The derivation of the numerical procedure from the mathematical component model.  The UM gives references for all numerical methods.  It explains the final form of the numerical model and its algorithms.  If the numerical model produces only an intermediate result, such as terms in a large set of linear equations that are later solved by another numerical model, then the UM explains how the model uses intermediate results.  The documentation also indicates those variables that are input to and output from the component model.

The Agency reviewed the UM for Version 8.0a (Wolery and Jarek 2003).  This document describes the functionality of EQ3/6, provides a code overview, describes material and element properties, and tells the analyst how to run EQ3/6.  The UM document requirements of NP 19-1 are satisfied by the UM (Table 6).

Table  6.	NP 19-1 Criteria Matrix for User's Manual
                              NP 19-1 UM Criteria
    User's Manual for EQ3/6 Version 8.0a Section that Satisfies Criteria
1.	Functional Requirements and System Limitations
The functional requirements for EQ3/6 are described in Requirements Document for EQ3/6 Version 8.0a.
EQ3/6 Version 8.0a runs on a PC-compatible with Microsoft Windows 95, 98, 2000, NT, or XP; EQ3/6 may operate on other Windows systems.
2.	Mathematical model and numerical models
Section 2.1 (Conceptual Background),
Appendix B (EQ3 Supplemental Information),
Appendix D (EQ6 Supplemental Information), and
Appendix E (ODE Integration Methods)
3.	Physical and mathematical assumptions
Section 2.1 (Conceptual Background),
Appendix B (EQ3 Supplemental Information),
Appendix D (EQ6 Supplemental Information), and
Appendix E (ODE Integration Methods)
4.	Capabilities and limitations
Section 5 (Allowable/Tolerable Ranges for Inputs and Outputs)
5.	User's interaction
Run instructions are provided in Section 2.2 (Operating the Software), and in the VVP/VD for EQ3/6 Version 8.0a.
Section 2 (User Interactions) provides an overview of the interactions of the individual programs in the EQ3/6 package and user's interaction needed to run the codes.
6.	Input parameters, formats, valid ranges
Section 3.1 (EQ3/6 Input Database Files),
Section 3.2 (EQ3 and EQ6 Input Files),
Section 3.3 (The EQ3 Input File),
Section 3.4 (The EQ6 Input File),
Section 4 (File Formats), and
Section 5 (Allowable/Tolerable Ranges for Inputs and Outputs)
7.	Messages initiated by improper input
Section 3.2.2 (Input File Processing and Error Control) and
Section 6 (Anticipated Errors and User Response)
8.	Output specs and formats
Section 3.5 (EQ3 Output Files),
Section 3.6 (EQ6 Output Files), and
Section 3.7 (EQ6 Tabulated ("Tab") Output File)
9.	Required training
Section 8 (Required Training)
10.	Components not tested
The components not tested are defined in the VVP/VD for EQ3/6 Version 8.0a.

Implementation Document (ID)  -  provides the information necessary for the re-creation of the code used in the WIPP PA calculations.  Using this information, the computer user can reconstruct the code or install it on an identical platform to that used in the WIPP PA calculations.  The document includes the source-code listing, the subroutine-call hierarchy, and code compilation information.

Since EQ3/6 is not in the public domain, and DOE does not have a copy of the source code, DOE has not developed an ID.  Instructions for installing EQ3NR (Version 8) onto a PC are provided in Appendix A of the VVP/VD, however.  If the DOE does replace FMT with EQ3/6, it will be the only major PA code in which the source code is not readily available to the PA investigators.

Validation Phase

The validation phase consists of executing and reviewing test cases identified in the VVP to demonstrate that the developed software meets the requirements defined for it in the RD.  The VD, produced during this phase, summarizes the results of the testing activities prescribed in the RD and VVP documents for the individual codes and provides evaluations based on those results.  The VD contains listings of sample input and output files from computer runs of a model.  The VD also contains reports on code verification, bench marking, and validation, and documents results of the QA procedures.

