Reactions

TuesdayReactions in PHREEQCPHREEQC mechanicsImportant geochemical reactions discussion and exercisesCarbonatesOxidation of organic carbonOxidation of pyriteAluminosilicate reactions

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Reaction Calculations

EQUILIBRATION REACTOR

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SOLUTIONChemical Composition of a WaterChemical analysispHTemperatureMajor elements Ca, Mg, Na, K, Alkalinity, Cl, SO4Trace elementsNutrients*

(Irreversible) REACTIONAdd/Remove elements to waterMake a solution 1 m NaCl and 2 m KBrStart with waterREACTIONNaCl 1KBr 21 mole*

EQUILIBRIUM_PHASESAssemblage of Minerals and Gases that react to equilibrium CalciteCaCO3 = Ca+2 + CO3-2

EquilibriumK = [Ca+2][CO3-2] *

EQUILIBRIUM_PHASES Data BlockMineral or gasSaturation stateAmount

Example EQUILIBRIUM_PHASES 5:CO2Log PCO2 = -2, 10 molesCalciteequilibrium 1 molesDolomiteequilibrium 1 molesFe(OH)3 equilibrium0 moles*

EXCHANGECation Exchange CompositionExchangeable cations in interlayers of clays

Ca+2 + 2NaX = CaX2 + 2Na+

Equilibrium:

*

EXCHANGE Data Block DefinitionExchanger nameNumber of exchange sitesChemical composition of exchanger

Example EXCHANGE 5:CaX2 0.05 moles (X is defined in databases)NaX0.05 molesOftenX 0.15 moles, Equilibrium with solution 1*

SURFACESurface CompositionTrace elements Zn, Cd, Pb, As, PSorption onto the surfaces of minerals and organic matter, usually hydrous ferric oxides

HfoOH + AsO4-3 = HfoOHAsO4-3

Equilibrium:*

SURFACE Data Block DefinitionSurface nameHfo is Hydrous Ferric OxideNumber of surface sitesChemical composition of surfaceExample SURFACE 21:Hfo_wOH0.001 molesHfo_sOH .00005 molesOftenHfo_w0.001 moles, Equilibrium with solution 1*

KINETICSNonequilibrium ReactionsCan affect any chemical constituentMonod KineticsRadioactive decaySilicate hydrolosisOrganic decompositionBiological processes*

KINETICS and RATES Data Block DefinitionsKinetic reaction nameStoichiometry of reactionRate expression (RATES) Example Kinetics 21:DOC_decayDoc -1 CH2O +1RATES10 Rate = 0.01*TOT(Doc)20 SAVE rate*TIME*

SOLID_SOLUTIONSComposition of one or more solid solutions

Trace elements and isotopesList of solid solutionsComponents of each solid solution

Example SOLID_SOLUTION 21:Calcite solid solutionCa[13C]O3CaCO3*

GAS_PHASEFinite gas phase in equilibrium with solutionGas bubbles that grow

Gas bubbles that fill a finite volume*

GAS_PHASEComposition of the gas phase

Fixed volume or Fixed pressureInitial volumeInitial pressureTemperaturePartial pressure of each gasExample GAS_PHASE 1:Fixed pressureCO2(g) 0.0CH4(g) 0.0*

PHREEQC ReactantsKeyword data blocks define reactants

SolutionsSOLUTIONIrreversible reactionREACTIONEquilibrium minerals and gasesEQUILIBRIUM_PHASESExchangersEXCHANGE SurfacesSURFACE Kinetic reactionsKINETICS and RATESSolid solutionsSOLID_SOLUTIONS

Store reactants on shelves by type and number*

PHREEQCReactionsFrom the shelfTo the beaker*

EQUILIBRIUM REACTIONSSURFACE EXCHANGE SOLID_SOLUTIONS EQUILIBRIUM_PHASES GAS_PHASE*

NON-EQUILIBRIUM REACTIONSMIXREACTIONREACTION_TEMPERATUREKINETICS*

CONCEPTUAL MODELInitial conditionSOLUTION or MIXAdd irreversible reactants REACTIONKINETICSREACTION_TEMPERATUREAdd reversible reactantsEQUILIBRIUM_PHASESSURFACEEXCHANGESOLID_SOLUTIONGAS_PHASECalculate new compositionSAVE compositions if needed

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Todays Geochemical ReactionsCarbonatesOxidation of organic carbonOxidation of pyriteAluminosilicate reactions

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Todays PHREEQC Data BlocksSOLUTIONMIXEQUILIBRIUM_PHASESREACTIONENDSAVE and USE(GAS_PHASE)*

ReactionsImplicit redox reactions*

MIX: One or more SOLUTIONSType solution number Type mixing fraction*

REACTION 1. Exercise Implicit Redox Reactions

mg/LDefine rainwater as SOLUTION 1 with log partial pressure of O2 = -0.7 and CO2 = -3.5.Define END.Define MIX by using solution 1 and mixing fraction 1.Define END.Run.*

Sheet1

SOLUTION_SPREAD

units mg/L

DescriptionTemppHO(0)CaMgNaKClS(6)C(4)N(5)N(-3)

Rainwater254.510.3840.0430.1410.0360.2361.310.2370.208

Sheet2

pHm_CO2m_HCO3-m_CO3-2

49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04

pHCm_CO2m_HCO3-m_CO3-2

66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Sheet2

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

Sheet3

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

Sheet4

Data in mmmo/kgw

SolutionFe(2)Fe(3)S(6)S(-2)PyriteGoethite

10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

Useful Minerals

CarbonatesPhosphates

CO2(g)CO2HydroxyapatiteCa5(PO4)3OH

CalciteCaCO3VivianiteFe3(PO4)2

DolomiteCaMgCO3Oxyhydroxides

SideriteFeCO3Fe(OH)3(a)Fe(OH)3

RhodochrositeMnCO3GoethiteFeOOH

SulfatesGibbsiteAl(OH)3

GypsumCaSO4BirnessiteMnO2

CelestiteSrSO4ManganiteMn(OH)3

BariteBaSO4Aluminosilicates

SulfidesSilica gelSiO2-2H2O

FeS(a)FeSSilica glassSiO2-H2O

MackinawiteFeSChalcedonySiO2

KaoliniteAl2Si2O5(OH)

R1. Questions1. Explain the differences between the initial solution composition and the reaction (mixed) solution composition, particularly pH, pe, N(5), N(0), and N(-3).*

R1. AnswersInitial solutionReaction solution pH 4.500 4.216 pe4.000 16.373 O(0)4.375e-0043.781e-004N(5)1.692e-0053.177e-005N(0)01.126e-016N(-3)1.485e-0050.000e+000

The differences are caused entirely by redox equilibration. Initial solution is in redox disequilibrium, the reaction solution is in redox equilibrium. In the reaction solution:

N(-3) has been oxidized to N(5) and N(0). O(0) has been reduced in the process of oxidizing N(-3). Oxidation tends to decrease pH. Redox is defined by O(0)/O(-2) and N(5)/N(0) redox couples, both will give the same pe.

*

Redox CalculationsInitial solutionAllows redox disequilibriaTotal N(5), N(-3), O(0)Reaction calculationsComplete aqueous redox equilibriumCan redefine elements for disequilibriumN, N(5), N(3), N(0), N(-3), Ngas, Amm*

ReactionsSequential Reactions*

SAVE and USESave results of reaction calculationsUse previously defined SOLUTIONs, EQUILIBRIUM_PHASES, REACTIONs, etc Use previously SAVEd SOLUTIONS, EQUILBRIUM_PHASES, etc*

SAVE results from a Reaction CalculationNote: SOLUTION defines an initial solution calculation, which is automatically saved. Index numbers are used to keep trackIndex numbers do not need to be sequential*

USE: Previously defined or SAVEdUSE includes KINETICS, MIX, REACTION, and REACTION_TEMPERATURE

Can USE previously SAVEd EQUILIBRIUM_PHASES, EXCHANGE, SOLID_SOLUTION, SOLUTION, SURFACE, or GAS_PHASE

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Initial Solution and Reaction Calculations*

REACTION: Reactants and stoichiometryChoose phase or type formulaDefine relative stoichiometryMust be charge balanced*

REACTION: Reaction amountsSteps are a number of equal incrementsorSteps are a specified listSpecify units*

EQUILIBRIUM_PHASESAssembly of minerals/gases that react to equilibrium or zero molesDefineMineral/gasTarget saturation indexMoles present*

Initial Solution and Reaction Calculations*

Initial Solution and Reaction CalculationsThe END statementENDdefines a SimulationWithin a simulationEvery SOLUTION results in an initial solution calculation (unique index)Reaction calculationSOLUTION + one of each reactant type before ENDReactants can be keyword blocksReactants be defined by USE ENDRun speciation calculationsRun reaction calculationsRun transport calculationsSAVE results*

Speciation and Reaction CalculationsThe enigmatic ENDSimulation 1Speciation calculation solution 1Speciation calculation solution 2Reaction calculationSOLUTION 1EQUILIBRIUM_PHASES 2REACTION 3Simulation 2Speciation calculation solution 3Reaction calculationSOLUTION 2EQUILIBRIUM_PHASES 1REACTION 3Simulation 3No speciation calculationNo reaction calculationNo Reactant defined*

REACTION 3.Exercise Sequential ReactionsMake an unsaturated zone water. Build on previous exercise with rainwater. Add SAVE solution 2 after MIX step and before END. After the END, add USE solution 2 and equilibrate (EQUILIBRIUM_PHASES) with CO2, log partial pressure 2, and calcite (SI = 0), save solution as solution 3. END.Use solution 3, add 1 mmol CO2 (REACTION), equilibrate with calcite (EQUILIBRIUM_PHASES), save as solution 4.*

R3. QuestionsWhat is the log pCO2 of the rainwater, rainwater, in redox equilibrium (the mixture), the mixture equilibrated with CO2 and calcite, and after reaction with CO2 and calcite?How many millimoles of calcite and CO2 reacted to make solution 3?How many millimoles of calcite reacted to make solution 4 from solution 3?

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R3.AnswersQuestion 1.Solution 1 RainwaterSolution 2 Rainwater, redox equilibriumSolution 3 Solution 2 + equilibrium with CO2 and CalciteSolution 4 Solution 3 + Reaction + equilibrium with Calcite

Solution 1Solution 2Solution 3Solution 4CO2(g)-3.50 -3.49 -2.00 -1.65

Question 2.Phase SI log IAP log KT Initial Final DeltaCalcite 0.00 -8.48 -8.48 1.000e+001 9.998e+000 -1.749e-003CO2(g) -2.00 -20.15 -18.15 1.000e+001 9.998e+000 -1.774e-003

1.74 mmol calcite dissolve.1.77 mmol CO2 dissolve.

