# Thermodynamic data in CHNOSZ

This vignette, produced on 2019-08-02, documents the sources of thermodynamic data in CHNOSZ version 1.3.3. All of these data, except for Optional Data, are used in the default database, which is loaded when the package is attached, or by running `reset()`.

The sections below correspond to CSV data files that are stored in the `extdata/OBIGT` package directory and read by `reset()` to create the database in the R session (`thermo()$obigt`). In each section, the primary references (`ref1` in `thermo()$obigt`) are listed in chronological order. Any secondary references (`ref2`) are listed with bullet points. Each reference is followed by the number of species, and a note (from `thermo()$refs`). Symbols show whether the data were present in the earliest of the sprons92.dat (ø), slop98.dat (*), slop07.dat (†), or slop16.dat (‡) datafiles for the SUPCRT92 package.

Any additional comments are placed at the beginning of the sections. Abbreviations used below are: Cp (heat capacity), GHS (standard Gibbs energy, enthalpy, entropy), HKF (Helgeson-Kirkham-Flowers equations), V (volume), T (temperature), P (pressure).

# Recent changes (2018 - 2019)

- Data from SUPCRT92 which have been superseded by the Berman data are listed under Optional Data / SUPCRT92.

- Superseded data from SLOP98 (including Al, As, and Au species) are listed under Optional Data / SLOP98.

# Sources of data

Use the tabs below to select a section for viewing. Select “All at once” to show all sections.

## Aqueous species

### `H2O` (3)

This file contains H2O, e-, and H+. The properties of H2O are listed as NA; CHNOSZ calculates its properties using a Fortran subroutine taken from SUPRCT92 (Johnson et al., 1992) (default) or using the IAPWS-95 equations (Wagner and Pruß, 2002) or the Deep Earth Water (DEW) model (Sverjensky et al., 2014).

By convention, the standard Gibbs energy of formation, entropy, and heat capacity of the aqueous proton (H+) are 0 at all T and P (e.g. Cox et al., 1989). The formation reaction of the proton can be expressed as ½H2,(g) + Z = H+, where Z is the “element” of positive charge. Because the conventional standard Gibbs energy of this reaction is 0 at all T, the standard entropy of the reaction is also constrained to be zero (cf. Puigdomenech et al., 1997). Therefore, the “element” of positive charge (Z) has zero thermodynamic properties except for an entropy, S°Tr, that is negative one-half that of H2,(g). The standard entropy of the aqueous electron, which is a solely a pseudospecies defined by e- = -Z, is opposite that of Z.**

Despite these considerations, the final column of the thermodynamic database (`thermo()$obigt`) lists a charge of “0” for both the aqueous proton and electron. Data in this this column are used in CHNOSZ only to specify the charge that is input to the “g-function” (Tanger and Helgeson, 1988; Shock and Helgeson, 1988). Setting it to zero prevents activation of the g-function, which would result in non-zero contributions to thermodynamic properties, conflicting with the conventions mentioned above. All other calculations in CHNOSZ obtain the elemental makeup, including the correct charge for the species, by parsing the chemical formulas stored in the database.^^

**Likewise, GEM-Selektor defines “independent components” to be stoichiometric units usually consisting of elements and charge; the latter, which is named Zz and has a standard molal entropy of -65.34 J/mol/K and heat capacity of -14.418 J/mol/K (negative one-half those of gaseous hydrogen), is negated in the formula of the fictive “aqueous electron” (Kulik, 2006).

^^ Relatedly, charged amino acid sidechain groups have a charge that is tabulated as zero, because other values would be incompatible with group additivity of cations and anions (which have derivatives of the omega parameter (ω) in the revised HKF equations of state that are not opposites of each other) to give a neutral species (for which the derivatives of ω are taken to be zero) (cf. Dick et al., 2006).

### `Inorganic` (837)

Shock and Helgeson (1988) – 57 ionic species (ø)

Shock et al. (1989) – 13 inorganic neutral species (ø)

Shock et al. (1989) – 1 aqueous SiO2 (ø)

Haas et al. (1995) – 249 complexes of rare earth elements (*)

- slop98.dat – 88 “Corrected values based on data from Haas et al. (1995)” (*)

McCollom and Shock (1997) – 2 MgSO4, NaSO4-, and HCl (*)

- slop98.dat – 2 “Data and parameters as used by McCollom and Shock (1997).” (*)

Shock et al. (1997) – 233 aqueous ions and hydroxide complexes (*)

- Shock and Helgeson (1988) – 25 values of GHS

- Sassani and Shock (1998) – 1 Rh+3 (*)

Sverjensky et al. (1997) – 93 metal complexes (*)

- CHNOSZ – 1 AuCl4- renamed to AuCl4-3

Shock et al. (1997b) – 15 uranium species (*)

Tagirov et al. (1997) – 1 aqueous HCl

Sassani and Shock (1998) – 41 platinum-group ions and complexes (*)

Akinfiev and Zotov (2001) – 15 M+, MCl2-, M(OH)2-, MCl, and MOH (M = Au+, Ag+, or Cu+)

Schulte et al. (2001) – 10 AsH3, CF4, CH3F, Cl2, ClO2, N2O, NF3, NO, PH3, and SF6

Tagirov and Schott (2001) – 17 aqueous Al+3 and complexes

- Diakonov et al. (1996) – 1 NaAl(OH)4

Nordstrom and Archer (2003) – 10 aqueous As oxides and sulfides

Akinfiev et al. (2006) – 1 AgCl3-2

Accornero et al. (2010) – 43 metal-chromate complexes

Akinfiev and Zotov (2010) – 6 MHS and M(HS)2- (M = Au+, Ag+, or Cu+)

- Pokrovski et al. (2014) – 1 corrected H of AuHS

Tagirov et al. (2013) – 11 Pd+2 and complexes

Akinfiev and Tagirov (2014) – 13 Zn+2 and complexes

Pokrovski and Dubessy (2015) – 1 trisulfur radical ion

Tagirov et al. (2015) – 5 Pt+2 and complexes

### `Organic` (681)

Shock and Helgeson (1990) – 47 organic species (ø)

- slop16.dat – 3 hexanol, heptanol, and octanol: “Minor differences in Gibbs energy, entropy, ω, a1, a2, a3, a4 and c1 values compared to Shock and Helgeson (1990).” (‡)

Shock (1993) – 2 ethylacetate and acetamide (*)

Shock and Koretsky (1993) – 104 metal-acetate complexes (*)

- slop16.dat – 32 “Enthalpy changed to be compatible with the equation ΔH=ΔG+TΔS for the formation reaction from elements.” (‡)

Shock and McKinnon (1993) – 3 CO, HCN, urea (*)

Schulte and Shock (1993) – 10 aldehydes (*)

- slop16.dat – 1 formaldehyde: “Entropy corrected to be compatible with the equation ΔH=ΔG+TΔS for the formation reaction from elements. See footnote i in table 2 of Schulte and Shock (1993).” (‡)

Shock and Koretsky (1995) – 226 metal-organic acid complexes (*)

- slop98.dat – 6 “These data were used in Shock and Koretsky (1995), but were not tabulated in the paper.” (*)

- slop16.dat – 55 “Enthalpy corrected to be compatible with the equation ΔG=ΔH-TΔS for the formation reaction from elements.” (‡)

Shock (1995) – 77 carboxylic acids (*)

- slop16.dat – 2 adipic acid and n-dodecanoate: “Gibbs free energy corrected to be compatible with the equation ΔG=ΔH-TΔS for the formation reaction from elements. See footnote y in table 4 of Shock (1995).” (‡)

- slop16.dat – 1 n-octanoate: “Enthalpy corrected to be compatible with the equation ΔG=ΔH-TΔS for the formation reaction from elements. See footnote ab in table 4 of Shock (1995).” (‡)

Dale et al. (1997) – 10 alkylphenols (*)

Shvedov and Tremaine (1997) – 1 dimethylammonium chloride HKF parameters

Haas and Shock (1999) – 6 chloroethylene species (†)

Prapaipong et al. (1999) – 151 metal-dicarboxylate complexes (†)

- CHNOSZ – 2 charge of NpO2(Oxal), La(Succ)+, NH4(Succ)-, and NpO2(Succ) as listed by Prapaipong et al. (1999)

Plyasunov and Shock (2001) – 11 aqueous nonelectrolytes (†)

Schulte and Rogers (2004) – 12 alkane thiols (†)

Hawrylak et al. (2006) – 2 methyldiethanolamine and methyldiethanolammonium chloride HKF parameters

Schulte (2010) – 7 organic sulfides

Dick et al. (2013) – 6 phenanthrene and methylphenanthrene isomers

LaRowe and Amend (2019) – 6 dimethylamine, trimethylamine, resorcinol, phloroglucinol, cyclohexane carboxylate, and cyclohexane carboxylic acid

- Shvedov and Tremaine (1997) – 1 dimethylamine HKF parameters

### `Biotic` (329)

Amend and Helgeson (1997) – 27 amino acids GHS (†)

- Dick et al. (2006) – 27 amino acids HKF parameters (†)

Amend and Plyasunov (2001) – 10 carbohydrates (†)

- slop07.dat – 10 high-temperature HKF parameters from Amend and Plyasunov (2001) (†)

LaRowe and Harold C. Helgeson (2006a) – 138 nucleic-acid bases, nucleosides, and nucleotides (†)

- Lowe et al. (2017) – 1 adenine HKF parameters

LaRowe and Harold C. Helgeson (2006a) – 4 citric acid and citrate

- Canovas and Shock (2016) – 4 citric acid species HKF a1–a4 parameters

LaRowe and Harold C. Helgeson (2006b) – 32 Mg-complexed adenosine nucleotides (ATP), NAD, and NADP (†)

Dick et al. (2006) – 38 amino acid, protein, and organic groups

- LaRowe and Dick (2012) – 1 methionine sidechain GHS

- CHNOSZ – 1 Incorrect values of HKF a1–a4 parameters for [-CH2NH2] were printed in Table 6 of Dick et al. (2006); corrected values are used here.

Dick et al. (2006) – 19 Gly-X-Gly tripeptides Cp, V, and HKF c1, c2, ω parameters

Dick (2007) – 4 glutathione, cystine, and cystine sidechain

LaRowe and Dick (2012) – 1 methionine GHS

- Dick et al. (2006) – 1 methionine HKF parameters (†)

Kitadai (2014) – 12 glycine, diglycine, and triglycine (zwitterions and ions); diketopiperazine, [Gly] and [UPBB] groups

- Shock (1992) – 1 diketopiperazine GHS

- Goldberg et al. (2002) – 6 glycine, diglycine, and triglycine (+1 and -1 ions) GHS

- Dick et al. (2006) – 3 glycine, [Gly], and [UPBB] HKF parameters

- Dick et al. (2006) – 1 triglycine Cp, V, and HKF c1, c2, ω parameters

Canovas and Shock (2016) – 22 citric acid cycle metabolites

Azadi et al. (2019) – 22 metal-glycinate complexes

- CHNOSZ – 20 recalculated values of Cp (those in Azadi et al. (2019) appear to be calculated using wrong sign on ω) and enthalpy (using ΔG=ΔH-TΔS and the entropies of the elements)

- CHNOSZ – 2 Tl(Gly) and Tl(Gly)2-: change Ti to Tl

## Solids

### `Inorganic` (134)

Chamosite,7A and witherite were present in sprons92.dat but not in slop98.dat or later files, and are not included in CHNOSZ.

The source of parameters used here for goethite is different from that in the slop files (Shock, 2009).

