MOL.20000801. 0001
OFFICE OF CIVIUAN RADIOACTIVE WASTE MANAGEMENT
CALCULATION COVER SHEET
2. Calcutaton Ttle
Precipftates/Sats Model Results for THC Abstracion
3. Document Identifier (including Revision Number)
CAL-EBS-PA-000008 REV 00
4. Total Attachments 5. Attachment Numbers - Number of pages In each
4 1 I-Z 11-7, 111-7. IV-7
1.k C0A PIRe: 1 Of 23
Print Name Signature Date
0. Originator Paul Mariner ---- 31/2
7. Checker Pengchu Zhang
S. Lead James Nowak 4A 2 fr, p19. Remarks
This calculation uses the Precipbtates/Salts model developed In the In-Drift Precipltates/Salts Analysis AMR (ANL-EBS-UD-000045 Rev. 00) to estimate pH, chloride concentration, and Ionic strength due to evaporaWe processes using the abstracted THC Incoming water composition developed In Abstraction of Drift Scale Coupled Processes (ANL-NBS-HS-00002= Rev. 00)
Revision History
10. Revision No.
00
11. Description of Revision
Initial Issue.
AP-3.12Q� I Rev. 0813011999
Rev. 0613011g99AP-&.12QL I
Precipitates/Salts Model Results for THC Abstraction
CONTENTS Page
FIGURES ................................................................................................................................... 3
TABLES ..................................................................................................................................... 3
ACRON YM S AND AB BREVIATION S .............................................................................. 4
I. PURPOSE ........................................................................................................................... 5
2. M ETH OD ........................................................................................................................... 5
3. ASSUM PTION S ......................................................................................................... 6 3.1 RELATIVE HUMIDITY VERSUS TIME ............................................................ 6 3.2 INCOMING NITRATE CONCENTRATION ..................................................... 6 3.3 SOLUBLE SULFATE .......................................................................................... 6
4. USE OF COMPUTER SOFTWARE AND MODELS ..................................................... 7 4.1 M ODELS ......................................................................................................... 7 4.2 SOFTW ARE ........................................................................................................ 7 4.3 SOFTW ARE ROUTINES ......................................................................................... 8
5. CALCULATION ................................................................................................................ 8 5.1 INPUT DATA AND PARAMETER VALUES ......................................................... 8
5.1.1 Thermodynamic Constants and Salt Properties ......................................... 8 5.1.2 Input Param eters ........................................................................................... 9
5.2 CALCULATION S .............................................................................................. 10 5.2.1 Relative Humidity and Temperature History ........................................... 10 5.2.2 Precipitates/Salts M odel ......................................................................... 10
6. RESULTS ......................................................................................................................... 11 6.1 RELATIVE HUMIDITY AND TEMPERATURE HISTORY ............................. 11 6.2 PRECIPITATES/SALTS MODEL RESULTS .................................................... 12
6.2.1 H igh Relative Hum idity M odel Results .................................................. 12 6.2.2 Low Relative Humidity Model Results .................................................. 15 6.2.3 Precipitates/Salts M odel Lookup Tables ................................................ 16 6.2.4 Lim itations ............................................................................................ 17
7. REFEREN CES ................................................................................................................. 21
s. ATTACHM ENTS ........................................................................................................ 23
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Precipitates/Salts Model Results for THC Abstraction
FIGURES
Page
Figure 1. Predictions of Bin-Weighted Mean Relative Humidity and Temperature
for the Invert Over Time .............................................................................................. 12
Figure 2. Steady State pH-, Ca Concentration, and I vs. ( - Re•) for Period 2 ......................... 13
Figure 3. Steady State pH, Cl Concentration, and Ivs. (I-R") for Period 3 ......................... 13
Figure 4. Steady State pH vs. (1- R) at Different Temperatures for Period 4 ....................... 14
Figure 5. Steady State Cl Concentration vs. (I- R") at Different Temperatures for Period 4 ............................................................................................................................. 14
Figure 6. Steady State I vs. (1-Rt ) at Different Temperatures for Period 4 .......................... 15
Figure 7. Ca and I vs. Rf/forRM Less than 85 Percent ......................................................... 16
TABLES
Page
Table 1. Incoming Seepage Composition Abstracted from THC Results ............................... 9
Table 2. Lookup Table for Period2 ..................................................................................... Is
Table 3. Lookup Table for Period 3 ..................................................................................... 19
Table 4. Lookup Table for Period 4 ..................................................................................... 20
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Precipitates/Salts Model Results for THC Abstraction
ACRONYMS AND ABBREVIATIONS
ACC AMR
ci CRWMS M&O
DIRS DOE DTN f.2 HRH I KTI LRH NFE NRC PAO
Rev. RH T I, TBV THC TIC Wb.i
Yb.,
accession number Analysis/Model Report concentration of component i in the incoming seepage Civilian Radioactive Waste Management Services Management and Operations Data Input Reference System Department of Energy Data Tracking Number carbon dioxide fugacity high relative humidity ionic strength key technical issues low relative humidity Near Field Environment Nuclear Regulatory Commission Performance Assessment Operations evaporation rate incoming seepage rate relative evaporation rate Revision relative humidity temperature time I to be verified thermohydrological-chemical Technical Information Center number bin weight of subset b of bins at time i overall bin-weighted mean RH or T at time I mean Rt or Tfor subset b of bins at time i
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Precipitates/Salts Model Results for THC Abstraction
1. PURPOSE
The purpose of this calculation is to assist Performance Assessment Operations (PAO) and the Engineered Barrier Performance Department in modeling the geochemical environment within a repository drift, thus allowing PAO to provide a more detailed and complete in-drift geochemical model abstraction and to answer the key technical issues (KTI) raised in the NRC Issue Resolution Status Report (IRSR) for the Evolution of the Near Field Environment (NFE) Revision 2 (NRC 1999). This calculation is associated to the activity directed by written development plan, Prode Sub-Models for the Physical and Chemical Environmental Abstraction Modelfor 7VPA-L4 (CRWMS M&O 1999a) and is developed using procedure AP3.12Q, CalculA2ions, Rev. 0, ICN 1.
The specific objective and scope of this calculation are to document the Precipitates/Salts model calculations performed for the thermohydrological-chemical (THC) abstraction. The Precipitates/Salts model was developed in Precipitates/&Aats Analysis AAR (CRWMS M&O 2000) according to procedure AP-3.10Q Analyses and Models, Rev. 2, ICN 0. It is used to estimate the pIt chloride concentration, and ionic strength of water on the drip shield or other location within the drift during the post-closure period resulting from evaporative processes.
The major inputs for the current calculation differ from those for the calculations performed in the Precipitates/Salts AMR (CRWMS M&O 2000) in the following ways:
@ Instead of average J-13 well water, the incoming seepage is represented by the THC abstractions for three periods from 50 to 100,000 years.
a Instead of a variable fugacity of carbon dioxide, the fugacity is fixed at the THC abstraction values in each period.
a Instead of a variable temperature for each incoming seepage composition, the temperature is fixed at abstracted values, except for the final period, in which the temperature is varied between 250C, 500C, and 75C.
9 A new history of mean relative humidity (RH) is used to calculate results when relative humidity is below 85 percent.
2. METHOD
The Precipitates/Salts model developed in Precipittes/5/•is An*aysis AR (CRWMS M&O 2000) was used to perform the calculations in this document. The model incorporates two submodels, the High Relative Humidity (HRH) model and the Low Relative Humidity (LRH) model. These models, listed and summarized in Section 4, are explained in detail in Precipitates/lSds AnalYsis AAM (CRWMS M&O 2000), as are the methods of calculation. Any deviations from these methods are explained in detail in Sections 3 and 5. Control of electronic management of data, as required by AP-SV.1Q, Control of the Electronic Management of Data, was accomplished in accordance with the controls specified the development plan.
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3. ASSUMPTIONS
The assumptions are nearly identical to those described in Section 5 of PrecipitatesdWas Analysis AMR (CRWMS M&O 2000). The only differences are described in the following subsections.
3.1 RELATIVE HUMIDITY VERSUS TIME
The LRH salts model requires an estimate of RH over time at the location where the salts model is applied. The location within the drift environment where RH is the lowest and temperature is highest over time is the within the invert It is assumed in this calculation that the predicted mean RH history within the invert is a reasonable approximation for the LRH model simulations (Assumption 3.1).
Uncertainty in the relative humidity predictions will not affect the pH, Cl concentration, and ionic strength predicted by the LRH salts model. The model only requires an estimate of the timing of these relative humidity values as a seed to generate the results which are independent of time. Thus, the timing of these relative humidity values is irrelevant in the final results. This assumption is considered reasonable for the bounding calculations performed and is therefore not TBV. This assumption replaces Assumption 5.2.4.1 stated in the Precipitates/Salts MR (CRWMS M&O 2000) and is used in Sections 6.1 and 6.2.2.
3.2 INCOMING NITRATE CONCENTRATION
The incoming seepage data provided by the THC abstraction (Table 1) do not include values for nitrate. Nitrate concentrations are necessary for the LRH model. It is assumed that the concentration ratio of nitrate to chloride in the THC-abstracted incoming seepage water is equivalent to that in average J-13 well water (Assumption 3.2). The basis for this assumption is the generally unreactive behavior of both chloride and nitrate. This assumption is reasonable and will not considerably affect the results of the model. Therefore, this assumption, which is used in Sections 6.2.1 and 6.2.2, is not TBV.
3.3 SOLUBLE SULFATE
In the Precipitates/Salts AMR (CRWMS M&O 2000), the carbonate concentration determined as input to the LRH salts model was assumed to be the "soluble" carbonate determined by the HRH model (Assumption 5.5.7, CRWMS M&O 2000). .The "soluble" carbonate was determined from the HRH model by evaporating water to 85 percent relative humidity (i.e., a water activity of 0.5). The carbonate that was in solution at that point was considered "soluble" because it excluded the carbonate that had precipitated. Beyond this point, the remaining "soluble" carbonate could only form soluble K or Na salts in significant quantities. There was no need to make a similar determination for sulfate because no sulfate had precipitated at that point or sulfate precipitation was negligible.
In the current calculation, sulfate precipitates considerably in HRH model results. Thus, both the incoming carbonate and sulfate concentrations used in the LRH model are assumed to be the "soluble" carbonate and sulfate concentrations determined by the HRH model at a water activity
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of 0.85 (Assumption 3.3). This reasonable assumption is consistent with the basis of Assumption 5.5.7 of CRWMS M&O (2000) and is used for all LRH calculations (Section 6.2.2). It does not affect the uncertainty in the model and is therefore not designated TBV.