Question 3.Phase SI log IAP log KT Initial Final DeltaCalcite 0.00 -8.48 -8.48 1.000e+001 9.999e+000 -5.767e-004

0.58 millimoles of calcite dissolve.*

REACTION 5. Extra Credit ExerciseUse MIX and REACTION to evaporate rainwater 20 fold (at constant pCO2) before reaction with CO2 and calcite. Hint: You must remove water and water has 55.5 mol per kg.*

R5. Answer

SOLUTION_SPREAD Description Temp pH O(0) Ca Mg Na K O2(g) -0.7 CO2(g) -3.5 Rainwater 25 4.5 1 0.384 0.043 0.141 0.036 ENDMIX 1 1 20REACTIONH2O55.5-19 molesEQUILIBRIUM_PHASESCO2(g)-3.5SAVE solution 2ENDUSE solution 2EQUILIBRIUM_PHASES 2 Calcite 0 10 CO2(g) -2 10SAVE solution 3ENDUSE solution 3REACTION 1 CO2 1 1 millimolesEQUILIBRIUM_PHASES 3 Calcite 0 10SAVE solution 4END*

REACTIONS in PHREEQCInitial-solution calculationReaction calculation includes any of the following:

Simulation/ENDSAVEUSEIndex numbersMIXREACTIONREACTION_TEMPERATUREEQUILIBRIUM_PHASESEXCHANGESURFACE SOLID_SOLUTION GAS_PHASEKINETICS*

ReactionsDedolomitization*

Dedolomitization

Anhydrite dissolution

Calcite precipitation

Dolomite dissolution*

REACTION 6. ExerciseMake a ground water with log pCO2 = -2, equilibrium with calcite and dolomite.

React 50 mmol of anhydrite (CaSO4) in increments of 10 mmol. Maintain equilibrium with calcite and dolomite, allow anhydrite to precipitate if it becomes saturated.

You need to use these data blocks: SOLUTION, EQUILIBRIUM_PHASES, REACTION, USE, SAVE in two simulations.*

REACTION 6.QuestionsWhat trends do you expect in water composition with anhydrite-driven dedolomitization?Why is the following reaction misleading?CaSO4 + CaMg(CO3)2 = 2CaCO3 + Mg+2 + SO4-2 3. How does the water composition change from step 4 to step 5?

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Reaction 6. Answers*

Chart1

4.29371.69551.259317.29095

4.24932.23681.67362.00017.22824

4.21342.7822.09253.00017.18027

4.18353.32992.51484.00017.14167

4.15793.87972.93945.00027.10951

4.13574.4313.36596.00027.08204

4.1164.98343.79397.00027.05811

4.09855.53684.2238.00037.03696

4.08276.09094.65319.00037.01803

4.06836.64575.084107.00091

4.05527.2015.5156116.98531

4.04317.75685.9477126.97099

4.03198.3136.3803136.95775

4.02158.86966.8134146.94546

4.01189.42657.2469156.93399

4.00289.98367.6806166.92325

3.994210.5418.114717.0016.91314

3.986211.0998.549118.0016.9036

3.978611.6578.983619.0016.89458

3.971512.2159.418420.0016.88601

3.964712.7739.853321.0016.87786

3.958213.33110.28822.0016.87009

3.95213.8910.72423.0016.86267

3.946214.44911.15924.0016.85557

3.940515.00811.59525.0016.84876

3.935215.56712.0326.0016.84221

3.9316.12612.46627.0016.83592

3.925116.68512.90228.0016.82986

3.920317.24513.33829.0016.82401

3.915817.80413.77430.0016.81837

3.911418.36414.2131.0016.81291

3.907218.92314.64632.0016.80763

3.903119.48315.08233.0016.80251

3.899120.04315.51834.0016.79754

3.895320.60315.95435.0016.79273

3.891621.16316.39136.0016.78805

3.888121.72316.82737.0016.7835

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

3.887621.80116.88837.146.78288

C

Ca

Mg

S

pH

r6a

pHreactionCCaMgSreactionCCaMgSpH

7.290951.00E-034.29E-031.70E-031.26E-031.00E-031.00E+004.29E+001.70E+001.26E+001.00E+007.29095

7.228242.00E-034.25E-032.24E-031.67E-032.00E-032.00E+004.25E+002.24E+001.67E+002.00E+007.22824

7.180273.00E-034.21E-032.78E-032.09E-033.00E-033.00E+004.21E+002.78E+002.09E+003.00E+007.18027

7.141674.00E-034.18E-033.33E-032.51E-034.00E-034.00E+004.18E+003.33E+002.51E+004.00E+007.14167

7.109515.00E-034.16E-033.88E-032.94E-035.00E-035.00E+004.16E+003.88E+002.94E+005.00E+007.10951

7.082046.00E-034.14E-034.43E-033.37E-036.00E-036.00E+004.14E+004.43E+003.37E+006.00E+007.08204

7.058117.00E-034.12E-034.98E-033.79E-037.00E-037.00E+004.12E+004.98E+003.79E+007.00E+007.05811

7.036968.00E-034.10E-035.54E-034.22E-038.00E-038.00E+004.10E+005.54E+004.22E+008.00E+007.03696

7.018039.00E-034.08E-036.09E-034.65E-039.00E-039.00E+004.08E+006.09E+004.65E+009.00E+007.01803

7.000911.00E-024.07E-036.65E-035.08E-031.00E-021.00E+014.07E+006.65E+005.08E+001.00E+017.00091

6.985311.10E-024.06E-037.20E-035.52E-031.10E-021.10E+014.06E+007.20E+005.52E+001.10E+016.98531

6.970991.20E-024.04E-037.76E-035.95E-031.20E-021.20E+014.04E+007.76E+005.95E+001.20E+016.97099

6.957751.30E-024.03E-038.31E-036.38E-031.30E-021.30E+014.03E+008.31E+006.38E+001.30E+016.95775

6.945461.40E-024.02E-038.87E-036.81E-031.40E-021.40E+014.02E+008.87E+006.81E+001.40E+016.94546

6.933991.50E-024.01E-039.43E-037.25E-031.50E-021.50E+014.01E+009.43E+007.25E+001.50E+016.93399

6.923251.60E-024.00E-039.98E-037.68E-031.60E-021.60E+014.00E+009.98E+007.68E+001.60E+016.92325

6.913141.70E-023.99E-031.05E-028.11E-031.70E-021.70E+013.99E+001.05E+018.11E+001.70E+016.91314

6.90361.80E-023.99E-031.11E-028.55E-031.80E-021.80E+013.99E+001.11E+018.55E+001.80E+016.9036

6.894581.90E-023.98E-031.17E-028.98E-031.90E-021.90E+013.98E+001.17E+018.98E+001.90E+016.89458

6.886012.00E-023.97E-031.22E-029.42E-032.00E-022.00E+013.97E+001.22E+019.42E+002.00E+016.88601

6.877862.10E-023.96E-031.28E-029.85E-032.10E-022.10E+013.96E+001.28E+019.85E+002.10E+016.87786

6.870092.20E-023.96E-031.33E-021.03E-022.20E-022.20E+013.96E+001.33E+011.03E+012.20E+016.87009

6.862672.30E-023.95E-031.39E-021.07E-022.30E-022.30E+013.95E+001.39E+011.07E+012.30E+016.86267

6.855572.40E-023.95E-031.44E-021.12E-022.40E-022.40E+013.95E+001.44E+011.12E+012.40E+016.85557

6.848762.50E-023.94E-031.50E-021.16E-022.50E-022.50E+013.94E+001.50E+011.16E+012.50E+016.84876

6.842212.60E-023.94E-031.56E-021.20E-022.60E-022.60E+013.94E+001.56E+011.20E+012.60E+016.84221

6.835922.70E-023.93E-031.61E-021.25E-022.70E-022.70E+013.93E+001.61E+011.25E+012.70E+016.83592

6.829862.80E-023.93E-031.67E-021.29E-022.80E-022.80E+013.93E+001.67E+011.29E+012.80E+016.82986

6.824012.90E-023.92E-031.72E-021.33E-022.90E-022.90E+013.92E+001.72E+011.33E+012.90E+016.82401

6.818373.00E-023.92E-031.78E-021.38E-023.00E-023.00E+013.92E+001.78E+011.38E+013.00E+016.81837

6.812913.10E-023.91E-031.84E-021.42E-023.10E-023.10E+013.91E+001.84E+011.42E+013.10E+016.81291

6.807633.20E-023.91E-031.89E-021.46E-023.20E-023.20E+013.91E+001.89E+011.46E+013.20E+016.80763

6.802513.30E-023.90E-031.95E-021.51E-023.30E-023.30E+013.90E+001.95E+011.51E+013.30E+016.80251

6.797543.40E-023.90E-032.00E-021.55E-023.40E-023.40E+013.90E+002.00E+011.55E+013.40E+016.79754

6.792733.50E-023.90E-032.06E-021.60E-023.50E-023.50E+013.90E+002.06E+011.60E+013.50E+016.79273

6.788053.60E-023.89E-032.12E-021.64E-023.60E-023.60E+013.89E+002.12E+011.64E+013.60E+016.78805

6.78353.70E-023.89E-032.17E-021.68E-023.70E-023.70E+013.89E+002.17E+011.68E+013.70E+016.7835

6.782883.80E-023.89E-032.18E-021.69E-023.71E-023.80E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782883.90E-023.89E-032.18E-021.69E-023.71E-023.90E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.00E-023.89E-032.18E-021.69E-023.71E-024.00E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.10E-023.89E-032.18E-021.69E-023.71E-024.10E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.20E-023.89E-032.18E-021.69E-023.71E-024.20E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.30E-023.89E-032.18E-021.69E-023.71E-024.30E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.40E-023.89E-032.18E-021.69E-023.71E-024.40E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.50E-023.89E-032.18E-021.69E-023.71E-024.50E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.60E-023.89E-032.18E-021.69E-023.71E-024.60E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.70E-023.89E-032.18E-021.69E-023.71E-024.70E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.80E-023.89E-032.18E-021.69E-023.71E-024.80E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782884.90E-023.89E-032.18E-021.69E-023.71E-024.90E+013.89E+002.18E+011.69E+013.71E+016.78288

6.782885.00E-023.89E-032.18E-021.69E-023.71E-025.00E+013.89E+002.18E+011.69E+013.71E+016.78288

r6a

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C

Ca

Mg

S

pH

Reaction 6.Answers

Question 1.

Increase in SO4, increase in Ca and Mg, constant or decrease in HCO3, decrease in pH, SIs near zero for calcite and dolomite.

Question 2.

You do not get a Mg+2 SO4-2 water composition. Ratio of Mg/Ca is approximately constant at .3 to 1 (depending on K for dolomite).

To get to the final water composition, the net reaction is approximately

37CaSO4 + 16CaMg(CO3)2 = 32CaCO3 + 21Ca+2 + 16Mg+2 + 37SO4-2

Question 3.

