH4 + 13 H2O -add_logk Log_K_CH4 CH4 + H2DO+ = CH3D + H3O+ log_k 0.124938736682999329 # log10(4/3) -add_logk Log_alpha_D_CH4(aq)/H3O+ 1.0 # CO3-2 + 9 H3O+ + H2DO+ + 8 e- = CH3D + 13 H2O # log_k 0.124938736682999329 # log10(4/3) # -add_logk Log_K_CH4 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 1.0 CH4 + HD2O+ = CH2D2 + H3O+ log_k 0.301029995663981198 # log10(2) -add_logk Log_alpha_D_CH4(aq)/H3O+ 2.0 # CO3-2 + 9 H3O+ + HD2O+ + 8 e- = CH2D2 + 13 H2O # log_k 0.301029995663981198 # log10(2) # -add_logk Log_K_CH4 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 2.0 CH4 + D3O+ = CHD3 + H3O+ log_k 0.602059991327962396 # log10(4) -add_logk Log_alpha_D_CH4(aq)/H3O+ 3.0 # CO3-2 + 9 H3O+ + D3O+ + 8 e- = CHD3 + 13 H2O # log_k 0.602059991327962396 # log10(4) # -add_logk Log_K_CH4 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 3.0 CH4 + 4H2DO+ = CD4 + 4H3O+ log_k -1.908485018878649742 # -4*log10(3) -add_logk Log_alpha_D_CH4(aq)/H3O+ 4.0 # CO3-2 + 6 H3O+ + 4H2DO+ + 8 e- = CD4 + 13 H2O # log_k -1.908485018878649742 # -4*log10(3) # -add_logk Log_K_CH4 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 4.0 [13C]O3-2 + 10 H3O+ + 8 e- = [13C]H4 + 13 H2O -add_logk Log_K_CH4 -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 CH4 + [13C]O3-2 + H2DO+ = [13C]H3D + CO3-2 + H3O+ log_k 0.124938736682999329 # log10(4/3) -add_logk Log_alpha_D_CH4(aq)/H3O+ 1.0 -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 -mole_balance [13C](-4)H3D # [13C]O3-2 + 9 H3O+ + H2DO+ + 8 e- = [13C]H3D + 13 H2O # log_k 0.124938736682999329 # log10(4/3) # -add_logk Log_K_CH4 # -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 1.0 CH4 + [13C]O3-2 + HD2O+ = [13C]H2D2 + CO3-2 + H3O+ log_k 0.301029995663981198 # log10(2) -add_logk Log_alpha_D_CH4(aq)/H3O+ 2.0 -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 -mole_balance [13C](-4)H2D2 # [13C]O3-2 + 9 H3O+ + HD2O+ + 8 e- = [13C]H2D2 + 13 H2O # log_k 0.301029995663981198 # log10(2) # -add_logk Log_K_CH4 # -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 2.0 CH4 + [13C]O3-2 + D3O+ = [13C]HD3 + CO3-2 + H3O+ log_k 0.602059991327962396 # log10(4) -add_logk Log_alpha_D_CH4(aq)/H3O+ 3.0 -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 -mole_balance [13C](-4)HD3 # [13C]O3-2 + 9 H3O+ + D3O+ + 8 e- = [13C]HD3 + 13 H2O # log_k 0.602059991327962396 # log10(4) # -add_logk Log_K_CH4 # -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 3.0 CH4 + 4H2DO+ + [13C]O3-2 = [13C]D4 + CO3-2 + 4H3O+ log_k -1.908485018878649742 # -4*log10(3) -add_logk Log_alpha_D_CH4(aq)/H3O+ 4.0 -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 # [13C]O3-2 + 6 H3O+ + 4H2DO+ + 8 e- = [13C]D4 + 13 H2O # log_k -1.908485018878649742 # -4*log10(3) # -add_logk Log_K_CH4 # -add_logk Log_alpha_13C_CH4(aq)/CO3-2 1.0 # -add_logk Log_alpha_D_CH4(aq)/H3O+ 4.0 -mole_balance [13C](-4)D4 PHASES CH4(g) CH4 = CH4 -add_logk Log_KH_CH4(g) 1.0 CH3D(g) CH3D = CH3D -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 1.0 CH2D2(g) CH2D2 = CH2D2 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 2.0 CHD3(g) CHD3 = CHD3 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 3.0 CD4(g) CD4 = CD4 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 4.0 [13C]H4(g) [13C]H4 = [13C]H4 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_13C_CH4(aq)/CH4(g) 1.0 [13C]H3D(g) [13C]H3D = [13C]H3D -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_13C_CH4(aq)/CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 