USE solution 0SOLUTION 1-101REACTION 0EQUILIBRIUM_PHASES 101...
USE SOLUTION 1SOLUTION 2 Median Black Sea rainfall concentrations from Alagha and Tunkel (2003). CO2(atm), O2(atm) added. Chloride charge balance temp 25 pH 5.15 pe 4 redox pe units ppm density 1 Al 3.37 Ca 1.8 Cl 1.01 charge # adapt Cl to obtain charge balance C(4) 1 CO2(g) -3.373 # equilibrium with atmospheric CO2 Fe 2.82 K 1.72 Mg 0.88 Mn 0.07 N(-3) 0.56 N(5) 1.5 Na 2 S(6) 2.52 O(0) 0.01 O2(g) -0.678 # equilibrium with atmospheric O2 -water 1 # kgEQUILIBRIUM_PHASES 1-100 # Equilibrate Solition 1 water with calcite precipitation Calcite_ppt 0 0 # Switch on calcite as a phase that can precipitate within daysMIX 1 Combine rainwater with (process/grid water + DAC) 1 0.88 # 1-(Rainfall_rate/(Rainfall_rate+Procwtr_rate), use fraction 0.88 of solution 1 2 0.12 # 1-(Procwtr_rate/(Rainfall_rate+Procwtr_rate), use fraction 0.12 of solution 2SAVE SOLUTION 0END
SOLUTION 2 Median Black Sea rainfall concentrations from Alagha and Tunkel (2003). CO2(atm), O2(atm) added. Chloride charge balance temp 25 pH 5.15 pe 4 redox pe units ppm density 1 Al 3.37 Ca 1.8 Cl 1.01 charge # adapt Cl to obtain charge balance C(4) 1 CO2(g) -3.373 # equilibrium with atmospheric CO2 Fe 2.82 K 1.72 Mg 0.88 Mn 0.07 N(-3) 0.56 N(5) 1.5 Na 2 S(6) 2.52 O(0) 0.01 O2(g) -0.678 # equilibrium with atmospheric O2 -water 1 # kgENDEQUILIBRIUM_PHASES 1-100 # Equilibrate Solition 1 water with calcite precipitation Calcite_ppt 0 0 # Switch on calcite as a phase that can precipitate within daysENDMIX 1 Combine rainwater with (process/grid water + DAC) 1 0.88 # 1-(Rainfall_rate/(Rainfall_rate+Procwtr_rate), use fraction 0.88 of solution 1 2 0.12 # 1-(Procwtr_rate/(Rainfall_rate+Procwtr_rate), use fraction 0.12 of solution 2USE equilibrium_phases 1SAVE SOLUTION 0END
USE SOLUTION 0SOLUTION 1-101 Simulated mixture of (process water, DAC) and rainwater. temp 25 pH 6.963 pe 13.64 redox pe units mol/kgw density 1 -water 1 # kgC(4) 5.06E-03Ca 3.52E-03Cl 2.12E-03Fe 3.94E-06K 1.07E-06Mg 1.93E-06N 2.79E-05Na 1.07E-05P 6.26E-06S(6) 6.45E-04# Evaporation of mixture of (process water, DAC) and rainwaterREACTION 0 # Remove / Evaporate water in steps H2O -1 11.1012 moles in 4 stepsEQUILIBRIUM_PHASES 101 DAC CO2 capture to 3% CO2(g) -1.523 10 # Calculated CO2 SI= -1.523, Amount of 10 mol available O2(g) -0.679 10 # Calculated O2 SI= -0.679, Amount of 10 mol available# N2(g) -0.107 10 # Calculated N2 , log 10 (0.7809), SI= -0.107, Amount of 10 mol available Calcite_ppt 0 0KINETICS 1-100Portlandite -formula Ca(OH)2 1 -m 14.43 # Initial moles of reactant. Mass conc port vs pores/ Molecular-mass_port -m0 14.43 # Default is equal to initial moles -parms 2.303 1 # Bulk area * Area% Port -tol 1e-08 # Default is 1?10-8 molLarnite -formula Ca2SiO4 1 -m 9.87 -m0 9.87 -parms 2.5 1 -tol 1e-08Calcite_diss -formula CaCO3 1 -m 9.49 -m0 9.49 -parms 1.682 1 -tol 1e-08Brucite -formula Mg(OH)2 1 -m 4.8 -m0 4.8 -parms 0.556 1 -tol 1e-08kin_HCO3 -formula HCO3-1 1 -m 0 -m0 0 -tol 1e-08# Define the Differential Equation solver, with parameters-steps 1-step_divide 0.1-runge_kutta 6-bad_step_max 500-cvode true-cvode_steps 100-cvode_order 5# CLOSED PONDSAVE equilibrium_phases 1-10SAVE solution 1-10END
SOLUTION 1-101 Simulated mixture of (process water, DAC) and rainwater. temp 25 pH 6.963 pe 13.64 redox pe units mol/kgw density 1 -water 1 # kgC(4) 5.06E-03Ca 3.52E-03Cl 2.12E-03Fe 3.94E-06K 1.07E-06Mg 1.93E-06N 2.79E-05Na 1.07E-05P 6.26E-06S(6) 6.45E-04ENDREACTION 0 # Remove / Evaporate water in steps H2O -1 11.1012 moles in 4 stepsENDEQUILIBRIUM_PHASES 101 DAC CO2 capture to 3% CO2(g) -1.523 10 # Calculated CO2 SI= -1.523, Amount of 10 mol available O2(g) -0.679 10 # Calculated O2 SI= -0.679, Amount of 10 mol available# N2(g) -0.107 10 # Calculated N2 , log 10 (0.7809), SI= -0.107, Amount of 10 mol available Calcite_ppt 0 0ENDKINETICS 1-100Portlandite -formula Ca(OH)2 1 -m 14.43 # Initial moles of reactant. Mass conc port vs pores/ Molecular-mass_port -m0 14.43 # Default is equal to initial moles -parms 2.303 1 # Bulk area * Area% Port -tol 1e-08 # Default is 1?10-8 molLarnite -formula Ca2SiO4 1 -m 9.87 -m0 9.87 -parms 2.5 1 -tol 1e-08Calcite_diss -formula CaCO3 1 -m 9.49 -m0 9.49 -parms 1.682 1 -tol 1e-08Brucite -formula Mg(OH)2 1 -m 4.8 -m0 4.8 -parms 0.556 1 -tol 1e-08kin_HCO3 -formula HCO3-1 1 -m 0 -m0 0 -tol 1e-08# Define the Differential Equation solver, with parameters-steps 1-step_divide 0.1-runge_kutta 6-bad_step_max 500-cvode true-cvode_steps 100-cvode_order 5ENDUSE SOLUTION 0USE reaction 0USE equilibrium_phases 101USE kinetics 1SAVE equilibrium_phases 1-10SAVE solution 1-10END
TITLE DATABASE C:\Users\ErdincCosgun\Documents\Projects\Databases\carbfix_2022.datTITLE TESTING KINETICS OF SPECIFIC SOLIDSTITLE 100 CELLS, 1CM HIGHTITLE FLOW-THROUGH TEST, 3 LITRETITLE === FULL ANTIMAGNETIC SUITE ===TITLE KARDEMIR PROCESS/GRID WATER MEAN VALUESTITLE REDOX CONTROLLED BY IRON SPECIES TITLE CHEMICAL SPECIATION TITLE PHASES FROM CARBFIX2022TITLE CALCITE DISSOLVES AS KINETIC PHASETITLE CALCITE PRECIPITATION AS EQUILIBRIUM PHASETITLE CO2 INJECTED FROM DAC TO SOLUTIONTITLE LI ADDED IN TRACE TO KARDEMIR SUPPLIED GRID WATER# Information following a # is not read########################## SWITCH OFF OUTPUT TO file.pqo ############################################################################################################## Need to increase speed of program and to cut down on the megabytes of output created# PRINT# -reset FALSE # suspend all print output# This can always be changed if specific runs need to be investigated.Using PRINT, I can modify the print to the output tab by setting output block identifiers true or false. These identifiers can be clicked and copied to the input tab after expanding keyword PRINT in the right window. The option -reset false is rather essential when doing transport simulations.This keyword data block is used to select which results are written to the output file. In addition, this data block enables or disables writing results to the selected-output file and writing a status line to the screen, which monitors the type of calculation being performed.# If used, this identifier should be the first identifier of the data block. If true, all data blocks described on Lines are printed to the output file; if false, these data blocks are excluded from the output file. If neither true nor false is entered on the line, true is assumed.# For long TRANSPORT and ADVECTION calculations with KINETICS, printing the status line [-status true (default)] may cause a significant increase in run time. In this case, setting -status false will speed up run times. Below status set to false.