System has reached equilibrium and does not change. However, it is not quite an invariant point.*

SELECTED_OUTPUT2. Reset all to falseFile name3. Set pH to true4. Set Reaction true1. Set file name (default selected.out)*

Selected Output: Total Molalities*

Selected Output*

Selected Output FileOpen with ExcelManipulate/plot dataPFW has built-in plotting capability

*

REACTION 8. QuestionsPlummer and Sprinkle, 2001Units are mg/L, S(-2) as H2S1. Are these the trends of dedolomitization?2. Anything else?*

Sheet1

Seawater

units ppm

DescriptionNumberTemppHCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.22412.31291.810768399.1141.6821935327120.002

Ok ground Water

units mg/L

DescriptionNumberTemppHCaMgNaKAlkalinityClS(6)N(5)N(-3)BaSrP

City of Jones 13N-01W-34 CAB17.57.44221121.5196128.10.490.330.23

Rainwater254.50.3840.0430.1410.0360.2361.30.2370.2080.0003

Charleston

NumberTemppHCaMgNaKAlkalinityClS(6)SiBSr

as CaCO3ug/lug/l

Recovered water617.4610.312.63.5330122912807519

Background1122.556.992126160041747180028040

Treated injection water22227.8202.3182.43223337.6

Cape Cod

Background water

Sewage plume

Florida, Flowpath II

S(-2) as H2Smg/L

NumberTemppHCaMgNaKAlkalinityClS(6)SiSrS(-2)

1.1124.77.76388.140.8143.96.912130.0810

2.4431.57.4510052122.9176.11434021241.92

2.6627.27.481147926517177.54121801915.32.6

Sheet2


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Sheet2

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

Sheet3

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

Sheet4

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

Sheet5

Useful Minerals















frac_swCalcite_dis_mmolDolomite_dis_mmol

0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

00

00

00

00

00

00

CALCITE

DOLOMITE

FRACTION OF SEAWATER

MMOL DISSOLVED

Reaction 8. AnswersYes, Increase in Ca, Mg, SO4; decrease in pH; not much change in alkalinity.Decrease in sulfate (number 4 to number 6) and H2S indicate sulfate reduction.Na and Cl indicate mixing with seawater*

EQUILIBRIUM_PHASE:Dissolve OnlyForce mineral not to precipitate*

REACTION 9. ExerciseMake a ground water with log pCO2 = -2, equilibrium with calcite and dolomite.Equilibrate seawater (major ions only) with calcite and dolomite; allow dolomite only to dissolve.Mix ground water with seawater in fractions of .25, 0.5, .75. Maintain equilibrium with calcite; allow dolomite only to dissolve.*

REACTION 9.QuestionsWhat reaction is calculated for seawater equilibration with calcite and dolomite?

What reactions are calculated for a carbonate reactions for the ground-water/seawater mixtures?*

Reaction 9. AnswersCalcite precipitates; dolomite does not react, but should precipitate. Seawater mixing zones have been suggested as a place where dolomitization could occur, but there is little evidence for present-day dolomitization. Apparently kinetics of dolomite formation are too slow, even though it should form according to thermodynamics.

Dolomite is always supersaturated and is not allowed to form by the problem definition. Calcite dissolves at the .75 ground-water mixing fraction and precipitates at .5 and .25. Saturation indices of mixtures are non-linear. Even though the ground water is saturated and seawater is supersaturated with calcite, 0.75 g-w mixture is undersaturated with calcite. In this case, it is an activity coefficient effect; the effect of the decrease in activity coefficients of the mixture is larger than the effect of the increase in concentration, which results in a negative saturation index for calcite and dissolution.*

Carbonate ReactionsCarbonate ground waterPCO2 -1 to -3.0Calcite, or calcite and dolomiteCO2 supply in the UZDedolomitizationAnhydrite dissolutionCalcite precipitationDolomite dissolutionOther reactionsSulfate reductionIon exchangeDolomitizationRareSeawater mixing can dissolve calcite*

ReactionsOrganic decomposition*

Organic Decomposition

Sequential removal of electron acceptors, usually in the sequence:O2NO3-MnO2Fe(OH)3SO4-2Organic carbon*

Redox EnvironmentsOxicDissolved O2 reductionCH2O + O2 = CO2 + H2OPost-oxicNO3-, MnO2, Fe(OH)3 reductionCH2O + 4Fe(OH)3 + 7CO2 = 4Fe+2 + 8HCO3- + 3H2OSulfidicSO4-2 reduction2CH2O + SO4-2 = 2HCO3- + H2SMethanicCH4CH2O = CO2 + CH4*

Redox Environments*

Chart5

03.30135.05420.28520.785

-12.2993.929419.2819.78

-21.29882.774918.2818.78

-30.298771.55817.2817.78

-4-0.701450.3128416.2816.78

-5-1.7036-0.9360815.2815.78

-6-2.7214-2.180514.2814.78

-7-3.7943-3.393813.2813.78

-8-4.91-4.547312.2812.78

-9-6.0365-5.676211.2811.78

-10-7.182-6.801610.2810.78

-11-8.3865-7.92689.289.78

-12-9.6361-9.05018.288.78

-13-10.911-10.1387.28057.7805

-14-12.21-11.1556.28616.7861

H2

Methanic

Sulfidic

Post-oxic

Oxic

pH

pe

Sheet1

Seawater

units ppm

DescriptionNumberTemppHpeCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.228.45412.31291.810768399.1141.6821935327120.002

Ok ground Water

units mg/L

DescriptionNumberTemppHO(0)CaMgNaKAlkalinityClS(6)N(5)N(-3)BaSrP

City of Jones 13N-01W-34 CAB17.57.44.14221121.5196128.10.490.330.23

Rainwater254.50.3840.0430.1410.0360.2361.30.2370.2080.0003

Charleston

NumberTemppHO(0)CaMgNaKAlkalinityClS(6)SiBSr

as CaCO3ug/lug/l

Recovered water617.4610.312.63.5330122912807519

Background1122.556.992126160041747180028040


Cape Cod

Background water

Sewage plume


S(-2) as H2Smg/L

NumberTemppHO(0)CaMgNaKAlkalinityClS(6)SiSrS(-2)

1.1124.77.760388.140.8143.96.912130.0810

2.4431.57.45010052122.9176.11434021241.92

2.6627.27.4801147926517177.54121801915.32.6

Sheet2


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Sheet2

m_CO2

m_HCO3-

m_CO3-2

Sheet3

C

m_CO2

m_HCO3-

m_CO3-2

Sheet4

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

Sheet5

Useful Minerals















Sheet6


0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

Sheet6

CALCITE

DOLOMITE


MMOL DISSOLVED

pHH2MethanicSulfidicPost-oxicOxic

00.00E+003.30E+005.05E+002.03E+012.08E+01

1-1.00E+002.30E+003.93E+001.93E+011.98E+01

2-2.00E+001.30E+002.77E+001.83E+011.88E+01

3-3.00E+002.99E-011.56E+001.73E+011.78E+01

4-4.00E+00-7.01E-013.13E-011.63E+011.68E+01

5-5.00E+00-1.70E+00-9.36E-011.53E+011.58E+01

6-6.00E+00-2.72E+00-2.18E+001.43E+011.48E+01

7-7.00E+00-3.79E+00-3.39E+001.33E+011.38E+01

8-8.00E+00-4.91E+00-4.55E+001.23E+011.28E+01

9-9.00E+00-6.04E+00-5.68E+001.13E+011.18E+01

10-1.00E+01-7.18E+00-6.80E+001.03E+011.08E+01

11-1.10E+01-8.39E+00-7.93E+009.28E+009.78E+00

12-1.20E+01-9.64E+00-9.05E+008.28E+008.78E+00

13-1.30E+01-1.09E+01-1.01E+017.28E+007.78E+00

14-1.40E+01-1.22E+01-1.12E+016.29E+006.79E+00

00.00E+00

1-1.00E+00

2-2.00E+00

3-3.00E+00

4-4.00E+00

5-5.00E+00

6-6.00E+00

7-7.00E+00

8-8.00E+00

9-9.00E+00

10-1.00E+01

11-1.10E+01

12-1.20E+01

13-1.30E+01

14-1.40E+01

03.30E+00

12.30E+00

21.30E+00

32.99E-01

4-7.01E-01

5-1.70E+00

6-2.72E+00

7-3.79E+00

8-4.91E+00

9-6.04E+00

10-7.18E+00

11-8.39E+00

12-9.64E+00

13-1.09E+01

14-1.22E+01

05.05E+00

13.93E+00

22.77E+00

31.56E+00

43.13E-01

5-9.36E-01

6-2.18E+00

7-3.39E+00

8-4.55E+00

9-5.68E+00

10-6.80E+00

11-7.93E+00

12-9.05E+00

13-1.01E+01

14-1.12E+01

02.03E+01

11.93E+01

21.83E+01

31.73E+01

41.63E+01

51.53E+01

61.43E+01

71.33E+01

81.23E+01

91.13E+01

101.03E+01

119.28E+00

128.28E+00

137.28E+00

146.29E+00

02.08E+01

11.98E+01

21.88E+01

31.78E+01

41.68E+01

51.58E+01

61.48E+01

71.38E+01

81.28E+01

91.18E+01

101.08E+01

119.78E+00

128.78E+00

137.78E+00

146.79E+00

H2

Methanic

Sulfidic

Post-oxic

Oxic

pH

pe

Redox Sequence at pH 7*

Redox couplepeO(-2)/O(0)12.9N(0)/N(5)11.8Se(4)/Se(6)7.7Cr(3)/Cr(6)7.0N(-3)/N(5)6.1Fe(2)/Fe(3) 3.9Se(-2)/Se(4)0.4U(4)/U(6)0.4As(3)/As(5)0.3V(3)/V(5)-2.3N(-3)/N(0) -3.2S(-2)/S(6)* (wateq4f.dat)-3.6C(-4)/C(4) -4.4

Organic decomposition REACTIONWRONG!

REACTIONCH2O -2SO4-2 -1HCO3- +2H2S +1 5 mmol2CH2O + SO4-2 = 2HCO3- + H2SRIGHT!

REACTIONCH2O 110 mmol

Or perhaps,REACTIONCH2O 1Doc -110 mmol

*

Organic Decomposition in PHREEQCMole balance of C increases H and O mole balances increase too, but equivalent to adding H2OIf there are electron acceptors, C ends up as CO3-2 speciesElectron acceptor effectively gives up O and assumes the more reduced stateThe choice of electron acceptor is thermodynamic*

REACTION 11a. ExerciseDilute seawater by 50 percent, equilibrate with atmospheric oxygen

React diluted seawater with 50 mmol of CH2O in 50 steps of 1 mmol. Equilibrate with .1 moles of Fe(OH)3(a) and 0.0 mol of mackinawite. Print moles of reaction (-rxn) and total concentrations of O(0), C(4), C(-4), Fe(2), Fe(3), S(6), S(-2) (-totals) and mackinawite (-equi) to the selected-output file (SELECTED_OUTPUT).*

REACTION 11a. QuestionsWhat sequence of electron acceptors is used? Where is Fe(3) important?Use Excel to plot the concentrations in the selected-output file (rxn is the x variable, set first line rxn from 99 to 0, omit d_mackinawite). 4.Why is C(4) not a straight line?5.Why does Fe(2) increase after 30 mmol of CH2O is reacted.Should a gas bubble form?What trends are observed for sulfate reduction?