Requirements are outlined in Section 2.0 of the RD for EQ3/6 (Version 8.0a).  The 16 functional requirements described in Section 2.0 are those necessary for PA code usage.  These include the following requirements:

Functional Requirements

EQ3/6 is required to perform the following functions:

R.1	Perform aqueous speciation calculations, given total concentrations of dissolved components and other parameters, such as pH, pH, Cl, Eh, pe, oxygen fugacity, and CO2 fugacity.

R.2	Perform aqueous speciation calculations with charge balancing on a specified ion.

R.3 	Perform aqueous speciation calculations with mineral equilibrium constraints.

R.4 	Perform "single point" thermodynamic equilibrium calculations.

R.5	Perform reaction-path calculations without inclusion of chemical kinetics.

R.6	Perform reaction-path calculations with inclusion of chemical kinetics.

R.7	Perform reaction-path calculations for fluid-center flow-through open system.

R.8	Determine activity coefficients using Pitzer's equations, assuming an appropriate Pitzer thermodynamic data file is provided.

Performance Requirements

There are no performance requirements for EQ3/6.

Attribute Requirements

There are no attribute requirements for EQ3/6.

External Interface Requirements

R.9	EQ3NR and EQ6 require a binary thermodynamic data file.

R.10	EQ3NR requires a text input file (.3i) describing the speciation-solubility problem.

R.11	EQ3NR generates a text output file (.3o) describing the results of the calculation.

R.12	EQ3NR generates a text "pickup" file (.3p) that contains a compact description of the aqueous solution.  It may be used as the bottom part of an EQ6 input file.

R.13 	 EQ6 requires a text input file (.6i) describing the reaction-path problem.

R.14 	EQ6 generates a text output file (.6o) describing the results of the calculation.

R.15 	EQ6 generates a text "tab" file (.6t) that contains certain data in tabular form suitable for supporting local graphics post-processing.

R.16 	EQ6 generates a text "pickup" file (.6p) that may be used as an input file to restart a reaction path calculation where a previous run segment ended.

Other Requirements

The ability of the software to meet requirements R.1 through R.16 has already been established (SNL 2006a).  The present requirements document adds a new one:

R.17	EQ3/6, using an appropriate translation of the FMT database used in the WIPP geochemistry model, must produce results for WIPP-relevant and near-relevant problems that are substantially the same as those produced by FMT.  The WIPP-relevant problems must include examples involving actinides, and some must include both actinides and organic complexing agents.

All testing was performed on a PC with AMD Athlon(TM) Processor, AT/AT Compatible with Microsoft Windows XP Professional Version 2002, Service Pack 2.

The test set for EQ3/6 consists of 19 test cases, identified as Test Case #1 through Test Case #19.
The cases have been designed to verify that EQ3/6 Version 8.0a satisfies the requirements specified in Section 2 of the RD.  Test cases are summarized in Table 3.  Each test is discussed in detail in Section 6 of the VVP/VD.  The requirements covered by each test case were shown previously in Table 4.  Most test cases are designed to specifically verify a limited set of requirements, although many of the requirements are implemented by each test case.

The description of test cases, input files, and acceptance criteria described in the VVP/VD exercise all code attributes required in the list provided in Section 2.0 of the RD.  In general, the techniques used to verify EQ3/6 are comparisons with independent codes with similar capabilities.

The different techniques typically align with the nature of the test case -- individual component, or small groups of components.  This approach is a conventional way of validating computer codes, i.e., by a series of comparisons with known solutions that test various combinations of code options.  Table 7 provides a summary of where the VVP/VD NP-19-1 criteria are presented.

Table 7.	NP 19-1 Criteria Matrix for the VVP/VD
                            NP 19-1 VVP/VD Criteria
                  EQ3/6 Report section that satisfies criteria
 Code Requirements
Functional; Performance; Attribute; External Interface; and Other Requirements pp. 7 - 8 (SNL 2006b)
 Code Functionality
pg 8 (SNL 2006b)
 Functional Testing
pp 9-59 (SNL 2006b)
 Installation and Regression Testing
pp 7-29 (SNL 2007)
 Input files
Appendix A (SNL 2007)
 Run Scripts
Appendix A (SNL 2007)

The Agency found that the EQ3/6 results satisfactorily met the acceptance criteria for all of the functional tests.  Although none of the EQ3/6 tests were designed expressly to test WIPP-specific geochemical conditions, many of the tests do encompass conditions that are similar to WIPP (e.g., high salinity).