Helgeson et al. (1978) – 56 data for minerals and phase transitions (ø)

- Pankratz and King (1970) – 2 bornite and chalcopyrite (ø)

- Wagman et al. (1982) – 1 manganosite (ø)

- Helgeson (1985) – 1 ferrosilite and siderite (ø)

- CHNOSZ – 15 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Robie et al. (1978) – 1 chlorargyrite (ø)

- Pankratz (1970) – 1 chlorargyrite (ø)

Robie et al. (1978) – 4 iron (ø)

- Kelley (1960) – 1 iron Cp (ø)

- CHNOSZ – 3 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Robie et al. (1978) – 1 gibbsite GHS

- Zimmer et al. (2016) – 1 Cp parameters listed in spronsbl.dat

Wagman et al. (1982) – 1 MgSO4

Jackson and Helgeson (1985) – 5 Sn minerals (ø)

- CHNOSZ – 1 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Reardon and Armstrong (1987) – 1 celestite GHS

- Helgeson et al. (1978) – 1 celestite V and Cp parameters (ø)

Ball and Nordstrom (1991) – 1 arsenopyrite: G

- Zimmer et al. (2016) – 1 data listed in spronsbl.dat

Hemingway et al. (1991) – 1 boehmite

- Zimmer et al. (2016) – 1 Cp parameters listed in spronsbl.dat

Parker and Khodakovskii (1995) – 1 melanterite

Robie and Hemingway (1995) – 1 gypsum GHS

- Kelley (1960) – 1 gypsum Cp

McCollom and Shock (1997) – 3 sulfur (*)

- slop98.dat – 3 “Data and parameters as used by McCollom and Shock (1997).” (*)

Shock et al. (1997) – 2 zincite and litharge (*)

- Helgeson et al. (1978) – 1 litharge S, V, and Cp parameters (ø)

- slop98.dat – 1 zincite and litharge; “These data were used in Shock et al. (1997), but were not tabulated in the paper.” (*)

Shock et al. (1997b) – 1 uraninite (*)

Sassani and Shock (1998) – 15 platinum-group solids (*)

Stoffregen et al. (2000) – 3 jarosite, natroalunite, and natrojarosite

Wood and Samson (2000) – 2 scheelite and ferberite; adopted values include Cp parameters for scheelite from Barin and Knacke (1973) and GHS and Cp parameters for ferberite from Polya (1990)

- Robie et al. (1978) – 1 scheelite GHS and V

- Robie et al. (1978) – 1 ferberite V

Amend and Shock (2001) – 3 selenium and molybdenite (†)

Mercury et al. (2001) – 8 polymorphs of ice

Juraj Majzlan, Grevel, et al. (2003) – 3 goethite, lepidocrocite, and maghemite GHS

- Juraj Majzlan, Lang, et al. (2003) – 3 goethite, lepidocrocite, and maghemite Cp

Nordstrom and Archer (2003) – 8 As oxide and sulfide minerals

- Zimmer et al. (2016) – 1 As(α): V listed in spronsbl.dat

Majzlan et al. (2004) – 1 hydronium jarosite

Zhu et al. (2005) – 2 barium arsenate and barium hydrogen arsenate: G

- Zimmer et al. (2016) – 2 data listed in spronsbl.dat

Langmuir et al. (2006) – 2 scorodite and amorphous ferric arsenate: G

- Zimmer et al. (2016) – 2 data listed in spronsbl.dat

Majzlan et al. (2006) – 3 coquimbite, ferricopiapite, and rhomboclase

Grevel and Majzlan (2009) – 4 kieserite, starkeyite, hexahydrite, and epsomite

Zimmer et al. (2016) – 1 dawsonite GHS

- Robie and Hemingway (1995) – 1 dawsonite: Cp coefficients corrected in Tutolo et al. (2014); Cp value at 25 °C from Bénézeth et al. (2007), citing Ferrante et al. (1976)

### `Organic` (479)

Tardy et al. (1997) – 5 humic acid, microflora, and plants

Helgeson et al. (1998) – 59 organic molecules and groups

Helgeson et al. (1998) – 20 amino acids

- LaRowe and Dick (2012) – 4 updated and corrected parameters for cysteine, glycine, leucine, and methionine

Richard and Helgeson (1998) – 311 organic molecules and groups

Richard (2001) – 8 organic sulfur compounds

LaRowe and Harold C. Helgeson (2006a) – 19 nucleic-acid bases, nucleosides, and nucleotides

LaRowe and Harold C. Helgeson (2006b) – 9 Mg-complexed adenosine nucleotides (ATP), NAD, and NADP

Helgeson et al. (2009) – 5 kerogens

Richard and Gaona (2011) – 13 organic iodine compounds

LaRowe and Dick (2012) – 30 4-hydroxyproline, 5-hydroxylysine, 4 dipeptides, and sidechain and backbone groups in proteins

### `Berman` (92)

This file gives the identifiying information for minerals whose properties are calculated using the formulation of Berman (1988). Note that thermodynamic properties for these minerals are listed as NA in `thermo()$obigt`; the actual data are stored separately, as CSV files in `extdata/Berman/*.csv`.

Berman (1988) – 65 minerals

- Berman (1990) – 2 almandine and ilmenite: modified H and/or S

- Sverjensky et al. (1991) – 9 G and H revisions for K- and Al-bearing silicates

- Sverjensky et al. (1991) – 1 phlogopite: H and S modified by Berman (1990), followed by G and H revision for K-bearing silicates (after Sverjensky et al., 1991)

- berman.dat (2017) – 1 antigorite: “Oct. 21, 2016: Revised volume coefficients consistent with Hilairet et al. (2006) and Yang et al. (2014)”

Berman (1990) – 1 annite

- Sverjensky et al. (1991) – 1 annite: G and H revision for K-bearing silicates (after Sverjensky et al., 1991)

Evans (1990) – 2 glaucophane and pumpellyite

- JUN92.bs (1992) – 2 data as listed in `JUN92.bs` data file

Vidal et al. (1992) – 1 sudoite

Zhu and Sverjensky (1992) – 10 F,Cl,OH biotite and apatite endmembers. GHS and V were taken from Table 6 of Zhu and Sverjensky (1992); heat capacity and volume parameters from `berman.dat`.

Vidal et al. (2001) – 2 daphnite and Mg-amesite

Gottschalk (2004) – 4 zoisite, clinozoisite, and epidote

Vidal et al. (2005) – 1 Fe-amesite

Delgado Martín and Soler i Gil (2010) – 5 hedenbergite, andradite, ferro-actinolite, grunerite, and ilvaite

Facq et al. (2014) – 1 aragonite; source of data: `berman.dat`

## Liquids

### `Organic` (532)

Helgeson et al. (1998) – 186 organic molecules and groups

Richard and Helgeson (1998) – 231 organic molecules and groups

Richard (2001) – 67 organic sulfur compounds

LaRowe and Harold C. Helgeson (2006b) – 2 pyridine and piperidine

Richard (2008) – 17 alkenes

Richard and Gaona (2011) – 29 organic iodine compounds

## Gases

### `Inorganic` (19)

Wagman et al. (1982) – 2 gases GHS (†)

- Amend and Shock (2001) – 2 NO and N2O (†)

Wagman et al. (1982) – 15 gases GHS (ø)

- Kelley (1960) – 15 gases Cp (ø)

Robie and Hemingway (1995) – 2 hydrogen fluoride and hydrogen chloride

### `Organic` (266)

Shock (1993) – 2 carbon monoxide and ethylene (*)

Dale et al. (1997) – 4 phenol, and cresol isomers (*)

Dale et al. (1997) – 6 dimethylphenol isomers

Helgeson et al. (1998) – 153 organic molecules and groups

Richard (2001) – 62 organic sulfur compounds

Richard and Gaona (2011) – 39 organic iodine compounds

## Optional Data

### `DEW` (199)

The Deep Earth Water (DEW) model extends the applicability of the revised HKF equations of state to 60 kbar. Accuracy of the thermodynamic calculations at these conditions is improved by revised correlations for the a1 HKF parameter, as described by Sverjensky et al., 2014. The data here were taken from the May 2017 version of the DEW spreadsheet (Dew Model, 2017). The following species are present in the spreadsheet, but are not used here because the parameters are unchanged from the default database in CHNOSZ: B(OH)3, Br-, Ca+2, Cl-, Cs+, F-, H+, H2, He, I-, K+, Kr, Li+, Mg+2, Na+, Ne, O2, Rb+, Rn.

Besides using `add.obigt('DEW')` to load these data, you should also run `water('DEW')` to activate the DEW equations in CHNOSZ. See `demo(DEW)` for some examples.

Shock and Helgeson (1988) – 2 ionic species

- Sverjensky et al. (2014) – 2 revisions for BO(OH) and BO2-

Shock and Helgeson (1990) – 3 formic acid, formate, and propanoate

- DEW model (2017) – 1 revised with new predicted a1 for ions

- DEW model (2017) – 1 revised with new predicted a1 for complex species

- DEW model (2017) – 1 propanoate: Revised a1 from new delVn correlation for -1 ions

Pokrovskii and Helgeson (1995) – 2 aluminum species

- Sverjensky et al. (2014) – 2 revisions for AlO2- and HAlO2

Ho and Palmer (1997) – 1 KOH

- Sverjensky et al. (2014) – 1 Fitted to Ho and Palmer (1997) data with a1 pred. from the sum of the ions and used to predict the volume

Plyasunov and Shock (2001) – 2 acetic acid, propanoic acid, and methane

- DEW model (2017) – 1 methane: revised with new predicted a1 for complex species

Facq et al. (2014) – 3 CO2, CO3-2, and HCO3-

Sverjensky et al. (2014) – 2 SiO2 and Si2O4

DEW model (2017) – 184 other data from Aqueous Species Table in spreadsheet (see detailed references there)

- DEW model (2017) – 1 acetate: revised January 26th, 2016; new a1 value from complexes and organics correlation.

- DEW model (2017) – 1 MgCl+: revised volume increased in order that a1 of the complex is the sum of the a1 values of the ions

- DEW model (2017) – 1 NaCl: revised with new predicted a1 for complex species

### `SUPCRT92` (180)

These minerals and aqueous species, taken from the SUPCRT92 database, were present in earlier versions of CHNOSZ but have since been superseded by Berman (1988) (minerals) and Nordstrom and Archer (2003) (H2AsO3-). The thermodynamic properties and parameters are kept here as optional data for reproducing published calculations and making comparisons with newer data. The minerals here include all of the silicates and Al-bearing minerals from Helgeson et al. (1978), as well as calcite, dolomite, hematite, and magnetite. Use `add.obigt("SUPCRT92")` to load the data. NOTE: Other minerals from SUPCRT92, including native elements, sulfides, halides, sulfates, and selected carbonates and oxides that do not duplicate those in the Berman dataset, are still present in the default database (inorganic_cr.csv).