*

Reaction 11a. Answers*

Chart1

00.002091200.00000004540.000571590.0143520.0000000003

00.003091100.0000000420.000780520.0139310.0000000003

00.004090900.00000003980.000982810.0135080.0000000003

00.005090600.00000003840.0011810.0130860.0000000003

00.006090300.00000003730.00137650.0126630.0000000003

00.0070900.00000003640.00157010.0122390.0000000002

00.008089600.00000003580.00176250.0118160.0000000002

00.009089100.00000003520.0019540.0113930.0000000002

00.01008900.00000003470.0021450.0109690.0000000002

00.01108800.00000003430.00233560.0105460.0000000002

00.01208700.0000000340.00252610.0101220.0000000002

00.01308700.00000003370.00271660.00969910.0000000002

00.01408600.00000003340.00290730.00927570.0000000002

00.01508500.00000003320.00309830.00885240.0000000002

00.01608400.0000000330.00328970.00842920.0000000002

00.01708300.00000003280.00348160.00800610.0000000002

00.01808300.00000003260.00367420.0075830.0000000002

00.01908200.00000003250.00386760.00716010.0000000002

00.0200800.00000003230.00406190.00673730.0000000002

00.02107900.00000003220.00425730.00631460.0000000002

00.02207800.00000003210.00445390.00589210.0000000002

00.02307700.0000000320.0046520.00546980.0000000002

00.02407600.0000000320.00485180.00504770.0000000002

00.02507400.00000003190.00505360.00462590.0000000002

00.02607300.00000003180.00525780.00420430.0000000002

00.02707100.00000003180.00546480.00378310.0000000002

00.0280700.00000003180.00567540.00336230.0000000002

00.02906800.00000003170.00589030.0029420.0000000002

00.03006700.00000003170.00611090.00252240.0000000002

00.03106500.00000003180.00633910.00210360.0000000002

00.03206300.00000003180.0065780.00168610.0000000001

00.03306100.00000003190.00683350.00127040.0000000001

00.03405900.00000003210.00711790.000857940.0000000001

00.03505700.00000003240.0074670.000452710.0000000001

00.0360550.00000000010.00000003350.00810540.0000796690.0000000001

00.0370470.00000148930.00000004360.0113710.00000000260.0000000001

00.0378170.000226610.00000005210.01356400

00.0384130.000628120.00000005380.01434600

00.0389870.00105210.00000005440.01494800

00.0395530.00148370.00000005460.0154900

00.0401160.0019190.00000005470.01600200

00.0406770.00235640.00000005470.01649700

00.0412360.00279520.00000005460.01698100

00.0417940.00323490.00000005450.01745700

00.0423520.00367540.00000005430.01792700

00.0429090.00411630.00000005420.01839300

00.0434660.00455770.0000000540.01885600

00.0440220.00499930.00000005380.01931700

00.0445780.00544120.00000005360.01977500

00.0451340.00588330.00000005330.02023200

O(0)

C(4)

C(-4)

Fe(3)

Fe(2)

S(6)

S(-2)

CH2O REACTED, IN MOLES

MOLES PER KILOGRAM WATER

r11

reactionpHpepHreactionO(0)C(4)C(-4)Fe(3)Fe(2)S(6)S(-2)mackinawited_mackinawite

1.00E-038.98184-5.029518.981841.00E-030.00E+002.09E-031.10E-134.54E-085.72E-041.44E-023.49E-102.76E-042.76E-04

2.00E-038.9177-4.952578.91772.00E-030.00E+003.09E-031.54E-134.20E-087.81E-041.39E-023.10E-106.97E-046.97E-04

3.00E-038.87273-4.899118.872733.00E-030.00E+004.09E-031.98E-133.98E-089.83E-041.35E-022.86E-101.12E-031.12E-03

4.00E-038.83854-4.858858.838544.00E-030.00E+005.09E-032.42E-133.84E-081.18E-031.31E-022.68E-101.54E-031.54E-03

5.00E-038.81122-4.827068.811225.00E-030.00E+006.09E-032.86E-133.73E-081.38E-031.27E-022.54E-101.96E-031.96E-03

6.00E-038.78867-4.801148.788676.00E-030.00E+007.09E-033.33E-133.64E-081.57E-031.22E-022.43E-102.39E-032.39E-03

7.00E-038.76961-4.779568.769617.00E-030.00E+008.09E-033.80E-133.58E-081.76E-031.18E-022.34E-102.81E-032.81E-03

8.00E-038.75323-4.76138.753238.00E-030.00E+009.09E-034.31E-133.52E-081.95E-031.14E-022.27E-103.23E-033.23E-03

9.00E-038.73895-4.745688.738959.00E-030.00E+001.01E-024.84E-133.47E-082.15E-031.10E-022.20E-103.66E-033.66E-03

1.00E-028.72638-4.732228.726381.00E-020.00E+001.11E-025.40E-133.43E-082.34E-031.05E-022.14E-104.08E-034.08E-03

1.10E-028.71522-4.720568.715221.10E-020.00E+001.21E-025.99E-133.40E-082.53E-031.01E-022.09E-104.50E-034.50E-03

1.20E-028.70524-4.710438.705241.20E-020.00E+001.31E-026.63E-133.37E-082.72E-039.70E-032.05E-104.93E-034.93E-03

1.30E-028.69628-4.701648.696281.30E-020.00E+001.41E-027.32E-133.34E-082.91E-039.28E-032.00E-105.35E-035.35E-03

1.40E-028.6882-4.694028.68821.40E-020.00E+001.51E-028.06E-133.32E-083.10E-038.85E-031.96E-105.77E-035.77E-03

1.50E-028.6809-4.687468.68091.50E-020.00E+001.61E-028.87E-133.30E-083.29E-038.43E-031.93E-106.20E-036.20E-03

1.60E-028.67428-4.681868.674281.60E-020.00E+001.71E-029.75E-133.28E-083.48E-038.01E-031.90E-106.62E-036.62E-03

1.70E-028.66829-4.677158.668291.70E-020.00E+001.81E-021.07E-123.26E-083.67E-037.58E-031.86E-107.04E-037.04E-03

1.80E-028.66285-4.673298.662851.80E-020.00E+001.91E-021.18E-123.25E-083.87E-037.16E-031.83E-107.47E-037.47E-03

1.90E-028.65794-4.670228.657941.90E-020.00E+002.01E-021.30E-123.23E-084.06E-036.74E-031.81E-107.89E-037.89E-03

2.00E-028.65352-4.667948.653522.00E-020.00E+002.11E-021.43E-123.22E-084.26E-036.31E-031.78E-108.31E-038.31E-03

2.10E-028.64956-4.666448.649562.10E-020.00E+002.21E-021.58E-123.21E-084.45E-035.89E-031.75E-108.73E-038.73E-03

2.20E-028.64604-4.665738.646042.20E-020.00E+002.31E-021.75E-123.20E-084.65E-035.47E-031.73E-109.16E-039.16E-03

2.30E-028.64295-4.665838.642952.30E-020.00E+002.41E-021.95E-123.20E-084.85E-035.05E-031.70E-109.58E-039.58E-03

2.40E-028.6403-4.66688.64032.40E-020.00E+002.51E-022.19E-123.19E-085.05E-034.63E-031.68E-101.00E-021.00E-02

2.50E-028.63809-4.668718.638092.50E-020.00E+002.61E-022.46E-123.18E-085.26E-034.20E-031.65E-101.04E-021.04E-02

2.60E-028.63634-4.671678.636342.60E-020.00E+002.71E-022.80E-123.18E-085.46E-033.78E-031.63E-101.08E-021.08E-02

2.70E-028.6351-4.675848.63512.70E-020.00E+002.81E-023.21E-123.18E-085.68E-033.36E-031.61E-101.13E-021.13E-02

2.80E-028.63443-4.681468.634432.80E-020.00E+002.91E-023.73E-123.17E-085.89E-032.94E-031.58E-101.17E-021.17E-02

2.90E-028.63443-4.688888.634432.90E-020.00E+003.01E-024.41E-123.17E-086.11E-032.52E-031.55E-101.21E-021.21E-02

3.00E-028.63526-4.698648.635263.00E-020.00E+003.11E-025.35E-123.18E-086.34E-032.10E-031.52E-101.25E-021.25E-02

3.10E-028.6372-4.711698.63723.10E-020.00E+003.21E-026.72E-123.18E-086.58E-031.69E-031.49E-101.29E-021.29E-02

3.20E-028.64077-4.729718.640773.20E-020.00E+003.31E-028.94E-123.19E-086.83E-031.27E-031.46E-101.34E-021.34E-02

3.30E-028.64713-4.756418.647133.30E-020.00E+003.41E-021.31E-113.21E-087.12E-038.58E-041.41E-101.38E-021.38E-02

3.40E-028.65957-4.802448.659573.40E-020.00E+003.51E-022.41E-113.24E-087.47E-034.53E-041.34E-101.42E-021.42E-02

3.50E-028.69872-4.934088.698723.50E-020.00E+003.61E-021.21E-103.35E-088.11E-037.97E-051.18E-101.45E-021.45E-02

3.60E-028.94937-5.737938.949373.60E-020.00E+003.70E-021.49E-064.36E-081.14E-022.64E-095.87E-111.46E-021.46E-02

3.70E-029.08396-6.169619.083963.70E-020.00E+003.78E-022.27E-045.21E-081.36E-021.03E-114.03E-111.46E-021.46E-02

3.80E-029.1061-6.250939.10613.80E-020.00E+003.84E-026.28E-045.38E-081.43E-023.36E-123.70E-111.46E-021.46E-02

3.90E-029.11413-6.288169.114133.90E-020.00E+003.90E-021.05E-035.44E-081.49E-021.90E-123.52E-111.46E-021.46E-02

4.00E-029.11746-6.310459.117464.00E-020.00E+003.96E-021.48E-035.46E-081.55E-021.30E-123.40E-111.46E-021.46E-02

4.10E-029.11851-6.325349.118514.10E-020.00E+004.01E-021.92E-035.47E-081.60E-029.84E-133.30E-111.46E-021.46E-02

4.20E-029.11825-6.335879.118254.20E-020.00E+004.07E-022.36E-035.47E-081.65E-027.86E-133.22E-111.46E-021.46E-02

4.30E-029.11719-6.343549.117194.30E-020.00E+004.12E-022.80E-035.46E-081.70E-026.53E-133.15E-111.46E-021.46E-02

4.40E-029.11557-6.349249.115574.40E-020.00E+004.18E-023.23E-035.45E-081.75E-025.57E-133.08E-111.46E-021.46E-02

4.50E-029.11358-6.353499.113584.50E-020.00E+004.24E-023.68E-035.43E-081.79E-024.85E-133.02E-111.46E-021.46E-02

4.60E-029.11133-6.356659.111334.60E-020.00E+004.29E-024.12E-035.42E-081.84E-024.29E-132.97E-111.46E-021.46E-02

4.70E-029.10889-6.358969.108894.70E-020.00E+004.35E-024.56E-035.40E-081.89E-023.85E-132.92E-111.46E-021.46E-02

4.80E-029.10631-6.36069.106314.80E-020.00E+004.40E-025.00E-035.38E-081.93E-023.48E-132.88E-111.46E-021.46E-02

4.90E-029.10363-6.361729.103634.90E-020.00E+004.46E-025.44E-035.36E-081.98E-023.18E-132.84E-111.46E-021.46E-02

5.00E-029.10089-6.362399.100895.00E-020.00E+004.51E-025.88E-035.33E-082.02E-022.93E-132.80E-111.46E-021.46E-02

r11

O(0)

C(4)

C(-4)

Fe(3)

Fe(2)

S(6)

S(-2)


MOLES PER KILOGRAM WATER

Reaction 11a. AnswersO2, Fe(OH)3(a), SO4, CH2O (-> CH4 + CO2).

Fe(3) is not important anywhere.

See plot.

Eventually, the reacted carbon is split between CO2 and CH4.

Fe(OH)3 dissolves as pe decreases. Fe is no longer being sequestered in mackinawite (FeS).

Depends on the depth of water, but certainly at atmospheric pressure a bubble will form. At the end of the reaction (50 mmol CH2O reacted) the partial pressure of methane is 10^.66 = 4.6 atmospheres. So if the ambient pressure is less than 4.6 atmospheres (< ~35 m water depth), bubbles should form.