Installation and Checkout Phase

The following documents are produced during the installation and checkout (I&C) phase:

 The Installation and Checkout (I&C) Form NP 19-1-8
 The Access Control Memorandum
 The Approved Users Memorandum

The I&C Form for EQ3/6 Version 8 provides access control information and a list of approved users (SNL 2006e).  SNL maintains a series of software codes for application at the WIPP site.  Each code must be validated prior to initial use on each new platform.  The EQ3/6 code was acquired from LLNL.  The validation of EQ3/6 Version 8.0a was conducted in 2009 on a PC with Windows XP and documented in the VVP/VD.

Regression testing must be conducted on each individual PC that runs EQ3/6 Version 8.0a for official WIPP work.  The I&C document for EQ3/6 covers the regression testing conducted to demonstrate the validity of EQ3/6 Version 8.0a on all "target" PCs listed below:

S843806 - Intel(R) Pentium(R) 4 CPU 2.80GHz
	Hardware Platform:  Intel Pentium 4 CPU 2.80GHz (S843806)
	Operating System:  Microsoft Windows XP Professional Version 2002 Service Pack 2

S838019 - Intel(R) Pentium(R) 4 CPU 2.20GHz
	Hardware Platform:  Dell Workstation PWS340, Intel Pentium 4 CPU 2.20GHz (S8380I9)
	Operating System:  Microsoft Windows 2000 5.00.2195 Service Pack 4

S864333 - Intel(R) Xeon(TM) CPU 3.40GHz
	Hardware Platform:  Dell Workstation PWS670, Intel Xeonm CPU 3.40GHz (S864333)
	Operating System:  Microsoft Windows XP Professional Version 2002 Service Pack 2

S881469 - Intel(R) Pentium(R) D CPU 3.60GHz
	Hardware Platform:  Intel Pentium D CPU 3.60GHz (S88 1469)
	Operating System:  Microsoft Windows XP Professional Version 2002 Service Pack 2

Before testing, EQ3/6 must be installed on the target PC.  Installation instructions are provided in Appendix A of the VVP/VD.  The software package contains the executable programs in folder Eq3-6v8.O\Bin.  The executable programs and interface codes used to run the program are listed on each line, as explained in Appendix B of the VVP/VD.

The I&C document presents the regression test results for the EQ3/6 Version 8.0a code on all target PCs listed above.  The tests for this code comprise the 19 test cases described in the VVP/VD.  Test results from EQ3/6 Version 8.0a run on each target PC were compared to results from the validation test of EQ3/6 Version 8.0a described in the VVP/VD.

NP 19-1 states that differences in run dates and times and execution statistics are acceptable.  These are the only differences expected in the EQ3/6 output files.  If all differences are found to be acceptable, it follows that the output of EQ3/6 Version 8.0a meets the acceptance criteria specified in the VVP/VD.  If the output of EQ3/6 Version 8.0a on each target PC meets the acceptance criteria specified in the VVP/VD, EQ3/6 Version 8.0a will be considered to be validated on each target PC in which it was tested.  The comparison found no differences in the numerical output of EQ3/6 Version 8.0a on any target PC and the VVP/VD validation.

The Agency concludes that EQ3/6 Version 8.0a meets the acceptance criteria in the VVP/VD and has passed the regression testing on all target PCs listed above.

Production Software and/or Baseline Document Change Control

When changes to the software baseline occur, the Change Control Form, Form NP 19-1-9, is used.  The following are types of changes that may be implemented:

 Major changes, including new requirements, new design, new models, new implementation, require a new baseline (i.e., SQAP, RD, DD, VVP, ID, UM, VD) to be documented.  In addition to revising every baseline document, a Change Control Form and an I&C Form are used.

 Minor changes do not affect the requirements or design, and can be documented with addenda (no more than three addenda per baseline document) or page changes to the affected baseline document, in addition to the Change Control Form and the I&C Form.