4. USE OF COMPUTER SOFTWARE AND MODELS
4.1 MODELS
The Precipitates/Salts model developed in Precipitates/Salts Anayss AAR (CRWMS M&O 2000) was used to perform the calculations in this document. The model incorporates two submodels, the Low Relative Humidity (LRH) model and the High Relative Humidity (HRH) model, also developed in CRWMS M&O (2000). These two sub-models are designed to provide a piece-wise continuous Precipitates/Salts model for relative humidity values from 0 to 100 percent.
The LRH model is used when the relative humidity is low (below about 85 percent), and the HRH model is used at higher relative humidity (above about 85 percent). The LRH model consists of a set of algebraic calculations performed within a MathSoft Mathcad version 7 file. The HRH model is simulated using the geochemical code EQ3/6 version 7.2b. These models are validated in CRWMS M&O (2000).
Use of the Precipitates/Salts model in this calculation is justified because the model was specifically designed to perform these calculations (CRWMS M&O 2000).
4.2 SOFTWARE
The HRH model calculations were performed using the code EQ3/6 v7.2b (CRWMS M&O 1999b) [CSCI: URCL-MA-110662 V7.2b, Wolery 1992a and 1992b, Wolery and Daveler 1992] with the solid-centered flow-through addendum [CSCI: URCL-MA-l 10662 V7.2b, MI: 30084M04-001 (Addendum Only), CRWMS M&O 1998]. This software code was obtained from Configuration Management and installed on an IBM-compatible computer. It is appropriate for the application and was used only within the range of validation in accordance with AP-SL IQ Sofware Aazgement and the Precipitates/Salts AMR (CRWMS M&O 2000). The Precipitates/Salts AMR. restricts the use of this code to a water activity of about 0.85 and higher.
MathSoft Mathcad 7 Professional, a commercially-available software package for technical calculations, was used to execute the LRH model. This software performed and displayed the routine algebraic calculations developed in Section 6A.1 of the Precipitates/Salts AMR (CRWMS M&O 2000). These equations and all calculations, shown in their entirety in Attachments IL a, and IV, have been hand-checked using a calculator to verify the software provided correct results. Ths software was appropriate for the application and used within the range of model validation established in the Precipitates/Salts AMR (CRWMS M&O 2000).
Microsoft Excel97, a commercially-available spreadsheet software package, was used to perform simple averaging and interpolation calculations and to chart data. Validation of the spreadsheet calculations was done by comparing input and output data in charts imbedded in the worksheets
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Precipitates/Salts Model Results for THC Abstraction
(DTN: MO0002SPABIN46.00). Visual inspection of these charts confirms that the spreadsheet application provided correct results.
4.3 SOFTWARE ROUTINES
No software routines were used.
5. CALCULATION
Section 5.1 presents the data and parameter values used as input to the calculation, and Section 5.2 describes the calculations performed.
5.1 INPUT DATA AND PARAMETER VALUES
The calculation requires the following types of input: 1) relevant thermodynamic properties of potentially important ground-water constituents, and 2) values for model input parameters.
5.1.1 Thermodynamic Constants and Salt Properties
The thermodynamic data used in the calculations are developed and documented in the Precipitates/Salts AMR (CRWMS M&O 2000). The HRH model uses the developed PT4 database (DTN: MO9912SPAPT4PD.001) which is currently to be verified (1'BV). The LRH model references the salt properties displayed in Tables 1 and 2 of CRWMS M&O (2000).
5.1.2 Input Parameters
The Precipitates/Salts model input parameters are:
0 Concentration or activity of each modeled component I in the incoming seepage (C,) * Temperature (7) * Relative humidity (RH) * Fugacity of carbon dioxide (fco2) * Seepage rate (Q1) * Relative evaporation rate (R")
The relative evaporation rate (or flux) (/f) refers to the steady state evaporation flux (Q divided by (or relative to) the incoming seepage rate (or flux) (Q):
R' =Q- (Eq. ) Q,
The model is designed for a range of)?" from 0 to 1. The values used in this analysis are: 0, 0.1, 0.5, 0.9, 0.99, and 0.999. These values are used to generate lookup tables that are intended to cover the range of values anticipated.
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The modeled incoming seepage includes the following components: Na, K, Ca, Mg, Cl, F, CO3, SO4, N0 3, SiO2, Fem), Al, , and H20.
Table 1. Incoming Seepage Composition Abstracted from THC Results
Transitional Cool- Extended CoolDawn Period 3 Down Period 4
Parameter Units BolilUg Period;2 (molal) (molal) Time Period years 60-1,000 1,000-2,000 2,000-100,000
Temperature ýC 96 90 50
log Co2 (g) voL fro. -. 5 -3.0 -2.0 Ca molal 6.4e-04 1.0e-M3 1.8e-03 Mg molal 3.2-07 1.6e-06 7.8e-06 Na molal 1.4e-03 2.6e-03 2.6e-03 K molel 8."e-05 3.1e-04 1.00-04 Si0 2 molal 1.5e-03 2.1e-03 1.2e-03 NOs molal nrr nr nr CO molol 1.99-04 3.0e-04 2.1@-03 Ci molal 1.Se-03 3.2e-03 3.3e-03 F mole! 25e-05 4.5e-05 4.5e-05
WO4 molal 6.6e-04 1.2e.-03 1.2e-03
Fe moill 7.9e-10 4.1e-10 2.4e-11
Al mola! 2.7e-07 6.8"-08 2.0e-09
pH pH unt1 8 .1b 7 .8 b 7.3 b
DTN: MO9912SPAPAI29.002 a not reported
b pH unfts
In this analysis, representative waters from three periods of time were used as incoming seepage. The specific compositions originate from the THC results. The abstracted representative incoming water compositions, temperatures, and CO0 (g) volume ftractions in the air for these periods are displayed in Table 1. These data are currently TBV.
As explained in Section 3.2, the ratio of nitrate to chloride in average J-13 well water is needed to estimate the concentration of nitrate in the THC-abstracted incoming seepage water. The nitrate:chloride ratio in the J-13 well water is 0.70:1 (DTN: LL980711104242.054).
In the calculation, T was varied between three values (750C, 500C, and 250C) for Period 4 to develop a response surface intended to cover the range of values anticipated in this period. RfI and Tas a function of time were developed as described in Section 5.2.1 from recent calculations for the invert. The acquired data used to develop the T and Ri! histories came from the following files in DTN: SN0001T0872799.006:
e RIP_RHnvavghiw_d0010500_bin0-3 mean * RIP RH'nvavg_hlw_dOO10500 bin3-10_mean 0 R/P_RHinvavghlw_dO000500_binlO-20_mean
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Precipitates/Salts Model Results for THC Abstraction
: RIP RI-rnvavg hlw dOO10500 bin20-60 mean R R IP Envavg hlw dOO10500_bin60_mean
* RIPTinvavgjhlw_d0010500 bin0-3 mean * RIP Tinvavghlw_dOO10500 bin34-0_mean SRIP_ Tinvavg_hlw.d0010500 binI0-20_mean
* RIPTinvavghlw_d0010500 bin20-60_mean * RIPTinvavg_hlw_dOO10500_bin60 mean
These data are currently TBV.
5.2 CALCULATIONS
Before the Precipitates/Salts model calculation could be performed, the relative humidity as a function of time had to determined. This initial calculation is developed in Section 5.2.1. The Precipitates/Salts model calculations are addressed in Section 5.2.2.
5.2.1 Relative Humidity and Temperature History
From the files listed in Section 5.1.2 (DTN: SN0001T0872799.006) mean, bin-averaged values for Rff and T for the invert were determined for the LRH model. These overall means were calculated by taking the bin-weighted averages of RM and T for numerous values of time from 0 to 100,000 years. The actual times that were used to determine the bin-weighted averages were selected such that the resolution ofRfl and Tas a function of time was captured.
Bin-weighted averages were calculated using the following equation:
YI -2YkIWbj (Eq. 2) b
where Yi is the overall bin-weighted mean RH or T at time i, yb,i is the mean RH or T for subset b of bins at time i, wb, is the bin weight of subset b of bins at time L. The summation of the bin weights for the bin subsets at time I equals one (i.e., : = 1).
b Many of the RPH and T values in the files are not for common times. As a result, interpolations had to be made for bin subsets before bin-weighted averages could be calculated. For the interpolations a linear relationship between RH and the logarithm of time (log t) and between T and log t were imposed such that:
A = 10gt9t7 1 -iogt 1_- (logte -logti.,)+y +..+ (Eq. 3) YAM~ - YO•-1
where i+1 and i-1 are the nearest values in the acquired data file to time ti.
5.2.2 Predpitates/alts Model
The HRH model calculations were performed using the solid-centered flow-through mode of EQ3/6 version 7.2b according to the procedures described in Section 6.4.2.2 of the
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Precipitates/Salts AMR (CRWMS M&O 2000). The only difference in the calculations were due to the different input values.
The LRH model calculations were performed according to Section 6.4.1 of the Precipitates/Salts AMR (CRWMS M&O 2000). These calculations were performed using the Mathcad 7 files displayed in Appendices IlI Il, and IV of this report.
For the LRH model there were three parameter values that were changed other than the adjustments to the incoming seepage composition explained in Sections 3.2 and 3.3. Two were the times at which the RN is determined to reach 50 peent and 85 percent They were set at 450 years and 1300 years based on the results of the calculation described in Section 5.2.1 (The results displayed in Figure 1.). The other change was the effective solubility of the non-nitrate salts. This value was adjusted to 2.9 or 3.0 molal to provide a smooth transition between the LRH and HRH model results. The values used to provide a smooth transition for J-13 seepage water ranged from 3.6 to 4.1 molal (CRWMS M&O 2000).
It is restated here that the ionic strength (/) parameter of the Precipitates/Salts model is not the true ionic strength. Instead, it is an approximation based on the following equation:
I=C4 +Cr +4(Cc, +Ct) (Eq. 4)
where C1 is the molality of component L For an explanation, refer to Section 6.3.2 of the Precipitates/Salts AMR (CRWMS M&O 2000).
6. RESULTS
Section 6.1 presents the results of the relative humidity and temperature predictions over time. Section 6.2 presents the results of the Precipitates/Salts model using THC inputs.