Decrease in sulfate, increase in alkalinity and pH. Usually, H2S does not accumulate in solution, but precipitates as FeS or escapes as a gas. pH changes are sensitive to Fe and S(-2) reactions.

*

REACTION 11b. QuestionsPotomac Estuary SedimentsHow are these analyses similar to the sulfate reduction simulation results?

How do these analyses differ from the simulation results?Units are mmol/L*

Sheet1

units ppm

DescriptionNumberTemppHCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.22412.31291.810768399.1141.6821935327120.002

units mg/L

DescriptionNumberTemppHCaMgNaKAlkalinityClS(6)N(5)N(-3)BaSrP


Rainwater254.50.3840.0430.1410.0360.2361.30.2370.2080.0003

NumberTemppHCaMgNaKAlkalinityClS(6)SiBSr

as CaCO3ug/lug/l

Recovered water617.4610.312.63.5330122912807519

Background1122.556.992126160041747180028040


Background water

Sewage plume

S(-2) as H2Smg/L

NumberTemppHCaMgNaKAlkalinityClS(6)SiSrS(-2)

1.1124.77.76388.140.8143.96.912130.0810

2.4431.57.4510052122.9176.11434021241.92

2.6627.27.481147926517177.54121801915.32.6

mmol/L

NumberTemppHCaMgNaKAlkalinityClS(6)FeS(-2)N(-3)DOC

V6, 1 cm1207.234.725.32165.96.4257100.00910.3510

V6, 5 cm5207.454.422.21905.3242230.50.0053.42.2711

V26D1156.991.80.70.50.15.40.50.620.0050.36

3157.062.40.80.60.28.30.50.040.481.47

343

Sheet2


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Sheet2

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

Sheet3

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

Sheet4

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

Sheet5

Useful Minerals















Sheet6


0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

Sheet6

00

00

00

00

00

00

CALCITE

DOLOMITE


MMOL DISSOLVED

Sheet7


00.00E+003.30E+005.05E+002.03E+012.08E+01

1-1.00E+002.30E+003.93E+001.93E+011.98E+01

2-2.00E+001.30E+002.77E+001.83E+011.88E+01

3-3.00E+002.99E-011.56E+001.73E+011.78E+01

4-4.00E+00-7.01E-013.13E-011.63E+011.68E+01

5-5.00E+00-1.70E+00-9.36E-011.53E+011.58E+01

6-6.00E+00-2.72E+00-2.18E+001.43E+011.48E+01

7-7.00E+00-3.79E+00-3.39E+001.33E+011.38E+01

8-8.00E+00-4.91E+00-4.55E+001.23E+011.28E+01

9-9.00E+00-6.04E+00-5.68E+001.13E+011.18E+01

10-1.00E+01-7.18E+00-6.80E+001.03E+011.08E+01

11-1.10E+01-8.39E+00-7.93E+009.28E+009.78E+00

12-1.20E+01-9.64E+00-9.05E+008.28E+008.78E+00

13-1.30E+01-1.09E+01-1.01E+017.28E+007.78E+00

14-1.40E+01-1.22E+01-1.12E+016.29E+006.79E+00

00.00E+00

1-1.00E+00

2-2.00E+00

3-3.00E+00

4-4.00E+00

5-5.00E+00

6-6.00E+00

7-7.00E+00

8-8.00E+00

9-9.00E+00

10-1.00E+01

11-1.10E+01

12-1.20E+01

13-1.30E+01

14-1.40E+01

03.30E+00

12.30E+00

21.30E+00

32.99E-01

4-7.01E-01

5-1.70E+00

6-2.72E+00

7-3.79E+00

8-4.91E+00

9-6.04E+00

10-7.18E+00

11-8.39E+00

12-9.64E+00

13-1.09E+01

14-1.22E+01

05.05E+00

13.93E+00

22.77E+00

31.56E+00

43.13E-01

5-9.36E-01

6-2.18E+00

7-3.39E+00

8-4.55E+00

9-5.68E+00

10-6.80E+00

11-7.93E+00

12-9.05E+00

13-1.01E+01

14-1.12E+01

02.03E+01

11.93E+01

21.83E+01

31.73E+01

41.63E+01

51.53E+01

61.43E+01

71.33E+01

81.23E+01

91.13E+01

101.03E+01

119.28E+00

128.28E+00

137.28E+00

146.29E+00

02.08E+01

11.98E+01

21.88E+01

31.78E+01

41.68E+01

51.58E+01

61.48E+01

71.38E+01

81.28E+01

91.18E+01

101.08E+01

119.78E+00

128.78E+00

137.78E+00

146.79E+00

Sheet7

00000

00000

00000

00000

00000

00000

00000

00000

00000

00000

00000

00000

00000

00000

00000

H2

Methanic

Sulfidic

Post-oxic

Oxic

pH

pe

reactionO(0)C(4)C(-4)Fe(3)Fe(2)S(6)S(-2)mackinawited_mackinawite

04.05E-041.09E-030.00E+000.00E+000.00E+001.46E-020.00E+000.00E+000.00E+00

1.00E-041.65E-041.19E-030.00E+002.57E-084.45E-181.46E-020.00E+000.00E+000.00E+00

2.00E-040.00E+001.29E-032.42E-392.52E-085.09E-051.46E-029.39E-360.00E+000.00E+00

1.00E-020.00E+001.11E-025.97E-133.58E-082.02E-031.02E-022.31E-104.46E-034.46E-03

2.00E-020.00E+002.11E-021.75E-123.38E-083.63E-035.56E-031.93E-109.06E-039.06E-03

3.00E-020.00E+003.11E-021.16E-113.38E-085.52E-039.98E-041.60E-101.36E-021.36E-02

4.00E-020.00E+003.83E-022.72E-035.82E-081.44E-026.76E-133.41E-111.46E-021.46E-02

5.00E-020.00E+004.37E-027.34E-035.60E-081.86E-022.34E-132.89E-111.46E-021.46E-02

00000000

00000000

00000000

00000000

00000000

00000000

00000000

00000000

O(0)

C(4)

C(-4)

Fe(3)

Fe(2)

S(6)

S(-2)

mackinawite


MOLES

Reaction 11b. Answers Sulfate decreases, alkalinity increases, pH increases, ammonium increases.

S(-2) is significant, Fe is negligible. pH 7.5 not 9.

*

REACTION 14.ExerciseWhat should happen if organic matter oxidizes in the presence of barite?

Develop a reaction simulation assuming 1 mmol of organic carbon reacts.

*

REACTION 14.QuestionsWhat is the barium concentration in mg/L?Are there reactions other than sulfate reduction?What other reactions could affect barium? *

Reaction 14. Answers0.32*137 = 43 mg/L Ba.

0.2 mmol/kgw methane was generated.

Cation exchange is a possibility. With much larger TDIC, witherite (BaCO3) is a possibility.

*

Sulfate ReductionNorman LandfillBarium concentration appears insignificant unless barium is lost to cation exchange or mineral precipitation.*

Sheet1

revised 10/16/021997-2002 Norman Master Reported

CozzarelliDatetimempelevlsdelevwaterelevelevelevtemp oCspecifpHDONH4+NO3-H2SCH4AlkAlkDOCCl-Br-NO3-SO42-Ca2+Mg2+SiFe2+Mn2+Na+Sr2+K+B3+Ba2+AgAl3+AsCdCoCrCsCuLiMoNiPbRbSbSeUVZnSiO2TeThTidD of H20dO18 of H2OdC13 of CO2NH4+NitriteNH4+orgNNO3+NO2MEQUIVMEQUIVDiff%

USGS Reston, VASamp.(EST)leveltopbotcen(avail)cond(ppm)(ppm)(ppm)(ppm)(HCO3)-(HCO3)-(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(mg/L)(ug/L)(mg/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(ug/L)(mg/L)(ug/L)(ug/L)(ug/L)(per mill)(per mill)(per mil)CationsAnionsCharge

metersscrnscrnscrnmS/cmchemet.Chemet.Chemet.ChemetGCmg/Lmg/LICICICICmg/Lmg/Lmg/Lmg/LBalance

WellfieldfieldfieldfieldfieldfieldfieldfieldlablabfieldlablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablablabNWQLNWQLNWQLNWQLRestonReston

MLSNPD -605/01/979:00333.869332.660ND323.760323.640323.70016.615677.010.042.1NSCNSCNSC6266202.9181.00.790.05113.60166.0052.608.700.131.9491.801.062.500.310.140.002.00

Cape Cod Sewage PlumeIron reductionNo sulfate reductionBlue Plains, Washington D.C.Potomac River Sediment Pore WaterIron reductionMinor sulfate reductionIntense methanogenesis*

Solutions

Seawater

units ppm

DescriptionpHpeCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.228.45412.31291.810768399.1141.6821935327120.002

Ok ground Water

units mg/L

DescriptionpHO(0)CaMgNaKAlkalinityClS(6)N(5)N(-3)BaSrP

as CaCO3as Nas N

Rainwater4.50.3840.0430.1410.0360.2361.30.2370.2080.0003


City of Wellston

Charleston

units mg/L

pHO(0)CaMgNaKAlkalinityClS(6)SiBSr

as CaCO3ug/lug/l

Recovered water10.312.63.5330122912807519

Background6.992126160041747180028040



units mg/L

pHO(0)CaMgNaKAlkalinityClS(6)SiSrS(-2)