1.0 [13C]H2D2(g) [13C]H2D2 = [13C]H2D2 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_13C_CH4(aq)/CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 2.0 [13C]HD3(g) [13C]HD3 = [13C]HD3 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_13C_CH4(aq)/CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 3.0 [13C]D4(g) [13C]D4 = [13C]D4 -add_logk Log_KH_CH4(g) 1.0 -add_logk Log_alpha_13C_CH4(aq)/CH4(g) 1.0 -add_logk Log_alpha_D_CH4(aq)/CH4(g) 4.0 #Hydrogen redox SOLUTION_MASTER_SPECIES D(1) D2O 0 18 18 D(0) HD 0 18 18 ISOTOPE_RATIOS R(D)_H2(aq) D R(D)_H2(g) D ISOTOPE_ALPHAS Alpha_D_H2(aq)/H2(g) Log_alpha_D_H2(aq)/H2(g) Alpha_D_H2(aq)/H3O+ Log_alpha_D_H2(aq)/H3O+ CALCULATE_VALUES R(D)_H2(aq) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("{H,D}2","D") 40 total_H = sum_species("{H,D}2","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_H2(g) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("H2(g)") <= 0) THEN GOTO 1000 40 total_D = SUM_GAS("{H,D,T}2", "D") 50 total_H = SUM_GAS("{H,D,T}2", "H") 60 if (total_H <= 0) THEN GOTO 1000 70 ratio = total_D/total_H 1000 save ratio -end Alpha_D_H2(aq)/H2(g) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("H2(g)") <= 0) THEN GOTO 1000 40 if (GAS("HD(g)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(D)_H2(aq)") 60 r2 = CALC_VALUE("R(D)_H2(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_H2(aq)/H3O+ -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(D)_H2(aq)") 60 r2 = CALC_VALUE("R(D)_H3O+") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end NAMED_EXPRESSIONS Log_KH_H2(g) H2 = H2 log_k -3.150 delta_h -1.759 kcal Log_K_H2 2 H3O+ + 2 e- = H2 + 2H2O log_k -3.15 delta_h -1.759 kcal Log_alpha_D_H2(aq)/H2(g) # -ln_alpha1000 0.0 Log_alpha_D_H2(aq)/H3O+ # -ln_alpha1000 0.0 SOLUTION_SPECIES H3O+ + H2DO+ + 2e- = HD + 2H2O log_k -0.176091259055 1.0 # -log10(1.5) -add_logk Log_K_H2 -add_logk Log_alpha_D_H2(aq)/H3O+ 1.0 -mole_balance H(0)D(0) H2 + HD2O+ = D2 + H3O+ log_k -0.477121254719 1.0 # -log10(3) -add_logk Log_alpha_D_H2(aq)/H3O+ 2.0 -mole_balance D(0)2 # H3O+ + HD2O+ + 2e- = D2 + 2H2O # log_k -0.477121254719 1.0 # -log10(3) # -add_logk Log_K_H2 # -add_logk Log_alpha_D_H2(aq)/H3O+ 2.0 PHASES H2(g) H2 = H2 -add_logk Log_KH_H2(g) HD(g) HD = HD -add_logk Log_KH_H2(g) -add_logk Log_alpha_D_H2(aq)/H2(g) 1.0 D2(g) D2 = D2 -add_logk Log_KH_H2(g) -add_logk Log_alpha_D_H2(aq)/H2(g) 2.0 #Oxygen redox SOLUTION_MASTER_SPECIES [18O](-2) H2[18O] 0 18 18 [18O](0) O[18O] 0 18 18 ISOTOPE_RATIOS R(18O)_O2(aq) [18O] R(18O)_O2(g) [18O] ISOTOPE_ALPHAS Alpha_18O_O2(aq)/O2(g) Log_alpha_18O_O2(aq)/O2(g) Alpha_18O_O2(aq)/H3O+ Log_alpha_18O_O2(aq)/H3O+ CALCULATE_VALUES R(18O)_O2(aq) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 100 30 total_18O = sum_species("{O,[18O]}2","[18O]") 40 total_O = sum_species("{O,[18O]}2","O") 50 if (total_O <= 0) THEN GOTO 100 60 ratio = total_18O/total_O 100 save ratio -end R(18O)_O2(g) -start 10 ratio = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (GAS("O2(g)") <= 0) THEN GOTO 1000 40 total_18O = SUM_GAS("{O,[18O]}2", "[18O]") 50 total_O = SUM_GAS("{O,[18O]}2", "O") 60 if (total_O <= 0) THEN GOTO 1000 70 ratio = total_18O/total_O 1000 save ratio -end Alpha_18O_O2(aq)/O2(g) -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 30 if (GAS("O2(g)") <= 0) THEN GOTO 1000 40 if (GAS("O[18O](g)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(18O)_O2(aq)") 