######################################################################################################################### DEFINE SOLID PHASES IN SLAG SYSTEM #########################################################################################################################################################################################################################################################################################################################################################################################################################################################PHASES # Minerals, Directly taken from Carbfix2022.dat PHASES.# PHASES keyword data block is used to define a name, chemical reaction, log K, and temperature dependence of log K for each gas component and mineral that can be used for speciation, batch-reaction and transport calculations. In addition, molar volumes can be defined for solids, and the critical temperature and pressure and the acentric factor can be defined for gases. Normally, this data block is included in the database file and only additions and modifications are included in the input file.# There are 4 mineral phases on Antimagnetic Slag that I need to write below so that model can identify the phases. These are Brucite, Calcite_diss (Slag calcite dissolves only), Calcite_ppt (Slag calcite precipitate only), Larnite and Portlandite.Calcite_diss # Calcite that dissolves only. Alphanumeric name of phase; no spaces are allowed. CaCO3 + H+ = Ca+2 + HCO3- # Dissolution reaction log_k 1.8487 # Log K at 25 ?C for the reaction -delta_H -25.7149 kJ/mol # Enthalpy of reaction at 25 ?C for the reaction# deltafH -288.552 kcal/mol -analytic -1.4978e2 -4.8370e-2 4.8974e3 6.0458e1 7.6464e1 # Identifier for coefficients for an analytical expression for the temperature dependence of log K.# Range 0-350 -Vm 36.934 # molar_volume, the molecular weight divided by the density of the solid at 25 ?C. Ex: Molecular Weight/Mass (g/mole)=100.09, Density (g/ml or g/cm3)= 2.71 therfore, Vm= 100.09 / 2.71 = 36.934# Extrapol supcrt92# Ref HDN+78Calcite_ppt # Calcite that percipitates only CaCO3 + H+ = Ca+2 + HCO3- # Dissolution reaction log_k 1.8487 # Log K at 25 ?C for the reaction -delta_H -25.7149 kJ/mol # Enthalpy of reaction at 25 ?C for the reaction# deltafH -288.552 kcal/mol -analytic -1.4978e2 -4.8370e-2 4.8974e3 6.0458e1 7.6464e1 # Identifier for coefficients for an analytical expression for the temperature dependence of log K.# Range 0-350 -Vm 36.934 # molar_volume, the molecular weight divided by the density of the solid at 25 ?C. Ex: Molecular Weight/Mass (g/mole)=100.09, Density (g/ml or g/cm3)= 2.71 therfore, Vm= 100.09 / 2.71 = 36.934# Extrapol supcrt92# Ref HDN+78Brucite Mg(OH)2 + 2 H+ = Mg+2 + 2 H2O # Dissolution reaction log_k 16.2980 # Log K at 25 ?C for the reaction -delta_H -111.34 kJ/mol # Enthalpy of reaction at 25 ?C for the reaction# deltafH -221.39 kcal/mol -analytic -1.0280e2 -1.9759e-2 9.0180e3 3.8282e1 1.4075e2 # Identifier for coefficients for an analytical expression for the temperature dependence of log K.# Range 0-350 -Vm 24.63 # molar_volume, the molecular weight divided by the density of the solid at 25 ?C. Ex: Molecular Weight/Mass (g/mole)=58.32, Density (g/ml or g/cm3)= 2.39 therfore, Vm= 58.32 / 2.39 = 24.40# Extrapol supcrt92# Ref HDN+78Larnite Ca2SiO4 + 4 H+ = SiO2 + 2 Ca+2 + 2 H2O # Dissolution reaction log_k 38.4665 # Log K at 25 ?C for the reaction -delta_H -227.061 kJ/mol # Enthalpy of reaction at 25 ?C for the reaction# deltafH -551.74 kcal/mol -analytic 2.6900e1 -2.1833e-3 1.0900e4 -9.5257 -7.2537e4 # Identifier for coefficients for an analytical expression for the temperature dependence of log K.# Range 0-300 -Vm 51.6 # HDN+78 # molar_volume, the molecular weight divided by the density of the solid at 25 ?C. Ex: Molecular Weight/Mass (g/mole)=172.24, Density (g/ml or g/cm3)= 3.28 therfore, Vm= 172.24 / 3.28 = 52.512# Extrapol Cp integration# Ref 82sar/barPortlandite Ca(OH)2 + 2 H+ = Ca+2 + 2 H2O # Dissolution reaction log_k 22.5552 # Log K at 25 ?C for the reaction -delta_H -128.686 kJ/mol # Enthalpy of reaction at 25 ?C for the reaction# deltafH -986.074 kJ/mol -analytic -8.3848e1 -1.8373e-2 9.3154e3 3.2584e1 1.4538e2 # Identifier for coefficients for an analytical expression for the temperature dependence of log K.# Range 0-300 -Vm 33.056 # thermo.com.V8.R6+.tdat # molar_volume, the molecular weight divided by the density of the solid at 25 ?C. Ex: Molecular Weight/Mass (g/mole)=74.09, Density (g/ml or g/cm3)= 2.23 therfore, Vm= 74.09 / 2.23 = 33.224# Extrapol Cp integration# Ref RHF79# All other solids are defined in the chosen database########################################################################################################### GEOCHAMICAL NODE 1 - MAKE UP WATER/GRID WATER OR WASTEWATER ######################################################################################################################################################################################################################################################################################################################################################################################################################################## Process water/grid water / makeup water is pumped from the Kardemir steel plant. This conceptual model is the Kardemir process water in the hypothetical scenario of no contact with atmosphere, still in the pumping/piping system. Mean Values are used. # Process SOLUTION Use of Kardemir water25062022 - MEAN CONCENTRATIONS (AVG) + Tracer = Li, Chloride charge balance. SOLUTION 1 Kardemir Process/grid water # Directly taken from KARDEMIR Steel Manufacturer Plant. Define the composition of an aqueous solution. Speciate an analysis, calculate saturation indices. temp 25 # temperature in degrees Celcius, default = 25 C, Kardemir 25C pH 8.25 # +-0.1,default pH = 7, Kardemir 8.5 pe 4 # pe = -log(electron activity), default = 4. redox pe # reduction-oxidation reactions units ppm # same as mg/l, default units ppm, mmol/kg water density 1 # density, default = 1 kg/L, Kardemir 1 Ca 160 # +-0.1,total dissolved Ca, Kardemir 140-180 #Mg 3.4 # +-0.1,total dissolved Mg # Speciate that can be in grid water. No presence of Mg in Kardemir water #N(5) 0.84 # 0.84% ppm or mg/l of Nitrogen # Speciate that can be in grid water. No presence of N(5) in Kardemir water N(-3) 0.35 # Kardemir NH3 0.2-0.5 #Na 22 # 11-33 mg/l,total dissolved Na # Speciate that can be in grid water. No presence of Na in Kardemir water #K 0.82 # total dissolved K # Speciate that can be in grid water. No presence of K in Kardemir water P 0.22 # 0.3% ppm or mg/l of Phosforous, Kardemir P2O5 0.15-0.30 Fe(2) 0.25 # total dissolved Fe,generally <0.01, Kardemir 0.2-0.3, assumed all to be as ferrous Fe(3) 1e-9 # ferric iron assumed as present in negligible quantities Alkalinity 240 # 30-400ppm reasonable range alkalinity for domestic drinking water,low alkalinity 0.4- 0.8, Kardemir 210-270 CaCo3 C(4) 4.620e-03 mol/kgs # equivalent of Alkalinity 240 and pH 8.25 Cl 85 charge # total dissolved Cl, Kardemir 50-120. Charged balanced. S(6) 70 # ppm or mg/l of Sulfate, total dissolved Sulfate, Kardemir 60-80 #Li 6.941E-03 # Lithium (1umol/L) is a tracer for Process Water #Si 2.80855 # mg/L = 0.1 mmol/L -water 1 # kg water, default = 1 kg# The solution is charge balanced. In Ionic solution, the sum of negative electrical charges equals to sum of positive electrical charges (C+ = A-).