as H2S

1.17.760388.140.8143.96.912130.0810

2.47.45010052122.9176.11434021241.92

2.67.4801147926517177.54121801915.32.6

Potomac Estuary

units mmol/L

pHO(0)CaMgNaKAlkalinityClS(6)FeS(-2)N(-3)DOC

meq/L

V6, 1 cm7.2304.725.32165.96.4257100.00910.3510

V6, 5 cm7.4504.422.21905.3242230.50.0053.42.2711

V26D, 1 cm6.9901.80.70.50.15.40.50.620.0050.36

V26D, 3 cm7.0602.40.80.60.28.30.50.040.481.47

Cape Cod

units umol/L

pHO(0)CaMgNaKC(4)ClS(6)FeMnP

Background5.625029312001028140860.642.3

343 6/18/966.4804832352202272125915932965719.4105

Sierra Spring

units mmol/L

pHO(0)CaMgNaKAlkalinityClS(6)Si

Ephemeral Spring6.20.0780.0290.1340.0280.3280.0140.010.273

Perennial Spring6.80.260.0710.2590.040.8950.030.0250.41

Norman, OK

Units mg/L

pHO(0)CaMgNaKAlkalinityClS(6)BrSiFe(2)MnSrBaN(5)N(-3)DOC

as HCO3as NO3as NH4

MLSNPD -67.010.0416652.691.82.5626180.98113.60.79318.600.131.941.060.140.052.12.9

MLS38-66.780.1151423260614.426421026.60.17.53635.9019.300.909.877.123.4815.0158.7

Madison

Units mmol/kgw

pHO(0)CaMgNaKC(4)ClS(6)S(-2)Fe(2)13-C34-S(6)34(S-2)14-C

Recharge7.51.21.010.020.024.30.020.1600.001-79.7-52.3

Mysse flowing well6.6111.284.5431.892.546.8717.8519.860.260.0004-2.316.3-22.10.8

Tar Creek

units mg/L

pHO(0)CaMgNaKAlkalinityClS(6)AlCdCuFePbMnZn

Admiralty5.7490250896.52602832001.40.013000.045.3150

SW site 83420110463.60821003.70.0020.008540.145.2100

Carbon


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Carbon

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

peRedox

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

UsefulMin

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

SWMix

Useful Minerals















RedoxEnv


0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

RedoxEnv

00

-0.473520.1681

-0.64250.25353

-0.597830.24851

-0.376520.16165

00

CALCITE

DOLOMITE


MMOL DISSOLVED

SO4Reduce


00.00E+003.30E+005.05E+002.03E+012.08E+01

1-1.00E+002.30E+003.93E+001.93E+011.98E+01

2-2.00E+001.30E+002.77E+001.83E+011.88E+01

3-3.00E+002.99E-011.56E+001.73E+011.78E+01

4-4.00E+00-7.01E-013.13E-011.63E+011.68E+01

5-5.00E+00-1.70E+00-9.36E-011.53E+011.58E+01

6-6.00E+00-2.72E+00-2.18E+001.43E+011.48E+01

7-7.00E+00-3.79E+00-3.39E+001.33E+011.38E+01

8-8.00E+00-4.91E+00-4.55E+001.23E+011.28E+01

9-9.00E+00-6.04E+00-5.68E+001.13E+011.18E+01

10-1.00E+01-7.18E+00-6.80E+001.03E+011.08E+01

11-1.10E+01-8.39E+00-7.93E+009.28E+009.78E+00

12-1.20E+01-9.64E+00-9.05E+008.28E+008.78E+00

13-1.30E+01-1.09E+01-1.01E+017.28E+007.78E+00

14-1.40E+01-1.22E+01-1.12E+016.29E+006.79E+00

00.00E+00

1-1.00E+00

2-2.00E+00

3-3.00E+00

4-4.00E+00

5-5.00E+00

6-6.00E+00

7-7.00E+00

8-8.00E+00

9-9.00E+00

10-1.00E+01

11-1.10E+01

12-1.20E+01

13-1.30E+01

14-1.40E+01

03.30E+00

12.30E+00

21.30E+00

32.99E-01

4-7.01E-01

5-1.70E+00

6-2.72E+00

7-3.79E+00

8-4.91E+00

9-6.04E+00

10-7.18E+00

11-8.39E+00

12-9.64E+00

13-1.09E+01

14-1.22E+01

05.05E+00

13.93E+00

22.77E+00

31.56E+00

43.13E-01

5-9.36E-01

6-2.18E+00

7-3.39E+00

8-4.55E+00

9-5.68E+00

10-6.80E+00

11-7.93E+00

12-9.05E+00

13-1.01E+01

14-1.12E+01

02.03E+01

11.93E+01

21.83E+01

31.73E+01

41.63E+01

51.53E+01

61.43E+01

71.33E+01

81.23E+01

91.13E+01

101.03E+01

119.28E+00

128.28E+00

137.28E+00

146.29E+00

02.08E+01

11.98E+01

21.88E+01

31.78E+01

41.68E+01

51.58E+01

61.48E+01

71.38E+01

81.28E+01

91.18E+01

101.08E+01

119.78E+00

128.78E+00

137.78E+00

146.79E+00

SO4Reduce

03.30135.05420.28520.785

-12.2993.929419.2819.78

-21.29882.774918.2818.78

-30.298771.55817.2817.78

-4-0.701450.3128416.2816.78

-5-1.7036-0.9360815.2815.78

-6-2.7214-2.180514.2814.78

-7-3.7943-3.393813.2813.78

-8-4.91-4.547312.2812.78

-9-6.0365-5.676211.2811.78

-10-7.182-6.801610.2810.78

-11-8.3865-7.92689.289.78

-12-9.6361-9.05018.288.78

-13-10.911-10.1387.28057.7805

-14-12.21-11.1556.28616.7861

H2

Methanic

Sulfidic

Post-oxic

Oxic

pH

pe

Sheet1


04.05E-041.09E-030.00E+000.00E+000.00E+001.46E-020.00E+000.00E+000.00E+00

1.00E-041.65E-041.19E-030.00E+002.57E-084.45E-181.46E-020.00E+000.00E+000.00E+00

2.00E-040.00E+001.29E-032.42E-392.52E-085.09E-051.46E-029.39E-360.00E+000.00E+00

1.00E-020.00E+001.11E-025.97E-133.58E-082.02E-031.02E-022.31E-104.46E-034.46E-03

2.00E-020.00E+002.11E-021.75E-123.38E-083.63E-035.56E-031.93E-109.06E-039.06E-03

3.00E-020.00E+003.11E-021.16E-113.38E-085.52E-039.98E-041.60E-101.36E-021.36E-02

4.00E-020.00E+003.83E-022.72E-035.82E-081.44E-026.76E-133.41E-111.46E-021.46E-02

5.00E-020.00E+004.37E-027.34E-035.60E-081.86E-022.34E-132.89E-111.46E-021.46E-02

Sheet1

00000000

00000000

00000000

00000000

00000000

00000000

00000000

00000000

O(0)

C(4)

C(-4)

Fe(3)

Fe(2)

S(6)

S(-2)

mackinawite


MOLES

DescriptionCity of Jones 13N-01W-34 CABRainwater

Units

tempTemp17.525

pHpH7.44.5

O(0)O(0)4.1

CaCa420.384

MgMg210.043

NaNa120.141

KK1.50.036

AlkalinityAlkalinity196

ClCl120.236

S(6)S(6)8.11.3

BrN(5)0.490.237

SiN(-3)0.208

Fe(2)Ba0.33

MnSr0.23

SrP0.0003

Ba

N(5)

N(-3)

DOC

Solutions

Seawater

units ppm

DescriptionpHCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.22412.31291.810768399.1141.6821935327120.002

Ok ground Water

units mg/L

DescriptionpHCaMgNaKAlkalinityClS(6)N(5)N(-3)BaP

as CaCO3as Nas N

Rainwater4.50.3840.0430.1410.0360.2361.30.2370.2080.0003

City of Jones 13N-01W-34 CAB7.44221121.5196128.10.490.33

City of Wellston

Charleston

units mg/L

pHCaMgNaKAlkalinityClS(6)SiSr

as CaCO3ug/l

Recovered water10.312.63.5330122912807519

Background6.992126160041747180028040



units mg/L

pHCaMgNaKAlkalinityClS(6)SiSrS(-2)

as H2S

1.17.76388.140.8143.96.912130.0810

2.47.4510052122.9176.11434021241.92

2.67.481147926517177.54121801915.32.6

Potomac Estuary

units mmol/L

pHCaMgNaKAlkalinityClS(6)FeS(-2)N(-3)

meq/L

V28, 1 cm7.021.80.80.80.26.80.60.0330.7

V28, 36 cm7.143.11.410.524.90.80.4317.8

Cape Cod

units umol/L

pHCaMgNaKC(4)ClS(6)FeMnP

Background5.629312001028140860.642.3

343 6/18/966.484832352202272125915932965719.4105

Sierra Spring

units mmol/L

pHCaMgNaKAlkalinityClS(6)Si



Norman, OK

Units mg/L

pHCaMgNaKAlkalinityClS(6)BrSiFe(2)SrBaN(5)N(-3)DOC

as HCO3as NO3as NH4

MLSNPD -67.0116652.691.82.5626180.98113.60.79318.600.131.060.140.052.12.9

MLS38-66.7851423260614.426421026.60.17.53635.9019.309.877.123.4815.0158.7

Madison

Units mmol/kgw

pHCaMgNaKC(4)ClS(6)S(-2)Fe(2)13-C34(S-2)14-C

Recharge7.51.21.010.020.024.30.020.1600.001-7-52.3

Mysse flowing well6.6111.284.5431.892.546.8717.8519.860.260.0004-2.3-22.10.8

Tar Creek

units mg/L

pHCaMgNaKAlkalinityClS(6)AlCdCuPbMnZn

Admiralty5.7490250896.52602832001.40.010.045.3150

SW site 83420110463.60821003.70.0020.0080.145.2100

Carbon


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Carbon

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

peRedox

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

UsefulMin

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

SWMix

Useful Minerals















RedoxEnv


0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

RedoxEnv

00

-0.473520.1681

-0.64250.25353

-0.597830.24851

-0.376520.16165

00

CALCITE

DOLOMITE


MMOL DISSOLVED

SO4Reduce


00.00E+003.30E+005.05E+002.03E+012.08E+01

1-1.00E+002.30E+003.93E+001.93E+011.98E+01

2-2.00E+001.30E+002.77E+001.83E+011.88E+01

3-3.00E+002.99E-011.56E+001.73E+011.78E+01

4-4.00E+00-7.01E-013.13E-011.63E+011.68E+01

5-5.00E+00-1.70E+00-9.36E-011.53E+011.58E+01

6-6.00E+00-2.72E+00-2.18E+001.43E+011.48E+01

7-7.00E+00-3.79E+00-3.39E+001.33E+011.38E+01

8-8.00E+00-4.91E+00-4.55E+001.23E+011.28E+01

9-9.00E+00-6.04E+00-5.68E+001.13E+011.18E+01

10-1.00E+01-7.18E+00-6.80E+001.03E+011.08E+01

11-1.10E+01-8.39E+00-7.93E+009.28E+009.78E+00

12-1.20E+01-9.64E+00-9.05E+008.28E+008.78E+00

13-1.30E+01-1.09E+01-1.01E+017.28E+007.78E+00

14-1.40E+01-1.22E+01-1.12E+016.29E+006.79E+00

00.00E+00

1-1.00E+00

2-2.00E+00

3-3.00E+00

4-4.00E+00

5-5.00E+00

6-6.00E+00

7-7.00E+00

8-8.00E+00

9-9.00E+00

10-1.00E+01

11-1.10E+01

12-1.20E+01

13-1.30E+01

14-1.40E+01

03.30E+00

12.30E+00

21.30E+00

32.99E-01

4-7.01E-01

5-1.70E+00

6-2.72E+00

7-3.79E+00

8-4.91E+00

9-6.04E+00

10-7.18E+00

11-8.39E+00

12-9.64E+00

13-1.09E+01

14-1.22E+01

05.05E+00

13.93E+00

22.77E+00

31.56E+00

43.13E-01

5-9.36E-01

6-2.18E+00

7-3.39E+00

8-4.55E+00

9-5.68E+00

10-6.80E+00

11-7.93E+00

12-9.05E+00

13-1.01E+01

14-1.12E+01

02.03E+01

11.93E+01

21.83E+01

31.73E+01

41.63E+01

51.53E+01

61.43E+01

71.33E+01

81.23E+01

91.13E+01

101.03E+01

119.28E+00

128.28E+00

137.28E+00

146.29E+00

02.08E+01

11.98E+01

21.88E+01

31.78E+01

41.68E+01

51.58E+01

61.48E+01

71.38E+01

81.28E+01

91.18E+01

101.08E+01

119.78E+00

128.78E+00

137.78E+00

146.79E+00

SO4Reduce

03.30135.05420.28520.785

-12.2993.929419.2819.78

-21.29882.774918.2818.78

-30.298771.55817.2817.78

-4-0.701450.3128416.2816.78

-5-1.7036-0.9360815.2815.78

-6-2.7214-2.180514.2814.78

-7-3.7943-3.393813.2813.78

-8-4.91-4.547312.2812.78

-9-6.0365-5.676211.2811.78

-10-7.182-6.801610.2810.78

-11-8.3865-7.92689.289.78

-12-9.6361-9.05018.288.78

-13-10.911-10.1387.28057.7805

-14-12.21-11.1556.28616.7861

H2

Methanic

Sulfidic

Post-oxic

Oxic

pH

pe

Sheet1


04.05E-041.09E-030.00E+000.00E+000.00E+001.46E-020.00E+000.00E+000.00E+00

1.00E-041.65E-041.19E-030.00E+002.57E-084.45E-181.46E-020.00E+000.00E+000.00E+00

2.00E-040.00E+001.29E-032.42E-392.52E-085.09E-051.46E-029.39E-360.00E+000.00E+00

1.00E-020.00E+001.11E-025.97E-133.58E-082.02E-031.02E-022.31E-104.46E-034.46E-03

2.00E-020.00E+002.11E-021.75E-123.38E-083.63E-035.56E-031.93E-109.06E-039.06E-03

3.00E-020.00E+003.11E-021.16E-113.38E-085.52E-039.98E-041.60E-101.36E-021.36E-02

4.00E-020.00E+003.83E-022.72E-035.82E-081.44E-026.76E-133.41E-111.46E-021.46E-02

5.00E-020.00E+004.37E-027.34E-035.60E-081.86E-022.34E-132.89E-111.46E-021.46E-02

Sheet1

00000000

00000000

00000000

00000000

00000000

00000000

00000000

00000000

O(0)