Helgeson et al. (1978) – 178 data for minerals and phase transitions (ø)

- Kelley (1960) – 1 larnite Cp (ø)

- Robie et al. (1978) – 4 dickite, fluorphlogopite, halloysite, and pyrope (ø)

- Plummer and Busenberg (1982) – 2 aragonite and calcite (ø)

- Helgeson (1985) – 1 ferrosilite and siderite (ø)

- sprons92.dat – 24 Ca-bearing minerals; “Gibbs free energies and enthalpies were corrected to be consistent with updated values of Gibbs free energies of Ca2+ and CO32- (Shock and Helgeson, 1988) together with the solubilities of calcite and aragonite reported by Plummer and Busenberg (1982)” (ø)

- slop98.dat – 1 daphnite; “Gf and Hf from Saccocia and Seyfried (1993) TMM” (*)

- CHNOSZ – 53 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Robie et al. (1978) – 2 rutile and titanite (ø)

- Bowers and Helgeson (1983) – 1 rutile (ø)

- sprons92.dat – 1 titanite: Bowers and Helgeson (1983) + “Gibbs free energies and enthalpies were corrected to be consistent with updated values of Gibbs free energies of Ca2+ and CO32- (Shock and Helgeson, 1988) together with the solubilities of calcite and aragonite reported by Plummer and Busenberg (1982)” (ø)

### `SLOP98` (169)

These species, which were taken from or are linked to slop98.dat (or later versions) and were present in earlier versions of CHNOSZ, have been replaced by or are incompatible with species currently in the default database, including aqueous Al species (Tagirov and Schott, 2001), As species (Nordstrom and Archer, 2003), Au, Ag, and Cu species (Akinfiev and Zotov, 2001; Akinfiev and Zotov, 2010), Pd species (Tagirov et al., 2013), Zn species (Akinfiev and Tagirov, 2014), and Pt species (Tagirov et al., 2015). This file also contains aqueous transuranic actinide complexes, for which estimated thermodynamic properties have been reported, but no entropies of the corresponding elements at 298.15 K are available to check the self-consistency of the GHS values for the complexes. Use `add.obigt("SLOP98")` to load the data. NOTE: Many other species found in slop98.dat and later versions are still present in the default database.

Shock and Helgeson (1988) – 1 H2AsO3- (ø)

Shock and Helgeson (1988) – 1 Ag+ (ø)

Shock and Koretsky (1993) – 9 Ag-, Au-, Cu(I)- and Al-acetate complexes (*)

McCollom and Shock (1997) – 1 aqueous HCl (*)

- slop98.dat – 1 “Data and parameters as used by McCollom and Shock (1997).” (*)

Shock et al. (1997) – 1 aqueous ions and hydroxide complexes (*)

Shock et al. (1997) – 2 Au+ and Cu+ (*)

- Shock and Helgeson (1988) – 2 values of GHS

Shock et al. (1997) – 6 arsenate and arsenite species (*)

Shock et al. (1997) – 5 Al+3 and Al-hydroxide complexes (*)

Shock et al. (1997) – 5 Zn+2 and Zn-hydroxide complexes (*)

- Shock and Helgeson (1988) – 1 values of GHS

Sverjensky et al. (1997) – 2 Au(HS)2- and Ag(HS)2- (*)

Sverjensky et al. (1997) – 10 Au-, Ag-, Cu- and Zn-chloride complexes (*)

Sverjensky et al. (1997) – 3 Zn-acetate complexes (*)

- slop16.dat – 1 Zn(Ac)3-: “Enthalpy changed to be compatible with the equation ΔH=ΔG+TΔS for the formation reaction from elements. See footnote h in table 2 of Sverjensky et al. (1997).” (‡)

Sassani and Shock (1998) – 20 Pd+2 and Pt+2 and their complexes (*)

Murphy and Shock (1999) – 38 actinides (†)

Prapaipong et al. (1999) – 9 metal-dicarboxylate complexes (†)

- slop07.dat – 1 corrected charge of Pu(Oxal)+2 (†)

- CHNOSZ – 2 charge of NpO2(Oxal), La(Succ)+, NH4(Succ)-, and NpO2(Succ) as listed by Prapaipong et al. (1999)

Prapaipong et al. (1999) – 2 Al(Mal)+ and Al(Oxal)+ (†)

Marini and Accornero (2007) – 52 metal-arsenate and metal-arsenite complexes; linked to properties of arsenate and arsenite from Shock et al. (1997)

- Marini and Accornero (2010) – 52 corrected values

Accornero et al. (2010) – 2 Np- and Am-chromate complexes

### `OldAA` (64)

Data for these amino acids and related species were present in earlier versions of CHNOSZ but have been replaced by or are incompatible with later updates (LaRowe and Dick, 2012; Kitadai, 2014; Azadi et al., 2019). Use `add.obigt("OldAA")` to load the data.

Shock (1992) – 4 diglycine, alanylglycine, leucylglycine, and diketopiperazine; not present in slop files after slop98.dat (*)

Shock and Koretsky (1995) – 54 alanate, glycinate and their complexes with metals. Values are taken from slop98.dat, which notes corrected values for some species. (*)

- Amend and Helgeson (1997) – 2 alanate and glycinate GHS

- CHNOSZ – 52 metal-amino acid complexes: GHS were recalculated by adding the differences between values from Shock and Koretsky (1995) and Amend and Helgeson (1997) for alanate or glycinate to the properties of the complexes reported by Shock and Koretsky (1995).

Amend and Helgeson (1997) – 3 glycine, glycinium, and methionine GHS

- Dick et al. (2006) – 3 amino acids HKF parameters

Dick et al. (2006) – 3 [Gly], [Met], and [UPBB]

### `AS04` (3)

This file has data for aqueous SiO2 from Apps and Spycher (2004) and a modified HSiO3- to be consistent with the SiO2 here. This file also has H4SiO4 from an earlier publication (Stefánsson, 2001) that is roughly consistent with SiO2 here (see `?add.obigt`). Use `add.obigt("AS04")` to load the data; see Regressing thermodynamic data for an example.

Sverjensky et al. (1997) – 1 HSiO3- (*)

- CHNOSZ – 1 GHS recalculated by adding difference from SiO2 (Sverjensky et al., 1997) to updated values for SiO2 (Apps and Spycher, 2004)

Stefánsson (2001) – 1 aqueous H4SiO4

Apps and Spycher (2004) – 1 aqueous SiO2

### `AkDi` (24)

This file has parameters for aqueous nonelectrolytes in the Akinfiev-Diamond model (Akinfiev and Diamond, 2003). Use `add.obigt("AkDi")` to load the data; see `demo(AkDi)` for an example.

Akinfiev and Diamond (2003) – 10 dissolved gas species; parameters estimated from the experimental Henry’s constant

Akinfiev and Diamond (2003) – 8 dissolved gas species; parameters estimated from standard-state properties at 25 ° C

Akinfiev and Plyasunov (2014) – 6 B(OH)3, Si(OH)4, and As(OH)3

## All at once

### Aqueous species

#### `H2O` (3)

This file contains H2O, e-, and H+. The properties of H2O are listed as NA; CHNOSZ calculates its properties using a Fortran subroutine taken from SUPRCT92 (Johnson et al., 1992) (default) or using the IAPWS-95 equations (Wagner and Pruß, 2002) or the Deep Earth Water (DEW) model (Sverjensky et al., 2014).

By convention, the standard Gibbs energy of formation, entropy, and heat capacity of the aqueous proton (H+) are 0 at all T and P (e.g. Cox et al., 1989). The formation reaction of the proton can be expressed as ½H2,(g) + Z = H+, where Z is the “element” of positive charge. Because the conventional standard Gibbs energy of this reaction is 0 at all T, the standard entropy of the reaction is also constrained to be zero (cf. Puigdomenech et al., 1997). Therefore, the “element” of positive charge (Z) has zero thermodynamic properties except for an entropy, S°Tr, that is negative one-half that of H2,(g). The standard entropy of the aqueous electron, which is a solely a pseudospecies defined by e- = -Z, is opposite that of Z.**

Despite these considerations, the final column of the thermodynamic database (`thermo()$obigt`) lists a charge of “0” for both the aqueous proton and electron. Data in this this column are used in CHNOSZ only to specify the charge that is input to the “g-function” (Tanger and Helgeson, 1988; Shock and Helgeson, 1988). Setting it to zero prevents activation of the g-function, which would result in non-zero contributions to thermodynamic properties, conflicting with the conventions mentioned above. All other calculations in CHNOSZ obtain the elemental makeup, including the correct charge for the species, by parsing the chemical formulas stored in the database.^^

**Likewise, GEM-Selektor defines “independent components” to be stoichiometric units usually consisting of elements and charge; the latter, which is named Zz and has a standard molal entropy of -65.34 J/mol/K and heat capacity of -14.418 J/mol/K (negative one-half those of gaseous hydrogen), is negated in the formula of the fictive “aqueous electron” (Kulik, 2006).

^^ Relatedly, charged amino acid sidechain groups have a charge that is tabulated as zero, because other values would be incompatible with group additivity of cations and anions (which have derivatives of the omega parameter (ω) in the revised HKF equations of state that are not opposites of each other) to give a neutral species (for which the derivatives of ω are taken to be zero) (cf. Dick et al., 2006).

#### `Inorganic` (837)

Shock and Helgeson (1988) – 57 ionic species (ø)

Shock et al. (1989) – 13 inorganic neutral species (ø)

Shock et al. (1989) – 1 aqueous SiO2 (ø)

Haas et al. (1995) – 249 complexes of rare earth elements (*)

- slop98.dat – 88 “Corrected values based on data from Haas et al. (1995)” (*)

McCollom and Shock (1997) – 2 MgSO4, NaSO4-, and HCl (*)

- slop98.dat – 2 “Data and parameters as used by McCollom and Shock (1997).” (*)

Shock et al. (1997) – 233 aqueous ions and hydroxide complexes (*)

- Shock and Helgeson (1988) – 25 values of GHS

- Sassani and Shock (1998) – 1 Rh+3 (*)

Sverjensky et al. (1997) – 93 metal complexes (*)

- CHNOSZ – 1 AuCl4- renamed to AuCl4-3

Shock et al. (1997b) – 15 uranium species (*)

Tagirov et al. (1997) – 1 aqueous HCl

Sassani and Shock (1998) – 41 platinum-group ions and complexes (*)

Akinfiev and Zotov (2001) – 15 M+, MCl2-, M(OH)2-, MCl, and MOH (M = Au+, Ag+, or Cu+)

Schulte et al. (2001) – 10 AsH3, CF4, CH3F, Cl2, ClO2, N2O, NF3, NO, PH3, and SF6

Tagirov and Schott (2001) – 17 aqueous Al+3 and complexes

- Diakonov et al. (1996) – 1 NaAl(OH)4

Nordstrom and Archer (2003) – 10 aqueous As oxides and sulfides

Akinfiev et al. (2006) – 1 AgCl3-2

Accornero et al. (2010) – 43 metal-chromate complexes

Akinfiev and Zotov (2010) – 6 MHS and M(HS)2- (M = Au+, Ag+, or Cu+)

- Pokrovski et al. (2014) – 1 corrected H of AuHS

Tagirov et al. (2013) – 11 Pd+2 and complexes

Akinfiev and Tagirov (2014) – 13 Zn+2 and complexes

Pokrovski and Dubessy (2015) – 1 trisulfur radical ion

Tagirov et al. (2015) – 5 Pt+2 and complexes

#### `Organic` (681)

Shock and Helgeson (1990) – 47 organic species (ø)

- slop16.dat – 3 hexanol, heptanol, and octanol: “Minor differences in Gibbs energy, entropy, ω, a1, a2, a3, a4 and c1 values compared to Shock and Helgeson (1990).” (‡)

Shock (1993) – 2 ethylacetate and acetamide (*)

Shock and Koretsky (1993) – 104 metal-acetate complexes (*)

- slop16.dat – 32 “Enthalpy changed to be compatible with the equation ΔH=ΔG+TΔS for the formation reaction from elements.” (‡)