(-4.15 meaning more negative ions) and balance adjustment may be required for future calculations, hence charge balance. Percentage error simply describes Cations and Anions balance. It should be noted that Percent error, 100*(Cat-|An|)/(Cat+|An|) is unitless and it is important to adjust the system to become electrically neutral/ balanced because PHREEQC will look for demand of equilibrium and will force charge balance with one of the components (that can be designated), as they solve the matrix of non-linear equations. # Only analyses of water samples with an ion-balance error < 5% are discussed to be tolerable (Appelo and Postma, 2005) and , (Wisotzky et al., 2018). If errors exceed 5% either not all ionic compounds were reflected in the analysis, or individual compound concentrations may be over- or underestimated or individual analysis results are incorrect (Appelo and Postma, 2005).# When the simulation run without charge balance, Electrical balance (eq) = -6.707e-16 is pretty close to 0 so it seems ok to use, no further adjustment needed# Values given in solution now converted in molality/moles. For example given Alkalinity (In PHREEQC the alkalinity is always stated as CaCO 3 equivalents) 240ppm is also equilvalent to 4.801e-03 moles.# All carbon in the form of carbonic acid species are given as C (4) which specifies element valence with brackets C (4)= 4.624e-03.Carbon speciation contrubution is HCO3- (4.246E-03/4.624e-03= 92%), CaCO3 (1.628E-04/4.624e-03= 3.5%), CaHCO3+ (1.18E-04/4.624e-03= 2.55%), CO2 (4.99E-05/4.624e-03= 1%) and CO3-2 (4.66E-05/4.624e-03= 1%).# The Ca concentrations is 3.996e-03 molar. It is listed in the order of Magnitude, most abandon is Ca+2 with 3.581e-03 molar. # Phase saturations, Calcite 1.37 : Supersaturated(expected to form), Fe(OH)3 -7.39 : Undersaturated(expected to dissolve) , CO2(g) -2.84 : Undersaturated(expected to dissolve), Portlandite -8.68 : Undersaturated(expected to dissolve) and O2(g) -34.12 : Undersaturated(expected to dissolve). # Iron is present in solution, such that ferrihydrite (Fe(OH)3) is understaurated. This is probably due to the pe of the system being arbitrarily set at 4.0.Iron redox behaviour is important because iron forms solid precipitates such as Fe(OH)3, often called ferrihydrite or amorphous ferric hydroxide, when a reduced solution is oxidized (usually by contact with the atmosphere). Ferrihydrite is a good adsorption surface and will remove many metals from solution. Ferrihydrite is gradually converted by de-hydration to limonite, goethite and finally, hematite.Ferrihydrite readily dissolves in the Kardemir process water system. It is likely that the redox status of the system is such that ferrous ion is stabilised in solution. Ferrous ion is much less likely to precipitate as an oxide. # It is also possible that calcite is remaining supersaturated during the lifetime of the pumping of process water. If this is true, there will be no scaling potential.Calcite is allowed to precipitate, though none of the other phases are allowed to do so due to kinetic reaction.SAVE SOLUTION 1 # SAVE keyword data block is used to save the composition of a solution, exchange assemblage, gas phase, equilibrium-phase assemblage, solid-solution assemblage, or surface assemblage following a batch-reaction calculation. The composition is stored internally in computer memory and can be retrieved subsequently with the USE keyword during the remainder of the computer run. SAVE affects only the internal storage of chemical-composition information during the current run; it does not save information between PHREEQC runs. The SAVE data block applies only at the end of batch-reaction calculations and has no effect following initial solution or transport calculations.END # Ends the program. The input file is then read and processed simulation by simulation (as defined by END keywords) until the end of the file.########################################################################################################### GEOCHAMICAL NODE 2 - RAINFALL AND HEAP LEACH IRRIGATION ############################################################################################################################################################################################################################################################################################################################################################################################################################################# The chemistry of the rainfall entering on the Kardemir slag heap is taken as the median concentrations from (Alagha and Tunkel, 2003) (DOI: 10.1023/A:1026049027446). # The alkalinity values for these chemical analyses are not reported. Therefore, C(4) is introduced at atmospheric concentration. Chloride is here chosen as the charge-balancing anion.# The pH drop of Kardemir make up water due to CO2 introduction promotes the dissolution of alkali earth metals such as calcium and magnesium. These metals react with the dissolved carbon bearing species such as bicarbonate or carbonate which result in the precipitation of carbonate minerals such as calcite. As an example, the reaction between carbonate and calcium leads to the precipitation of calcite. Interaction among CO2- water-slag heap produces a complex series of reactions that varies depending on the chemical composition of the fluid and the mineralogy of the slag. (Rosenbauer et al., 2005) defined similar complex reactions between CO2-brine-rock. These complex reactions may promote the change in porosity of Slag heap. Excess dissolution of slag heap mineral will possibly lead to porosity increase which is desirable since it increases the CO2 storage capacity of a slag. When precipitation of new or existing mineral is dominant, porosity decrease will be observed.# USE SOLUTION 1 # USE keyword data block is used to specify explicitly which solution is to be used in the batch-reaction calculation of a simulation. USE also can specify kinetically controlled reactions (KINETICS data block) and mixing parameters (MIX data block) to be used in a batch-reaction calculation.