C(4)

C(-4)

Fe(3)

Fe(2)

S(6)

S(-2)

mackinawite


MOLES


Units

tempTemp17.525

pHpH7.44.5

O(0)O(0)4.1

CaCa420.384

MgMg210.043

NaNa120.141

KK1.50.036


ClCl120.236

S(6)S(6)8.11.3

BrN(5)0.490.237

SiN(-3)0.208

Fe(2)Ba0.33

MnSr0.23

SrP0.0003

Ba

N(5)

N(-3)

DOC

Central OklahomaNo organic matter or reduced minerals*

-units mg/LDescriptionNumberTemppHO(0)CaMgNaKAlkalinityClS(6)N(5)N(-3)as CaCO3as Nas NCity of Jones 13N-01W-34 CAB17.57.44.14221121.5196128.10.49

Organic DecompositionSourcesO2Atmosphere, DO negligibleNO3Atmosphere, ag chemicalsFe(3)Iron oxyhydroxidesSO4Seawater, atmosphere, gypsumOrganic carbonCH4 and CO2Organic carbon can be absent*

Redox Sequence at pH 7*

Redox couplepeO(-2)/O(0)12.9N(0)/N(5)11.8Se(4)/Se(6)7.7Cr(3)/Cr(6)7.0N(-3)/N(5)6.1Fe(2)/Fe(3) 3.9Se(-2)/Se(4)0.4U(4)/U(6)0.4As(3)/As(5)0.3V(3)/V(5)-2.3N(-3)/N(0) -3.2S(-2)/S(6)* (wateq4f.dat)-3.6C(-4)/C(4) -4.4

REACTION 16. QuestionsHow would you make the redox table of the previous slide?Iron is soluble as reduced ferrous iron, uranium is soluble as oxidized U(6). As organic carbon reacts, which would you observe first: (a) increase in iron, (b) decrease in uranium?Thermodynamically, which nitrogen species do you expect to see in an oxygenated ground water? In a methanic water?*

Reaction 16. AnswersDefine equal amounts (1 umol/kgw) of each redox state Se(6), Se(4); As(5), As(3); etc. in SOLUTION with pH 7. Look at pe table that is printed.

(a) increase in iron concentration should occur first if ferric oxyhydroxides are in the system. Equal Fe(2)/Fe(3) at pe ~ 4, Equal U(4)/U(6) at pe ~ -1.

NO3- in oxic water, NH4+ in methanic water. However, NO3- generally is reduced to N2 (denitrification), not NH4+. NH4+ does nitrify to NO3-.*

ReactionsSulfide oxidation*

Sulfide Oxidation

Pyrite/Marcasite are most important reactants

Need Pyrite, Oxygen, Water, and bugs

Oxidation of pyrite and formation of ferric hydroxide complexes and minerals generates acidic conditions*

Iron Mountain, CaliforniaSulfide deposits at the top of a mountainLots of precipitationUnsaturated conditionsTunnels drain

*

Picher, OklahomaFlat topographyMines 200 to 500 ft below land surfaceSaturated after dewatering ceasedCut off the supply of oxygen

*

Simplified ReactionsHigh pHFeS2 + 15/4O2 + 4HCO3- = Fe(OH)3 + 2SO4-2 + 4CO2 + 1/2H2O

OrFeS2 + 15/4O2 + 7/2H2O = Fe(OH)3 + 2SO4-2 + 4H+

Low pH FeS2 + 15/4O2 + 1/2H2O = Fe+3 + SO4-2 + HSO4-*

Additional reactionsHydrous ferric oxidesFerrihydriteGoethiteJarositeAluminum hydroxidesAluniteCarbonatesGypsum

*

Modeling Pyrite OxidationFeS2 + 15/4O2 + 7/2H2O = Fe(OH)3 + 2SO4-2 + 4H+

Pick the irreversible reactant: O2 or FeS2Oxygen rich environment of a tailings pileWe are going to react up to 50 mmol FeS2Equilibrium reactions

*

REACTION 18. ExerciseReact the pure water with 10 mmol of pyrite, maintaining equilibrium with atmospheric oxygen.React the pure water with 10 mmol of mackinawite, maintaining equilibrium with atmospheric oxygen.React the pure water with 10 mmol of sphalerite, maintaining equilibrium with atmospheric oxygen.

*

REACTION 18. QuestionsWrite qualitative reactions that explain the pH of the 3 solutions.What pH buffer starts to operate at pHs below 3?Run the input file with wateq4f.dat database. What minerals may precipitate during pyrite oxidation?*

Reaction 18. Answers

Question 1Pyrite oxidation:FeS2 + xO2 + yH2O -> Fe+3 + 2SO4-2 + H+In addition, a little ferric iron hydrolizes to make additional H+:Fe+3 + H2O = FeOH+2 + H+With net acid production to give pH 2.

Mackinawite oxidation:FeS + 2.25O2 + H+ -> Fe+3 + SO4-2 + .5H2OBut a majority ferric iron hydrolizesFe+3 + xH2O = Fe(OH)x+y + H+With a net acid production that give pH 4.

Sphalerite oxidation:ZnS + 2O2 -> Zn+2 + SO4-2 Zinc hydrolosis is minimalZn+2 + H2O = ZnOH+ + H+Net result is pH 7.

2. HSO4-/SO4-2

3. Iron oxyhydroxides, goethite (and often Fe(OH)3(a)) and jarosite. There is also a potassium jarosite and other solid solutions of jarosites. Aluminum has analogous minerals named alunite.

*

REACTION 20.Extra Credit ExerciseReact the pure water with 20 mmol of pyrite, maintaining equilibrium with atmospheric oxygen and goethite.Acid mine drainage is usually treated with limestone. Use the results of part 1 and equilibrate with O2, goethite, and calcite. *

REACTION 20.QuestionsWrite a net reaction for the PHREEQC results for the low-pH simulation.What are the pH values with and without calcite equilibrium.Looking at the results of the calcite-equilibrated simulation, what additional reactions should be considered?*

Reaction 20. Answers

20FeS2 + 75O2 = 19FeOOH + .8Fe(+3) + 27HSO4- + 12SO4-2 + 50H+

pHs are 1.4 and 5.8 without and with calcite equilibrium

Gypsum is supersaturated, and probably would precipitate.

pCO2 is 1 atmosphere. If O2 reacts to equilibrium with the atmosphere, logically, CO2 would also.

*

Picher Oklahoma Abandoned Pb/Zn Mine

mg/LMines are suboxicCarbonates are presentIron oxidizes in stream*

Solutions

Seawater

units ppm

DescriptionNumberTemppHpeCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.228.45412.31291.810768399.1141.6821935327120.002

Ok ground Water

units mg/L

DescriptionNumberTemppHO(0)CaMgNaKAlkalinityClS(6)N(5)N(-3)BaSrP

as CaCO3as Nas N

Rainwater254.50.3840.0430.1410.0360.2361.30.2370.2080.0003

City of Jones 13N-01W-34 CAB17.57.44.14221121.5196128.10.490.330.23

City of Wellston

Charleston

units mg/L

NumberTemppHO(0)CaMgNaKAlkalinityClS(6)SiBSr

as CaCO3ug/lug/l

Recovered water617.4610.312.63.5330122912807519

Background1122.556.992126160041747180028040



units mg/L

NumberTemppHO(0)CaMgNaKAlkalinityClS(6)SiSrS(-2)

as H2S

1.1124.77.760388.140.8143.96.912130.0810

2.4431.57.45010052122.9176.11434021241.92

2.6627.27.4801147926517177.54121801915.32.6

Potomac Estuary

units mmol/L

NumberTemppHO(0)CaMgNaKAlkalinityClS(6)FeS(-2)N(-3)DOC

meq/L

V6, 1 cm1207.2304.725.32165.96.4257100.00910.3510

V6, 5 cm5207.4504.422.21905.3242230.50.0053.42.2711

V26D, 1 cm1156.9901.80.70.50.15.40.50.620.0050.36

V26D, 3 cm3157.0602.40.80.60.28.30.50.040.481.47

Cape Cod

units umol/L

NumberTemppHO(0)CaMgNaKC(4)ClS(6)FeMnP

Background145.625029312001028140860.642.3

343 6/18/966.4804832352202272125915932965719.4105

Sierra Spring

units mmol/L

NumberTemppHO(0)CaMgNaKAlkalinityClS(6)Si



Norman, OK

Units mg/L

temppHO(0)CaMgNaKAlkalinityClS(6)BrSiFe(2)MnSrBaN(5)N(-3)DOC

as HCO3as NO3as NH4

MLSNPD -616.67.010.0416652.691.82.5626180.98113.60.79318.600.131.941.060.140.052.12.9

MLS38-6ND6.780.1151423260614.426421026.60.17.53635.9019.300.909.877.123.4815.0158.7

Madison

Units mmol/kgw

temppHO(0)CaMgNaKC(4)ClS(6)S(-2)Fe(2)13-C34-S(6)34(S-2)14-C

Recharge9.97.51.21.010.020.024.30.020.1600.001-79.7-52.3


Tar Creek

units mg/L

temppHO(0)CaMgNaKAlkalinityClS(6)

