diff --git a/phreeqc3-doc/Phreeqc_3_2013_manual_fromPDF.docx b/phreeqc3-doc/Phreeqc_3_2013_manual_fromPDF.docx new file mode 100644 index 00000000..8a2686d4 Binary files /dev/null and b/phreeqc3-doc/Phreeqc_3_2013_manual_fromPDF.docx differ diff --git a/phreeqc3-doc/RELEASE.TXT b/phreeqc3-doc/RELEASE.TXT index 53a367d7..d7870b7e 100644 --- a/phreeqc3-doc/RELEASE.TXT +++ b/phreeqc3-doc/RELEASE.TXT @@ -1,4 +1,169 @@ Version @PHREEQC_VER@: @PHREEQC_DATE@ + ----------------- + May 3, 2024 + ----------------- + PHREEQC: The -dw identifier of SOLUTION_SPECIES now has up to 7 items. + + -dw Dw(25C) dw_T a a2 visc a3 a_v_dif + + where, + Dw(25C)—Tracer diffusion coefficient for the species at 25 °C, m 2 /s. + dw_T—Temperature dependence for diffusion coefficient. + a—Debye-Huckel ion size. + a2—exponent. + Visc—Viscosity exponent. + a3—Ionic strength exponent. + A_v_dif—Exponent for (viscosity_0/viscosity). + + The diffusion coefficient is calculated as follows: + Dw = Dw(25C) * exp(dw_T / T - dw_T / 298.15) + ka = DH_B * a2 * I0.5/ (1 + a3) + av = (viscos_0/viscos)a_v_diff + ff = av * exp(-a * DH_A * z * I0.5 / (1 + ka)) + Dw = Dw * ff + Where T is temperature in Kelvin, DH_B is the Debye-Huckel B parameter, + I is ionic strength, viscos_0 is the viscosity of pure water at T, viscos is + the viscosity of the solution at T, DH_A is the Debye-Huckel A parameter, + and z is the charge on the species,the viscosity of the solution. + See Robinson and Stokes, 2002, Chpt 11 for examples. + The Dw and a_v_dif can be set in a USER_ program with + setdiff_c("name", Dw, a_v_dif), for example: + 10 print setdiff_c("H+", 9.31e-9, 1). + The diffusion coefficient of H+ is handled differently with + Falkenhagen equations. + + ----------------- + May 3, 2024 + ----------------- + PHREEQC: The ionic strength correction is for electromigration calculations + (Appelo, 2017, CCR 101, 102). The correction is applied when the 6th parameter + option is set to true for -multi_D in TRANSPORT: + + -multi_d true/false 1e-9 0.3 0.05 1.0 true/false # multicomponent diffusion + + true/false, multicomponent diffusion is used, + default tracer diffusion coefficient (used in case -dw is not defined for a species), + porosity (por = 0.3), + limiting porosity (0.05) below which diffusion stops, + exponent n (1.0) used in calculating the effect of tortuosity on the + porewater diffusion coefficient Dp = Dw * por^n, + true/false: correct Dw for ionic strength (false by default). + + ----------------- + May 3, 2024 + ----------------- + Database: Added new database phreeqc_rates.dat. The database augments + phreeqc.dat with rate parameters from Palandri and Kharaka (2004), + Sverdrup, Oelkers, Lampa, Belyazid, Kurz, and Akselsson (2019) (only + Albite and quartz), and Hermanska, Voigt, Marieni, Declercq, + and Oelkers (2023). Parameters are defined in data blocks + RATE_PARAMETERS_PK, RATE_PARAMETERS_SVD, and RATE_PARAMETERS_HERMANSKA. + All minerals with rate parameters have been added in a PHASES + data block. Example RATES definitions using the different RATE_PARAMETERS_ + parameters are provided for Albite and Quartz. + + ----------------- + April 27, 2024 + ----------------- + Databases: Added new keyword data block MEAN_GAMMAS. Each line + of the data block defines how to calculate the mean activity + coefficient for a salt with a series of pairs of + aqueous species and stoichiometric coefficient. Phreeqc.dat, + Amm.dat, pitzer.dat, and phreeqc_rates.dat have this data block. + + MEAN_GAMMAS + MgCl2 Mg+2 1 Cl 2 + + A new Basic function MEANG will calculate mean activity coefficients + for salts listed in the MEAN_GAMMAS data block. + + 10 g_MgCl2 = MEANG("MgCl2") + + + ----------------- + April 27, 2024 + ----------------- + PHREEQC: Added new keyword data blocks RATE_PARAMETERS_PK, RATE_PARAMETERS_SVD, + and RATE_PARAMETERS_HERMANSKA and Basic functions RATE_PK, RATE_SVD, and + RATE_HERMANSKA + + RATE_PARAMETERS_PK +# Acid Neutral Base +# log K E n(H+) log K E log K E n(OH-) +# ======== ======== ======== ======== ======== ======== ======== ======== +Quartz -30 0 0 -13.4 90.9 -30 0 0 # Table 4 +# Acid Neutral P_CO2 +# log K E n(H+) log K E log K E n(P_CO2) Table +# ======== ======== ======== ======== ======== ======== ======== ======== ======== +calcite -0.3 14.4 1 -5.81 23.5 -3.48 35.4 1 33 # specify Table number for P_CO2^n(P_CO2) +# Acid and Fe+3 Neutral and O2 Base +# log K E n(H+) n(Fe+3) log K E n(O2) log K E n(OH-) Table +# ======== ======== ======== ======== ======== ======== ======== ======== ======== ======== ======== +pyrite -7.52 56.9 -0.5 0.5 -4.55 56.9 0.5 -30 0 0 35 # specify Table number for Fe+3 and O2 + + Three rate equations from Palandri and Kharaka (2004) can be entered. Most minerals use + use the first form above with 8 parameters. Table 33 has a term for CO2 as in + the calcite example above; parameters from table 33 are identified with a 33 in the 9th + field following 8 parameters. Table 35 has additional terms and data from this table + is identified with 35 in field 11 following 10 rate parameters. The rates for the + the minerals listed in the data block can be calculated with the Basic function RATE_PK. + The calculated rate does not include factors for surface area or affinity. + + 10 rate = RATE_PK("Calcite") + + RATE_PARAMETERS_SVD +# Table 4: E's Table 3: H+-reaction H2O-reaction CO2-reaction Organic_acids OH--reaction Table 5 +# H+ H2O CO2 Org_acids OH- pkH nH yAl CAl xBC CBC pkH2O yAl CAl xBC CBC zSi CSi pkCO2 nCO2 pkOrg nOrg COrg pkOH- wOH- yAl CAl xBC CBC zSi CSi # Num Mineral Formula +# ====== ====== ====== ========= ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ===== ====== ====== ====== ====== ====== ====== ====== ====== ====== ====== ======= ====== +Albite 3350 2500 1680 1200 3100 14.6 0.5 0.4 0.4 0.4 0.5 16.8 0.15 4 0.15 200 3 900 16.05 0.6 14.7 0.5 5 15.4 0.3 0.1 12 0.5 5 3 900 # 1.6 Albite NaAlSi3O8 + + Rate parameters from Sverdrup, Oelkers, Lampa, Belyazid, Kurz, and Akselsson (2019) + can be specified with the RATE_PARAMETERS_SVD data block. A total of 31 parameters + are entered for each mineral. The rates for minerals minerals listed in the data + block can be calculated with the Basic function RATE_SVD. The calculated rate does + not include factors for surface area or affinity. + + 10 rate = RATE_SVD("Albite") + +RATE_PARAMETERS_HERMANSKA +# Acid mechanism Neutral mechanism Basic mechanism +# logk25 Aa Eaa n(H+) logk25 Ab Eab logk25 Ac Eac n(OH) # Formula +# ======== ========= ======== ======== ======== ========= ======== ======== ========= ======== ======== ========================================= +# Amphiboles +Anthophyllite -12.4 5.70E-04 52 0.4 -13.7 5.00E-06 48 0 0 0 0 + + Rate parameters from Hermanska, Voigt, Marieni, Declercq, and Oelkers (2023) can + be specified with the RATE_PARAMETERS_HERMANSKA data block. A total of 11 parameters + are entered for each mineral. The rates for minerals listed in the data block can + be calculated with the Basic function RATE_HERMANSKA. The calculated rate does not + include factors for surface area or affinity. + + 10 rate = RATE_HERMANSKA("Anthophyllite") + + + ----------------- + April 21, 2024 + ----------------- + PHREEQC: Added Basic functions GET$ and PUT$. They are are the same as + GET and PUT, except the first argument is a character string. You may + one or more indices as needed to identify the value that is put or + gotten. + + PUT$("MgCl2", 1, 1, 1) + x$ = GET$(1, 1, 1) + + ----------------- + April 19, 2024 + ----------------- + DATABASE: Kinec.v2.dat is a new llnl.dat style database from the + CarbFix2 and GECO projects that is included in new distributions of + PHREEQC. This database contains the parameters for calculating mineral + dissolution rates for primary and secondary silicate minerals using the + equations and parameters reported by Hermanska et al. (2022, 2023) + and dissolution rates for other non-silicate mineral systems using the + equations and parameters reported by Oelkers and Addassi (2024, in + preparation). + ----------------- April 15, 2024 ----------------- @@ -15,15 +180,6 @@ Version @PHREEQC_VER@: @PHREEQC_DATE@ ----------------- March 25, 2024 ----------------- - DATABASES phreeqc.dat and Amm.dat: Three CALCULATE_VALUES definitions for - calculating the kinetic dissolution of silicate minerals have been defined - that can be invoked by copying a line of numbers from tables in Palandri - and Kharaka (2004), Sverdrup et al. (2019), or Hermanská et al. (2022, - 2023). The CALCULATE_VALUES definitions are included in the databases and - can be used in RATES definitions. Rate definitions Albite_PK, Albite_Svd, - and Albite_Hermanska in the databases use the CALCULATE_VALUES definitions. - More details are available at https://hydrochemistry.eu/ph3/release.html. - DATABASES phreeqc.dat, Amm.dat, and pitzer.dat: The calculation of the specific conductance can now be done with a Debye-Hückel-Onsager equation that has both the electrophoretic and the relaxation term. (The standard @@ -1553,7 +1709,7 @@ Version 3.6.1: January 7, 2020 Eliminated prints of Total Carbon and Total CO2 in "Description of solution" when values are zero. - Pring and punch of cells in transport calculations with + Print and punch of cells in transport calculations with stagnant zones follows the order of the cell numbers. Enabled multicomponent diffusion among boundary and stagnant