# SOLUTION 1 is the process/grid water that is used to irrigate the slag heapSOLUTION 2 Median Black Sea rainfall concentrations from Alagha and Tunkel (2003). CO2(atm), O2(atm) added. Chloride charge balance temp 25 pH 5.15 pe 4 redox pe units ppm density 1 Al 3.37 Ca 1.8 Cl 1.01 charge # adapt Cl to obtain charge balance C(4) 1 CO2(g) -3.373 # equilibrium with atmospheric CO2 Fe 2.82 K 1.72 Mg 0.88 Mn 0.07 N(-3) 0.56 N(5) 1.5 Na 2 S(6) 2.52 O(0) 0.01 O2(g) -0.678 # equilibrium with atmospheric O2 -water 1 # kgEND# Fugacity of CO2(g) in the atmosphere is approximately 0.000424, or 0.04%. Saturation Index of the CO2(g) in the atmosphere is therefore Saturation Index CO2 (-pCO2)= SI(CO2(g) = log10(fugacity) = log10(0.000424) = -3.373. The gas pressure can be varied, setting SI. The SI is equal to log(gas pressure / 1 atm).This is the number used in the PHREEQC calculations.# The saturation state of O2 is more complex. Oxygen readily dissolves in aqueous solutions exposed to atmosphere. Equilibrate water with O2(g) 209460ppm = 0.20946= SI(CO2(g) = log10(fugacity=0.20946) =-0.678. (https://en.wikipedia.org/wiki/Atmosphere_of_Earth). Thus, the anticipated SI of oxygen is log10(0.209) = -0.678. This is the number used in the PHREEQC calculations.EQUILIBRIUM_PHASES 1-100 # Equilibrate SOLUTION 1 water with calcite precipitation # Brucite 0 4.733 dissolve_only # 4.733 (mol_mineral/L_pores)calculated, see supporting document# Calcite_diss 0 9.49 dissolve_only # Slag calcite dissolves, 9.49 (mol_mineral/L_pores)calculated, see supporting document Calcite_ppt 0 0 # Switch on calcite as a phase that can precipitate within days# Larnite 0 9.87 dissolve_only # 9.87 (mol_mineral/L_pores)calculated, see supporting document# Portlandite 0 14.43 dissolve_only # 14.43 (mol_mineral/L_pores)calculated, see supporting documentEND############################################################################################### CALCULATE FLOW RATES THROUGH CELLS, AS RETENTION TIMES AND DEPTHS FOR SSANTIMAGNETIC ################################################################################################################################################################################################################################################################################################################################################################################################################################ Depth or height of cell (-lengths) 0.01 metres = 1cm# Number of horizontal slices 100# No ponding on the surface of the slag heap is assumed, therefore the advective ingress of rainfall may be estimated as follows. Total annual millimetres of rainfall can be extracted to be 522.1 (mm/a)(https://en.wikipedia.org/wiki/Karab%C3%BCk). A broad average of rainfall, in terms of metres per second is thus calculated:# Total annual millimetres of rainfall 522.1 mm/a# Convert to m/a= 522.1/1000= 0.522 m/a# Year = 365.25 d/a# Convert to m/d= 0.522/ 365.25 = 1.429E-03 m/d# Convert to s/d = 60x60x24 = 86400 s/d# Convert to m/s = 1.429E-03 / 86400 = 1.654E-08 m/s. Annual average precipitation is thus 1.654E-08 m/s.# Slag porosity for Antimagnetic is calculated at: 46% pore volume/slag bulk volume and 56% pore volume on Magnetic.see supporting document# Advective velocity of rainfall through the Antimagnetic slag heap is thus 1.654E-08/0.46 m/s. ########## Advective velocity of rainfall through the slag heap is 3.596E-08 m/s. and 2.953E-08 (Magnetic) ########### The slag heap is 1 metre high and is constantly irrigated with Process-water/grid water and rainwater. The irrigation rate is 10 millimetres per day. The velocity of the irrigation water before it enters the heap is 10 mm_irrigation/day.# Convert to milimetres per second 10mm/86400sec = 1.160E-04 mm_irrigation/second.# Convert to metres per second irrigation 1.160E-04/ 1000 = 1.160E-07 m_irrgation/second.# Porosity of Anti Magnetic slag 0.46 L_pores/L_slag. ########## Thus the velocity of pore waters is 1.160E-07/0.46 = 2.520E-07 m/s. and 2.07E-07 (Magnetic)########### Combined velocity of pore waters = 3.596E-08 m/s + 2.520E-07 m/s = ########## 2.88E-07 m/s. and 2.366E-07 (Magnetic) ########### Proportion of total for Rain water = 3.60E-08 / 2.88E-07 = ########## 0.125. and 0.124. (Magnetic) ########### Proportion of total for Process water = 2.52E-07 / 2.88E-07 = ########## 0.875. and 0.875.(Magnetic) ########### Retention time for rainwater leach only = 0.01m / 3.596E-08 = ########## 278086.7. and 338638.6 (Magnetic) ########### Retention time for process water leach only = 0.01m / 2.520E-07 = ########## 39682.5. and 48309.2.(Magnetic)########### Retention time for combined water leach = 0.01m / 2.88E-07 = ########## 34722.2. and 42265.4.(Magentic) ###########SS Antimagnetic Velocity in pores (m_pw/s) Proportion of total Retention time in cells (-time_step/s)#Rain water 3.60E-08 0.12 278086.7 # This is retention time for rainwater leach only#Process water 2.52E-07 0.88 39682.5 # This is fictitious, for calculation only#Combined 2.88E-07 1 34722.2 # This is retention time for Rainwater + DACMIX 1 Combine rainwater with (process/grid water + DAC) 1 0.88 # 1-(Rainfall_rate/(Rainfall_rate+Procwtr_rate), use fraction 0.88 of solution 1 2 0.12 # 1-(Procwtr_rate/(Rainfall_rate+Procwtr_rate), use fraction 0.12 of solution 2# MIXing two or more aqueous solutions in specified proportions. This procedure effectively increases the total mass (or volume) of the aqueous phase but maintains the same concentrations. Often the question of the compatibility of the supplied water with used water needs to be addressed. Supplied water can be mixed it with used water. Mixing results in a batch-reaction calculation, which produces aqueous equilibrium, including redox equilibrium. Mixing may be used alone, in combination with additional reactions, or during advection or transport calculations. All applications of MIX result in a batch-reaction calculation that produces aqueous equilibrium, including redox equilibrium. Mixing solution represents 1 L for each solution meaning 50% of each. In mixing, each solution is multiplied by its mixing fraction and a new solution is calculated by summing over all the fractional solutions. The mass of water is multiplied by the same fractions. USE equilibrium_phases 1SAVE SOLUTION 0 END## USE SOLUTION 0# SOLUTION 0, the leaching solution (https://speciation.net/Glossary/column-leaching-;938), is combination: rainwater with (process/grid water + DAC)SOLUTION 1-101 Simulated mixture of (process water, DAC) and rainwater. temp 25 pH 6.963 pe 13.64 redox pe units mol/kgw density 1 -water 1 # kgC(4) 5.06E-03Ca 3.52E-03Cl 2.12E-03Fe 3.94E-06K 1.07E-06Mg 1.93E-06N 2.79E-05Na 1.07E-05P 6.26E-06S(6) 6.45E-04END# Evaporation of mixture of (process water, DAC) and rainwaterREACTION 0 # Remove / Evaporate water in steps. All solutions defined by SOLUTION input are scaled to have exactly 1 kg (approximately 55.5 mol) of water, unless -water identifier is used. H2O -1 # Evaporate 11.1012 moles(= 0.2 * 55.506), 20% evaporation from pond in 4 step. # 11.1012 mole in 4 step. # The first step removes(-) 2.775e+00 moles of reaction (units are ?moles?) to the initial solution; the second step removes 5.551e+00 moles of reaction to the initial solution; the third 8.326e+00 moles; and the fourth 1.110e+01 moles; each reaction step begins with the same initial solution and removes only the amount of reaction specified. 