Shock and McKinnon (1993) – 3 CO, HCN, urea (*)

Schulte and Shock (1993) – 10 aldehydes (*)

- slop16.dat – 1 formaldehyde: “Entropy corrected to be compatible with the equation ΔH=ΔG+TΔS for the formation reaction from elements. See footnote i in table 2 of Schulte and Shock (1993).” (‡)

Shock and Koretsky (1995) – 226 metal-organic acid complexes (*)

- slop98.dat – 6 “These data were used in Shock and Koretsky (1995), but were not tabulated in the paper.” (*)

- slop16.dat – 55 “Enthalpy corrected to be compatible with the equation ΔG=ΔH-TΔS for the formation reaction from elements.” (‡)

Shock (1995) – 77 carboxylic acids (*)

- slop16.dat – 2 adipic acid and n-dodecanoate: “Gibbs free energy corrected to be compatible with the equation ΔG=ΔH-TΔS for the formation reaction from elements. See footnote y in table 4 of Shock (1995).” (‡)

- slop16.dat – 1 n-octanoate: “Enthalpy corrected to be compatible with the equation ΔG=ΔH-TΔS for the formation reaction from elements. See footnote ab in table 4 of Shock (1995).” (‡)

Dale et al. (1997) – 10 alkylphenols (*)

Shvedov and Tremaine (1997) – 1 dimethylammonium chloride HKF parameters

Haas and Shock (1999) – 6 chloroethylene species (†)

Prapaipong et al. (1999) – 151 metal-dicarboxylate complexes (†)

- CHNOSZ – 2 charge of NpO2(Oxal), La(Succ)+, NH4(Succ)-, and NpO2(Succ) as listed by Prapaipong et al. (1999)

Plyasunov and Shock (2001) – 11 aqueous nonelectrolytes (†)

Schulte and Rogers (2004) – 12 alkane thiols (†)

Hawrylak et al. (2006) – 2 methyldiethanolamine and methyldiethanolammonium chloride HKF parameters

Schulte (2010) – 7 organic sulfides

Dick et al. (2013) – 6 phenanthrene and methylphenanthrene isomers

LaRowe and Amend (2019) – 6 dimethylamine, trimethylamine, resorcinol, phloroglucinol, cyclohexane carboxylate, and cyclohexane carboxylic acid

- Shvedov and Tremaine (1997) – 1 dimethylamine HKF parameters

#### `Biotic` (329)

Amend and Helgeson (1997) – 27 amino acids GHS (†)

- Dick et al. (2006) – 27 amino acids HKF parameters (†)

Amend and Plyasunov (2001) – 10 carbohydrates (†)

- slop07.dat – 10 high-temperature HKF parameters from Amend and Plyasunov (2001) (†)

LaRowe and Harold C. Helgeson (2006a) – 138 nucleic-acid bases, nucleosides, and nucleotides (†)

- Lowe et al. (2017) – 1 adenine HKF parameters

LaRowe and Harold C. Helgeson (2006a) – 4 citric acid and citrate

- Canovas and Shock (2016) – 4 citric acid species HKF a1–a4 parameters

LaRowe and Harold C. Helgeson (2006b) – 32 Mg-complexed adenosine nucleotides (ATP), NAD, and NADP (†)

Dick et al. (2006) – 38 amino acid, protein, and organic groups

- LaRowe and Dick (2012) – 1 methionine sidechain GHS

- CHNOSZ – 1 Incorrect values of HKF a1–a4 parameters for [-CH2NH2] were printed in Table 6 of Dick et al. (2006); corrected values are used here.

Dick et al. (2006) – 19 Gly-X-Gly tripeptides Cp, V, and HKF c1, c2, ω parameters

Dick (2007) – 4 glutathione, cystine, and cystine sidechain

LaRowe and Dick (2012) – 1 methionine GHS

- Dick et al. (2006) – 1 methionine HKF parameters (†)

Kitadai (2014) – 12 glycine, diglycine, and triglycine (zwitterions and ions); diketopiperazine, [Gly] and [UPBB] groups

- Shock (1992) – 1 diketopiperazine GHS

- Goldberg et al. (2002) – 6 glycine, diglycine, and triglycine (+1 and -1 ions) GHS

- Dick et al. (2006) – 3 glycine, [Gly], and [UPBB] HKF parameters

- Dick et al. (2006) – 1 triglycine Cp, V, and HKF c1, c2, ω parameters

Canovas and Shock (2016) – 22 citric acid cycle metabolites

Azadi et al. (2019) – 22 metal-glycinate complexes

- CHNOSZ – 20 recalculated values of Cp (those in Azadi et al. (2019) appear to be calculated using wrong sign on ω) and enthalpy (using ΔG=ΔH-TΔS and the entropies of the elements)

- CHNOSZ – 2 Tl(Gly) and Tl(Gly)2-: change Ti to Tl

### Solids

#### `Inorganic` (134)

Chamosite,7A and witherite were present in sprons92.dat but not in slop98.dat or later files, and are not included in CHNOSZ.

The source of parameters used here for goethite is different from that in the slop files (Shock, 2009).

Helgeson et al. (1978) – 56 data for minerals and phase transitions (ø)

- Pankratz and King (1970) – 2 bornite and chalcopyrite (ø)

- Wagman et al. (1982) – 1 manganosite (ø)

- Helgeson (1985) – 1 ferrosilite and siderite (ø)

- CHNOSZ – 15 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Robie et al. (1978) – 1 chlorargyrite (ø)

- Pankratz (1970) – 1 chlorargyrite (ø)

Robie et al. (1978) – 4 iron (ø)

- Kelley (1960) – 1 iron Cp (ø)

- CHNOSZ – 3 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Robie et al. (1978) – 1 gibbsite GHS

- Zimmer et al. (2016) – 1 Cp parameters listed in spronsbl.dat

Wagman et al. (1982) – 1 MgSO4

Jackson and Helgeson (1985) – 5 Sn minerals (ø)

- CHNOSZ – 1 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Reardon and Armstrong (1987) – 1 celestite GHS

- Helgeson et al. (1978) – 1 celestite V and Cp parameters (ø)

Ball and Nordstrom (1991) – 1 arsenopyrite: G

- Zimmer et al. (2016) – 1 data listed in spronsbl.dat

Hemingway et al. (1991) – 1 boehmite

- Zimmer et al. (2016) – 1 Cp parameters listed in spronsbl.dat

Parker and Khodakovskii (1995) – 1 melanterite

Robie and Hemingway (1995) – 1 gypsum GHS

- Kelley (1960) – 1 gypsum Cp

McCollom and Shock (1997) – 3 sulfur (*)

- slop98.dat – 3 “Data and parameters as used by McCollom and Shock (1997).” (*)

Shock et al. (1997) – 2 zincite and litharge (*)

- Helgeson et al. (1978) – 1 litharge S, V, and Cp parameters (ø)

- slop98.dat – 1 zincite and litharge; “These data were used in Shock et al. (1997), but were not tabulated in the paper.” (*)

Shock et al. (1997b) – 1 uraninite (*)

Sassani and Shock (1998) – 15 platinum-group solids (*)

Stoffregen et al. (2000) – 3 jarosite, natroalunite, and natrojarosite

Wood and Samson (2000) – 2 scheelite and ferberite; adopted values include Cp parameters for scheelite from Barin and Knacke (1973) and GHS and Cp parameters for ferberite from Polya (1990)

- Robie et al. (1978) – 1 scheelite GHS and V

- Robie et al. (1978) – 1 ferberite V

Amend and Shock (2001) – 3 selenium and molybdenite (†)

Mercury et al. (2001) – 8 polymorphs of ice

Juraj Majzlan, Grevel, et al. (2003) – 3 goethite, lepidocrocite, and maghemite GHS

- Juraj Majzlan, Lang, et al. (2003) – 3 goethite, lepidocrocite, and maghemite Cp

Nordstrom and Archer (2003) – 8 As oxide and sulfide minerals

- Zimmer et al. (2016) – 1 As(α): V listed in spronsbl.dat

Majzlan et al. (2004) – 1 hydronium jarosite

Zhu et al. (2005) – 2 barium arsenate and barium hydrogen arsenate: G

- Zimmer et al. (2016) – 2 data listed in spronsbl.dat

Langmuir et al. (2006) – 2 scorodite and amorphous ferric arsenate: G

- Zimmer et al. (2016) – 2 data listed in spronsbl.dat

Majzlan et al. (2006) – 3 coquimbite, ferricopiapite, and rhomboclase

Grevel and Majzlan (2009) – 4 kieserite, starkeyite, hexahydrite, and epsomite

Zimmer et al. (2016) – 1 dawsonite GHS

- Robie and Hemingway (1995) – 1 dawsonite: Cp coefficients corrected in Tutolo et al. (2014); Cp value at 25 °C from Bénézeth et al. (2007), citing Ferrante et al. (1976)

#### `Organic` (479)

Tardy et al. (1997) – 5 humic acid, microflora, and plants

Helgeson et al. (1998) – 59 organic molecules and groups

Helgeson et al. (1998) – 20 amino acids

- LaRowe and Dick (2012) – 4 updated and corrected parameters for cysteine, glycine, leucine, and methionine

Richard and Helgeson (1998) – 311 organic molecules and groups

Richard (2001) – 8 organic sulfur compounds

LaRowe and Harold C. Helgeson (2006a) – 19 nucleic-acid bases, nucleosides, and nucleotides

LaRowe and Harold C. Helgeson (2006b) – 9 Mg-complexed adenosine nucleotides (ATP), NAD, and NADP

Helgeson et al. (2009) – 5 kerogens

Richard and Gaona (2011) – 13 organic iodine compounds

LaRowe and Dick (2012) – 30 4-hydroxyproline, 5-hydroxylysine, 4 dipeptides, and sidechain and backbone groups in proteins

### `Berman` (92)

This file gives the identifiying information for minerals whose properties are calculated using the formulation of Berman (1988). Note that thermodynamic properties for these minerals are listed as NA in `thermo()$obigt`; the actual data are stored separately, as CSV files in `extdata/Berman/*.csv`.

Berman (1988) – 65 minerals

- Berman (1990) – 2 almandine and ilmenite: modified H and/or S

- Sverjensky et al. (1991) – 9 G and H revisions for K- and Al-bearing silicates

- Sverjensky et al. (1991) – 1 phlogopite: H and S modified by Berman (1990), followed by G and H revision for K-bearing silicates (after Sverjensky et al., 1991)

- berman.dat (2017) – 1 antigorite: “Oct. 21, 2016: Revised volume coefficients consistent with Hilairet et al. (2006) and Yang et al. (2014)”

Berman (1990) – 1 annite

- Sverjensky et al. (1991) – 1 annite: G and H revision for K-bearing silicates (after Sverjensky et al., 1991)

Evans (1990) – 2 glaucophane and pumpellyite

- JUN92.bs (1992) – 2 data as listed in `JUN92.bs` data file

Vidal et al. (1992) – 1 sudoite

Zhu and Sverjensky (1992) – 10 F,Cl,OH biotite and apatite endmembers. GHS and V were taken from Table 6 of Zhu and Sverjensky (1992); heat capacity and volume parameters from `berman.dat`.