60 r2 = CALC_VALUE("R(18O)_O2(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_18O_O2(aq)/H3O+ -start 10 alpha = -9999.999 20 if (TOT("[18O]") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(18O)_O2(aq)") 60 r2 = CALC_VALUE("R(18O)_H3O+") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end NAMED_EXPRESSIONS Log_KH_O2(g) O2(g) = O2(aq) log_k -2.960 delta_h -1.844 kcal Log_K_O2 6 H2O = O2 + 4 H3O+ + 4 e- log_k -86.08 delta_h 134.79 kcal Log_alpha_18O_O2(aq)/O2(g) -ln_alpha1000 0.0 Log_alpha_18O_O2(aq)/H3O+ -ln_alpha1000 0.0 SOLUTION_SPECIES 6H2O + H3[18O]+ = O[18O] + 5H3O+ + 4e- log_k 0.301029995663 # log10(2) -add_logk Log_K_O2 -add_logk Log_alpha_18O_O2(aq)/H3O+ 1.0 -mole_balance O(0)[18O](0) O2 + 2H3[18O]+ = [18O]2 + 2H3O+ -add_logk Log_alpha_18O_O2(aq)/H3O+ 2.0 -mole_balance [18O](0)2 # 6H2O + 2H3[18O]+ = [18O]2 + 6H3O+ + 4e- # -add_logk Log_K_O2 # -add_logk Log_alpha_18O_O2(aq)/H3O+ 2.0 PHASES O2(g) O2 = O2 -add_logk Log_KH_O2(g) O[18O](g) O[18O] = O[18O] -add_logk Log_KH_O2(g) -add_logk Log_alpha_18O_O2(aq)/O2(g) 1.0 [18O]2(g) [18O]2 = [18O]2 -add_logk Log_KH_O2(g) -add_logk Log_alpha_18O_O2(aq)/O2(g) 2.0 # # Sulfur system # SOLUTION_MASTER_SPECIES [34S] [34S]O4-2 0 [34S]O4 33.967 [34S](6) [34S]O4-2 0 [34S]O4 [34S](-2) H[34S]- 0 H[34S] ISOTOPES S # Coplen and others, 2002 -isotope [34S] permil 0.04416264 # VCDT, Vienna Canyon Diablo Troilite -isotope [34S](6) permil 0.04416264 # VCDT -isotope [34S](-2) permil 0.04416264 # VCDT S(6) -isotope [34S](6) permil 0.04416264 # VCDT S(-2) -isotope [34S](-2) permil 0.04416264 # VCDT ISOTOPE_RATIOS R(34S)_SO4-2 [34S] R(34S)_HSO4- [34S] R(34S)_HS- [34S] R(34S)_H2S(aq) [34S] R(34S)_H2S(g) [34S] R(D)_HSO4- D R(D)_HS- D R(D)_H2S(aq) D R(D)_H2S(g) D R(34S)_Gypsum [34S] R(34S)_Anhydrite [34S] R(D)_Gypsum D ISOTOPE_ALPHAS Alpha_34S_HS-/SO4-2 Log_alpha_34S_HS-/SO4-2 Alpha_34S_H2S(aq)/H2S(g) Log_alpha_34S_H2S(aq)/H2S(g) Alpha_34S_HSO4-/SO4-2 Log_alpha_34S_HSO4-/SO4-2 Alpha_34S_H2S(aq)/HS- Log_alpha_34S_H2S(aq)/HS- # Alpha_34S_S-2/HS- Log_alpha_34S_S-2/HS- Alpha_D_H2S(aq)/H2S(g) Log_alpha_D_H2S(aq)/H2S(g) Alpha_D_H2S(aq)/HS- Log_alpha_D_H2S(aq)/HS- # Alpha_D_H2S(aq)/H3O+ Log_alpha_D_H2S(aq)/H3O+ # Alpha_D_HS-/H3O+ Log_alpha_D_HS-/H3O+ CALCULATE_VALUES R(34S)_SO4-2 -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 100 30 total_34S = sum_species("*[34S]O4*","[34S]") - sum_species("*{H,D,T}[34S]O4*","[34S]") 40 total_S = sum_species("*SO4*","S") - sum_species("*{H,D,T}SO4*","S") 50 if (total_S <= 0) THEN GOTO 100 60 ratio = total_34S/total_S 100 save ratio -end R(34S)_HSO4- -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 100 30 total_34S = sum_species("*{H,D,T}{S,[34S]}O4*","[34S]") 40 total_S = sum_species("*{H,D,T}{S,[34S]}O4*","S") 50 if (total_S <= 0) THEN GOTO 100 60 ratio = total_34S/total_S 100 save ratio -end R(34S)_HS- -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 100 30 total_34S = sum_species("*{H,D,T}[34S]*","[34S]") - sum_species("*{H,D,T}[34S]O4*","[34S]") 40 total_S = sum_species("*{H,D,T}S*","S") - sum_species("*{H,D,T}SO4*","S") 50 if (total_S <= 0) THEN GOTO 100 60 ratio = total_34S/total_S 100 save ratio -end R(34S)_H2S(aq) -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 100 30 total_34S = sum_species("*{H,D,T}2[34S]*","[34S]") - sum_species("*{H,D,T}2[34S]O4*","[34S]") 40 total_S = sum_species("*{H,D,T}2S*","S") - sum_species("*{H,D,T}2SO4*","S") 