11.1012 moles in 4 stepsEND############################################################################################################################# GEOCHAMICAL NODE 3 - DAC INTRODUCTION AND AMBIENT AIR ####################################################################################################################################################################################################################################################################################################################################################################################################################################### DAC is expected to raise the concentration in the gas from 0.04% atmospheric CO2(atm) to >3% CO2(g) .Fugacity of CO2(g) in this gas is at minimum 0.03. Gas phase equilibrium incorporated into calculation using DAC avg 3% CO2, ppm_CO2/Air log10(fugacity) = log10(0.03)= -1.5230. These are the numbers used in the PHREEQC calculations.# The saturation state of oxygen is more problematic. Oxygen readily dissolves in aqueous solutions exposed to atmosphere. Equilibrate water with O2(g) 209460ppm = 0.20946= SI(CO2(g) = log10(fugacity=0.20946) =-0.679. (https://en.wikipedia.org/wiki/Atmosphere_of_Earth). Thus, the anticipated SI of oxygen is log10(0.209) = -0.679.# Addition of DAC to process and rain waterEQUILIBRIUM_PHASES 101 DAC CO2 capture to 3% CO2(g) -1.523 10 # Calculated CO2 SI= -1.523, Amount of 10 mol available O2(g) -0.679 10 # Calculated O2 SI= -0.679, Amount of 10 mol available# N2(g) -0.107 10 # Calculated N2 , log 10 (0.7809), SI= -0.107, Amount of 10 mol available. Calcite_ppt 0 0 END#REACTION 1 # ferric iron assumed as present in negligible quantities# Fe+3 1# 1e-08 molesUSER_PRINT10 p = SYS("equi", count , name$ , type$ , moles )20 FOR i = 1 to count30 dv = PHASE_VM(name$(i))*EQUI_DELTA(name$(i))40 delta_v = delta_v + dv50 PRINT name$(i), dv, " cm^3"60 NEXT i70 PRINT "Total change in mineral volume: ", delta_v, " cm^3"80 END# -Vm, Identifier for the molar volume of the solid phase. It identifies for parameters used to calculate the specific volume (cm3/mol) of aqueous species with a Redlich-type equation (Redlich and Meyer, 1964). The molecular weight divided by the density of the solid at 25 ?C. Mineral volume is directly disproportional with Porosity which means if slag property volume decreases (-) , porosity increases. # Porosity is defined as the ratio of the volume of voids (the spaces between the grains) in a rock to the bulk volume (the overall volume of the voids plus the grains) of that rock (Amyx et al., 1960). In this case rock is replaced by Slag heap. Porocity (%) = (1-bulk density slag/particle density slag) ? 100# The mineral volume increased by Calcite_ppt 1.5205e-03 cm^3. Total change in mineral volume: 1.5205e-03 cm^3 = 0.0015 cm^3 which means the porosity decreases. Increase in volume is 0.0015 / 1000= 0.0000015 L is very small. ############################################################################################################################ DEFINE RATES IN SLAG SYSTEM ######################################################################################################################################################################################################################################################################################################################################################################################################################################################################## RATES# The rate equation for Larnite in carbfix is reproduced here for study purposes. # Since the rate is embedded in the carbfix2022.dat it does not ordinary have to be reproduced.# Larnite #Ca2SiO4;M 172.237 g/mol, from chemical composition database.##------------------Kinetic calculation---------------------## # parameters#1000 Aa = k_acid = 5.25e8 # mol.m-2.s-1#1001 Ac = k_base = 8.25e5 # mol.m-2.s-1#1002 An = k_neut = 0 # mol.m-2.s-1#1003 Ea = eapp_acid = 70400 # J/mol#1004 Ec = eapp_base = 60900 # J/mol#1005 En = eapp_neut = 0 # J/mol#1006 R = r = 8.314 #J.deg-1.mol-1 #1007 na = n_acid = 0.44#1008 nc = n_base = 0.22#1009 temp = 1/TK#1010 hplus = ACT("H+")#1011 a0 = PARM(1)# parm(1) is surface area in the unit of m2/kgw#1012 parm(2) is a correction factor# 1e-3 converts mmol to mol#1013 v = 1 #1014 M is current moles of minerals#1015 M0 is the initial moles of minerals#1016 sr_mineral = SR("Larnite")#1017 si_mineral = SI("Larnite") #rate equations#2000 r_acid = k_acid*EXP((-eapp_acid/r)*temp)*(hplus^n_acid)# acid rate expression#2001 r_neut = k_neut*EXP((-eapp_neut/r)*temp) # neutral rate expression#2002 r_base = k_base*EXP((-eapp_base/r)*temp)*(hplus^n_base)# base rate expression#2003 r_all = r_acid+r_neut+r_base#2004 rate = (a0/v)*(M/M0)^0.67*r_all*(1-sr_mineral)*PARM(2) # 2/3*si_mineral)=0.67#2005 moles = rate*TIME#2006 SAVE moles#-end# KINETICS 1-100#-------------------------Mineral---------------------------------# Larnite # #-formula Ca2SiO4 1#----------------------------Mass--------------------------------- #-m0 9.883 #moles Larnite per litre pore-water #-------------------------Surface area---------------------------- # The mineral surface area is specified using 3 parameters.# The first parameter specifies if the specific surface area is calculated per g of rock (0) or kg of water (1)# The second parameter specifies the specific surface area of the mineral in m2/g# The third parameters define how the surface area changes during dissolution and has three possible values:# 0: The surface area is constant# 1: The surface area changes linearly with the moles of the mineral present# 2: The surface area changes according to the geometry of dissolving cubes# 3: The surface area changes according to the geometry of dissolving spheres# Here, parameter #1 is 1, so that parameter #2 is the surface area# in m2 per kg of water. See readme file for details. #-parms 1 2.5 2# 2.500 m2_Larnite/L_pores - calcs from Erdinc's data #-tol 1e-08#-------------------------Mineral--------------------------------- #Brucite #-formula Mg(OH)2 1#----------------------------Mass--------------------------------- #-m0 4.733 #moles Brucite per litre pore-water #-------------------------Surface area---------------------------- #-parms 1 0.556 2# 0.556 m2_Brucite/L_pores - calcs from Erdinc's data #-tol 1e-08#-------------------------Mineral--------------------------------- #Calcite_diss #-formula CaCO3 1#----------------------------Mass--------------------------------- #-m0 9.46 #moles Calcite per