Vidal et al. (2001) – 2 daphnite and Mg-amesite

Gottschalk (2004) – 4 zoisite, clinozoisite, and epidote

Vidal et al. (2005) – 1 Fe-amesite

Delgado Martín and Soler i Gil (2010) – 5 hedenbergite, andradite, ferro-actinolite, grunerite, and ilvaite

Facq et al. (2014) – 1 aragonite; source of data: `berman.dat`

### Liquids

#### `Organic` (532)

Helgeson et al. (1998) – 186 organic molecules and groups

Richard and Helgeson (1998) – 231 organic molecules and groups

Richard (2001) – 67 organic sulfur compounds

LaRowe and Harold C. Helgeson (2006b) – 2 pyridine and piperidine

Richard (2008) – 17 alkenes

Richard and Gaona (2011) – 29 organic iodine compounds

### Gases

#### `Inorganic` (19)

Wagman et al. (1982) – 2 gases GHS (†)

- Amend and Shock (2001) – 2 NO and N2O (†)

Wagman et al. (1982) – 15 gases GHS (ø)

- Kelley (1960) – 15 gases Cp (ø)

Robie and Hemingway (1995) – 2 hydrogen fluoride and hydrogen chloride

#### `Organic` (266)

Shock (1993) – 2 carbon monoxide and ethylene (*)

Dale et al. (1997) – 4 phenol, and cresol isomers (*)

Dale et al. (1997) – 6 dimethylphenol isomers

Helgeson et al. (1998) – 153 organic molecules and groups

Richard (2001) – 62 organic sulfur compounds

Richard and Gaona (2011) – 39 organic iodine compounds

### Optional Data

#### `DEW` (199)

The Deep Earth Water (DEW) model extends the applicability of the revised HKF equations of state to 60 kbar. Accuracy of the thermodynamic calculations at these conditions is improved by revised correlations for the a1 HKF parameter, as described by Sverjensky et al., 2014. The data here were taken from the May 2017 version of the DEW spreadsheet (Dew Model, 2017). The following species are present in the spreadsheet, but are not used here because the parameters are unchanged from the default database in CHNOSZ: B(OH)3, Br-, Ca+2, Cl-, Cs+, F-, H+, H2, He, I-, K+, Kr, Li+, Mg+2, Na+, Ne, O2, Rb+, Rn.

Besides using `add.obigt('DEW')` to load these data, you should also run `water('DEW')` to activate the DEW equations in CHNOSZ. See `demo(DEW)` for some examples.

Shock and Helgeson (1988) – 2 ionic species

- Sverjensky et al. (2014) – 2 revisions for BO(OH) and BO2-

Shock and Helgeson (1990) – 3 formic acid, formate, and propanoate

- DEW model (2017) – 1 revised with new predicted a1 for ions

- DEW model (2017) – 1 revised with new predicted a1 for complex species

- DEW model (2017) – 1 propanoate: Revised a1 from new delVn correlation for -1 ions

Pokrovskii and Helgeson (1995) – 2 aluminum species

- Sverjensky et al. (2014) – 2 revisions for AlO2- and HAlO2

Ho and Palmer (1997) – 1 KOH

- Sverjensky et al. (2014) – 1 Fitted to Ho and Palmer (1997) data with a1 pred. from the sum of the ions and used to predict the volume

Plyasunov and Shock (2001) – 2 acetic acid, propanoic acid, and methane

- DEW model (2017) – 1 methane: revised with new predicted a1 for complex species

Facq et al. (2014) – 3 CO2, CO3-2, and HCO3-

Sverjensky et al. (2014) – 2 SiO2 and Si2O4

DEW model (2017) – 184 other data from Aqueous Species Table in spreadsheet (see detailed references there)

- DEW model (2017) – 1 acetate: revised January 26th, 2016; new a1 value from complexes and organics correlation.

- DEW model (2017) – 1 MgCl+: revised volume increased in order that a1 of the complex is the sum of the a1 values of the ions

- DEW model (2017) – 1 NaCl: revised with new predicted a1 for complex species

#### `SUPCRT92` (180)

These minerals and aqueous species, taken from the SUPCRT92 database, were present in earlier versions of CHNOSZ but have since been superseded by Berman (1988) (minerals) and Nordstrom and Archer (2003) (H2AsO3-). The thermodynamic properties and parameters are kept here as optional data for reproducing published calculations and making comparisons with newer data. The minerals here include all of the silicates and Al-bearing minerals from Helgeson et al. (1978), as well as calcite, dolomite, hematite, and magnetite. Use `add.obigt("SUPCRT92")` to load the data. NOTE: Other minerals from SUPCRT92, including native elements, sulfides, halides, sulfates, and selected carbonates and oxides that do not duplicate those in the Berman dataset, are still present in the default database (inorganic_cr.csv).

Helgeson et al. (1978) – 178 data for minerals and phase transitions (ø)

- Kelley (1960) – 1 larnite Cp (ø)

- Robie et al. (1978) – 4 dickite, fluorphlogopite, halloysite, and pyrope (ø)

- Plummer and Busenberg (1982) – 2 aragonite and calcite (ø)

- Helgeson (1985) – 1 ferrosilite and siderite (ø)

- sprons92.dat – 24 Ca-bearing minerals; “Gibbs free energies and enthalpies were corrected to be consistent with updated values of Gibbs free energies of Ca2+ and CO32- (Shock and Helgeson, 1988) together with the solubilities of calcite and aragonite reported by Plummer and Busenberg (1982)” (ø)

- slop98.dat – 1 daphnite; “Gf and Hf from Saccocia and Seyfried (1993) TMM” (*)

- CHNOSZ – 53 GHS (Tr) of the phase that is stable at 298.15 K was combined with Htr and the Cp coefficients to calculate the metastable GHS (Tr) of the phases that are stable at higher temperatures.

Robie et al. (1978) – 2 rutile and titanite (ø)

- Bowers and Helgeson (1983) – 1 rutile (ø)

- sprons92.dat – 1 titanite: Bowers and Helgeson (1983) + “Gibbs free energies and enthalpies were corrected to be consistent with updated values of Gibbs free energies of Ca2+ and CO32- (Shock and Helgeson, 1988) together with the solubilities of calcite and aragonite reported by Plummer and Busenberg (1982)” (ø)

#### `SLOP98` (169)

These species, which were taken from or are linked to slop98.dat (or later versions) and were present in earlier versions of CHNOSZ, have been replaced by or are incompatible with species currently in the default database, including aqueous Al species (Tagirov and Schott, 2001), As species (Nordstrom and Archer, 2003), Au, Ag, and Cu species (Akinfiev and Zotov, 2001; Akinfiev and Zotov, 2010), Pd species (Tagirov et al., 2013), Zn species (Akinfiev and Tagirov, 2014), and Pt species (Tagirov et al., 2015). This file also contains aqueous transuranic actinide complexes, for which estimated thermodynamic properties have been reported, but no entropies of the corresponding elements at 298.15 K are available to check the self-consistency of the GHS values for the complexes. Use `add.obigt("SLOP98")` to load the data. NOTE: Many other species found in slop98.dat and later versions are still present in the default database.

Shock and Helgeson (1988) – 1 H2AsO3- (ø)

Shock and Helgeson (1988) – 1 Ag+ (ø)

Shock and Koretsky (1993) – 9 Ag-, Au-, Cu(I)- and Al-acetate complexes (*)

McCollom and Shock (1997) – 1 aqueous HCl (*)

- slop98.dat – 1 “Data and parameters as used by McCollom and Shock (1997).” (*)

Shock et al. (1997) – 1 aqueous ions and hydroxide complexes (*)

Shock et al. (1997) – 2 Au+ and Cu+ (*)

- Shock and Helgeson (1988) – 2 values of GHS

Shock et al. (1997) – 6 arsenate and arsenite species (*)

Shock et al. (1997) – 5 Al+3 and Al-hydroxide complexes (*)

Shock et al. (1997) – 5 Zn+2 and Zn-hydroxide complexes (*)

- Shock and Helgeson (1988) – 1 values of GHS

Sverjensky et al. (1997) – 2 Au(HS)2- and Ag(HS)2- (*)

Sverjensky et al. (1997) – 10 Au-, Ag-, Cu- and Zn-chloride complexes (*)

Sverjensky et al. (1997) – 3 Zn-acetate complexes (*)

- slop16.dat – 1 Zn(Ac)3-: “Enthalpy changed to be compatible with the equation ΔH=ΔG+TΔS for the formation reaction from elements. See footnote h in table 2 of Sverjensky et al. (1997).” (‡)

Sassani and Shock (1998) – 20 Pd+2 and Pt+2 and their complexes (*)

Murphy and Shock (1999) – 38 actinides (†)

Prapaipong et al. (1999) – 9 metal-dicarboxylate complexes (†)

- slop07.dat – 1 corrected charge of Pu(Oxal)+2 (†)

- CHNOSZ – 2 charge of NpO2(Oxal), La(Succ)+, NH4(Succ)-, and NpO2(Succ) as listed by Prapaipong et al. (1999)

Prapaipong et al. (1999) – 2 Al(Mal)+ and Al(Oxal)+ (†)

Marini and Accornero (2007) – 52 metal-arsenate and metal-arsenite complexes; linked to properties of arsenate and arsenite from Shock et al. (1997)

- Marini and Accornero (2010) – 52 corrected values

Accornero et al. (2010) – 2 Np- and Am-chromate complexes

#### `OldAA` (64)

Data for these amino acids and related species were present in earlier versions of CHNOSZ but have been replaced by or are incompatible with later updates (LaRowe and Dick, 2012; Kitadai, 2014; Azadi et al., 2019). Use `add.obigt("OldAA")` to load the data.

Shock (1992) – 4 diglycine, alanylglycine, leucylglycine, and diketopiperazine; not present in slop files after slop98.dat (*)

Shock and Koretsky (1995) – 54 alanate, glycinate and their complexes with metals. Values are taken from slop98.dat, which notes corrected values for some species. (*)

- Amend and Helgeson (1997) – 2 alanate and glycinate GHS

- CHNOSZ – 52 metal-amino acid complexes: GHS were recalculated by adding the differences between values from Shock and Koretsky (1995) and Amend and Helgeson (1997) for alanate or glycinate to the properties of the complexes reported by Shock and Koretsky (1995).

Amend and Helgeson (1997) – 3 glycine, glycinium, and methionine GHS

- Dick et al. (2006) – 3 amino acids HKF parameters

Dick et al. (2006) – 3 [Gly], [Met], and [UPBB]

#### `AS04` (3)

This file has data for aqueous SiO2 from Apps and Spycher (2004) and a modified HSiO3- to be consistent with the SiO2 here. This file also has H4SiO4 from an earlier publication (Stefánsson, 2001) that is roughly consistent with SiO2 here (see `?add.obigt`). Use `add.obigt("AS04")` to load the data; see Regressing thermodynamic data for an example.

Sverjensky et al. (1997) – 1 HSiO3- (*)

- CHNOSZ – 1 GHS recalculated by adding difference from SiO2 (Sverjensky et al., 1997) to updated values for SiO2 (Apps and Spycher, 2004)

Stefánsson (2001) – 1 aqueous H4SiO4

Apps and Spycher (2004) – 1 aqueous SiO2

#### `AkDi` (24)

This file has parameters for aqueous nonelectrolytes in the Akinfiev-Diamond model (Akinfiev and Diamond, 2003). Use `add.obigt("AkDi")` to load the data; see `demo(AkDi)` for an example.

Akinfiev and Diamond (2003) – 10 dissolved gas species; parameters estimated from the experimental Henry’s constant

Akinfiev and Diamond (2003) – 8 dissolved gas species; parameters estimated from standard-state properties at 25 ° C

Akinfiev and Plyasunov (2014) – 6 B(OH)3, Si(OH)4, and As(OH)3

# Total count of species

3372 of 3372 entries in `thermo()$obigt` and 639 optional data entries are documented here.