6.1 RELATIVE HUMIDITY AND TEMPERATURE HISTORY
The results of the averaging and interpolation of relative humidity and temperature over time are displayed in Figure 1. These results represent the approximated average predicted values and trends for RH and Tfor the invert and in the drift in general (Assumption 3.1). For the purposes of the LRH model, Rllreaches 50 and 85 percent at 450 and 1300 years, respectively.
These calculations are based on RI! and T predictions that are currently unqualified and TBV (DTN: SN0001T0872799.006). The data developed in this calculation (DTN: MO0002SPABIN46.00S) are therefore TBV. However, because these results are used only as a reference in the LRH model calculations to support Assumption 3.1, they do not affect the qualification or TBV status of the LRH model calculations. LRH model output is independent of time and is not a function the exact timing of RH and Tvalues.
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250 - 100%
00% 1300 O
200- 80%
70% it
~'150- -i-ep60%7
050%2
100 + RH 50% and 85% 40%
30%g
50 20%
10% 0 .. . 0%
1 10 100 1000 10000 100000 1000000 lime (yr.)
DTN: MOOOO2SPABIN48.008
Figure 1. Predictions of Bin-Weighted Mean Relative Humidity and Temperature for the Invert Over Time
6.2 PRECIPITATES/SALTS MODEL RESULTS
The Precipitates/Salts model output consists of calculations for pH, chloride concentration, and ionic strength (in molality) for the input parameter values described in Section 5.1. The results of the HRH and LRH models are presented in Sections 6.2.1 and 6.2.2, respectively. A complete set of these outputs is summarized in Section 6.2.3 in a set of lookup tables that can be used to interpolate model results for input conditions within the ranges modeled. Finally, the limitations of these calculations are addressed in Section 6.2.4.
6.2.1 High Relative Humidity Model Results
Figure 2 and Figure 3 display the HRH model results for Period 2. These plots show that while Cl and I are highly sensitive to relative evaporation rate, pH remains around 9 in Period 2 and around 8 in Period 3.
Figure 4, Figure 5, and Figure 6 show the pH Cl, and I results, respectively, for Period 4 at three different temperaures. These data indicate that the results are not highly sensitive to temperature. Cl and I maintain their strong dependence on relative evaporation rate, and the pH drops to around 7.
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12
11
10
8
7
64-0.001
10
1
0.1
0.01
0.001
0.01 0.1 1
1- Res
DTN: MOOOOIMWDEQ34.0O07
Figure 2. Steady State pH, C1 Concentration, and Ivs. (1- R") for Period 2
a.
12
11
10
9
8
7
64
0.001
10
I
01 ~
0.1
0.01
0.0010.01 0.1 1
1- Res
DTN MOOOIMWDEQS4S.007
Figure 3. Steady State pH, CI Concentration, and I vs. (1- RI) for Period 3
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12
11 -
10.
x CL 9.
8
7-
6
0.001 0.01 0.1 1
I - Res
DTN: MOOO1MWMDEQ346.007
Figure 4. Steady State pH vs. (1- R*) at Different Temperatures for Period 4
10
I
U
(.>
0.1
0.01
0.001 10.001 0.01 0.1 I
I - Res
DTN: MOO0I1MWME0346.007
Figure 5. Steady State CI Concentration vs. (1- Re) at Dferent Temperatures for Period 4
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I-o-76C~
1�
a -
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10
0
0.1
0.010.001 0.01 0.1 1
1 - Res
DTN: M0001IMWDEQ34a.007
Figure 6. Steady State I vs. (1 -R*) at Different Temperatures for Period 4
6.2.2 Low Relative Humidity Model Results
The results of the LRH model for Cl and I are displayed in Figure 7. These results are approximately the same for each period. In general, the CI concentration is much higher and I is slightly lower than the results for average J-13 well water seepage (CRWMS M&O 2000).
As explained in the Precipitates/Salts AMR (CRWMS M&O 2000), the LRH model is insensitive to the value of the incoming seepage flux and the cumulative masses and volumes of salts and brine. Complete Mathcad calculations and files are presented in Attachments ]I, ýI, and IV.
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100
10 S I
0.1 -- C rl
0.01 .....
40% 50% 60% 70% 80% 90%
RH
DTN: MOOOO2SPALRH46.000
Figure 7. C1 and I vs. RH for RH Less than 85 Percent
6.2.3 Precipitates/Salts Model Lookup Tables
The outputs required from the Precipitates/Salts model are the values for p-I Cl concentration, and ionic strength for a given set of inputs intended to encompass the likely scenarios that could occur. These outputs are summarized in a set of lookup tables presented in Table 2 through Table 4. The important independent variables are the incoming seepage composition (C'), relative humidity (RU), temperature (7), relative evaporation rate (Ri), and the fugacity of carbon dioxide (fco2). These lookup tables include outputs from the LRH salts model (RU < or =
85 percent) and the HRH salts model (R/I> 85 percent).
As explained in the Precipitates/Salts AMR (CRWMS M&O 2000), the LRH salts model incorporates a functional relationship between RI! and time. For the lookup tables, time is avoided as an independent input variable by imposing a linear relationship between RU and time. Increasing RH linearly with time from 50 to 85 percent provides the abstraction used to generate the lookup values for RH less than or equal to 85 percent.
The ionic strength values presented in the lookup tables are an approximation of the tue ionic strength, as described in Section 5.2.2. An additional approximation is required for lookup table pH values when the RIH is less than or equal to 85 percent. Because pH cannot be calculated using the LRH salts model, it is approximated by using the HRH model to perform a simple evaporation of the incoming seepage water to a water activity of 0.85. These values for pH are included in the lookup tables for cases in which RH is less than or equal to 85 percent
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Precipitates/Salts Model Results for THC Abstraction
Finally, for the case in which the relative evaporation rate (Rj) is one or greater, the ionic strength and Cl concentrations are set at the values obtained by the LRH model at 85 percent relative humidity for the given carbon dioxide fugacities and temperatures. This is done to approximate a reasonable trsition between the LRH and HRH model results.
Compared to the Precipitates/Salts model results for J-13 water at similar carbon dioxide fulgacities (CRWMS M&O 2000), CI is consistently an order of magnitude higher in the abstracted THC cases due to the higher initial Cl concentrations (Table I). pH is generally lower in the THC cases by approximately two pH units for similar carbon dioxide fugacities, likely due to the higher calcium to carbonate ratios in the THC seepage water (Table 1). Ionic strength values for the THC cases stay approximately in the same range as the J-13 calculations.
6.2.4 Limitations
This document may be affected by technical product input information that requires confirmation. Any changes to the document or its conclusions that may occur as a result of completing the confirmation activities will be reflected in subsequent revisions. The status of the input information quality may be confirmed by review of the Document Input Reference System database.
The Precipitate/Salts model calculations documented in this report (DTNs: MOOOO MWDEQ346.007, MO0002SPALRH46.009, and MO0002SPALOO46.010) are unqualified and TBV because two of the inputs are unqualified and TBV (DTNs: M09912SPAPAI29.002 and MO9912SPAPT4PD.001). Once these input data are confirmed, the resulting calculations can be used without TBV tracking controls. The uncertainty and limitations of these calculations are summarized in the conclusions of the Precipitates/Salts AMR (CRWMS M&O 2000).
CAL-EBS-PA-OOO005 REV 00 17 June 2000CAL-EBS-PA-000008 REV 00 17 June 2000
Precipitates/Salts Model Results for THC Abstraction
Table 2. Lookup Table for Perod 2
Input Parameters P pItate•s•at Model output
P.H () T(-C) Re PH Cl (molal) I(mrolal) < 60.3% not na dry dry dry
50.3% 969 no 9.40 3.71E-03 2.47E+01 51.0% '96 na 9.40 5.68E-02 2.42E+01
53.1% 96 na 9.40 4.09E-01 2.15E+01 55.2% 96 "a 9.40 6.85E-01 11.93E+01 60.5% 96 na 9.40 1.68E+00 1.15E+01 65.7% 96 no 9.40 2.40E+00 5.89E+00
71.0% 96 no 9.40 263E+00 4.04E+00 76.2% 96 no 9.40 2.68E+00 3.63E+50 81.5% 96 na 9.40 2.63E+00 4.09E+00 85.0% 96 no 9.40 2.55E+00 4.69SE+00
* 85% 96 0 8.58 1.80E-03 6.OOE-03 > 85% 96 0.1 8.62 2.00E-03 7.OOE-03 * 85% 96 0.5 8.87 3.59E-03 1.20E-02 * 85% 96 0.9 9.21 1.SOE-02 5.70E-02 > 85% 96 0.09 9.28 1.77E-01 3.78E-01 * 85% 98 0.999 9.41 1.55E+00 3.04E+00 * 85% 96 > 0.999 9.40 2.44E+00 4.94E+00 DTN: M0002SPALOO4&.010 a not applicable
CAL-EBS-PA-000008 REV 00 19 Ame 2000
Precipitates/Salts Model Results for THC Abstraction
Table 3. Lookup Table for Period 3
Input Parameters Preclpltatesafts Model Output RH(%) T(rC) RpH CI (molal) I(molal)
< 50.3% ha" no dry dry dry 50.3% 9O na 7.64 3,73E-03 2.44E+01 51.0% 90 na 7.64 5.70E-02 2.40E+01 53.1% 90 na 7.64 4.06E-01 2.11E+01 55.2% 90 na 7.64 6.77E-01 1.89E+01 60.5% 90 nr 7.64 1.63E+00 1.10E+01 65.7% g90 rn 7.64 2.28E+00 5.65E+00 71.0% 90 na 7.64 2.49E+00 3.91E+00 76.2% 90 no 7.64 253E+00 3.64E+00 81.5% 90 na 7.64 2.48E+00 3.96E+00 85.0% 90 no 7.64 2.41E*00 4.53E+00 > 85% 90 0 7.72 3.10E-03 1.03E-02 * 85% 90 0.1 7.71 3.56E-03 1.14E-02 * 85% 90 0.5 7.64 6.40E-03 1.98E-02 * 85% 9D 0.9 7.45 3.20E-02 9.48E-02 *85% s0 0.09 7.58 3.15E-01 0.60E-01 * 85% 90 0.9988 7.64 2.36E+00 4.69E+00
8 65% 90 > 0.9988 7.64 2.41E+00 4.53E+00 DTN: MO0go2SPALOO46.010 a not applicable
June 2000•J•J.,-•D °I",,-UU I5 ll vu 19
Preedpitates/Salts Model Results for THC Abstraction
Table 4. Lookup Table for Period 4
In Put Parameters P.Jpftates/Safts Model Ot, R T R" Tp Cl (molal) I (molal)
< 50.3% no no dry dry dry
50.3% 75 no 7.02 3.85E-03 2.43E+01 51.0% 75 no 7.02 5.88E-02 2.39E+01 53.1% 75 na 7.02 4.17E-01 2.09E+01 55.2% 76 no 7.02 6.93E-01 1.86E+01 60.6% 75 no 7.02 1.64E+00 !.08E+01 65.7% 75 no 7.02 2.28E+00 5.56E.00 71.0% 75 no 7.02 2.49E+00 3.87E+00 76.2% 75 no 7.02 2.63E+00 3.51E+00 81.5% 75 na 7.02 2.48E+00 3.92E+00 85.0% 75 nf 7.02 2.42E+00 4.47E+00 >85% 75 0 7.19 3.30E-03 1.21E-02 > 85% 75 0.1 7.18 3.67E-03 1.32E-02 > 85% 75 0.5 7.14 6.60E-03 2.16E-02 > 85% 75 0.9 6.97 3.30E-02 9.85E-02 > 85% 75 0.99 7.02 3.24E-01 6.911E-01 > 65% 75 0.9988 7.02 2.41E+00 4.75E00 > 85% 75 > 0.9988 7.02 2.41E+00 4.47E+00 085% 50 0 7.22 3.30E-03 1.36E-02
> 85% 50 0.1 7.22 3.67E-03 1.47E-02 * 85% 50 0.5 7.18 6.60E-03 2.31E-02 * 85% 50 0.9 7.03 3.29E-02 9.96E-02 * 85% 50 0.99 6.95 3.25E-01 7.45E-01 * 85% 50 0.9988 6.86 2.41E+00 4.87E+00 > 85% 50 > 0.9988 7.02 2.41E+00 4.47E+00 >85% 25 0 7.05 3.30E-03 1.36E-02 * 85% 25 0.1 7.09 3.67E-03 1.51E-02 * 85% 25 0.5 7.23 6.60E-03 2.6SE-02 > 85% 25 0.9 7.11 3.29E-02 1.02E-01 * 85% 25 0.99 6.99 3.25E-01 7.80E-01 > 85% 25 0.9988 6.78 2.46E+00 5.iOE+00 > 85% 25 > 0.9988 7.02 2.41E+00 4.47E+00 DTN: MOOOO2SPALOO4S.010 8 not applicable
ir A 1rJ -C A m u
June 2000'•-"•.L.GIU-• " ."ml., oAr.l v u 20
Precipitates/Salts Model Results for THC Abstraction
7. REFERENCES
AP-3.10Q, Rev. 2, ICN 0. Analyses and Models. Washington, D.C.: U.S. Department of Energy, Office of Civilian Radioactive Waste Management. ACC: MOL.20000217.0246.