litre pore-water #-------------------------Surface area---------------------------- #-parms 1 1.683 2# 1.683 m2_Calcite/L_pores - calcs from Erdinc's data #-tol 1e-08#-------------------------Mineral--------------------------------- #Portlandite #-formula Ca(OH)2 1#----------------------------Mass--------------------------------- #-m0 14.389 #moles Calcite per litre pore-water #-------------------------Surface area---------------------------- #-parms 1 2.303 2# 2.303 m2_Calcite/L_pores - calcs from Erdinc's data #-tol 1e-08 #-steps 1 # Time steps over which to integrate the rate expressions(s). The -steps identifier is used only during batch-reaction calculations; it is not needed for transport calculations. By default, the list of time steps are considered to be independent times, all starting from zero. #-step_divide 0.1 # This parameter affects integration by the Runge-Kutta solver. If step_divide is greater than 1.0, the first time interval of each integration is set to time step / step_divide; at least two time intervals must be integrated to reach the total time of time step?0 to time step / step_divide and time step / step_divide to time step. If step_divide is less than 1.0, then step_divide is the maximum moles of reaction that can be added during a kinetic integration subinterval. Frequently reaction rates are fast initially, thus requiring small time intervals to produce an accurate integration of the rate expressions. #-runge_kutta 6 # This parameter affects integration by the Runge-Kutta solver. It designates the preferred number of time subintervals to use when integrating rates and is related to the order of the integration method. A value of 6 specifies that a 5th order embedded Runge-Kutta method, which requires six intermediate rate evaluations, will be used for all integrations. For values of 1, 2, or 3, the program will try to limit the rate evaluations to this number. #-bad_step_max 500 # Defines the maximum number of attempts at integrating a set of kinetic reactions over a time step. For the Runge-Kutta method, it is the maximum number of times the integration fails in integrating over a time interval. For the CVODE method, it is the number of times that CVODE is invoked in integrating over a time interval. Default is 500. #-cvode true # Specifies whether to use the explicit Runge-Kutta method or the implicit CVODE method (Cohen and Hindmarsh, 1996) to integrate the kinetic rate equations. Default is false. A value of true indicates the CVODE implicit integration method is used. #-cvode_steps 100 # Specifies the maximum number of steps that will be taken during one invocation of CVODE. Default is 100 if -cvode_steps is not included. #-cvode_order 5 # Specifies the number of terms to use in the extrapolation of rates when using the CVODE method. Default is 5. RATES Calcite_diss # calcite dissolving only-start # Identifier marks the beginning of a Basic program by which the moles of reaction for a time subinterval are calculated. 5 REM Formula = CaCO3 10 REM Rate law modified from Zhang et al. 2019 20 REM Rate law from Marty et al 2015 30 REM unit should be J, m2, mol,kgw-1 and second-1 40 REM parm(1) is surface area in the unit of m2/kgw 50 REM calculation of surface area can be found in the note 60 REM M is current moles of minerals. M0 is the initial moles of minerals 70 REM parm(2) is a correction factor 80 REM Affinity ON 90 sr_mineral = SR("Calcite") # Calculate calcite saturation ratio 95 si_mineral = SI("Calcite") # Calculate calcite saturation index100 moles = 0110 REM rate=0 if mineral supersaturated in solution120 IF(M <= 0 OR sr_mineral > 1) THEN GOTO 320130 a0 = PARM(1)132 REM Volume is 1 litre solution135 v = 1 140 temp = 1/TK145 REM acid solution parameters150 k_acid = 0160 eapp_acid = 0170 n_acid = 0175 REM neutral solution parameters180 k_neut = 6.59E+04190 eapp_neut = 66000195 REM base solution parameters200 k_base = 1.04E+09210 eapp_base = 67000220 n_base = 1.6225 REM Rate Law in TST form230 hplus = ACT("H+")240 r = 8.314250 r_acid = k_acid*EXP((-eapp_acid/r)*temp)*(hplus^n_acid)260 r_neut = k_neut*EXP((-eapp_neut/r)*temp)270 REM Base in terms of bicarbonate280 r_base = k_base*EXP((-eapp_base/r)*temp)*(ACT("HCO3-")^n_base)290 r_all = r_acid+r_neut+r_base300 rate = (a0/v)*(M/M0)^0.67*r_all*(1-sr_mineral)*PARM(2) # Calculate overall rate, factor310 moles = rate*TIME # Calculate moles of reaction over time interval given by TIME. Note that the multiplication of the rate by TIME must be present in one of the Basic lines.320 SAVE moles # Return moles of reaction for time subinterval with ?SAVE?. A SAVE statement must always be present in a rate program.-end # Identifier marks the end of a Basic program by which the number of moles of a reaction for a time subinterval is calculated. Brucite-start 5 REM Formula = Mg(OH)2 10 REM Rate parameters from Zhang et al. 2019 database 20 REM Rate law from Palandri and Kharaka (2004) 25 REM experimental condition range T=25-75C, pH=1-5 30 REM unit should be J, m2, mol,kgw-1 and second-1 40 REM parm(1) is surface area in the unit of m2/kgw 50 REM calculation of surface area can be found in the note 60 REM M is current moles of minerals. M0 is the initial moles of minerals 70 REM parm(2) is a correction factor 80 REM Affinity ON 90 sr_mineral = SR("Brucite") 95 si_mineral = SI("Brucite")100 moles = 0110 REM rate=0 if mineral supersaturated in solution120 IF(M <= 0 OR sr_mineral > 1) THEN GOTO 380130 a0 = PARM(1)140 REM Volume is 1 litre solution150 v = 1160 temp = 1/TK170 REM acid solution parameters180 k_acid = 4.00E+05190 eapp_acid = 59000200 n_acid = 0.500210 REM neutral solution parameters220 k_neut = 1.30E-01230 eapp_neut = 42000240 REM base solution parameters 250 k_base = 0260 eapp_base = 0270 n_base = 0280 REM Rate Law in TST form290 hplus = ACT("H+")300 r = 8.314310 r_acid = k_acid*EXP((-eapp_acid/r)*temp)*(hplus^n_acid)320 r_neut = k_neut*EXP((-eapp_neut/r)*temp)340 r_base = k_base*EXP((-eapp_base/r)*temp)*(hplus^n_base)350 r_all = r_acid+r_neut+r_base360 rate = (a0/v)*(M/M0)^0.67*r_all*(1-sr_mineral)*PARM(2)370 moles = rate*TIME380 SAVE moles-end Larnite-start 5 REM Formula = Ca2SiO4 10 REM Rate parameters from Carbfix_2022 database 20 REM Rate law from Palandri and Kharaka (2004) 30 REM unit should be J, m2, mol,kgw-1 and second-1 40 REM parm(1) is surface area in the unit of m2/kgw 50 REM calculation of surface area can be found in the note 60 REM M is current moles of minerals. M0 is the initial moles of minerals 70 REM parm(2) is a correction factor 80 REM Affinity ON 90 sr_mineral = SR("Larnite") 95 si_mineral = SI("Larnite")100 moles = 0110 REM rate=0 if mineral supersaturated in solution120 IF(M <= 0 OR sr_mineral > 1) THEN GOTO 380130 a0 = PARM(1)140 REM Volume is 1 litre solution150 v = 1160 temp = 1/TK170 REM acid solution parameters180 k_acid = 5.25e8190 eapp_acid = 