50 if (total_S <= 0) THEN GOTO 100 60 ratio = total_34S/total_S 100 save ratio -end R(34S)_H2S(g) -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (GAS("H2S(g)") <= 0) THEN GOTO 1000 40 total_34S = SUM_GAS("{H,D,T}2[34S]", "[34S]") 50 total_S = SUM_GAS("{H,D,T}2S", "S") 60 if (total_S <= 0) THEN GOTO 1000 70 ratio = total_34S/total_S 1000 save ratio -end R(D)_HSO4- -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("*{H,D,T}{S,[34S]}O4*","D") 40 total_H = sum_species("*{H,D,T}{S,[34S]}O4*","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_HS- -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("*D{S,[34S]}*","D") - sum_species("*D{S,[34S]}O4*","D") 40 total_H = sum_species("*H{S,[34S]}*","H") - sum_species("*H{S,[34S]}O4*","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_H2S(aq) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("*{H,D,T}2{S,[34S]}*","D") - sum_species("*{H,D,T}2{S,[34S]}O4*","D") 40 total_S = sum_species("*{H,D,T}2{S,[34S]}*","H") - sum_species("*{H,D,T}2{S,[34]}SO4*","S") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_H2S(g) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("H2S(g)") <= 0) THEN GOTO 1000 40 total_D = SUM_GAS("{H,D,T}2{S,[34S]}", "D") 50 total_H = SUM_GAS("{H,D,T}2{S,[34S]}", "H") 60 if (total_H <= 0) THEN GOTO 1000 70 ratio = total_D/total_H 1000 save ratio -end Alpha_34S_HS-/SO4-2 -start 10 alpha = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (TOT("S(6)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(34S)_HS-") 60 r2 = CALC_VALUE("R(34S)_SO4-2") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_34S_H2S(aq)/H2S(g) -start 10 alpha = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (TOT("S(6)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(34S)_H2S(aq)") 60 r2 = CALC_VALUE("R(34S)_H2S(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_34S_HSO4-/SO4-2 -start 10 alpha = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (TOT("S(6)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(34S)_HSO4-") 60 r2 = CALC_VALUE("R(34S)_SO4-2") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_34S_H2S(aq)/HS- -start 10 alpha = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (TOT("S(-2)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(34S)_H2S(aq)") 60 r2 = CALC_VALUE("R(34S)_HS-") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_H2S(aq)/H2S(g) -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (TOT("S(-2)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(D)_H2S(aq)") 60 r2 = CALC_VALUE("R(D)_H2S(g)") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_D_H2S(aq)/HS- -start 10 alpha = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (TOT("S(-2)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(D)_H2S(aq)") 60 r2 = CALC_VALUE("R(D)_HS-") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end R(34S)_Gypsum -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (S_S("Gypsum") <= 0) THEN GOTO 1000 40 total_34S = SUM_S_S("Gypsum", "[34S]") 50 total_S = SUM_S_S("Gypsum", "S") 60 if (total_S <= 0) THEN GOTO 1000 70 ratio = total_34S/total_S 1000 save ratio -end R(34S)_Anhydrite -start 10 ratio = -9999.999 20 if (TOT("[34S]") <= 0) THEN GOTO 1000 30 if (S_S("Anhydrite") <= 0) THEN GOTO 1000 40 total_34S = SUM_S_S("Anhydrite", "[34S]") 50 total_S = SUM_S_S("Anhydrite", "S") 60 if (total_S <= 0) THEN GOTO 1000 70 ratio = total_34S/total_S 1000 save ratio -end R(D)_Gypsum -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (S_S("Gypsum") <= 0) THEN GOTO 1000 40 total_D = SUM_S_S("Gypsum", "D") 50 total_H = SUM_S_S("Gypsum", "H") 60 if (total_H <= 0) THEN GOTO 1000 70 ratio = total_D/total_H 1000 save ratio -end NAMED_EXPRESSIONS Log_KH_H2S(g) H2S = H2S log_k -0.997 delta_h -4.570 kcal Log_K_SO4-2_HSO4- SO4-2 + H3O+ = HSO4- + H2O log_k 1.988 delta_h 3.85 kcal -analytic -56.889 0.006473 2307.9 19.8858 0.0 Log_K_SO4-2_HS- SO4-2 + 9 H3O+ + 8 e- = HS- + 4 H2O log_k 33.65 delta_h -60.140 kcal Log_K_HS-_H2S HS- + H3O+ = H2S log_k 6.994 delta_h -5.300 kcal -analytical -11.17 0.02386 3279.0 Log_K_HS-_S-2 HS- + H2O = S-2 + H3O+ log_k -12.918 delta_h 12.1 kcal Log_alpha_34S_HSO4-/SO4-2 -ln_alpha1000 0.0 Log_alpha_D_HSO4-/H3O+ -ln_alpha1000 0.0 Log_alpha_34S_HS-/SO4-2 -ln_alpha1000 0.0 Log_alpha_D_HS-/H3O+ -ln_alpha1000 0.0 Log_alpha_D_H2S(aq)/HS- -ln_alpha1000 0.0 Log_alpha_34S_H2S(aq)/HS- -ln_alpha1000 0.0 Log_alpha_34S_S-2/HS- -ln_alpha1000 0.0 Log_alpha_34S_H2S(aq)/H2S(g) -ln_alpha1000 0.0 Log_alpha_D_H2S(aq)/H2S(g) -ln_alpha1000 0.0 Log_K_Gypsum log_k -4.580 delta_h -0.109 kcal -analytic 68.2401 0.0 -3221.51 -25.0627 Log_alpha_34S_SO4-2/Gypsum -ln_alpha1000 0.0 Log_K_Anhydrite log_k -4.360 delta_h -1.710 kcal -analytic 197.52 0.0 -8669.8 -69.835 Log_alpha_34S_SO4-2/Anhydrite -ln_alpha1000 0.0 Log_alpha_D_H2O/Gypsum -ln_alpha1000 0.0 SOLUTION_SPECIES SO4-2 + H3O+ = HSO4- + H2O -add_logk Log_K_SO4-2_HSO4- SO4-2 + 9 H3O+ + 8 e- = HS- + 13 H2O -add_logk Log_K_SO4-2_HS- -gamma 3.5000 0.0000 HS- + H3O+ = H2S + H2O -add_logk Log_K_HS-_H2S HS- + H2O = S-2 + H3O+ -add_logk Log_K_HS-_S-2 -gamma 5.0000 0.0000 [34S]O4-2 = [34S]O4-2 -log_k 0.0 -gamma 5.0000 -0.0400 [34S]O4-2 + H3O+ = H[34S]O4- + H2O -add_logk Log_K_SO4-2_HSO4- 1.0 -add_logk Log_alpha_34S_HSO4-/SO4-2 1.0 SO4-2 + H2DO+ = DSO4- + H2O log_k -0.477121254719 # -log10(3) -add_logk Log_K_SO4-2_HSO4- 1.0 -add_logk Log_alpha_D_HSO4-/H3O+ 1.0 [34S]O4-2 + H2DO+ = D[34S]O4- + H2O log_k -0.477121254719 # -log10(3) -add_logk Log_K_SO4-2_HSO4- 1.0 -add_logk Log_alpha_D_HSO4-/H3O+ 1.0 -add_logk Log_alpha_34S_HSO4-/SO4-2 1.0 [34S]O4-2 + 9 H3O+ + 8 e- = H[34S]- + 13 H2O -add_logk Log_K_SO4-2_HS- 1.0 -add_logk Log_alpha_34S_HS-/SO4-2 1.0 -gamma 3.5000 0.0000 HS- + H2DO+ = DS- + H3O+ log_k -0.477121254719 # -log10(3) -add_logk Log_alpha_D_HS-/H3O+ 1.0 -mole_balance DS(-2) -gamma 3.5000 0.0000 H2DO+ + HS- + [34S]O4-2 = D[34S]- + H3O+ + SO4-2 log_k -0.477121254719 # -log10(3) -add_logk Log_alpha_D_HS-/H3O+ 1.0 -add_logk Log_alpha_34S_HS-/SO4-2 1.0 -gamma 3.5000 0.0000 -mole_balance D[34S](-2) DS- + H3O+ = HDS + H2O log_k 0.301029995663 # log10(2) -add_logk Log_K_HS-_H2S 1.0 -add_logk Log_alpha_D_H2S(aq)/HS- 1.0 -mole_balance HDS(-2) DS- + H2DO+ = D2S + H2O log_k -0.477121254719 # -log10(3) -add_logk Log_K_HS-_H2S 1.0 -add_logk Log_alpha_D_H2S(aq)/HS- 2.0 -add_logk Log_alpha_D_HS-/H3O+ 1.0 -mole_balance D2S(-2) H[34S]- + H3O+ = H2[34S] + H2O -add_logk Log_K_HS-_H2S 1.0 -add_logk Log_alpha_34S_H2S(aq)/HS- 1.0 -mole_balance H2[34S](-2) D[34S]- + H3O+ = HD[34S] + H2O log_k 0.301029995663 # log10(2) -add_logk Log_K_HS-_H2S 1.0 -add_logk Log_alpha_34S_H2S(aq)/HS- 1.0 -add_logk Log_alpha_D_H2S(aq)/HS- 1.0 -mole_balance HD[34S](-2) D[34S]- + H2DO+ = D2[34S] + H2O log_k -0.477121254719 # -log10(3) -add_logk Log_K_HS-_H2S 1.0 -add_logk Log_alpha_D_H2S(aq)/HS- 2.0 -add_logk Log_alpha_D_HS-/H3O+ 