AP-3.12Q, Rev. 0, ICN 1. Calculations. Washington, D.C.: U.S. Department of Energy, Office of Civilian Radioactive Waste Management. ACC: MOL.20000512.0065.
AP-SI.lQ, Rev. 2, ICN 4. Software MaWgement. Washington, D.C.: U.S. Department of Energy, Office of Civilian Radioactive Waste Management ACC: MOL.20000223.0508.
AP-SV. 1Q, Rev. 0. Control of the Electronic Mangement of Data Washington, D.C.: U.S. Department of Energy, Office of Civilian Radioactive Waste Management.
CRWMS M&O 1998. Software QuaUfrction Report (SQP) Addendum to Fristing LLNL Document UCRL-A -110662 PTIY: Implementation of a Solid-Centered Flow-Through Mode for EQ6 Version 7.2B. CSCI: UCRL-MA-110662 V 7.2b. SCR- LSCR198. Las Vegas, Nevada: CRWMS M&O. ACC: MOL.19990920.0169.
CRWMS M&O 1999. Provide Sub-Models for the Physical and Chemical Environmental Abs•taction Modelfor TSPA-LA. TDP-WIS-MD-000006 REV 00. Las Vegas, Nevada: CRWMS M&O. ACC: MOL.19990902.0450.
CRWMS M&O 1999b. Software Code: EQ3/6, Version 7.2bLV. V7.2bLV. 10075-7.2bLV-00.
CRWMS M&O 2000. Precipitates S•ats Analysis AMR. Input Transmittal 00097.T. Las Vegas, Nevada: CRWMS M&O. ACC: MOL.20000309.0497.
LL980711104242.054. Report of the Committee to Review the Use of 1-13 Well Water in Nevada Nuclear Waste Storage Investigations. Submittal date: 08/05/1998. MO9912SPAPAI29.002. PA Initial Abstraction of THC Model Chemical Boundary Conditions. Submittal date: 01/11/2000. Submit to RPC URN-0282
MO9912SPAPT4PD.001. PT4 Pitzer Database for EQ3/6. Submittal date: 12/06/1999.
NRC (U.S. Nuclear Regulatory Commission) 1999. Issue Resolution Status Report Key Technical Issue: Evolution of the Near-FiedFvironment. Rev. 2. Washington, D.C.: U.S. Nuclear Regulatory Commission. ACC: MOL. 19990810.0640.
SN0001T0872799.006. In-Drift Thermodynamic Environment and Percolation Flux. Submittal date: 01/2712000.
Wolery, T.J. 1992a. EQ316, A Software Package for Geochemical Modeling ofAqueous Systems. Package Overview and Instadlation Guide (Version 7.0). UCRL-MA- 110662 PT I. Livermore, California: Lawrence Livermore National Laboratory. TIC: 205087.
K�v LX) 21 June 2000Eut.-=5P~bA-AOOW0s REV 00 21 June 2000
Precipitates/Salts Model Results for THC Abstraction
Wolery, TI. 1992b. EQ3NI A Computer Program for Geochemical Aqueous SpeclationSolubility Calculations. TheoreticaliManual, User's Guide, andRelated Documentation (Version 7.0). UCRL-MA-1 10662 PT IIL Livermore, California: Lawrence Livermore National Laboratory. TIC: 205154.
Woley, TJ. and Daveler, S.& 1992. TheoreticalManul, User's Guide, andRelated Documentation, Version 7.0. Volume IV of EQ6, A Computer Program for Reaction Path Modeling ofAqueous Geochemical Systems. UCRL-MA- 110662. Draft 1.1. Livermore, California: Lawrence Livermore National Laboratory. TIC: 238011.
&'q'A~~rLwAJ T ~ MM CJJune 2000"K-.M-JVVA rjr. V W 22
J
Precipitates/Salts Model Results for THC Abstraction
8. AITACHMENTS
Attachment Title
I Document Input Reference Sheet (DIRS)
II Low Relative Humidity (LRH) Salts Model THC Period 2 Abstraction (Calculations using Mathcad 7)
III Low Relative Humidity (LRH) Salts Model THC Period 3 Abstraction (Calculations using Mathcad 7)
IV Low Relative Humidity (LRH) Salts Model THC Period 4 Abstraction (Calculations using Mathcad 7)
fA- UL"w.ArfwA.,o VWJme20I.,'t•-.=,•O£'t,-U•VO '.r.y w 23 uAme 2000
Prtcilitcs/Sa~ts Model Results for THC Abstraction
OFFICE OF CIVILIAN RADIOACTIVE WASTE MANAGEMENT DOCUMENT INPUT REFERENCE SHEET
1. Document Identifier NoJRev.: hange: itle: -EBS-PA-000009 Rev. 00 PA VTATESA ALTS MODEL RESULTS FOR THC ABSTACTION
(as of 3 1-may-2000 09:51:04 ..... ............. _•)_._.I . , -Input Document 4 6.7. B.. TEYDue To
Technical Product Input Source Title . Input Section 6. Input Description nqual UFrom l Ued n-P, 2a. andSection Status Used In BD Uncontrolled nfirr
Identifier(s) with Version s..S. . ed.Priority Source ed S 0C 1998. Software WA- 4.2 efonce to EQ3/6 NA N/A N/A . N/A
alfiction Report (SQ)R) Adden fsow bo Elfing MM Document UCRU Kc 4-10662 PTBI." Implementation of
I Solid-Centered Fow-Through Mode or FQ6 Vereon 7.2U. CSCL UCRL
-110662 V7.2b. SCIL LSCRI98. Vegas Nevada: CRWMS M&O.
_ CC: M0L.19990920.0169. WMS5019a.ProdeSub- -Me A-. I Reference too .... •/A N/A N/A N/A
• tode/for he Physical and Chemical ef- diction for this iroimnentalAbstraction MAidelfor ce Calculation
2 A-. TDP-WIS-MD.000006 00. Las Vegas Nevada:
•WMS &O. ACC' _ 0L.19990902.0450. CRWMS M&O. 1999b. Software 4.ire A- 2 3/6software IA N/A N/A N/A Code EQ316, Version Z2bLV. Vadwg for 3 V7.2bLV. 10075-7.2bLV-00. Con goienilmodeling
ed IContr
______________________ led WMS M&O 2000. Precipitates tire A - ltates/Salts WA N/A N/A N/A ltsAnazisAM1 Input Transmlalecni model used for THC
4 .T. Las Vegas. Nevada: straction VWA M&O. ACC: c
.OL20000309.0497. S... ... . ...... . .... . • utl
980711104242.054. Rcportofthe -tire A- 5.1.2 verageJ-13 well N/A N/A N/A N/A mmitee to Review the Use of 1-13 ater composition dl Water In Nevada Nudear Waste
5 torage vcstigations. Submittal date: erific 5/1998. mon
Leel
MO9912SPAPAI29.002. PA nitiial i V- 5.1.2, C abstractions for 2 X N/A N/A A0actio Of THC Model (emlcal 577 .2.4 csage and gas
6 om Conditions. Submittal date: npositlon and 1/1 12000. Submit to RPC URN- temperature in the d
r282
Attachment I DIPS I-1 CAL-EBS-PA-00000 Rev. 00
Predpiiatalm'fts Modul Reslts for THC Abstmracon
O992SPAPT4PD.001. FM Pit=~tr V_ 5.1.1, EVLOE X N/A N/A 7 for EQ3/6. Submittal date: 922 6.2.4 1ZRDATABASE
1999. EQ3/6 -~ g A-I critefia for A N/A N/
iilson)n199. Issue Reso hdlon eere oeseapplication Report Key Technical Issue:c
nodon of die Near-Field y
,Rev. 2. Washington, C:U.S. Nudlearflegulatoiy
m l ion
-C C O.19990910.0640. --
00 T0672799.006. hi-Dri~ft lies V- 5.1.2, IN AVERAGED 2 X N/A N/A ermodynamic Emviromunerit and -REH 4564 5.2.1, AND HLW
ercolation Frrlux. Submittal date: g bil G.1 PRDRIFT 12f000 . dlOALL
009Ll tf=2000.dOOlO
9 _ _ _ _ __ _ _ _ mean O M A fU
10 G~fdCW01h~sfm_0010f
Wolery, 7T.J. 7 199 16, QK' A A.afi W-4.2 softwne aren Nor/A N/AX N/A NIA mpurer Progrwn for Geochemical andr ovevie
queflis Sp~qeilo-olubih 4jem
110e OvrvGidew and Ielmedo Wie(Vertion Vrson .). UCRL-MA -10662 PT [L Livermore.lfmi
Lwreno e L ivermore, alw all0oral Lbrtory. TIC: 205154. _____
clay1 TJ. 10ndb Daci WA. 1992. rc IA..2 craemmlfor N/A NIA N/A N/A
12omputerPogus f Geochemical remtemL
Camr clafionx Laworefica/mu
IeorNaoalLaboratory. TI C:0554 T.1 1 an -aelr -A - -. -jnim -.