 Patch changes can be used for very small fixes to the code, usually one or two lines of source code or expanding a field's character length, etc.  Patch changes can be documented and tested with the Change Control Form and I&C Form.
The Change Control Form for EQ3/6 Version 8.0 indicates that a number of changes have been made to the code since the release of Version 7.2c (SNL 2006f).  Version 8.0 of EQ3/6 represents a complete rewrite of the Version 7 series software, which dates back to the start of EQ3/6 at Northwestern University in the mid-1980s.  Because it is a complete rewrite, SNL notes that Version 8.0 may not be as stable as Version 7.2c, which benefited from years of feedback by code users.  On the other hand, Version 8.0 does contain several improvements over previous versions.  The latest software is mostly dynamically dimensioned, including everything with regard to the supporting data file.  A few items in the input files are still statically dimensioned, however, like the number of ion exchange phases.  The menu-style input file format has been simplified and should be easier to understand and use.  The ordinary differential equation (ODE) integrator has been expanded into a full predictor corrector method with stiff-system capability.  The stiff-system solver uses a true Jacobian matrix.  This should eliminate those cases where the step sizes become stuck at very small values, because the system of rate equations becomes intractable.

Associated with this development are several enhancements including:

       The availability of a new option for treating surface areas (i.e., constant particle number/geometric growth).
       A new high-temperature Pitzer modeling capability.
       An upgrade to the code numerics in dealing with extremely concentrated.
       The addition of a generic multi-exchanger, multi-site ion exchange model.
       Input file entries to specify exchanger phases and sites and associated thermodynamic data.
       The addition of high-pressure capability.  This is associated with the use of some data files (e.g., data0.shv, data0.500, data0.2kb, and data0.5kb) derived from SUPCRT92 and its own associated data files.  Each file has a reference pressure (the shv file follows the classic 1 atm steam saturation pressure curve), but EQ3/6 will extrapolate to other pressures as specified on the input file.
       Specified redox disequilibria for reaction path runs.
       Options for separating fluids from associated minerals and for facilitating fluid mixing calculations.

The Change Control Form also indicates that the VVP/VD contained an error in the tolerance of the log fugacity of CO2 in Test Case #2.  This tolerance was subsequently expanded to +-0.2.  No other changes to the VVP/VD were made and no other QA documents were changed.  No changes to the code were required.

The Change Control Form for EQ3/6 Version 8.0a indicates that a number of changes have been made to the code since the release of Version 8.0 (SNL 2009).  These revisions are presented in Section A.3.iv.

System Software and Hardware Change Control

Coding Documentation Standards.  Any change to software must be accompanied by documentation describing the change, the date the change was made, and the name of the person responsible for implementing the change.  This documentation should be clearly identified and placed in the code in the vicinity of the change, as well as at the top of the code prior to the first executable line.  The code reviewer shall determine if this documentation is clear and sufficient.

Significant System Software or Hardware Changes.  The Code Team/Sponsor (single-user systems) or System Administrator (multi-user systems) proposes significant system software or hardware changes using the Change Control Form NP 19-1-9.  Examples of significant changes to system software or hardware are as follows:

 Changes to the operating system, such that the version or level identifier changes
 Changes to the Central Processing Unit (CPU)
 Database management system change
In general, changes are significant if they impact the results generated by production software or cause recompilation of production software.

Since EPA's certification of the WIPP CCA, SNL has added computer hardware and upgraded the computer software.  In order to maintain compliance with 40 CFR 194.22 and 194.23, SNL is required to conduct regression testing on the computer codes to ensure that they still function properly on new hardware and software.

Tests #1 through #15 in the VVP/VD for Version 8.0a were tested with previous versions of EQ3/6.  DOE notes, however, that changes to the input and output files for these tests make standard "regression testing" difficult, so SNL has validated these tests on a case-by-case basis by comparing model predicted output values to experimental results or to values calculated by independent codes.

Software Problem Report (SPR).  Whenever a software problem is identified, the Code Team/Sponsor evaluates the problem to determine if it is, indeed, a problem (as opposed to user error).  If it is a problem, the SPR process is followed.