# References

Accornero M, Marini L, Lelli M. 2010. Prediction of the thermodynamic properties of metal-chromate aqueous complexes to high temperatures and pressures and implications for the speciation of hexavalent chromium in some natural waters. Applied Geochemistry 25(2): 242–260. doi: 10.1016/j.apgeochem.2009.11.010

Akinfiev NN, Diamond LW. 2003. Thermodynamic description of aqueous nonelectrolytes at infinite dilution over a wide range of state parameters. Geochimica et Cosmochimica Acta 67(4): 613–629. doi: 10.1016/S0016-7037(02)01141-9

Akinfiev NN, Plyasunov AV. 2014. Application of the Akinfiev-Diamond equation of state to neutral hydroxides of metalloids (B(OH)3, Si(OH)4, As(OH)3) at infinite dilution in water over a wide range of the state parameters, including steam conditions. Geochimica et Cosmochimica Acta 126: 338–351. doi: 10.1016/j.gca.2013.11.013

Akinfiev NN, Tagirov BR. 2014. Zn in hydrothermal systems: Thermodynamic description of hydroxide, chloride, and hydrosulfide complexes. Geochemistry International 52(3): 197–214. doi: 10.1134/S0016702914030021

Akinfiev NN, Voronin MV, Zotov AV, Prokof’ev VY. 2006. Experimental investigation of the stability of a chloroborate complex and thermodynamic description of aqueous species in the B-Na-Cl-O-H system up to 350°C. Geochemistry International 44(9): 867–878. doi: 10.1134/S0016702906090035

Akinfiev NN, Zotov AV. 2001. Thermodynamic description of chloride, hydrosulfide, and hydroxo complexes of Ag(I), Cu(I), and Au(I) at temperatures of 25-500°C and pressures of 1-2000 bar. Geochemistry International 39(10): 990–1006. Available at http://www.maik.ru/cgi-perl/search.pl?type=abstract&name=geochem&number=10&year=1&page=990.

Akinfiev NN, Zotov AV. 2010. Thermodynamic description of aqueous species in the system Cu-Ag-Au-S-O-H at temperatures of 0-600°C and pressures of 1-3000 bar. Geochemistry International 48(7): 714–720. doi: 10.1134/S0016702910070074

Amend JP, Helgeson HC. 1997. Calculation of the standard molal thermodynamic properties of aqueous biomolecules at elevated temperatures and pressures. Part 1. l-α-amino acids. Journal of the Chemical Society, Faraday Transactions 93(10): 1927–1941. doi: 10.1039/A608126F

Amend JP, Plyasunov AV. 2001. Carbohydrates in thermophile metabolism: Calculation of the standard molal thermodynamic properties of aqueous pentoses and hexoses at elevated temperatures and pressures. Geochimica et Cosmochimica Acta 65(21): 3901–3917. doi: 10.1016/S0016-7037(01)00707-4

Amend JP, Shock EL. 2001. Energetics of overall metabolic reactions of thermophilic and hyperthermophilic Archaea and Bacteria. FEMS Microbiology Reviews 25(2): 175–243. doi: 10.1111/j.1574-6976.2001.tb00576.x

Apps J, Spycher N. 2004. Data qualification for thermodynamic data used to support THC calculations. Las Vegas, NV: Bechtel SAIC Company, LLC. Report No.: ANL-NBS-HS-000043 REV 00 (DOC.20041118.0004).

Azadi M, Karrech A, Attar M, Elchalakani M. 2019. Data analysis and estimation of thermodynamic properties of aqueous monovalent metal-glycinate complexes. Fluid Phase Equilibria 480: 25–40. doi: 10.1016/j.fluid.2018.10.002

Ball JW, Nordstrom DK. 1991. User’s manual for WATEQ4F, with revised thermodynamic data base and text cases for calculating speciation of major, trace, and redox elements in natural waters. Menlo Park, CA: U. S. Geological Survey. Report No.: 91-183. Available at https://pubs.er.usgs.gov/publication/ofr91183.

Barin I, Knacke O. 1973. Thermochemical Properties of Inorganic Substances. Berlin: Springer-Verlag. Available at http://www.worldcat.org/oclc/695258.

Bénézeth P, Palmer DA, Anovitz LM, Horita J. 2007. Dawsonite synthesis and reevaluation of its thermodynamic properties from solubility measurements: Implications for mineral trapping of CO2. Geochimica et Cosmochimica Acta 71(18): 4438–4455. doi: 10.1016/j.gca.2007.07.003

Berman RG. 1988. Internally-consistent thermodynamic data for minerals in the system Na2O–K2O–CaO–MgO–FeO–Fe2O3–Al2O3–SiO2–TiO2–H2O–CO2. Journal of Petrology 29(2): 445–522. doi: 10.1093/petrology/29.2.445

Berman RG. 1990. Mixing properties of Ca-Mg-Fe-Mn garnets. American Mineralogist 75(3-4): 328–344. Available at http://ammin.geoscienceworld.org/content/75/3-4/328.

berman.dat. 2017. Data file in SUPCRT92b.zip on the DEW website. Last updated on 2017-02-03. Accessed on 2017-05-04. Available at http://www.dewcommunity.org/resources.html.

Bowers TS, Helgeson HC. 1983. Calculation of the thermodynamic and geochemical consequences of nonideal mixing in the system H2O-CO2-NaCl on phase relations in geologic systems: Equation of state for H2O-CO2-NaCl fluids at high pressures and temperatures. Geochimica et Cosmochimica Acta 47(7): 1247–1275. doi: 10.1016/0016-7037(83)90066-2

Canovas PA III, Shock EL. 2016. Geobiochemistry of metabolism: Standard state thermodynamic properties of the citric acid cycle. Geochimica et Cosmochimica Acta 195: 293–322. doi: 10.1016/j.gca.2016.08.028

CHNOSZ. 2019. Thermodynamic Calculations and Diagrams for Geochemistry. Available at https://cran.r-project.org/package=CHNOSZ.

Cox JD, Wagman DD, Medvedev VA, editors. 1989. CODATA Key Values for Thermodynamics. New York: Hemisphere Publishing Corporation. Available at http://www.worldcat.org/oclc/18559968.

Dale JD, Shock EL, MacLoed G, Aplin AC, Larter SR. 1997. Standard partial molal properties of aqueous alkylphenols at high pressures and temperatures. Geochimica et Cosmochimica Acta 61(19): 4017–4024. doi: 10.1016/S0016-7037(97)00212-3

Delgado Martín J, Soler i Gil A. 2010. Ilvaite stability in skarns from the northern contact of the Maladeta batholith, Central Pyrenees (Spain). European Journal of Mineralogy 22(3): 363–380. doi: 10.1127/0935-1221/2010/0022-2021

DEW model. 2017. Dew_model_may_2017.zip (Excel spreadsheet). Last updated on 2017-05-19. Accessed on 2017-09-26. Available at http://www.dewcommunity.org/resources.html.

Diakonov I, Pokrovski G, Schott J, Castet S, Gout R. 1996. An experimental and computational study of sodium-aluminum complexing in crustal fluids. Geochimica et Cosmochimica Acta 60(2): 197–211. doi: 10.1016/0016-7037(95)00403-3

Dick JM. 2007. Calculation of the relative stabilities of proteins as a function of temperature, pressure, and chemical potentials in subcellular and geochemical environments [Ph.D. dissertation]. University of California.

Dick JM, Evans KA, Holman AI, Jaraula CMB, Grice K. 2013. Estimation and application of the thermodynamic properties of aqueous phenanthrene and isomers of methylphenanthrene at high temperature. Geochimica et Cosmochimica Acta 122: 247–266. doi: 10.1016/j.gca.2013.08.020

Dick JM, LaRowe DE, Helgeson HC. 2006. Temperature, pressure, and electrochemical constraints on protein speciation: Group additivity calculation of the standard molal thermodynamic properties of ionized unfolded proteins. Biogeosciences 3(3): 311–336. doi: 10.5194/bg-3-311-2006

Evans BW. 1990. Phase relations of epidote-blueschists. Lithos 25(1): 3–23. doi: 10.1016/0024-4937(90)90003-J

Facq S, Daniel I, Montagnac G, Cardon H, Sverjensky DA. 2014. In situ Raman study and thermodynamic model of aqueous carbonate speciation in equilibrium with aragonite under subduction zone conditions. Geochimica et Cosmochimica Acta 132(Supplement C): 375–390. doi: 10.1016/j.gca.2014.01.030

Ferrante MJ, Stuve JM, Richardson DW. 1976. Thermodynamic Data for Synthetic Dawsonite. U. S. Bureau of Mines. (Report of investigations; Vol. 8129). Available at http://www.worldcat.org/oclc/932914138.

Goldberg RN, Kishore N, Lennen RM. 2002. Thermodynamic quantities for the ionization reactions of buffers. Journal of Physical and Chemical Reference Data 31(2): 231–370. doi: 10.1063/1.1416902

Gottschalk M. 2004. Thermodynamic properties of zoisite, clinozoisite and epidote. Reviews in Mineralogy and Geochemistry 56(1): 83–124. doi: 10.2138/gsrmg.56.1.83

Grevel K-D, Majzlan J. 2009. Internally consistent thermodynamic data for magnesium sulfate hydrates. Geochimica et Cosmochimica Acta 73(22): 6805–6815. doi: 10.1016/j.gca.2009.08.005

Haas JR, Shock EL. 1999. Halocarbons in the environment: Estimates of thermodynamic properties for aqueous chloroethylene species and their stabilities in natural settings. Geochimica et Cosmochimica Acta 63(19-20): 3429–3441. doi: 10.1016/S0016-7037(99)00276-8

Haas JR, Shock EL, Sassani DC. 1995. Rare earth elements in hydrothermal systems: Estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochimica et Cosmochimica Acta 59(21): 4329–4350. doi: 10.1016/0016-7037(95)00314-P

Hawrylak B, Palepu R, Tremaine PR. 2006. Thermodynamics of aqueous methyldiethanolamine (MDEA) and methyldiethanolammonium chloride (MDEAH+Cl−) over a wide range of temperature and pressure: Apparent molar volumes, heat capacities, and isothermal compressibilities. Journal of Chemical Thermodynamics 38(8): 988–1007. doi: 10.1016/j.jct.2005.10.013

Helgeson HC. 1985. Errata. II. Thermodynamics of minerals, reactions, and aqueous solutions at high pressures and temperatures. American Journal of Science 285(9): 845–855. doi: 10.2475/ajs.285.9.845

Helgeson HC, Delany JM, Nesbitt HW, Bird DK. 1978. Summary and critique of the thermodynamic properties of rock-forming minerals. American Journal of Science 278A: 1–229. Available at http://www.worldcat.org/oclc/13594862.

Helgeson HC, Owens CE, Knox AM, Richard L. 1998. Calculation of the standard molal thermodynamic properties of crystalline, liquid, and gas organic molecules at high temperatures and pressures. Geochimica et Cosmochimica Acta 62(6): 985–1081. doi: 10.1016/S0016-7037(97)00219-6

Helgeson HC, Richard L, McKenzie WF, Norton DL, Schmitt A. 2009. A chemical and thermodynamic model of oil generation in hydrocarbon source rocks. Geochimica et Cosmochimica Acta 73(3): 594–695. doi: 10.1016/j.gca.2008.03.004

Hemingway BS, Robie RA, Apps JA. 1991. Revised values for the thermodynamic properties of boehmite, AlO(OH) , and related species and phases in the system Al-H-O. American Mineralogist 76(3-4): 445–457. Available at http://pubs.er.usgs.gov/publication/70016664.