Admiralty155.7490250896.5260283200

SW site 8303420110463.6082100

AlCdCuFePbMnZn

Admiralty1.40.013000.045.3150

SW site 83.70.0020.008540.145.2100

Carbon


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Carbon

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

peRedox

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

UsefulMin

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

SWMix

Useful Minerals















RedoxEnv


0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

RedoxEnv

00

-0.473520.1681

-0.64250.25353

-0.597830.24851

-0.376520.16165

00

CALCITE

DOLOMITE


MMOL DISSOLVED

SO4Reduce


00.00E+003.30E+005.05E+002.03E+012.08E+01

1-1.00E+002.30E+003.93E+001.93E+011.98E+01

2-2.00E+001.30E+002.77E+001.83E+011.88E+01

3-3.00E+002.99E-011.56E+001.73E+011.78E+01

4-4.00E+00-7.01E-013.13E-011.63E+011.68E+01

5-5.00E+00-1.70E+00-9.36E-011.53E+011.58E+01

6-6.00E+00-2.72E+00-2.18E+001.43E+011.48E+01

7-7.00E+00-3.79E+00-3.39E+001.33E+011.38E+01

8-8.00E+00-4.91E+00-4.55E+001.23E+011.28E+01

9-9.00E+00-6.04E+00-5.68E+001.13E+011.18E+01

10-1.00E+01-7.18E+00-6.80E+001.03E+011.08E+01

11-1.10E+01-8.39E+00-7.93E+009.28E+009.78E+00

12-1.20E+01-9.64E+00-9.05E+008.28E+008.78E+00

13-1.30E+01-1.09E+01-1.01E+017.28E+007.78E+00

14-1.40E+01-1.22E+01-1.12E+016.29E+006.79E+00

00.00E+00

1-1.00E+00

2-2.00E+00

3-3.00E+00

4-4.00E+00

5-5.00E+00

6-6.00E+00

7-7.00E+00

8-8.00E+00

9-9.00E+00

10-1.00E+01

11-1.10E+01

12-1.20E+01

13-1.30E+01

14-1.40E+01

03.30E+00

12.30E+00

21.30E+00

32.99E-01

4-7.01E-01

5-1.70E+00

6-2.72E+00

7-3.79E+00

8-4.91E+00

9-6.04E+00

10-7.18E+00

11-8.39E+00

12-9.64E+00

13-1.09E+01

14-1.22E+01

05.05E+00

13.93E+00

22.77E+00

31.56E+00

43.13E-01

5-9.36E-01

6-2.18E+00

7-3.39E+00

8-4.55E+00

9-5.68E+00

10-6.80E+00

11-7.93E+00

12-9.05E+00

13-1.01E+01

14-1.12E+01

02.03E+01

11.93E+01

21.83E+01

31.73E+01

41.63E+01

51.53E+01

61.43E+01

71.33E+01

81.23E+01

91.13E+01

101.03E+01

119.28E+00

128.28E+00

137.28E+00

146.29E+00

02.08E+01

11.98E+01

21.88E+01

31.78E+01

41.68E+01

51.58E+01

61.48E+01

71.38E+01

81.28E+01

91.18E+01

101.08E+01

119.78E+00

128.78E+00

137.78E+00

146.79E+00

SO4Reduce

03.30135.05420.28520.785

-12.2993.929419.2819.78

-21.29882.774918.2818.78

-30.298771.55817.2817.78

-4-0.701450.3128416.2816.78

-5-1.7036-0.9360815.2815.78

-6-2.7214-2.180514.2814.78

-7-3.7943-3.393813.2813.78

-8-4.91-4.547312.2812.78

-9-6.0365-5.676211.2811.78

-10-7.182-6.801610.2810.78

-11-8.3865-7.92689.289.78

-12-9.6361-9.05018.288.78

-13-10.911-10.1387.28057.7805

-14-12.21-11.1556.28616.7861

H2

Methanic

Sulfidic

Post-oxic

Oxic

pH

pe

Sheet1


04.05E-041.09E-030.00E+000.00E+000.00E+001.46E-020.00E+000.00E+000.00E+00

1.00E-041.65E-041.19E-030.00E+002.57E-084.45E-181.46E-020.00E+000.00E+000.00E+00

2.00E-040.00E+001.29E-032.42E-392.52E-085.09E-051.46E-029.39E-360.00E+000.00E+00

1.00E-020.00E+001.11E-025.97E-133.58E-082.02E-031.02E-022.31E-104.46E-034.46E-03

2.00E-020.00E+002.11E-021.75E-123.38E-083.63E-035.56E-031.93E-109.06E-039.06E-03

3.00E-020.00E+003.11E-021.16E-113.38E-085.52E-039.98E-041.60E-101.36E-021.36E-02

4.00E-020.00E+003.83E-022.72E-035.82E-081.44E-026.76E-133.41E-111.46E-021.46E-02

5.00E-020.00E+004.37E-027.34E-035.60E-081.86E-022.34E-132.89E-111.46E-021.46E-02

Sheet1

00000000

00000000

00000000

00000000

00000000

00000000

00000000

00000000

O(0)

C(4)

C(-4)

Fe(3)

Fe(2)

S(6)

S(-2)

mackinawite


MOLES


Units

tempTemp17.525

pHpH7.44.5

O(0)O(0)4.1

CaCa420.384

MgMg210.043

NaNa120.141

KK1.50.036


ClCl120.236

S(6)S(6)8.11.3

BrN(5)0.490.237

SiN(-3)0.208

Fe(2)Ba0.33

MnSr0.23

SrP0.0003

Ba

N(5)

N(-3)

DOC

Pyrite OxidationRequiresPyrite/MarcasiteO2H2OBacteriaProduces Ferrihydrite/Goethite, jarosite, aluniteGypsum if calcite is availableEvaporitesPossibly sideriteAcid generation Pyrite > FeS > ZnS*

ReactionsAluminosilicate reactions*

Aluminosilicate ReactionsOlivinePyroxene (augite)Amphibole (hornblende)Biotite mica Disseminated calcite important in silicate terranes Bowen/Goldich reaction seriesCa-FeldsparPlagioclaseNa-FeldsparK-FeldsparMuscoviteQuartz*

AluminosilicatesPrimary minerals react to form gibbsite, kaolinite, smectite, zeolites, SiO2Thermodynamic data is not reliableCompositional uncertaintiesRange of stabilitiesDifficult to measure aluminumKinetics are slow *

Add Reactant to Phase BoundaryKAlSiO8 is added (or removed) until gibbsite equilibrium is reachedSI is target SI for GibbsiteAmount is amount of KAlSiO8 available*

REACTION 22.Exercise Use phreeqc.datDissolve just enough Anorthite (CaAl2Si2O8) to come to equilibrium with gibbsite. Dissolve just enough Anorthite to come to equilibrium with kaolinite.Dissolve just enough Anorthite to come to equilibrium with Ca-Montmorillonite.Dissolve Anorthite to equilibrium, allow gibbsite, kaolinite, and Ca-Montmorillonite to precipitate.*

REACTION 22.QuestionsGiven the thermodynamic data, which mineral should precipitate first? What is the stable phase assemblage in a water/anorthite system?Does quartz need to be included in this calculation?*

Reaction 22. AnswersGibbsite requires the least amount of Anorthite to dissolve to become saturated.Solution, anorthite, gibbsite, kaolinite?! Quartz is undersaturated in all calculations.

*

Sierra Nevada Springs

mmol/kgwIncrease in Ca, Alkalinity, pHIncrease in SiO2Slight increase in Mg, K, Cl, SO4*

Solutions

Seawater

units ppm

DescriptionpHCaMgNaKAlkalinityClS(6)Fe

as HCO3

Seawater8.22412.31291.810768399.1141.6821935327120.002

Ok ground Water

units mg/L

DescriptionpHCaMgNaKAlkalinityClS(6)N(5)N(-3)BaSrP

as CaCO3as Nas N

Rainwater4.50.3840.0430.1410.0360.2361.30.2370.2080.0003

City of Jones 13N-01W-34 CAB7.44221121.5196128.10.490.330.23

City of Wellston

Charleston

units mg/L

pHCaMgNaKAlkalinityClS(6)SiBSr

as CaCO3ug/lug/l

Recovered water10.312.63.5330122912807519

Background6.992126160041747180028040



units mg/L

pHCaMgNaKAlkalinityClS(6)SiSrS(-2)

as H2S

1.17.76388.140.8143.96.912130.0810

2.47.4510052122.9176.11434021241.92

2.67.481147926517177.54121801915.32.6

Potomac Estuary

units mmol/L

pHCaMgNaKAlkalinityClS(6)FeS(-2)N(-3)DOC

meq/L

V6, 1 cm7.234.725.32165.96.4257100.00910.3510

V6, 5 cm7.454.422.21905.3242230.50.0053.42.2711

V26D, 1 cm6.991.80.70.50.15.40.50.620.0050.36

V26D, 3 cm7.062.40.80.60.28.30.50.040.481.47

Cape Cod

units umol/L

pHCaMgNaKC(4)ClS(6)FeMnP

Background5.629312001028140860.642.3

343 6/18/966.484832352202272125915932965719.4105

Sierra Spring

units mmol/L

pHCaMgNaKAlkalinityClS(6)Si



Norman, OK

Units mg/L

pHCaMgNaKAlkalinityClS(6)BrSiFe(2)MnSrBaN(5)N(-3)DOC

as HCO3as NO3as NH4

MLSNPD -67.0116652.691.82.5626180.98113.60.79318.600.131.941.060.140.052.12.9

MLS38-66.7851423260614.426421026.60.17.53635.9019.300.909.877.123.4815.0158.7

Madison

Units mmol/kgw

pHCaMgNaKC(4)ClS(6)S(-2)Fe(2)13-C34-S(6)34(S-2)14-C

Recharge7.51.21.010.020.024.30.020.1600.001-79.7-52.3


Tar Creek

units mg/L

pHCaMgNaKAlkalinityClS(6)AlCdCuFePbMnZn

Admiralty5.7490250896.52602832001.40.013000.045.3150

SW site 83420110463.60821003.70.0020.008540.145.2100

Carbon


49.96E-044.47E-062.15E-12

59.57E-044.28E-052.04E-10

66.89E-043.11E-041.52E-08

71.80E-048.20E-044.12E-07

82.13E-059.74E-044.92E-06

92.08E-069.50E-044.83E-05

101.42E-076.57E-043.43E-04

113.29E-091.54E-048.46E-04

123.31E-111.61E-059.84E-04


66.34E-034.34E-032.00E-031.04E-07

72.43E-034.34E-042.00E-031.04E-06

82.03E-034.29E-051.98E-031.03E-05

91.90E-033.90E-061.80E-039.43E-05

101.41E-031.98E-079.18E-044.89E-04

115.19E-041.77E-098.22E-054.37E-04

Carbon

000

000

000

000

000

000

000

000

000

m_CO2

m_HCO3-

m_CO3-2

peRedox

0000

0000

0000

0000

0000

0000

C

m_CO2

m_HCO3-

m_CO3-2

UsefulMin

Data in mmmo/kgw


10.740.2611.00E-64-929.7

21NA11.00E-64-92NA

3NA111.00E-64NA10.3

40.740.261NANA9.7

50.840.16NA1.00E+00-289.5

61111.00E-68-9810.3

SWMix

Useful Minerals















RedoxEnv


0.00E+000.00E+000.00E+00

2.00E-01-4.74E-011.68E-01

4.00E-01-6.43E-012.54E-01

6.00E-01-5.98E-012.49E-01

8.00E-01-3.77E-011.62E-01

1.00E+000.00E+000.00E+00

RedoxEnv

00

-0.473520.1681

-0.64250.25353

-0.597830.24851

-0.376520.16165

00

CALCITE

DO

Reactions

Documents

na equilibrium

solutions equilibrium

equilibrium calcitecaco3

solid solutionexample

phases gas

solid solutionstrace

gas phase fixed volume

phasefinite gas phase