dnemn o / I / /
Attachment I DIRS 2CA-S-AO00Rc.01-2 CAL-EBS-PA-000009 Rm 00
PrecdpltatealSalts Model Results for THC Abstrction
Low Relative Humldity (.RH) Salts Model THC Perlod 2 Abstraction
Conceptual Model. Water seeps Into "reactor" (Le, drip shield or backlill) at a constant rate during the period. In the reactor, seepage water vaporizes and salts accumulate. Salts begin to dissolve when the relative hurmidity rises above 50%. This model (LRO) approximates the buldup and dissolution of soluble salts In the Na-K-N-S-Cl-C system. All fluid (brine) generated during each time Interval flows out of reactor at the end of each time Interval; however, mixing is allowed between half time Intervals. The end point Is designed to be equivalent to the evaporative evolution of seepage water to a stolchlometnlc Ionic stren.th of 10 morn9, as calculated using the E0316 Pitzer model. The LRH salts model Is a simplified approximation of sat accumulation and eventual dissolution caused by Increasing relative humidiy. It maintains mass and charge balance and estimates brine generation as a function of effective solublities. Its purpose is to provide bounding and scoping calculations for an evaporite system that has not been deeply studied.
Seepage - Constant rate and co: sant composNon are assumed.
Seepage Comp. (molal) Valency
N03
CI
Soluble S04
Soluble C03
K
Na
Charge Balance Error
7
Cs, :z 0.0013.mol-kg-1
C.2 0.001S.mol.kg-1
Cs3 := 0.0001Smol.kg-1
Cs4 := 5.]10-~mol~kg"
Cs6 ;z 0.000085mol-kg-1
Cs7 0- O.0034.mol-kg-1
4 -
Cs1 z - C6
IS-i,
21l:= 1
Z2 1
z3 . 2
z4 :" 1.33
Z7 1
E- 3.59l073 E - 0.36-%
Dry Period. Salts accumulate. No stable brine Is generated. to level where nitrate salts are no longer stable.
Time Nitrate Salts Become Unstable: t5O := 450-yr (
I - -7
N03
SO4
Soluble C03
K
Na
Total Accumulation In Dry Period
Msto :a Cs1'Qs't5O
Seepage Rate
Os kg
Yr
Seepage Name:
3 :: "THC criod 2"
COg (g) Fugaclt.
f0o2 l.-10-
Because nitrate Is not Included in the THC results, Cs1 Is adjusted to achieve a CI:NO3 ratio equivalent to the ratio In average J-13 well water. Cs3 and C64 are adjusted to achieve Na:S0 4 and Na:CO3 ratios equivalent to Me 0.85-water-activity solution calculated from the EQ316 Pilzr model. Soluble Irries the faction that precipitates with Na or K.
This charge balance error Is approximately maintained for the entire calculation.
Period ends when relative humidity (RH) rises
time when RH exceeds -50%)
. Molecular Weight
Mst 1,o - 0.SSSmol WI : 62.gm-morl
Mst2 ,0 - 0.S1.mol W2 = 35.5.gm-mol" 1
Mst 3 ,0 - 0.0oimo W3. 96.gmmmor1
Mst4,0 - 2.310"5 moIW4 z 6ogm-mor
Mstý. 0 0.038-mol W6 ;= 39.gn.mtol
Mst 7,0 a 1.53,mol W7.= 23.gmrmor-I
Atachment II File: SaftsP2.mcd 11-1 CAL-EBS-PA-000008 Rev. 00
PrecipitateslSalts Model Results for THC Abstacdion
Wet Period. Nitrate salts are unstable. Water vapor condenses to form nitrate brine. Soluble salts begin to dissolve as RH Increases end completely dissolve by the end of the period.
Time Discretization In Wet Period
End of Wet At RH 85%, soluble salts are dissolved and the activity Period at 65% RH t85 = 1300-yr of water is approximately 0.85.
Time Increments in Wet Period Constant'lime Increment
Salt Solubilites
:= 0. 100
dolt - t, - to
Effective Solubilhty at 10 C (molal)
Srd tfic Times o Increments
delt - 9-5-yr
tj t50 + (t85 - t5O) - i
N03 S1 = 24.5.mol-kgo (pure phase solubility at Il0C for KNO3) Other Salts k . 2- 4 Sk : 3.0.mol kgo" (assumed 'effective" solubllity to match EQ6 model
results - "effective" due to mixture of salts) Mass of Total Mst1 0 (assumes accumulated Condensed mwl .1 Mto (assums dissolato Water at Start of m -9 mw- 0.024 - nitrate sits dissolve to Period 2 solubility)
Fraction of Soluble Salts Dissolved. While N03 salts are assumed to dissolve completely at the beginning of the wet period, the other salts are assumed to dissolve increasingly as relative humidity Increases over tEre.
Percentages of Salts Dissolved In Wet Period Percentage of Salts Percentage Salts
System Assumptions Dissolved at Start Dissolved at End of Wet of Wet Period Period
NO3 safts are 100% K-Na-NO3 dissolved at an fll := 100.% f12 = 100.% times In Wet Period. k:a 1. 2
K-Na-CI-=04-C03
I , 1. 1004.(tj - t66)
ffj -- 10 ta5-- t
Percentage dissolved within reactor assumed to increase exponentially from 0% to 100% within Wet Period.
a
I 0
0
0.
t0
S/, 0.1O
0.01 1.10-3•
1.10-4/
0 s00 1000 1500 Time lyrt)
N03 Salts Other Salts
Percentages of Salts Dissolved
I:= 1. 6
N03
Other Anions k :a 2.4
K
Initial Percentage Dissolved Vdn Reactor fl, "= 0
fk, 0 0
f6,0 0
Percentaj
Within Reactor
fl,) fit fk,j : ff1 f6j:= fl1
(Na percentage calculated by charge balance later.)
Attachment II File: SattsP2.mcd 11-2 CAL-EBS-PA-000008 Rev. 00
PrecipitatesSalts Model Results for THC Abstraction
Calculations
Incoming Seepage
Moles Added to Reactor In Incoming Seepage During Time Increment Cumulative Moles In Incoming Seepage
Reactor Calculations
Moles in Reactor at Each Half dek Increment
MrhN, 0 Msio(Ilnfial moles)
j 0.. 100
Moles In Reactor at Time t
Moles (Mass) of Dissolved Ions Generated at lime t
I = 1. 7
Msi = Cs 1.Os-delt
j := 1. 100
"Mst,- := Mstj- I M
i"-z1 . 6 k - 1- 200
- (previous moles) + (seepage moles) - (runoff moles)
1 1 Mrhik - Mrhi.k_, + 'ZMs - '.-MrhlNk .- 'f r( -)
Mrij :7 Mrhii.2
MdiI :2 Mrlj'fil
Dissolved Mass:
mdi, --- MdioW1
Mass of Water In Brine Generated at Time tj (calculated frm anions)
Dissolved Concentration at Time
Na Moles In Reactor (calculated by charge balance, Includes charge Imbalance error term)
Na Dissolved Concentration (calculated by charge balance, Includes charge Imbalance error term)
Dissolved Moles (Mass) of Na In Reactor (calculated by charge balance, Includes charge Imbalance error term)
Percentage Na Dissolved In Reactor
Cumulative Water Runoff j := 1..
Cumulative Mass of Total Dissolved mdto Solids Generated at TimeUi
100
0 kg
mw := Mdi j I. l -i-'•
Mdjj
4 4 Mr7 , :- .. Mr j*-z1 - Mr6,'z 6 + E- 2-Mr1 1,zi1( 4+ E)
4 4 C7,j I C C, z, - C6,1,z6 + E. 2C1,j-z( I t E)
4 4 Md 7'j := Md1 ,i'z1 - Md6 ,J-z6 + E. E 2-Md1j.1 z.(1 1+ E)
Dissolved Mass:
f7, I C?,I'mwj md7,.1 Md 7 ,j'W7
mwt 0 :X Okg mwt% : mwt. 1._ + mw,
4 7
mdt := mdt,-+ rx md, i + E md1,i i-1 1=6
Attachment II File: SaltsP2.mcd 11-3 CAL-EBS-PA-000008 Rev. 00
Preciptates/Safts Model Results for THC Abstrac~on
I.'z 1-7 J -.=. 100
0.5
A
0 500 1000 Time lyrs)
- N03 -C1
-- - S04 -.... Soluble C03
- Na . . . . . . .K
1500
&U.
I
0.11-
0.01 j-
1.10. 4 -
0 50 I00Soo IO00
Time (yrs)
N03 Cl S04 Soluble C03 Na K
10
0
I 05
1500
I
0.11ý-
0.01 -
elO"-3.