The Code Team/Sponsor classifies the problem as major if it could significantly impact previous uses of code, or if it will require significant modification to the software; otherwise it is classified as minor.  For major problems, the responsible manager identifies affected users to be notified of the problem, and designates qualified personnel to identify and evaluate the impact of the software problem.  The affected analyses are revised as necessary, and the evaluation and resolution of the software problem are documented in Part II of the SPR and Evaluation Form.  For minor problems, this evaluation can be performed by the Code Team/Sponsor.

No SPRs have been generated for EQ3/6 Version 8.0a.

Configuration Management (Configuration Identification and Status Accounting).  Configuration Management refers to the process for defining the configuration of software products, establishing software configuration baselines, and tracking the status of baseline changes.  A software configuration baseline consists of the source code and baseline documents, providing objective evidence of technical adequacy.

The Software Configuration Management (SCM) Coordinator maintains a Software Baseline List and makes it available upon request.  The SCM Coordinator performs a completeness review to ensure compliance with the procedure, and to ensure that necessary components of configuration management are present.  The Software Baseline List contains the following:

 Code name and version
 Code version date
 Code Team/Sponsor name
 Code classification
 RD version
 VVP version
 DD version
 ID version
 UM version
 VD version
 List of approved users (may be listed by name, organization, group, or task, etc.)
 List of approved system software/hardware configurations
 List of outstanding SPR numbers
 Status of approved changes in process
 I&C (Installation and Checkout) date

Such documentation shall include, but shall not be limited to the following:

c.1) 	Description of the theoretical backgrounds of each model and the method of analysis or assessment,
Theoretical aspects of the model construction are described in Sections 2 and 3 of Wolery and Daveler (1992c) and Section 2 of Wolery (1992a) and are summarized below.

EQ3NR is an aqueous solution speciation-solubility modeling code.  It is part of the EQ3/6 software package for geochemical modeling.  It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations that describe the thermodynamic activity coefficients of these species.  The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, Eh, pe, and oxygen fugacity.  The input may also include a desired electrical balancing adjustment and various constraints, which impose equilibrium with specified pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities).  The code evaluates the degree of disequilibrium in terms of the saturation index for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself.  Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples.  Equilibrium fugacities are computed for gas species.  The code is highly flexible in dealing with various parameters as either model inputs or outputs.  The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.  The output consists of an output file and a pickup file, which can be used to initialize an EQ6 reaction path calculation.  EQ3NR may be used by itself or to initialize a reaction path calculation by EQ6, its companion code in the EQ3/6 package.

EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery 1979).  It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems.  Speciation in aqueous solution is an integral part of these calculations; EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solving "single-point" thermodynamic equilibrium problems.  A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations.  Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure.  These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids.  The code computes the appearance and disappearance of phases in solubility equilibrium with the water.  It finds the identities of these phases automatically.  The user may specify which potential phases are allowed to form and which are not.  There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir.  Rate laws for irreversible reactions may be either relative rates or actual rates.  EQ6 is able to model both mineral dissolution and growth kinetics.  The user can specify modification or substitution of equilibrium constants by using options on the input file.  The output consists of an output file, a tab file (tables of output parameters), and a pickup file, which allows a restart capability.  The chief numerical method employed for equilibrium calculations is a hybrid Newton-Raphson technique.  This is supported by a set of algorithms which create and optimize starting values.  When actual rate laws are used, EQ6 integrates the resulting equations using a finite difference-based ODE solver.  EQ6 reads a secondary unformatted data file by EQPT, the EQ3/6 data file preprocessor.  There is currently a set of five data files.  Three of these may be used with either the Davies equation or the B-dot equation to describe the activity coefficients, and their use is restricted to modeling dilute solutions.  The other two of these use Pitzer's equations and are suitable for modeling solutions to high concentrations, though with fewer chemical components.  The temperature range of the thermodynamic data in the data files varies from 0 to 100°C.  The companion code EQ3NR must be used to initialize a reaction path calculation by EQ6.  EQ6 and the other codes in the EQ3/6 package are written in FORTRAN 77 and were originally developed to run under the UNIX operating system on computers ranging from workstations to supercomputers.

            c.2)  	General descriptions of the models, discussions of the limits of the applicability of each model, detailed instructions for executing the computer codes, including hardware and software requirements, input and output formats and explanations of each input and output variable and parameter (e.g., parameter name and units); listings of input and output files from a sample computer run; and reports on code verification, bench marking, validation, and quality assurance procedures.