70400200 n_acid = 0.44210 REM neutral solution parameters220 k_neut = 0230 eapp_neut = 0240 REM base solution parameters250 k_base = 8.25e5260 eapp_base = 60900270 n_base = 0.22280 REM Rate Law in TST form290 hplus = ACT("H+")300 r = 8.314310 r_acid = k_acid*EXP((-eapp_acid/r)*temp)*(hplus^n_acid)320 r_neut = k_neut*EXP((-eapp_neut/r)*temp)330 IF(k_base = 0) THEN GOTO 350340 r_base = k_base*EXP((-eapp_base/r)*temp)*(hplus^n_base)350 r_all = r_acid+r_neut+r_base360 rate = (a0/v)*(M/M0)^0.67*r_all*(1-sr_mineral)*PARM(2)370 moles = rate*TIME375 REM PRINT "SI(Larnite) = " si_mineral ", Molar adjustment = " moles380 SAVE moles-end Portlandite-start 5 REM Formula = Ca(OH)2 10 REM Rate law modified from Zhang et al. 2019 20 REM Rate law from marty et al 2015 25 REM experimental condition range T=25-80C, pH=5-7 30 REM units should be J, m2, mol,kgw-1 and second-1 40 REM parm(1) is surface area in the unit of m2/kgw 50 REM calculation of surface area can be found in the note 60 REM M is current moles of minerals. M0 is the initial moles of minerals 70 REM parm(2) is a correction factor 80 REM Affinity ON 90 sr_mineral = SR("Portlandite") 95 si_mineral = SI("Portlandite")100 moles = 0110 REM rate=0 if mineral supersaturated in solution120 IF(M <= 0 OR sr_mineral > 1) THEN GOTO 320130 a0 = PARM(1)132 REM Volume is 1 litre solution135 v = 1 140 temp = 1/TK145 REM acid solution parameters150 k_acid = 1.10E+10160 eapp_acid = 75000170 n_acid = 0.600175 REM neutral solution parameters180 k_neut = 3.04E+05190 eapp_neut = 75000195 REM base solution parameters200 k_base = 0210 eapp_base = 0220 n_base = 0225 REM Rate Law in TST form230 hplus = ACT("H+")240 r = 8.314250 r_acid = k_acid*EXP((-eapp_acid/r)*temp)*(hplus^n_acid)260 r_neut = k_neut*EXP((-eapp_neut/r)*temp)270 REM Base in terms of bicarbonate280 r_base = k_base*EXP((-eapp_base/r)*temp)*(ACT("OH-")^n_base)290 r_all = r_acid+r_neut+r_base300 rate = (a0/v)*(M/M0)^0.67*r_all*(1-sr_mineral)*PARM(2)310 moles = rate*TIME320 SAVE moles-end# Moles of a kinetic reactant(HCO3).Kinetic_reactants?Identifier allows definition of a list of kinetically controlled reactants for which two values are written to the selected-output file: (1) the current moles of the reactant, and (2) the moles transferred of the reactant. Optionally, kin, -k[inetics. Carbon capture by charge balance (as generation of bicarbonate ion = HCO3. Bicarbonate (HCO3?) is most commonly employed as the electrolyte anion because it is known to facilitate CO2 electroreduction.In particular, HCO3-(Seifritz, 1990; Lackner et al., 1995; Schuiling and Krijgsman, 2006; K?hler et al., 2010; Kelemen et al., 2011; Hartmann et al., 2013). This process of increasing # HCO3- export is known as enhanced weathering (Schuiling and Krijgsman, 2006). The majority of studies concerning enhanced weathering have evaluated the potential of mafic silicate rocks (e.g., basalt) and minerals (e.g., forsterite, Mg2SiO4 and wollastonite, CaSiO3) as reactants (Schuiling and Tickell, 2010; Moosdorf et al., 2014; Renforth et al., 2015; Taylor et al., 2016; Griffioen, 2017; Montserrat et al., 2017; Rigopoulos et al., 2018; Andrews and Taylor, 2019; Haque et al., 2019)kin_HCO3-start10 REM20 kin_ca=1*KIN_DELTA("Portlandite")+2*KIN_DELTA("Larnite")+0*KIN_DELTA("Brucite")+1*KIN_DELTA("Calcite_diss")30 kin_mg=0*KIN_DELTA("Portlandite")+0*KIN_DELTA("Larnite")+1*KIN_DELTA("Brucite")+0*KIN_DELTA("Calcite_diss")60 moles = -2*(kin_ca+kin_mg) 70 print kin_ca, kin_mg, moles320 SAVE moles-end############################################################################################################################################################### DEFINE KINETIC PHASES IN ANTIMAGNETIC SLAG SYSTEM ################################################################################################################################################################################################################################################################################################################################################################################################################# Here, the initial amounts of minerals in the slag system are defined# The KINETICS keyword specifies which of the cells in the 1D flow path contain the kinetic minerals# Kinetics blocks refer to the RATES expressions. # -parms: parm(1) is surface area in the unit of m2/kgw, parm(2)is an adjustment factor on the rate expressionKINETICS 1-100Portlandite -formula Ca(OH)2 1 -m 14.43 -m0 14.43 -parms 2.303 1 -tol 1e-08Larnite -formula Ca2SiO4 1 -m 9.87 -m0 9.87 -parms 2.5 1 -tol 1e-08Calcite_diss -formula CaCO3 1 -m 9.49 -m0 9.49 -parms 1.682 1 -tol 1e-08Brucite -formula Mg(OH)2 1 -m 4.8 -m0 4.8 -parms 0.556 1 -tol 1e-08kin_HCO3 -formula HCO3-1 1 -m 0 -m0 0 -tol 1e-08-steps 1-step_divide 0.1-runge_kutta 6-bad_step_max 500-cvode true -cvode_steps 200-cvode_order 5ENDUSE SOLUTION 0USE REACTION 0USE equilibrium_phases 101USE KINETICS 1SAVE equilibrium_phases 1-10SAVE solution 1-10END############## GRAPHICAL OUTPUT GENERATED WHILST PHREEQC RUNS FOR ANTIMAGNETIC ############################################################################################################## THE FOLLOWING GRAPHS ARE PRESENTED WHILST PHREEQC RUNS### GRAPH 1 AND GRAPH 2 ARE THE QUANTITY OF SLAG MATERIALS DISSOLVED IN EACH STEP, AND THE SI IN EACH STEP.### GRAPH 3 IS THE pH OVER THE ENTIRE COLUMN. THESE GRAPHS ARE EXPECTED TO HAVE A "SAWTOOTH" PROFILE### GRAPH 4 AND 5 DEFINING MOLES CO2 CAPTURED VS DAYS AND TIME### KIN_DELTA is the change in the amount of each kinetic reactant. So, the function KIN("Portlandite") is the total amount of Portlandite available at any time; its initial value is set with -M in KINETICS (1 mole by default). If portlandite decreases, KIN("Portlandite") decreases and KIN_DELTA is negative. The reaction will stop when there is no kinetic reactant goes to zero.USER_GRAPH 1 -headings d_Portlandite d_Larnite d_Brucite d_Calcite -axis_titles "Days" "Dissolved mnrl (mol/L)" "" -chart_title "KARDEMIR ANTIMAGNETIC SLAG FLOW THROUGH TESTS - DISSOLVED MINERALS" -axis_scale y_axis auto 0.005 auto auto -initial_solutions true -connect_simulations true -plot_concentration_vs t -start 1 REM do not Save as emf 5 REM IF(TOTAL_TIME = 0) THEN GOTO 100 7 REM (CELL_NO < 11) THEN GOTO 100 10 PLOT_XY TOTAL_TIME/86400, KIN_DELTA("Portlandite"), color = Green, line_width = 2, y-axis = 1 20 PLOT_XY TOTAL_TIME/86400, KIN_DELTA("Larnite"), color = Blue, line_width = 2, y-axis = 1 30 PLOT_XY TOTAL_TIME/86400, KIN_DELTA("Brucite"), color = Orange, line_width = 2, y-axis = 1 40 PLOT_XY TOTAL_TIME/86400, KIN_DELTA("Calcite_diss"), color = Magenta, line_width = 2, y-axis = 1100 REM END -end -active true######################################################################################################################################################################################################USER_GRAPH 