Hilairet N, Daniel I, Reynard B. 2006. Equation of state of antigorite, stability field of serpentines, and seismicity in subduction zones. Geophysical Research Letters 33(2): L02302. doi: 10.1029/2005GL024728

Ho PC, Palmer DA. 1997. Ion association of dilute aqueous potassium chloride and potassium hydroxide solutions to 600°C and 300 MPa determined by electrical conductance measurements. Geochimica et Cosmochimica Acta 61(15): 3027–3040. doi: 10.1016/S0016-7037(97)00146-4

Holland TJB, Powell R. 2011. An improved and extended internally consistent thermodynamic dataset for phases of petrological interest, involving a new equation of state for solids. Journal of Metamorphic Geology 29(3): 333–383. doi: 10.1111/j.1525-1314.2010.00923.x

Jackson KJ, Helgeson HC. 1985. Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin. II. Interpretation of phase relations in the Southeast Asian tin belt. Economic Geology 80(5): 1365–1378. doi: 10.2113/gsecongeo.80.5.1365

Johnson JW, Oelkers EH, Helgeson HC. 1992. SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000°C. Computers & Geosciences 18(7): 899–947. doi: 10.1016/0098-3004(92)90029-Q

JUN92.bs. 1992. JUN92.bs database supplied with Theriak/Domino software. Last updated on 2017-02-04. Accessed on 2017-10-01. Available at http://titan.minpet.unibas.ch/minpet/theriak/prog170204/.

Kelley KK. 1960. Contributions to the Data in Theoretical Metallurgy XIII: High Temperature Heat Content, Heat Capacities and Entropy Data for the Elements and Inorganic Compounds. U. S. Bureau of Mines. (Bulletin 584). Available at http://www.worldcat.org/oclc/693388901.

Kitadai N. 2014. Thermodynamic prediction of glycine polymerization as a function of temperature and pH consistent with experimentally obtained results. Journal of Molecular Evolution 78(3-4): 171–187. doi: 10.1007/s00239-014-9616-1

Kulik DA. 2006. Dual-thermodynamic estimation of stoichiometry and stability of solid solution end members in aqueous–solid solution systems. Chemical Geology 225(3): 189–212. doi: 10.1016/j.chemgeo.2005.08.014

Langmuir D, Mahoney J, Rowson J. 2006. Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4·2H2O) and their application to arsenic behavior in buried mine tailings. Geochimica et Cosmochimica Acta 70(12): 2942–2956. doi: 10.1016/j.gca.2006.03.006

LaRowe DE, Amend JP. 2019. The energetics of fermentation in natural settings. Geomicrobiology Journal 36(6): 492–505. doi: 10.1080/01490451.2019.1573278

LaRowe DE, Dick JM. 2012. Calculation of the standard molal thermodynamic properties of crystalline peptides. Geochimica et Cosmochimica Acta 80: 70–91. doi: 10.1016/j.gca.2011.11.041

LaRowe DE, Helgeson HC. 2006a. Biomolecules in hydrothermal systems: Calculation of the standard molal thermodynamic properties of nucleic-acid bases, nucleosides, and nucleotides at elevated temperatures and pressures. Geochimica et Cosmochimica Acta 70(18): 4680–4724. doi: 10.1016/j.gca.2006.04.010

LaRowe DE, Helgeson HC. 2006b. The energetics of metabolism in hydrothermal systems: Calculation of the standard molal thermodynamic properties of magnesium-complexed adenosine nucleotides and NAD and NADP at elevated temperatures and pressures. Thermochimica Acta 448(2): 82–106. doi: 10.1016/j.tca.2006.06.008

Lowe AR, Cox JS, Tremaine PR. 2017. Thermodynamics of aqueous adenine: Standard partial molar volumes and heat capacities of adenine, adeninium chloride, and sodium adeninate from T = 278.15 K to 393.15 K. Journal of Chemical Thermodynamics 112: 129–145. doi: 10.1016/j.jct.2017.04.005

Majzlan J, Grevel K-D, Navrotsky A. 2003. Thermodynamics of Fe oxides: Part II. Enthalpies of formation and relative stability of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe2O3). American Mineralogist 88(5-6): 855–859. doi: 10.2138/am-2003-5-614

Majzlan J, Lang BE, Stevens R, Navrotsky A, Woodfield BF, Boerio-Goates J. 2003. Thermodynamics of Fe oxides: Part I. Entropy at standard temperature and pressure and heat capacity of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe2O3). American Mineralogist 88(5-6): 846–854. doi: 10.2138/am-2003-5-613

Majzlan J, Navrotsky A, McCleskey RB, Alpers CN. 2006. Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5. European Journal of Mineralogy 18(2): 175–186. doi: 10.1127/0935-1221/2006/0018-0175

Majzlan J, Stevens R, Boerio-Goates J, Woodfield BF, Navrotsky A, Burns PC, Crawford MK, Amos TG. 2004. Thermodynamic properties, low-temperature heat-capacity anomalies, and single-crystal X-ray refinement of hydronium jarosite, (H3O)Fe3(SO4)2(OH)6. Physics and Chemistry of Minerals 31(8): 518–531. doi: 10.1007/s00269-004-0405-z

Marini L, Accornero M. 2007. Prediction of the thermodynamic properties of metal-arsenate and metal-arsenite aqueous complexes to high temperatures and pressures and some geological consequences. Environmental Geology 52(7): 1343–1363. doi: 10.1007/s00254-006-0578-5

Marini L, Accornero M. 2010. Prediction of the thermodynamic properties of metal-arsenate and metal-arsenite aqueous complexes to high temperatures and pressures and some geological consequences (vol 52, pg 1343, 2007). Environmental Earth Sciences 59(7): 1601–1606. doi: 10.1007/s12665-009-0369-x

McCollom TM, Shock EL. 1997. Geochemical constraints on chemolithoautotrophic metabolism by microorganisms in seafloor hydrothermal systems. Geochimica et Cosmochimica Acta 61(20): 4375–4391. doi: 10.1016/S0016-7037(97)00241-X

Mercury L, Vieillard P, Tardy Y. 2001. Thermodynamics of ice polymorphs and ‘ice-like’ water in hydrates and hydroxides. Applied Geochemistry 16(2): 161–181. doi: 10.1016/S0883-2927(00)00025-1

Murphy WM, Shock EL. 1999. Environmental aqueous geochemistry of actinides. Reviews in Mineralogy and Geochemistry 38(1): 221–253. Mineralogical Society of America. Available at http://rimg.geoscienceworld.org/content/38/1/221.

Nordstrom DK, Archer DG. 2003. Arsenic thermodynamic data and environmental geochemistry. In: Welch AH; Stollenwerk KG, editors. Arsenic in Groundwater. New York: Springer. pp. 1–25. doi: 10.1007/0-306-47956-7_1

Pankratz LB. 1970. Thermodynamic Data for Silver Chloride and Silver Bromide. U. S. Bureau of Mines. (Report of investigations; Vol. 7430). Available at http://www.worldcat.org/oclc/14154245.

Pankratz LB, King EG. 1970. High-Temperature Enthalpies and Entropies of Chalcopyrite and Bornite. U. S. Bureau of Mines. (Report of investigations; Vol. 7435). Available at http://www.worldcat.org/oclc/14154292.

Parker VB, Khodakovskii IL. 1995. Thermodynamic properties of the aqueous ions (2+ and 3+) of iron and the key compounds of iron. Journal of Physical and Chemical Reference Data 24(5): 1699–1745. doi: 10.1063/1.555964

Plummer LN, Busenberg E. 1982. The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O. Geochimica et Cosmochimica Acta 46(6): 1011–1040. doi: 10.1016/0016-7037(82)90056-4

Plyasunov AV, Shock EL. 2001. Correlation strategy for determining the parameters of the revised Helgeson-Kirkham-Flowers model for aqueous nonelectrolytes. Geochimica et Cosmochimica Acta 65(21): 3879–3900. doi: 10.1016/S0016-7037(01)00678-0

Pokrovski GS, Akinfiev NN, Borisova AY, Zotov AV, Kouzmanov K. 2014. Gold speciation and transport in geological fluids: Insights from experiments and physical-chemical modelling. Geological Society, London, Special Publications 402(1): 9–70. doi: 10.1144/SP402.4

Pokrovski GS, Dubessy J. 2015. Stability and abundance of the trisulfur radical ion in hydrothermal fluids. Earth and Planetary Science Letters 411: 298–309. doi: 10.1016/j.epsl.2014.11.035

Pokrovskii VA, Helgeson HC. 1995. Thermodynamic properties of aqueous species and the solubilities of minerals at high pressures and temperatures: The system Al2O3-H2O-NaCl. American Journal of Science 295(10): 1255–1342. doi: 10.2475/ajs.295.10.1255

Polya DA. 1990. Pressure-dependence of wolframite solubility for hydrothermal vein formation. Transactions of the Institutions of Mining and Metallurgy, Section B: Applied Earth Science 99: B120–B124.

Prapaipong P, Shock EL, Koretsky CM. 1999. Metal-organic complexes in geochemical processes: Temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands. Geochimica et Cosmochimica Acta 63(17): 2547–2577. doi: 10.1016/S0016-7037(99)00146-5

Puigdomenech I, Rard JA, Plyasunov AV, Grenthe I. 1997. Temperature corrections to thermodynamic data and enthalpy calculations. In: Grenthe I; Puigdomenech I, editors. Modelling in Aquatic Chemistry. OECD Nuclear Energy Data Bank. pp. 427–493. Available at http://www.oecd-nea.org/dbtdb/pubs/book-pdf/427-494.pdf.

Reardon EJ, Armstrong DK. 1987. Celestite (SrSO4(s)) solubility in water, seawater and NaCl solution. Geochimica et Cosmochimica Acta 51(1): 63–72. doi: 10.1016/0016-7037(87)90007-X

Richard L. 2001. Calculation of the standard molal thermodynamic properties as a function of temperature and pressure of some geochemically important organic sulfur compounds. Geochimica et Cosmochimica Acta 65(21): 3827–3877. doi: 10.1016/S0016-7037(01)00761-X

Richard L. 2008. Personal communication.

Richard L, Gaona X. 2011. Thermodynamic properties of organic iodine compounds. Geochimica et Cosmochimica Acta 75(22): 7304–7350. doi: 10.1016/j.gca.2011.07.030

Richard L, Helgeson HC. 1998. Calculation of the thermodynamic properties at elevated temperatures and pressures of saturated and aromatic high molecular weight solid and liquid hydrocarbons in kerogen, bitumen, petroleum, and other organic matter of biogeochemical interest. Geochimica et Cosmochimica Acta 62(23-24): 3591–3636. doi: 10.1016/S0016-7037(97)00345-1

Robie RA, Hemingway BS. 1995. Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures. Washington, D. C.: U. S. Geological Survey. (Bulletin 2131). doi: 10.3133/b2131

Robie RA, Hemingway BS, Fisher JR. 1978. Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures. U. S. Geological Surv. (Bulletin 1452). Available at http://pubs.er.usgs.gov/publication/b1452.

Saccocia PJ, Seyfried WE. 1993. A resolution of discrepant thermodynamic properties for chamosite retrieved from experimental and empirical techniques. American Mineralogist 78(5-6): 607–611. Available at http://ammin.geoscienceworld.org/content/78/5-6/607.