A general description of EQ3/6 Version 8.0a is provided in the UM, including detailed instructions for executing the code (Wolery and Jarek 2003).  Lists of variable names are also provided in Wolery and Daveler (1992c) and Wolery (1992b).  Hardware and software requirements, and input and output formats with explanations of variables are provided in the UM with additional information in the VVP/VD (Wolery and Daveler 1992c and Wolery 1992b).  A series of listings of example input and output files are given in the UM, and additional files are provided in Wolery and Daveler (1992c) and Wolery (1992b).  Reports on code verification and validation are provided in the VVP/VD.  The verification and validation study involved 18 test cases that cover the functional requirements of the EQ3/6 code.  The UM and VVP/VD have been subjected to internal peer review, as indicated by QA sign-off sheets attached to the references.

Since the application of EQ3/6 to future CRAs has not yet been defined, potential limits of applicability for EQ3/6 will have to be evaluated on a case-by-case basis.  However, it is anticipated that EQ3/6 will be employed to simulate actinide chemistry.

c.3)  	Detailed descriptions of the structure of computer codes and complete listings of the source codes,

The generalized structure of the file system and information flow for the EQ3/6 code is summarized in Figure 1 of the UM (Wolery and Jarek 2003).  EQ3/6 is written in FORTRAN 77.  The hardware platform for EQ3/6 is any personal computer running a 32-bit Windows operating system (e.g., Windows 95 and onward).  Support for UNIX computers has been discontinued.  Hard disk drive space requirements will depend on the users' typical output file size.  EQ3NR output files (extension .3o) are quite small, typically <100 KB, whereas EQ6 output files (extension .6o) range from a typical 1 MB to tens of MBs, depending upon the time (reaction path) and printout intervals.

The EQ3/6 code was acquired from LLNL, and SNL does not have the source code.

c.4) 	Detailed descriptions of data collection procedures, sources of data, data reduction and analysis, and code input parameter development,

The EQ3/6 code depends on a database of thermodynamic constants characteristic of specific reactions.  Chemical potentials and Pitzer ion interaction parameters for the major elements are included in the EQ3/6 database.  Presumably, the EQ3/6 database will be similar to that used by FMT.  Constants for the actinides relevant to specific reactions described in Appendix SOTERM [CRA-2004] are taken from a variety of sources published in the scientific peer-reviewed literature.  As described in Appendix SOTERM, constants for the actinides were generated from fits to solubility data using the NONLIN program (Docket A-93-02, II-G-1, Ref. #477, and SNL 1996, cited in Appendix SOTERM).  The NONLIN program contains the same database of Pitzer ion interaction parameters and chemical potentials as used by EQ3/6, so that internal consistency is maintained in the generation of new constants for inclusion in the EQ3/6 database.  Details on the use of the NONLIN code are not provided in Appendix SOTERM of the CCA, but the reader is referred to the references above.  Although Appendix SOTERM identifies specific sources of thermodynamic data for the FMT code, it does not provide an indication of the specific database used for the PA calculations presented in the CCA.  Supplementary references cited in Appendix SOTERM also do not indicate which thermodynamic database was used for model calculations of actinide concentrations for the PA as presented in Table SOTERM-2 of Appendix SOTERM.  The database has undergone continuous revision since the CCA, which has probably resulted in improvements in its values and completeness, but has apparently obscured the identity of the database version specifically used for the CCA.  This issue is raised because the results of chemical equilibrium problems are primarily dependent on the thermodynamic data used to represent pertinent reactions.  As noted earlier, a complete copy of the database is included in Novak 1997, and this updated version was included in the EPA mandated PAVT (Docket A-93-02, II-G-26).

      c.5) 	Any necessary licenses,

The EQ3/6 code was acquired and licensed from LLNL.

            c.6)  	An explanation of the manner in which models and computer codes incorporate the effects of parameter correlation.