2 -headings SI_Portlandite SI_Larnite SI_Brucite SI_Calcite -axis_titles "Days" "Saturation Index" -chart_title "KARDEMIR ANTIMAGNETIC SLAG FLOW THROUGH TESTS - SATURATION INDICES" -axis_scale y_axis -20 20 auto auto -initial_solutions true -connect_simulations true -plot_concentration_vs t -start 1 REM do not Save as emf 5 REM IF(TOTAL_TIME = 0) THEN GOTO 100 7 REM IF(CELL_NO < 11) THEN GOTO 10010 PLOT_XY TOTAL_TIME/86400, SI("Portlandite"), color = Green, line_width = 2, y-axis = 120 PLOT_XY TOTAL_TIME/86400, SI("Larnite"), color = Blue, line_width = 2, y-axis = 130 PLOT_XY TOTAL_TIME/86400, SI("Brucite"), color = Orange, line_width = 2, y-axis = 1 40 PLOT_XY TOTAL_TIME/86400, SI("Calcite"), color = Magenta, line_width = 2, y-axis = 1100 REM END -end -active true######################################################################################################################################################################################################USER_GRAPH 3 -headings pH -axis_titles "Days" "pH" -chart_title "KARDEMIR ANTIMAGNETIC SLAG FLOW THROUGH TESTS - pH EVOLUTION" -axis_scale y_axis auto auto auto auto -initial_solutions true -connect_simulations true -plot_concentration_vs t -start 1 REM do not Save as emf 5 REM IF(TOTAL_TIME = 0) THEN GOTO 10090 PLOT_XY TOTAL_TIME/86400, -LA("H+"), color = Red, line_width = 2, y-axis = 1100 REM END -end -active true######################################################################################################################################################################################################USER_GRAPH 4 -headings time HCO3 -axis_titles "Time, seconds" "Moles CO2 captured" "" -chart_title "KARDEMIR ANTIMAGNETIC SLAG FLOW THROUGH TESTS - MOLES CO2 CAPTURED" -initial_solutions false -connect_simulations true -plot_concentration_vs x -start 1 REM do not Save as emf 7 REM IF(CELL_NO < 11) THEN GOTO 100 10 IF (TOTAL_TIME = 0) THEN PUT(0,1) 20 kin_ca=1*KIN_DELTA("Portlandite")+2*KIN_DELTA("Larnite")+0*KIN_DELTA("Brucite")+1*KIN_DELTA("Calcite_diss") 30 kin_mg=0*KIN_DELTA("Portlandite")+0*KIN_DELTA("Larnite")+1*KIN_DELTA("Brucite")+0*KIN_DELTA("Calcite_diss") 60 kin_hco3 = 2*(kin_ca+kin_mg)100 GRAPH_X TOTAL_TIME # Time interval for which moles of reaction are calculated in rate programs, automatically set in the time-step algorithm of the numerical integration method, in seconds.110 GRAPH_Y kin_hco3 -end -active true######################################################################################################################################################################################################USER_GRAPH 5 -headings Depth HCO3 -axis_titles "Distance, meters" "Moles CO2 captured" "" -chart_title "KARDEMIR ANTIMAGNETIC SLAG FLOW THROUGH TESTS - MOLES CO2 CAPTURED" -initial_solutions false -connect_simulations true -plot_concentration_vs x -start 1 REM do not Save as emf 7 REM IF(CELL_NO < 11) THEN GOTO 100 10 IF (DIST = 0) THEN PUT(0,1) 20 kin_ca=1*KIN_DELTA("Portlandite")+2*KIN_DELTA("Larnite")+0*KIN_DELTA("Brucite")+1*KIN_DELTA("Calcite_diss") 30 kin_mg=0*KIN_DELTA("Portlandite")+0*KIN_DELTA("Larnite")+1*KIN_DELTA("Brucite")+0*KIN_DELTA("Calcite_diss") 60 kin_hco3 = 2*(kin_ca+kin_mg)100 GRAPH_X DIST110 GRAPH_Y kin_hco3 -end -active true################## TRANSPORT - THROUGH SLAG HEAP PHREEQC RUNS FOR ANTIMAGNETIC ############################################################################################################## TRANSPORT keyword data block is used to simulate one-dimensional (1D) transport of solutes, water, colloids, and heat due to the processes of advection and dispersion, diffusion, and diffusion into stagnant zones adjacent to the 1D flow system. Purely advective transport plus reactions?without diffusion, dispersion, or stagnant zones?can be simulated with the ADVECTION data block.TRANSPORT -cells 101 # 100 cells slag heap, last cell closed pond (1 litre) # -shifts 303 # 3 passes of pore water through the slag heap -shifts 101 # 1 passes of pore water through the slag heap -lengths 0.01 # 1cm cells -time_step 34722.2 # seconds retention time in cells - Antimagnetic = 0.401 days. Shift (101) x Timestep(34722.2) = The total time of the simulation (40.5896 days). -print_cells 1, 100-101 # -print_cells 10-11 -print_frequency 303 # Print only at end # -print_frequency 33 # Print only at end######################################################################################################################################################################################################USER_PUNCH 1 # This keyword data block is used to define Basic programs that print user-defined quantities to the selected-output file. Any Basic ?PUNCH? statement will write to the selected-output file. -headings kin_hco3 Pore_vol # Cum-C-heading -start 7 REM IF(CELL_NO < 101) THEN GOTO 10010 IF (TOTAL_TIME = 0) THEN PUT(0,1)20 kin_ca=1*KIN_DELTA("Portlandite")+2*KIN_DELTA("Larnite")+0*KIN_DELTA("Brucite")+1*KIN_DELTA("Calcite_diss")30 kin_mg=0*KIN_DELTA("Portlandite")+0*KIN_DELTA("Larnite")+1*KIN_DELTA("Brucite")+0*KIN_DELTA("Calcite_diss")60 kin_hco3 = -2*(kin_ca+kin_mg)65 PUT(GET(1)+kin_hco3,1)67 cum_c = GET(1)68 PUNCH kin_hco3#70 PUNCH cum_c75 REM punch pore volumes, no_cells = 10077 no_cells = 10080 PUNCH (STEP_NO + .5) / no_cells100 REM END -endEND############################################################################################################################################################################################################################################################################################################## SETUP OUTPUT PUNCH TSV FILE ANTIMAGNETIC ######################################################################################################################################################################################################################################################################################################################################################SELECTED_OUTPUT 0 -file 230828_1125_Antimag_1cm_101cell_DAC_FlowThru_1pw-flush_dt-dx_Cal-KinEqu_CV5_Si_Init-solns_05Sept2024BASEV2dlp.tsv -reset false -distance true -ionic_strength true -totals Ca C(4) Si -molalities Ca+2 CaCO3 CO3-2 HCO3- CO2 -equilibrium_phases Calcite Calcite_ppt CO2(g) O2(g) -saturation_indices Calcite Larnite Brucite Portlandite CO2(g) -kinetic_reactants Calcite_diss Larnite Brucite PortlanditeSELECTED_OUTPUT 1 -file 230828_1125_Antimag_1cm_101cell_DAC_FlowThru_1pw-flush_dt-dx_Cal-KinEqu_CV5_Si_adv-react_05Sept2024BASEV2dlp.tsv -distance true -ionic_strength true -totals Li Ca C(4) Si -molalities Ca+2 CaCO3 CO3-2 HCO3- CO2 -equilibrium_phases Calcite Calcite_ppt CO2(g) O2(g) -saturation_indices Calcite Larnite Brucite Portlandite CO2(g) -kinetic_reactants Calcite_diss Larnite Brucite Portlandite kin_HCO3