1.0 -add_logk Log_alpha_34S_H2S(aq)/HS- 1.0 -mole_balance D2[34S](-2) H[34S]- + H2O = [34S]-2 + H3O+ -add_logk Log_K_HS-_S-2 1.0 -add_logk Log_alpha_34S_S-2/HS- 1.0 -gamma 5.0000 0.0000 Ca+2 + [34S]O4-2 = Ca[34S]O4 log_k 2.300 delta_h 1.650 kcal Ca+2 + H[34S]O4- = CaH[34S]O4+ log_k 1.08 Ca+2 + DSO4- = CaDSO4+ log_k 1.08 Mg+2 + [34S]O4-2 = Mg[34S]O4 log_k 2.370 delta_h 4.550 kcal Na+ + [34S]O4-2 = Na[34S]O4- log_k 0.700 delta_h 1.120 kcal K+ + [34S]O4-2 = K[34S]O4- log_k 0.850 delta_h 2.250 kcal -analytical 3.106 0.0 -673.6 PHASES H2[34S](g) H2[34S] = H2[34S] -add_logk Log_KH_H2S(g) 1.0 -add_logk Log_alpha_34S_H2S(aq)/H2S(g) 1.0 HDS(g) HDS = HDS -add_logk Log_KH_H2S(g) 1.0 -add_logk Log_alpha_D_H2S(aq)/H2S(g) 1.0 D2S(g) D2S = D2S -add_logk Log_KH_H2S(g) 1.0 -add_logk Log_alpha_D_H2S(aq)/H2S(g) 2.0 HD[34S](g) HD[34S] = HD[34S] -add_logk Log_KH_H2S(g) 1.0 -add_logk Log_alpha_34S_H2S(aq)/H2S(g) 1.0 -add_logk Log_alpha_D_H2S(aq)/H2S(g) 1.0 D2[34S](g) D2[34S] = D2[34S] -add_logk Log_KH_H2S(g) 1.0 -add_logk Log_alpha_34S_H2S(aq)/H2S(g) 1.0 -add_logk Log_alpha_D_H2S(aq)/H2S(g) 2.0 Gypsum CaSO4:2H2O = Ca+2 + SO4-2 + 2 H2O log_k -4.580 delta_h -0.109 kcal -analytic 68.2401 0.0 -3221.51 -25.0627 Ca[34S]O4:2H2O Ca[34S]O4:2H2O = Ca+2 + [34S]O4-2 + 2 H2O -add_logk Log_K_Gypsum -add_logk Log_alpha_34S_SO4-2/Gypsum Ca[34S]O4 Ca[34S]O4 = Ca+2 + [34S]O4-2 -add_logk Log_K_Anhydrite -add_logk Log_alpha_34S_SO4-2/Anhydrite CaSO4:H2O:HDO CaSO4:H2O:HDO = Ca+2 + SO4-2 + H2O + HDO -add_logk Log_K_Gypsum -add_logk Log_alpha_D_H2O/Gypsum # # Nitrogen system # SOLUTION_MASTER_SPECIES [15N] [15N]O3- 0 [15N]O3 15.00010897312 [15N](5) [15N]O3- 0 [15N] [15N](3) [15N]O2- 0 [15N] [15N](0) [15N]N 0 [15N] [15N](-3) [15N]H4+ 0 [15N] ISOTOPES N # Coplen and others, 2002 -isotope [15N] permil 0.003676867 # Air -isotope [15N](5) permil 0.003676867 # Air -isotope [15N](3) permil 0.003676867 # Air -isotope [15N](0) permil 0.003676867 # Air -isotope [15N](-3) permil 0.003676867 # Air N(5) -isotope [15N](5) permil 0.003676867 # Air N(3) -isotope [15N](3) permil 0.003676867 # Air N(0) -isotope [15N](0) permil 0.003676867 # Air N(-3) -isotope [15N](-3) permil 0.003676867 # Air ISOTOPE_RATIOS R(15N)_NO3- [15N] R(15N)_N2 [15N] R(15N)_NH3 [15N] R(15N)_NH4+ [15N] R(15N)_NH3(g) [15N] R(D)_NH3 D R(D)_NH4+ D R(D)_NH3(g) D ISOTOPE_ALPHAS Alpha_15N_N2/NO3- Log_alpha_15N_N2/NO3- Alpha_15N_NH4+/NO3- Log_alpha_15N_NH4+/NO3- CALCULATE_VALUES R(15N)_NO3- -start 10 ratio = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 100 30 total_15N = TOT("[15N](5)") 40 total_N = TOT("N(5)") 50 if (total_N <= 0) THEN GOTO 100 60 ratio = total_15N/total_N 100 save ratio -end R(15N)_N2 -start 10 ratio = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 100 30 total_15N = TOT("[15N](0)") 40 total_N = TOT("N(0)") 50 if (total_N <= 0) THEN GOTO 100 60 ratio = total_15N/total_N 100 save ratio -end R(15N)_NH3 -start 10 ratio = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 100 30 total_15N = sum_species("{[15N],N}{H,D,T}3","[15N]") 40 total_N = sum_species("{[15N],N}{H,D,T}3","N") 50 if (total_N <= 0) THEN GOTO 100 60 ratio = total_15N/total_N 100 save ratio -end R(15N)_NH4+ -start 10 ratio = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 100 30 total_15N = sum_species("*{[15N],N}{H,D,T}4*","[15N]") 40 total_N = sum_species("*{[15N],N}{H,D,T}4*","N") 50 if (total_N <= 0) THEN GOTO 100 60 ratio = total_15N/total_N 100 