I I
I' , .
a S * S
a. / ' : / all
SI a /
II1.1o-41 1 , I 0 500 1000 1500
Time (yrs) - N03 S..... Cl -- - S04 -.... Soluble C03
-- Na -. K
Attachment II File: SaftP2.mncd
Results
I
�1 .5
0
"lime (yrs) N03 C' S04 Soluble C03 Na K
0€
_= U .50
I I
* 'a-
I I
0
11-4 CAL-EBS-A-00000 Rev. 00
Precipltates/Saft Model Resuft for THO Abstracton
Sorld-Phase (Undissolved) Motes in Reactor over lime
Mui, ,= Mri,1 - Mdii
Note: Mp for N03 and K is zero when RH exceeds 50%.
I= 1- 100
100 -
0 11 U
I I .3 U)
3 * U
N03 CI S04 Soluble C03 K Na
10
I
0.1
0.01
- I I
- -.- .'
1-
1.10- I I
0 500 1000 1500 Time (yre
- N03 ..... CI
S04 -.... Soluble C03
Na K
5 I
0 Soo 1000 1500 Time (ym)
- Water Generated During Time Increment -----. Cumulative Water Generated
--- Cumulative Dissolved Ions Generated
Atachment II File: SalftP2.mcd
I I
I
11-5 CAL-EBS-PA-O0000 Rev. 00
1
]
0
Precipitates/Saltsr Model Results for THC Abstraction
Summary and Cross-Check'
Concentrations at End of Wet Period
N03
CI
S04
Soluble C03
K
NaC6, 100
C7 0
1.6 .mol~kg' 1
2.549 -moI- kg
0.255 emo-kg-1
7.223-10-5.rnol kg-1
0.103 .mol-kg'I
4.5988 mol- kg 1
Cumulative Mass of Dissolved Solids In Incoming Seepage at End of Wet Period
Cumulative Mass of Dissolved Solids Generated at End of Wet Period
Cumulative Mass of Water In Generated Brine at End of Wet Period
Cumul-alive Mass of Brine Generated at End of Wet Period
Charge Balance Error Maintained Over Time
j - 1. 10- 100
Concentrations Calculated by EQ316 Model at RH 85%
1.76 -mol -kg
2.44-mol kg-.
O.2Smol-kg71
9.1 105mol kg 1l
4.56-mol kg-1
4
SMst-,1ooW 1 +
Total Motes In Reactor at End of Wet Perlod
Mrj,10 ,
Mr2 , 0 I.
Mr3,100 x
Wr4, 100
Mr6 , 100 a
Mr7, 100
"0.110mol
1.7614104qol
4.989910- 'Imol
7.225.10-4.mol
0.032*mol
7
E Msti, t00 -Wi a 0.316.kg I -6
mdt100 0.337.kg
mwt100 = 0.954 okg
mwt1 00 + mdt100 - 1.291.1cc
7
1 -6
4
- C1,j.Zl
Ci,.Z1'
Output Files:
C*X..Vrh-tids
t
[a CJL.rtj~stads
Mst m~o
12rc~l
C-kg
CA%..rtkujdxs
IF
C:UlrhjiwLds
mwt
CX'JMrthj~rds
Mr m~o
121 C:Ulr*hrrrwad Ci.Vrh mdb~ds
mw mdt
12 0 C1.. lrh M~d~s C:L..lMrh-Mu.xls
Md MU mo0
Attachment 11 File: SaftsP2.mcd I- A-B-A000 e.0
3.59- 1O-3
3.69-103 3.59-103.59-10i3.5-9-1-07 3.69-103.59- 10
3.59-10-3.59-10
13.59-10~
Ej --
11-6 CAL-ESS-PA-000008 Rev. 00
Precipitates/SaIhs Model Resuftt for THC Abstracfion
Response Surface Calculations
Relative humridity as a Imction of tune (approximaon) RHj !; 0.5 1-t * 035
Evaluation points:
11 - I h m J3 9 14zl 1 5 1530
J6m4 J7 = 60 jg 75 j.9 90 ho0 z100
1001 1 1
to F
60 V
40
k := I 10
I I I I 0 500 1000 1500
rime tyrru
Lookup Table for Given Seepage Composition
s= -THC Period r
10O(fCO2) --6.5
Input Parameter
Relative Hurnidity
Culvtd Parameters
CI Concentration Na + K Concentration
C2 -Jk
3.7145 10-3 kg1 -moI 0.0568-kg 'moI O.4085-kg *-mol O.6852-kg- moI 1 .683s -kg m-oi 2.39698kg-l'mol 2.6330-kg- mol 2.6843.kc-'*mol 2.6261 kg- =rnol 2.5491 -kg-' mol
C6,k+ C7,Jk
24.65*kg-t moI 24.23-kg-lmoI 21.47-kg *mlfO 19.31-kg-Imol 11.48-kg m-o-I
C.89 -kg--- molI 4.04-kg- mol 8.63-kg- *mol 4.09-k9g rmoI 4.69-kg- moI
100 1 1 1
10 1-
1F-
0.11ý-
0.011-.
1.10-3 40 60 10 100
-C1
-Na+ K
Attachment 11 Fie: SaltsPZmcd I- A-B-A000 e.0
j ;= 0. 100
Jk 11
3 VTF w w VT ,IF VT FM
RHk
0.563-
11-7 CAL-EBS-PA-DOODOS Rev. 00
PrecipitateslSalts Model Results for THO Abstr•cion
Low Relative Humidity (LH) Salts Model 1TC Period 3 Abstraction
Conceptual Model Water seeps Into 'reactor (.e, drip shield or backfill) at a constant rate during the period. In the reactor, seepage water vaporizes and salts accumulate. Salts begin to dissolve when the relative humicdity rises above 50%. This model (LRH) approximates the buildup and dissolution of soluble salts In the Na-K-N-S-CI-C system. All fluid (brine) generated during each time Interval flows out of reactor at the end of each time Interval; however, mixing Is allowed between half time intervals. The end point is designed to be equivalent to the evaporative evolution of seepage water to a stolchlometric Ionic strength of 10 molal, as calculated using the EQ316 Pitzer model. The LRH salts model Is a simprified approximation of salt accumulation and eventual dissolution caused by Increasing relative humidity. It maintains mass and charge balance and estimates brine generation as a function of effective solubiities. Its purpose Is to provide bounding and soeping calculations for an evaporite system that has not been deeply studied.
Seepage - Constant rate and constant composition are assumed.
Seepage Comp. (molal) Valency
N03 Cs1
Cl CS2
Soluble 804 Cs3
Soluble C03 Cs4
K Cs6
Na Cs 7
Charge Balance Error Approximaton
7
:= 0.0023.mol-kg- 1
: 0.0032.mol.kg-1
:r 0.00041]mol-kg-1
:e 8.3. 10-7 .mol-kg-1
3 0.00031.mol-kg-1
0.0060.mol-kg-1
z4 :z 1.33 z 6 =] Z6 :,
4
Seepage Rate
yr
Seepage Name:
s - TMC Poriod 39
CO2 (g) Fugacity.
fCo2 :- 1.10-3
Because nitrate Is not Included In the THC results, Csc Is adjusted to achieve a CI:N0 3 ratio equivalent to the ratio In average J-13 well water. sand C64 are adjusted to achieve Na:SO4
Na.'CO3 ratios equivalent to the 0.85-water-actvity solution calculated from the EQ316 Pitzer model. Soluble Implies the fraction that precipitates with Na or K.
ZCý2 E C iz, 1=6 1 - 1 7
I-I-Z
E a -8.791.10-4This charge balance error approximation Is E -0.0o9 ,% approximately maintained for the entire calculation.
Dry Period. Salts accumulate. No stable brine is generated. Period ends when relative humdRity (RH) rises to level where nitrate salts are no longer stable.
Time Nitrate Salts Become Unstable: t5e := 450-yr (tme when RH exceeds -50%)
Total Accumulation In Dry Period
Ms; 0o := Csi-Qs-t5O Mste,o - 1.035.mol
Mst 2 ,* a 1.44.mol
Mst 3 , a 0.184,mol
Mst 4 ,o - 3.7.I0"4.mol
Mst 6,o - 0.139.mol
Mst 7 ,e - 2.7Tmol
Molecular Weight
WI 62-gm-morl
W2 35.5.gm-morl
W3: 96.gm-morl
w = 60gm.morl
W6= 39.gm.mortI
W7:. 23.gm.morl
Attachment III Fie: SaftP3.mcd
I:= 1- 7
N03
C!
S04
Soluble C03
K
Na
II!-1 CAL-EB$-PA-000008 Rev. 00
PrecpltateslSalls Model Results for THC Abstraction
Wet Period. Nitrate salts are unstable. Water vapor condenses to form nitrate brine. Soluble salts begin to dissolve as RH Increases and completely dissolve by the end of the period.
Time Discretiztion In Wet Period
End of Wet At RH 85%, soluble salts are dissolved and lhe activty Period at 85% RH t85 :a 1300-yr of water Is approximately 0.85.
Time Increments In Wet Period Constant Time Increment
Salt Solubilities
N03
Other Salts k.- 2.4
j = 0 100
delt v. tj - to
Effective Solubility at 100'C (molafl S1 x 24.5.mol-kgo
Sk := 2.9.moltkg" 1
dolt - 8.5 *yr
(pure phase solubility at 100C for KNO 3)
(assumed "effective" solubility to match EQ6 model results - "effective" due to mixture of sats)
Mass of Total Mstlo (assumes accumulated Condensed m!: w .4 k Water atStart of mw . 0.042kg. nitrate salts dissolve to Period 2 solubility)
Fraction of Soluble Salts Dissolved. Wille N03 salts are assumed to dissolve completely at the beginning of the wet period, the other salts are assumed to dissolve Increasingly as relative hurnmcity Increases over time.
Percentages of Salts Dssolved In Wet Period Percentage of Salts Percentage Salts
System Assumptions Dissolved at Start Dissolved at End of Wet of Wet Period Period
K-Na-NO3 N03 salts are 100% dissolved ata ft 100.% f1 2 .- 100'% times in Wet Period. k 1.2
K-Na-CI-=04-CO3
I-. . 100
Percentage dissolved within reactor assumed to Increase exponentially from 0% to 100% within Wet Period.
a
I C *2
I
A.0 Soo 1000 I0s
"Time lym) - - - - - - -N03 Salts
-- Other Salts
Percentages of Salts Dissolved
I := 1 6
N03
Other Anions k . 2-4
K
Initial Percentage Dissolved Within Reactor flO := 0
fk,0 := 0 f6 ,0 0
Percentaje Dissolver
Wilhin Reactor fl~j = fli
fk,J I ffj
f6,J:= f11
(Na percentage calculated by charge balance later.)
