Office of Civilian Radioactive Waste Management …S. Lead James Nowak 4A 2 fr, p1 9. Remarks This calculation uses the Precipbtates/Salts model developed In the In-Drift Precipltates/Salts

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

CAL-EBS-PA-OOX*00 REV 00 2 Jume 2000


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

V' AT V finl~r~mI~t*.U./D•-Jt"•.'PJ•NJ JfV w 3 Jima 2M0


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

CAL-�BS-PA-O000OS EBV 00 4 June 2000CAL-IEBSy-PA-000008 REV 00 4 June 2000


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.

LAL-�U�-YA-I�ARJU5 IL�V UAJ J�me 20001-J.=-I•AAM J8iVV 00 5 June "M0


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

OwL.t~l•-M-PA-000009A RE 00 6 June 2M0


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

LA-1ZS~-'A4IUUU5K~v JO 7J~me2I 0CMA-M-P.A-AM000.REV 00 7 June 2000


(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.

CAL-EBS-PA-000008 REV 00 8 lime 2000CAL-EBS-PA-000008 REV 00 8 Jane 2000


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

CAL-EBS-PA-000009) REV 00 9 June 2000


: 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

C.AtL-EBS -PA-000 REV OD 10 Am2000

Precipitates/Salts Model Results for THC Abstation

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

CAL-EBS-PA-000008 REV 00 14 June 2000

I-o-76C~

1�

a -

CAL-EB S-PA-6000008 REV 00 14 Ame 2000

Precipitates/Salts Model Results'for THC AbsMtaion

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.

CAL-EBS-PA-00000S REV 00 '5 June 2000CAL-EBS-PA-00000 REV 00 is June 2000

Precipitates/Salts Model Resuts for THC Abstraction

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

CAL-EBS-PA.O00008 REV 00 16 June 2000


CAL-EBS-PA-000008 REV 00 16 June 2000


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


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


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


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


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


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.


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%)


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


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


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


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


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)



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)


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)


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


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 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-kgmoi 2.4120-kg 'moi

CG5,k *C7iJk

24.43-kg 1 -mol 23.99-kg *Wo-l 21.10-kg '-mol 18.86-kgmoi 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.


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%)


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


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


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


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


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)



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)


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)


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


Solid-Phase (Undissolved) Moles in Reactor over Time

Mul,1 :z Mrjj - Mdi,j


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


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 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

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Documents

Office of Civilian Radioactive Waste Management …S. Lead James Nowak 4A 2 fr, p1 9. Remarks This calculation uses the Precipbtates/Salts model developed In the In-Drift Precipltates/Salts