save ratio -end R(D)_NH3 -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("{[15N],N}{H,D,T}3","D") 40 total_H = sum_species("{[15N],N}{H,D,T}3","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end R(D)_NH4+ -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 100 30 total_D = sum_species("*{[15N],N}{H,D,T}4*","D") 40 total_H = sum_species("*{[15N],N}{H,D,T}4*","H") 50 if (total_H <= 0) THEN GOTO 100 60 ratio = total_D/total_H 100 save ratio -end Alpha_15N_N2/NO3- -start 10 alpha = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 1000 30 if (TOT("N(5)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(15N)_N2") 60 r2 = CALC_VALUE("R(15N)_NO3-") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end Alpha_15N_NH4+/NO3- -start 10 alpha = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 1000 30 if (TOT("N(5)") <= 0) THEN GOTO 1000 50 r1 = CALC_VALUE("R(15N)_NH4+") 60 r2 = CALC_VALUE("R(15N)_NO3-") 70 if (r2 <= 0) THEN GOTO 1000 80 if (r1 <= -9999) THEN GOTO 1000 90 alpha = r1/r2 1000 save alpha -end R(15N)_NH3(g) -start 10 ratio = -9999.999 20 if (TOT("[15N]") <= 0) THEN GOTO 1000 30 if (GAS("NH3(g)") <= 0) THEN GOTO 1000 40 total_15N = SUM_GAS("[15N]{H,D,T}3", "[15N]") 50 total_N = SUM_GAS("N{H,D,T}3", "N") 60 if (total_N <= 0) THEN GOTO 1000 70 ratio = total_15N/total_N 1000 save ratio -end R(D)_NH3(g) -start 10 ratio = -9999.999 20 if (TOT("D") <= 0) THEN GOTO 1000 30 if (GAS("NH3(g)") <= 0) THEN GOTO 1000 40 total_D = SUM_GAS("{[15N],N}{H,D,T}3", "D") 50 total_H = SUM_GAS("{[15N],N}{H,D,T}3", "H") 60 if (total_H <= 0) THEN GOTO 1000 70 ratio = total_D/total_H 1000 save ratio -end NAMED_EXPRESSIONS Log_K_NO3-_N2 2 NO3- + 12 H+ + 10 e- = N2 + 6 H2O log_k 207.080 delta_h -312.130 kcal Log_K_NH4+_NH3 NH4+ + H2O = NH3 + H3O+ log_k -9.252 delta_h 12.48 kcal -analytic 0.6322 -0.001225 -2835.76 Log_K_NO3-_NH4+ NO3- + 10 H+ + 8 e- = NH4+ + 3 H2O log_k 119.077 delta_h -187.055 kcal Log_K_NO3-_NO2- NO3- + 2 H3O+ + 2 e- = NO2- + 3H2O log_k 28.570 delta_h -43.760 kcal Log_KH_N2(g) N2(g) = N2 log_k -3.260 delta_h -1.358 kcal Log_KH_NH3(g) NH3(g) = NH3 log_k 1.770 delta_h -8.170 kcal Log_alpha_15N_N2/NO3- -ln_alpha1000 0.0 Log_alpha_15N_NH4+/NO3- -ln_alpha1000 0.0 Log_alpha_15N_N2/NO3- -ln_alpha1000 0.0 Log_alpha_D_NH4+/H3O+ -ln_alpha1000 0.0 Log_alpha_15N_NO2-/NO3- -ln_alpha1000 0.0 Log_alpha_15N_NH3/NH4+ -ln_alpha1000 0.0 Log_alpha_D_NH3/NH4+ -ln_alpha1000 0.0 Log_alpha_15N_N2(aq)_N2(g) -ln_alpha1000 0.0 Log_alpha_15N_NH3(aq)_NH3(g) -ln_alpha1000 0.0 Log_alpha_D_NH3(aq)_NH3(g) -ln_alpha1000 0.0 SOLUTION_SPECIES NO3- + 2 H3O+ + 2 e- = NO2- + 3H2O -add_logk Log_K_NO3-_NO2- 1.0 # log_k 28.570 # delta_h -43.760 kcal -gamma 3.0000 0.0000 2 NO3- + 12 H3O+ + 10e- = N2 + 18 H2O -add_log_k Log_K_NO3-_N2 1.0 NH4+ + H2O = NH3 + H3O+ -add_log_k Log_K_NH4+_NH3 1.0 NO3- + 10 H3O+ + 8 e- = NH4+ + 13 H2O -add_log_k Log_K_NO3-_NH4+ 1.0 -gamma 2.5000 0.0000 NH4+ + SO4-2 = NH4SO4- log_k 1.11 [15N]O3- = [15N]O3- -log_k 0.0 -gamma 3.0000 0.0000 NO3- + [15N]O3- + 12H3O+ + 10e- = [15N]N + 18H2O log_k 0.301029995663 # log10(2) -add_logk Log_K_NO3-_N2 1.0 -add_logk Log_alpha_15N_N2/NO3- 1.0 -mole_balance [15N](0)N(0) N2 + 2[15N]O3- = [15N]2 + 2NO3- -add_logk Log_alpha_15N_N2/NO3- 2.0 -mole_balance [15N](0)2 [15N]O3- + 10H3O+ + 8e- = [15N]H4+ + 13H2O -add_logk Log_K_NO3-_NH4+ 1.0 -add_logk Log_alpha_15N_NH4+/NO3- 1.0 -mole_balance [15N](-3)H4 -gamma 2.5000 0.0000 [15N]O3- + 