Attachment II FRe: SaltsP3.mcd
ft := 10 tab-t5O
10
1
0.1
0.01
1.10-3
of merits Ij x t50 + ( t85 - t~o)-J'l•
111-2 CAL-EBS-PA-O00008 Raw. 00
PrecpltatesSafls Model Results for THO Abstraction
Calculations
Incoming Seepage
Moles Added to Reactor In Incoming Seepage During Time Increment Cumulative Moles in Incoming Seepage
Reactor Calculations
Moles In Reactor at Each Half delt Increment
Mrh, 0 -= Mstio(Indflal moles)
J= 0. 100
Moles In Reactor at Time 11
Moles (Mass) of Dissolved Ions Generated at Time tý
Mass of Water in Brine Generated at Time tI (calculated from anions)
Dissolved Concentration at Time
Na Moles In Reactor (calculated by charge balance, Includes charge Imbalance error term)
Na Dissolved Concentration (calculated by charge balance, Includes charge Imbalance error term)
Dissolved Moles (Mass) of Na in Reactor (calculated by charge balance, includes charge Imbalance error term)
Percentage Na Dissolved In Reactor
Cumulative Water Runoff j :z 1.
Cumulative Mass of Total Dissolved mdt= Solids Generated at Time if
.-- 1.7 j.1. -00
Msi = Cs%.Qs-delt
Mstij := MVIj_ I + M&I
1.- 1.6 k= 1. 200
= (previous moles) + (seepage moles) - (runoff moles) 1 1
Mrhi,2Mrhk.A- 1 ÷"Mh- 7 "Mrhi, k- 'f (..)
Mri,j ="Mrhi~j.=
Md :-Mr,
Md, Mdj
mw E I -, 1 i-i -,
100
0. kg
Dissolved Mass:
md1,1 w Mdi,Wi
Md1,1
4 4 Mr.,j :2 Mrl,1 'zI - Mr6 ,1'z6 + E- • 2.Mr1,1jz 1 .( 1 + E)
i =1 Ii =
4 4
C7,j j. C.z, - C6,j., + E- 2 2-C%,.z( 1 + EI i :t I =1
4 4
uM • j Md1,.'z. - Md6,.jkz,. E 2 2M.%d.jj. I + E)
Dissolved Mass:
C7 ,1'mwj md 7 ., := Md7 ,j'W 7 % =--ar37,j
mwt0 := 0-kg mwtj := mwtj 1 + mwJ
4 7 mdt= mdt + _ mdji, j + E6 mdij i -I t -6
Attachment III File: SaltsP3.mcd 111-3 CAL-EBS-PA-O00008 Rev. 00
PredpltateslSalts Model Resufs for THC Abstraction
I:= 1 7 J := 0. 100
6
I vI.
Tim. (yrs)
N03 Cl S04 Soluble C03 Na K
0.1 -
0.011-
o Soo 1000 Tim.e yr.)
- N03 -.. . CI
-- - S04 Soluble C03
- Na -. K
o.$
ii c
I
05
I
!o
is00
500 1000 Time (yrs)
- NO3 - -- S04 . Soluble C03
- Na "* ." K
0 5oo 1000 Tim (y")
- N03
----- S04 S.... Soluble C03
- Na K
Atachment III File: SatsP3.mcd
Results
1U.
I
C
I C
.5
i I
I I
1300
15001.10-4
1-10-31_
111-4 CAL-EBS-PA-000008 Rev. 00
Predpitates/Saft Model Results for THC Abstracdion
Solid-Phase (Undissolved) Moles In Reactor over Time
MuI,1 :r Mrij - Mda,I
Note: Mp for N03 and K is zero when RH exceeds 50%.
10[- I I =1
I -
Z I 0.011-
1.10
1.104 1 1.10.
0 500 1000 1500 Trn. (yrs)
- N03 -a
----- S04 Soluble C03
- Na -..K
I =1. 100
0.1
0,01
ST '" .-'S0
Slbe C03
a .. ', ,
* /
Na
a,
0 50 1000 1500
- N03 "*.---- Cl --- S04 -.... Soluble CO3
- Na
2
Lss
0.5
0 0 500 1000 1500
Time tyr) - Water Generated During Tine Increment
-----.Cumulative Water Generated - - - Cumulative Dissolved Ions Generated
Attachment III File: SaltsP3.mcd
100
C a *1 I 0
U
i a
0.11
1610.3ý
10
1
111-5 CAL-EBS-PA-00008 Rev. 00
PReplotatess/Salts Model Results for THO Abstraction
Summary and Cross-Check
Conicentrations at End of Wet Period
C2ý, 100 - 2.412.mol-kg-1
C3 ,100 -0.309.mol-kg 1
C.10-6256.10-4.mo-kg-1
C.IDa O.203.niol-kg-1
C7 0 4.326*mol-kg'1
Concentrations Calculated by E03115 Model at RH 85%
1.68 -molgI
2.34 -mol- kg-t
0.30-mcl- kg-t
6.0-1O-4 -mol-kg-1
0.226-moBl- kg-1
4.36 -mol-kg-1
Total Moles In Reactor at End of Wet Period
Mrj,1 0, i0
Mr2, 100 *
MW3, 100 .
Mr4,100
2r, 0
Mr7,100
0.02amol
0.03 Ismol
4.01-10--o 8.1 19.1O 6.znol
2.635-e10-mo
0.036*mol
Cumrulative Mass of Dissolved Solids In Incoming Seepage at End of Wet Perod
Cumulative Mass of Dissolved Solids Generated at End of Wet Period
Cumulative Mass of Water In Generated Brine at End of Wet Period
Cumulative Mass of Brine Generated at End of Wet Period
4 7
=1 -=6
mdti 00 O.616-kS
mwt1l 3 1.790 .kg
mwt100 +- mdt1OO 2.407.kg
Charge Balance En-or Maintained Over lime
j :a 1, 10. 100
7 4
1=6 cij,Jzi
7
Outpu Files:
C:%O.rh-tids
t
w
12 C-' .VrhCads
la C.Ulrhnmwitds
mwtC kg mol
C:.¶Lr*hn-iw. CA.WhmdL*d
mw mdt
Ci.llrtimst*d
Mst
C:%l.rt f.ads
f
C.:L*h Mr.XIS
Mr mci
C:'i.rh-Md.ids
Md
C:%Ulrh-Mu.)ds
Mu
Attachment III Rie: SaftsP3.mcd 1-CAESP-008Re.0
N03
CI
S04
Soluble C03
K
Na
-8.791 .1U-8.791-10-1 -8.78 1-10-8.791.10
-8.791-10-8.791-10-8.7,91 -10F
-8.791-10-8.7911.10-4
-8.791-10-8.79 1-10-
111-6 CAL-EBS-PA4X*M Rev. 00
PrecipitaesiSaits model Results for THC Abstraction
Response Sudface Calculatlions.
Relative humiclity as a funcdon of timne (appro~dmalion)
RH-I := 0.5 +100 1 1 1
Evaluation points:
III= 12 x f3 J x9 14 15 JS x30
J, z4 17 :-60 Ig~ := 75 90 jl1 0:= 100
k := 1-. 10
Lookup Table for Given Seepage Composition
cc
to
60
400 So0 1000 1500
Time (ymI
log(fCO2) - -3
ninxu Parameter
Relative Humid-ty
Outnut Parameters
Ca Concentration Na + K Concentration
C2.Jk
3.7321 10-3 kg1 .MoI 0.0570-kg rnol 0.4064+kg mol 0.6772kg *-mol 1.6251+9kg mol 2.2759kg *-mol 2.4866+9kgmoi 2.5321 kg 'mol 2.4804-kg- moi 2.4120-kg 'moi
CG5,k *C7iJk
24.43-kg 1 -mol 23.99-kg *Wo-l 21.10-kg '-mol 18.86-kg- moi 11.03-kg- *mol
5-.65-kg ifMol 3.Sl-kg lmoI 3.54-kg *mroi 3.965kg mol 4.53-kg- mol
k3
100
10
I
0.1
0.01
40 60 to 100 RH 4%)
-cl
-Na+ K
Attachmnent III Rle: SaftsP3.mcd 1-CAESPA000Re.0
j -0 100
ikRI4j1
0.503
( - ý - t5o .0.35 kt65 - t5O)
111-7 CAL-EBS-PA-000008 Rev. 00
PreclpltatesSlts Model Results for THC Abstraction
Low Relative Humidity (.RH) Salts Model THC Period 4 Abstraction
Conceptual Model. Water seeps Into "reactor" 0.e, drip shield or backtil) at a constant rate during the period. In Vw reactor, seepage water vaporizes and salts accumulate. Salts begin to dissolve when the relative humidity rises above 50%. This model (LRH) approximates 1ie buildup and dissolution of soluble salts In the Na-K-N-S-Cl-C system. All luid (brine) generated during each time Interval flows out of reactor at the end of each time Interval; however, mixing Is allowed between halftime Intervals. The endpoint Is designed to be equivalent to the evaporative evolution of see age water to a stolchometric Ionic strengith of 10 mola, as calculated using the E03•• Pitzer model. The LRH cbs mode Is a slmpniffed approximation of salt accumulation and eventual dissolution caused by increasing relative humlcd. It maintains mass and charge balance and estimatesrine generation as a function of effective solubilites. its purpose Is to provide bounding and scoping calculations tr an evaporite system that has not been deeply studied.
Seepage - Constant rate and constant composition are assumed.
Seepage Comp. (molal) Valency
N03 Cl
Soluble S04
Soluble C03
K
Na
C81
CS2
CS3
Cs 4
Cs6
CS7
a 0.0023-mol.kg-1
0.0033.mol-kg-1
:z 0.00042-moW. kg"1
:2 2.?. 10"6.mol-kg"
:= 0.0001.mol-kg-t
:z 0.O063.mol-kg"1
Charge Balance Enor Approximation
7 4
2:Csj-z1 - E Cs1.z1 1 -6 7 I -!
i -1
z1 :0
Z2 ;
z4
Z67 Z.7 M=
1
1
2
1.33
1
1
Seepage Rate Qsz I-kg
yr
Seepage Name:
s :a I"HC Peuiod 4 (75rC)"
CO2 (g) Fugactyr.
fco2 X 1.10-2
Because nitrate Is not Included in the THC results, Cs1 is adjusted to achieve a CI:NO3 ratio equivalent to the ratio In average J-13 well water. Cs3 and Cs4 are adjusted to achieve Na:S0 4 and Na.CO3 ratios equivalent to the 0.85-water-actvty solution calculated from the EQ316 Plizer model. Sofuble implies the fraction that precipitates with Na or K.