Sassani DC, Shock EL. 1998. Solubility and transport of platinum-group elements in supercritical fluids: Summary and estimates of thermodynamic properties for ruthenium, rhodium, palladium, and platinum solids, aqueous ions, and complexes to 1000°C and 5 kbar. Geochimica et Cosmochimica Acta 62(15): 2643–2671. doi: 10.1016/S0016-7037(98)00049-0

Schulte M. 2010. Organic sulfides in hydrothermal solution: Standard partial molal properties and role in organic geochemistry of hydrothermal environments. Aquatic Geochemistry 16(4): 621–637. doi: 10.1007/s10498-010-9102-3

Schulte MD, Rogers KL. 2004. Thiols in hydrothermal solution: Standard partial molal properties and their role in the organic geochemistry of hydrothermal environments. Geochimica et Cosmochimica Acta 68(5): 1087–1097. doi: 10.1016/j.gca.2003.06.001

Schulte MD, Shock EL. 1993. Aldehydes in hydrothermal solution: Standard partial molal thermodynamic properties and relative stabilities at high temperatures and pressures. Geochimica et Cosmochimica Acta 57(16): 3835–3846. doi: 10.1016/0016-7037(93)90337-V

Schulte MD, Shock EL, Wood RH. 2001. The temperature dependence of the standard-state thermodynamic properties of aqueous nonelectrolytes. Geochimica et Cosmochimica Acta 65(21): 3919–3930. doi: 10.1016/S0016-7037(01)00717-7

Shock EL. 1992. Stability of peptides in high-temperature aqueous solutions. Geochimica et Cosmochimica Acta 56(9): 3481–3491. doi: 10.1016/0016-7037(92)90392-V

Shock EL. 1993. Hydrothermal dehydration of aqueous organic compounds. Geochimica et Cosmochimica Acta 57(14): 3341–3349. doi: 10.1016/0016-7037(93)90542-5

Shock EL. 1995. Organic acids in hydrothermal solutions: Standard molal thermodynamic properties of carboxylic acids and estimates of dissociation constants at high temperatures and pressures. American Journal of Science 295(5): 496–580. doi: 10.2475/ajs.295.5.496

Shock EL. 2009. Minerals as energy sources for microorganisms. Economic Geology 104(8): 1235–1248. doi: 10.2113/gsecongeo.104.8.1235

Shock EL, Helgeson HC. 1988. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C. Geochimica et Cosmochimica Acta 52(8): 2009–2036. doi: 10.1016/0016-7037(88)90181-0

Shock EL, Helgeson HC. 1990. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of organic species. Geochimica et Cosmochimica Acta 54(4): 915–945. doi: 10.1016/0016-7037(90)90429-O

Shock EL, Helgeson HC, Sverjensky DA. 1989. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species. Geochimica et Cosmochimica Acta 53(9): 2157–2183. doi: 10.1016/0016-7037(89)90341-4

Shock EL, Koretsky CM. 1993. Metal-organic complexes in geochemical processes: Calculation of standard partial molal thermodynamic properties of aqueous acetate complexes at high pressures and temperatures. Geochimica et Cosmochimica Acta 57(20): 4899–4922. doi: 10.1016/0016-7037(93)90128-J

Shock EL, Koretsky CM. 1995. Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures. Geochimica et Cosmochimica Acta 59(8): 1497–1532. doi: 10.1016/0016-7037(95)00058-8

Shock EL, McKinnon WB. 1993. Hydrothermal processing of cometary volatiles—Applications to Triton. Icarus 106(2): 464–477. doi: 10.1006/icar.1993.1185

Shock EL, Sassani DC, Betz H. 1997b. Uranium in geologic fluids: Estimates of standard partial molal properties, oxidation potentials, and hydrolysis constants at high temperatures and pressures. Geochimica et Cosmochimica Acta 61(20): 4245–4266. doi: 10.1016/S0016-7037(97)00240-8

Shock EL, Sassani DC, Willis M, Sverjensky DA. 1997. Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes. Geochimica et Cosmochimica Acta 61(5): 907–950. doi: 10.1016/S0016-7037(96)00339-0

Shvedov D, Tremaine PR. 1997. Thermodynamic properties of aqueous dimethylamine and dimethylammonium chloride at temperatures from 283 K to 523 K: Apparent molar volumes, heat capacities, and temperature dependence of ionization. Journal of Solution Chemistry 26(12): 1113–1143. doi: 10.1023/A:1022977006327

slop07.dat. 2007. Sequential-access thermodynamic datafile used by PROGRAM supcrt92. Last updated on 2008-04-17. Accessed on 2019-04-08. doi: 10.5281/zenodo.2630820

slop16.dat. 2016. Sequential-access thermodynamic datafile used by PROGRAM supcrt92. Last updated on 2019-03-12. Accessed on 2019-04-08. doi: 10.5281/zenodo.2630820

slop98.dat. 1998. Sequential-access thermodynamic datafile used by PROGRAM supcrt92. Last updated on 1998-08-20. Accessed on 2019-04-08. doi: 10.5281/zenodo.2630820

sprons92.dat. 1992. S[equential-access] pro[perties of] n[atural] s[ubstances].dat; datafile used by PROGRAM supcrt91. Included with the SUPCRT92 package (Johnson et al., 1992). Last updated on 1991-02-15.

Stefánsson A. 2001. Dissolution of primary minerals of basalt in natural waters. I. Calculation of mineral solubilities from 0°C to 350°C. Chemical Geology 172: 225–250. doi: 10.1016/S0009-2541(00)00263-1

Stoffregen RE, Alpers CN, Jambor JL. 2000. Alunite-jarosite crystallography, thermodynamics, and geochronology. In: Sulfate Minerals: Crystallography, Geochemistry and Environmental Significance. Mineralogical Society of America. pp. 453–479. doi: 10.2138/rmg.2000.40.9

Sverjensky DA, Harrison B, Azzolini D. 2014. Water in the deep Earth: The dielectric constant and the solubilities of quartz and corundum to 60 kb and 1,200 °C. Geochimica et Cosmochimica Acta 129: 125–145. doi: 10.1016/j.gca.2013.12.019

Sverjensky DA, Hemley JJ, D’Angelo WM. 1991. Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria. Geochimica et Cosmochimica Acta 55(4): 989–1004. doi: 10.1016/0016-7037(91)90157-Z

Sverjensky DA, Shock EL, Helgeson HC. 1997. Prediction of the thermodynamic properties of aqueous metal complexes to 1000°C and 5 kb. Geochimica et Cosmochimica Acta 61(7): 1359–1412. doi: 10.1016/S0016-7037(97)00009-4

Tagirov B, Schott J. 2001. Aluminum speciation in crustal fluids revisited. Geochimica et Cosmochimica Acta 65(21): 3965–3992. doi: 10.1016/S0016-7037(01)00705-0

Tagirov BR, Baranova NN, Bychkova YV. 2015. Thermodynamic properties of platinum chloride complexes in aqueous solutions: Derivation of consistent parameters from literature data and experiments on Pt(cr) solubility at 400–475°C and 1 kbar. Geochemistry International 53(4): 327–340. doi: 10.1134/S0016702915040084

Tagirov BR, Baranova NN, Zotov AV, Akinfiev NN, Polotnyanko NA, Shikina ND, Koroleva LA, Shvarov YV, Bastrakov EN. 2013. The speciation and transport of palladium in hydrothermal fluids: Experimental modeling and thermodynamic constraints. Geochimica et Cosmochimica Acta 117: 348–373. doi: 10.1016/j.gca.2013.03.047

Tagirov BR, Zotov AV, Akinfiev NN. 1997. Experimental study of dissociation of HCl from 350 to 500°C and from 500 to 2500 bars: Thermodynamic properties of HCl°(aq). Geochimica et Cosmochimica Acta 61(20): 4267–4280. doi: 10.1016/S0016-7037(97)00274-3

Tanger JC IV, Helgeson HC. 1988. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Revised equations of state for the standard partial molal properties of ions and electrolytes. American Journal of Science 288(1): 19–98. doi: 10.2475/ajs.288.1.19

Tardy Y, Schaul R, Duplay J. 1997. Domaines de stabilité thermodynamiques des humus, de la microflore et des plantes. Comptes Rendus de l’Academie des Sciences, Serie IIa: Sciences de la Terre et des Planetes 324(12): 969–976. doi: 10.1016/S1251-8050(97)83981-X

Tutolo BM, Kong X-Z, Seyfried J William E., Saar MO. 2014. Internal consistency in aqueous geochemical data revisited: Applications to the aluminum system. Geochimica et Cosmochimica Acta 133: 216–234. doi: 10.1016/j.gca.2014.02.036

Vidal O, Goffé B, Theye T. 1992. Experimental study of the stability of sudoite and magnesiocarpholite and calculation of a new petrogenetic grid for the system FeO–MgO–Al2O3–SiO2–H2O. Journal of Metamorphic Geology 10(5): 603–614. doi: 10.1111/j.1525-1314.1992.tb00109.x

Vidal O, Parra T, Trotet F. 2001. A thermodynamic model for fe-mg aluminous chlorite using data from phase equilibrium experiments and natural pelitic assemblages in the 100° to 600°C, 1 to 25 kb range. American Journal of Science 301(6): 557–592. doi: 10.2475/ajs.301.6.557

Vidal O, Parra T, Viellard P. 2005. Thermodynamic properties of the Tschermak solid solution in Fe-chlorite: Application to natural examples and possible role of oxidation. American Mineralogist 90(2-3): 347–358. Mineralogical Society of America. doi: 10.2138/am.2005.1554

Wagman DD, Evans WH, Parker VB, Schumm RH, Halow I, Bailey SM, Churney KL, Nuttall RL. 1982. The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C1 and C2 organic substances in SI units. Journal of Physical and Chemical Reference Data 11(Suppl. 2): 1–392. Available at https://srd.nist.gov/JPCRD/jpcrdS2Vol11.pdf.

Wagner W, Pruß A. 2002. The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use. Journal of Physical and Chemical Reference Data 31(2): 387–535. doi: 10.1063/1.1461829

Wood SA, Samson IM. 2000. The hydrothermal geochemistry of tungsten in granitoid environments: I. Relative solubilities of ferberite and scheelite as a function of T, P, pH, and mNaCl. Economic Geology 95(1): 143–182. doi: 10.2113/gsecongeo.95.1.143

Yang C, Inoue T, Yamada A, Kikegawa T, Ando J-i. 2014. Equation of state and phase transition of antigorite under high pressure and high temperature. Physics of the Earth and Planetary Interiors 228(Supplement C): 56–62. doi: 10.1016/j.pepi.2013.07.008

Zhu C, Sverjensky DA. 1992. F-Cl-OH partitioning between biotite and apatite. Geochimica et Cosmochimica Acta 56(9): 3435–3467. doi: 10.1016/0016-7037(92)90390-5

Zhu Y, Zhang X, Xie Q, Chen Y, Wang D, Liang Y, Lu J. 2005. Solubility and stability of barium arsenate and barium hydrogen arsenate at 25 °C. Journal of Hazardous Materials 120(1): 37–44. doi: 10.1016/j.jhazmat.2004.12.025

Zimmer K, Zhang Y, Lu P, Chen Y, Zhang G, Dalkilic M, Zhu C. 2016. SUPCRTBL: A revised and extended thermodynamic dataset and software package of SUPCRT92. Computers & Geosciences 90: 97–111. doi: 10.1016/j.cageo.2016.02.013