2 H3O+ + 2 e- = [15N]O2- + 3H2O -add_logk Log_K_NO3-_NO2- 1.0 -add_logk Log_alpha_15N_NO2-/NO3- 1.0 delta_h -43.760 kcal -gamma 3.0000 0.0000 2[15N]O3- + N2 = [15N]2 + 2NO3- -add_logk Log_alpha_15N_N2/NO3- 2.0 -mole_balance [15N](0)2 NH4+ + H2DO+ = NH3D+ + H3O+ log_k 0.124938736682999329 # log10(4/3) -add_logk Log_alpha_D_NH4+/H3O+ 1.0 -gamma 2.5000 0.0000 NH4+ + HD2O+ = NH2D2+ + H3O+ log_k 0.301029995663 # log10(2) -add_logk Log_alpha_D_NH4+/H3O+ 2.0 -gamma 2.5000 0.0000 NH4+ + D3O+ = NHD3+ + H3O+ log_k 0.602059991327962396 # log10(4) -add_logk Log_alpha_D_NH4+/H3O+ 3.0 -gamma 2.5000 0.0000 NH4+ + 4H2DO+ = ND4+ + 4H3O+ log_k -1.908485018878649742 # -4*(log10(3)) -add_logk Log_alpha_D_NH4+/H3O+ 4.0 -gamma 2.5000 0.0000 [15N]H4+ + H2O = [15N]H3 + H3O+ -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_15N_NH3/NH4+ 1.0 NH3D+ + H2O = NH2D + H3O+ logk -0.124938736682999329 # log10(3/4) -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_D_NH3/NH4+ 1.0 NH2D2+ + H2O = NHD2 + H3O+ logk -0.301029995663 # log10(1/2) -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_D_NH3/NH4+ 2.0 NHD3+ + H2O = ND3 + H3O+ logk -0.6020599913279623960000 # log10(1/4) -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_D_NH3/NH4+ 3.0 [15N]H4+ + H2DO+ = [15N]H3D+ + H3O+ log_k 0.124938736682999329 # log10(4/3) -add_logk Log_alpha_D_NH4+/H3O+ 1.0 -gamma 2.5000 0.0000 [15N]H4+ + HD2O+ = [15N]H2D2+ + H3O+ log_k 0.301029995663 # log10(2) -add_logk Log_alpha_D_NH4+/H3O+ 2.0 -gamma 2.5000 0.0000 [15N]H4+ + D3O+ = [15N]HD3+ + H3O+ log_k 0.602059991327962396 # log10(4) -add_logk Log_alpha_D_NH4+/H3O+ 3.0 -gamma 2.5000 0.0000 [15N]H4+ + 4H2DO+ = [15N]D4+ + 4H3O+ log_k -1.908485018878649742 # -4*(log10(3)) -add_logk Log_alpha_D_NH4+/H3O+ 4.0 -gamma 2.5000 0.0000 [15N]H3D+ + H2O = [15N]H2D + H3O+ logk -0.124938736682999329 # log10(3/4) -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_15N_NH3/NH4+ 1.0 -add_logk Log_alpha_D_NH3/NH4+ 1.0 [15N]H2D2+ + H2O = [15N]HD2 + H3O+ logk -0.301029995663 # log10(1/2) -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_15N_NH3/NH4+ 1.0 -add_logk Log_alpha_D_NH3/NH4+ 2.0 [15N]HD3+ + H2O = [15N]D3 + H3O+ logk -0.6020599913279623960000 # log10(1/4) -add_logk Log_K_NH4+_NH3 1.0 -add_logk Log_alpha_15N_NH3/NH4+ 1.0 -add_logk Log_alpha_D_NH3/NH4+ 3.0 PHASES N2(g) N2 = N2 -add_logk Log_KH_N2(g) 1.0 [15N]N(g) [15N]N = [15N]N -add_logk Log_KH_N2(g) 1.0 -add_logk Log_alpha_15N_N2(aq)_N2(g) 1.0 [15N]2(g) [15N]2 = [15N]2 -add_logk Log_KH_N2(g) 1.0 -add_logk Log_alpha_15N_N2(aq)_N2(g) 2.0 NH3(g) NH3 = NH3 -add_logk Log_KH_NH3(g) 1.0 [15N]H3(g) [15N]H3 = [15N]H3 -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_15N_NH3(aq)_NH3(g) 1.0 NH2D(g) NH2D = NH2D -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_D_NH3(aq)_NH3(g) 1.0 NHD2(g) NHD2 = NHD2 -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_D_NH3(aq)_NH3(g) 2.0 ND3(g) ND3 = ND3 -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_D_NH3(aq)_NH3(g) 3.0 [15N]H2D(g) [15N]H2D = [15N]H2D -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_D_NH3(aq)_NH3(g) 1.0 -add_logk Log_alpha_15N_NH3(aq)_NH3(g) 1.0 [15N]HD2(g) [15N]HD2 = [15N]HD2 -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_D_NH3(aq)_NH3(g) 2.0 -add_logk Log_alpha_15N_NH3(aq)_NH3(g) 1.0 [15N]D3(g) [15N]D3 = [15N]D3 -add_logk Log_KH_NH3(g) 1.0 -add_logk Log_alpha_D_NH3(aq)_NH3(g) 3.0 -add_logk Log_alpha_15N_NH3(aq)_NH3(g) 1.0 END