E - -3.394.10"This charge balance error approximation is E -0.34 , % approximately maintained for the entire calculation.
Dry Period. Salts accumulate. No stable brine Is generated. Period ends when relative humidity (RH) rises to level where nitrate salts are no longer stable.
"lime Nitrate Salts Become Unstable: t50 - 450. yr (time when RH exceeds -50%)
Total Accumulation In Dry Period
Mst, 0 . Cs 1 i.Ot0 Mstl, 0 a
Mst2 ,0
Mst3 ,0 x
Mst4, 0 a
Mst 7 00
1.035-mol
1.485.mol
0.189,0mol
1.2o10"3,mol
0.045.mol
2.835*mol
Molecular Weight
W,= 62.gm.mor
W2:= 35.5'gm.morl
W3= .96gm'mor'
W4 x 60-gm.morl
Ws .-- 39.gm-mol"'
W7.-- 23.gmimor'
Attachment IV File: SaltsP4.ncd
I := 1- 7
N03
Cl
S04
Soluble C03
K
Na
IV-11 CAL-EBS.-PA.OW000 Rev. 00
Precipitates/Safts Model Results for THC Abstraction
Wet Period. Nitrate salts are unstable. Water vapor condenses to form nitrate brine. Soluble salts begin to dissolve as RH Increases and completely dissolve by the end of the period.
Time Dlscretization in Wet Period
End of Wet At RH 85%, soluble salts are dissolved and the activity Period at 85% RH t85 := 1300.yr of water Is approximately 0.85.
Tkne Increments In Wet Period Constant Time Increment
Salt Solubilties
N03
Other Salts k 2. 4
j.= 0. 100
delt - t, - to
Effective Solubilty at 100'C (molall S1 = 24.5.mol-kg"
Sk 2.9.mol-kg°!
Specific Times of Increments t: = t50 * (t85 - t5o). I
delt -8.5 ,yr
(pure phase solubilty at 10WC for KNO3)
(assumed *effective solubiltly to match EQ6 model results - "effective" due to mixture of salts)
Mass of Total Mst1,0 (assumes accumulated Condensed mw. M aates dissolvto Water at Start of m mw1 - 0.042-kg njt salts dissolvetto Period 2 solubtrty)
Fraction of Soluble Salts Dissolved. While NO3 salts are assumed to dissolve completely at the beginning of the wet period, the other salts are assumed to dissolve increasingly as relative humidity Increases over time.
Percentages of Salts Dissolved In Wet Period Percentage of Salts Percentage Salts
System Assumptions Dissolved at Start Dissolved at End of Wet of Wet Period Period
N03 salts are 100% K-Na-NO3 dissolved at all fl := 10D.% f12 : 100-%
times in Wet Period. k: 1. 2
K-Na-Cl-S04-C03
J . 1. 100
Percentage dissolved within reactor assumed to Increase exponentially from 0% to 100% within Wet Period.
0
I I
I' 0 0 0 a. 0 O00 100o 1500
Time lyrs)
- - - - - - -N03 Salts - Other Salts
Percentages of Salts Dissolved
Ia 1-6
N03
OtherAnions k .- 2- 4
K
Initial Percentage Dissolved Within Reactor f, : 0
fk,O := 0
f6,0 *: 0
Percentage Dissolved Vvithin Reactor ft., '-- fl,
fk,J :z ffJ
fg,j :" flI
(Na percentage calculated by charge balance later.)
Attachment IV Fie: SaltsP4.mcd
fft - teo
ff ; 0 -- t
IV-,? CAL-EBS-PA-O00006 Rev. 00
Precipliates/Sts Model Results for THC Abstraction
Calculations
Incoming Seepage
Moles Added to Reactor In Incoming Seepage During Time Increment Cumulative Moles In Incoming Seepage
Reactor Calculations
Moles in Reactor at Each Half delt Increment
MrhN, 0 :- Msýt,onflial moles)
j - 0. 100
Moles In Reactor at Time
Moles (Mass) of Dissolved Ions Generated at Time tl
Mass of Water In Brine Generated at Time Ij (calculated from anions)
Dissolved Concentration at Time
Na Moles In Reactor (calculated by charge balance, Includes charge Imbalance error term)
Na Dissolved Concentration (calculated by charge balance, includes charge Imbalance error term)
Dissolved Moles (Mass) of Na In Reactor (calculated by charge balance, includes charge Imbalance error term)
Percentage Na Dissolved In Reactor
Cumulative Water Runoff j ] -1100
I :z 1- 7 j := I- 100
"a ; Csri.s-delt
Mati := MstA,I- I + Ms.
I -= 1.6 k : 1. 200
- (previous moles) + (seepage moles) - (runoff moles)
1 MrWl, k ýO Mrhl, k -I + 7"Msi
Mr1,1 -= Mrhl,1.2
Dissolved Mass:
mdi, z Md1 1iWt
mMd 1 ,i
mwI: Mdi1
4 4
Mr 7,1 Mr, 1z1 - Mr6 ,1.z 6 + E. 2-Mri, 1 z1 .( I + El I- =1I=I
4
C7,1 •,j'Zi - C6 ,1'z 6 + E" I =1
4
Md7,1 := I1=
C7Tj-mwJ
mwt0 := O'kg
4
.2"Ci,l-Zi-1 - E)
4
- Md 6 ,1"z6 + E" 2.Mdi.j1 z.( I t E)
Dissolved Mass: md7 ,j aMd7,j'W
nwtj ==mwt - I +" mw|
Cumulative Mass of Total Dissolved Solids Generated at lime U1
mdt0 ;a O'kg mdtj 1 mdt_ -I +4
mnd11
7 + E md1,j
I =-6
Attachment IV File: SaltsP4.mcd
I
Iz .MrN, k - 1'f I . floor (k- I (4!)
IV-3 CAL-EBS-PA-000008 Rev. 00
Precipitates/Salts Model Results for T-C Abskaction
Results I:u 1. 7 j :M 0. 100
I
S .5S
I
1500 0 500 1000 Time (yrs)
- N03 ..... Cl
S04 . - - -Soluble C03
- Na ..................K
0.01 1-
0 500 1000 Time (yra)
- N03 -a
S04 - ---. Soluble C03
- Na K
0
7Z
3
1500
1 I I
O*
0.01 I! \
1.1 " /
I / / SI,
1.104 #1
o 500 1000 1500 "rime (yra)
- N03 -Cl
-- - S04 S.... Soluble C03
Na -K
Attachment IV File: SaftsP4.mcd
i wID C
Time (yrs)
N03 Cl S04 Soluble C03 Na K
3500
ul.
* 0 U U E
.5
I
0.1-
- . ......-- --
* I
1.10-4
CAL-EBS-PA-0000 Rev. 00
I | I
lIRI
I I
1,1o0 -3
IV-4
Precipitates/Salts Model Results for THC Abstraction
Solid-Phase (Undissolved) Moles in Reactor over Time
Mul,1 :z Mrjj - Mdi,j
Note: Mp for N03 and K is zero when RH exceeds 50%.
0
£
U U .5
I = 0
9�
101
0.1
I I -
0.01 -
1.10-4
1. 10 -•
1
'I
II II o Soo 1000 1500
Time (yrs) - N03
C! --- S04 -.... Soluble C03
- Na --K
J := - 100
100r- I I
I10-
2
1.3
1I
, / S
0 500 1000 1500 Time (yrs)
- N03
S04 - -... Soluble C03
-NK -Na
0.5
0
5/ 4
0 Soo 100 1500 T•m (yr')
- Water Generated During Time Increment Cumulative Water Generated
- - - Cumulative Dissolved Ions Generated
Attachment IV FiHe: SalP4.mcd
1
B
I
0.1
0.01
1.10-3 _
$ | t
I1.-s _
I
IV-6 CAL-EBS-PA-000006 Rev. 00
Precipitates/Safts Model Results for THC Absftction
Summnary and Cross-Check
Concentrations at End of Wet Period
N03
Cl
S04
Soluble C03
K
Na
C1 . 10o0
C2.100 =
C3.100
C4, 100
C6,100.
C-1, 1to
1.464 .mol kg1l
2.417 omol kg 1I
0.309 wmnl- kg1
1.97810 emol Ikg-1
0.064 'mol kg 1I
4.405 ormol- kg-1
Cumulatlve Mass of Dissolved Solids In Incoming Seepage at End of Wet Period
Cumulative Mass of Dissolved SoUds Generated at End of Wet Period
Cumulative Mass of Water In Generated Brine at End of Wet Period
Cumulative Mass of Brine Generated at End of Wet Period
Charge Balance Error Maintained Over Time
j :2 1, 10- 100
Concentrations Calculated by EQ316 Model at RH 85%
1.60-mol-kg-1
2.30mol-kg-1
0.29 mol-k#-1
1.9.lO3 -mo[ kg-t
0.070-mol kg1l
4.38 mol-kg-t
4
SMs%; 100,W 1
Total Moles In Reactor at End of Wet Period
Mfi. 1w S
Mr2 , 100 * Mr3,1w00
Mr4 100 '
Mr6.100 =
Mr7,1W0 '
0.02#mol
0.032*mol
4.108.10-mol
2.641.10-5'mol g.5.10-4.mol
0.059'mol
7
E Msti 100.wi -0-584'kg 1 -6
mdt100 0.62.kg
mwt 100 1.94249k
mnwt1 00 + rrmdt100 22.462*kg
7 4
E CI,j-Z1 E ,J 1 6 1 -1
Output FleV.
CA1rJ2 l
t
CA-Arti.CAds
C.kg mci
12 C:1L..WhLMwLds
mnwt -Erg
12 12 CAUr..n MdS C:ULh.mdbds
mw mdt
-3.394-10
-3. 3-94105Y- 3.394 1-05
_-3.394-10-3.3994 1-07i-339-4 71-0 -T339471-0-- 3.394. 103 - 3.394-103 7-3394-107F.394-10'-
12 C~kh."Mstad
Mst
C:X..Mrhjads
f
12 CA..rtMrids
Mr M70
12 12 C*'..Urtj~d.xls Ct.LArh-Mu.xls
Md Mu mol
Attachment IV File: SultsP4.mod I- A-B-A000 e.0
7
IV-6 CAL-EBS-PA-000008 Rev. 00
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