The effects of parameter correlation are not explicitly discussed in the UM and VVP/VD.  However, it is generally understood that equilibrium reactions result in nonlinear correlations between concentrations and master variables, such as pH or CO2(g) fugacity, because of various hydrolysis and complexation reactions.  These effects are explicitly accounted for in the reaction
stoichiometries in the  EQ3/6 thermodynamic database and related constants.
      d) 	The Administrator or the Administrator's authorized representative may verify results of computer simulations used to support any compliance application by performing independent simulations.  Data files, source codes, executable versions of computer software for each model, other material or information needed to permit the Administrator or the Administrator's authorized representative to perform independent simulations, and access to necessary hardware to perform such simulations, shall be provided within 30 calendar days of a request by the Administrator or the Administrator's authorized representative.

The Agency may elect to conduct independent evaluations of EQ3/6 at a later date.

EPA Findings

EPA reviewed all of the relevant documentation pertaining to EQ3/6 Version 8.0a as described above (e.g., UM, VVP/VD, and VD), as well as supplementary information provided by SNL.  The test cases summarized by SNL (2011) adequately represent calculations performed for WIPP PA and results of the test case calculations show that the EQ3/6 performance is acceptable.  However, as summarized in Section a.3.iv, some minor errors identified in the report should be corrected.

With the exception of the source code not being readily available, EPA found that SNL's QA requirements for PA and compliance assessment are in agreement with those specified in § 194.22, and that the code documentation for EQ3/6 is adequate and meets the requirements of  40 CFR Part 194.  SNL's documentation includes plan(s) for QA software, software requirements documentation, software design and implementation documentation, software verification and validation documentation, and user documentation.

References

ASME (American Society of Mechanical Engineers) 1990.  NQA-2a-1990 addenda, part 2.7, to ASME NQA-2-1989 edition, "Quality Assurance Requirements for Nuclear Facility Applications;" IBR approved for Sec. 194.22 and Sec. 194.23.

Babb, S.C. and C.F. Novak, 1997.  User's Manual for FMT Version 2.3:  A Computer Code Employing the Pitzer Activity Coefficient Formalism for Calculating Thermodynamic Equilibrium in Geochemical Systems to High Electrolyte Concentrations.  Document Version 2.3, Sandia National Laboratories, WPO # 43037.
Brush, L.H., Y. Xiong, J.W. Garner, A. Ismail, and G.T. Roselle, 2006.  Consumption of Carbon Dioxide by Precipitation of Carbonate Minerals Resulting from Dissolution of Sulfate Minerals in the Salado Formation in Response to Microbial Sulfate Reduction in the WIPP.  Sandia National Laboratories, Carlsbad, New Mexico.
Brush, L.H., Y. Xiong and J.J. Long, 2009.  Results of the Calculations of Actinide Solubilities for the WIPP CRA-2009 PABC.  Sandia National Laboratories, Carlsbad, New Mexico, October 2009, ERMS 552201.

Bynum, R.V., 1996.  "Analysis to Estimate the Uncertainty for Predicted Actinide Solubilities."  WBS <IP_ADDRESS>.1, Rev. 0, effective date 9/3/96 (WPO41374).
Chavez, M.J., 2011.  Re:  Input and Output File Request.  E-mail to J.A. Schramke (SC&A) from M.J. Chavez (SNL), February 9, 2011.
Clegg, S.L. and P. Brimblecombe, 1990.  "The solubility and activity coefficient of oxygen in salt solutions."  Geochimica Cosmochimica Acta 54:3315-3328.
DOE (U.S. Department of Energy) 1996.  Title 40 CFR Part 191 Compliance Certification Application for the Waste Isolation Pilot Plant, DOE/CAO-1996-2184, October 1996, Carlsbad Field Office, Carlsbad, New Mexico.

DOE (U.S. Department of Energy) 2004.  Title 40 CFR 191 Parts B and C Compliance Recertification Application, U.S. Department of Energy Field Office, March 2004.  Docket A-98-49 Category II-B2.
EPA (U.S. Environmental Protection Agency) 2006.  Technical Support Document for Section 194.24:  Evaluation of the Compliance Recertification Actinide Source Term and Culebra Dolomite Distribution Coefficient Values.  Office of Radiation and Indoor Air, Docket No: A-98-49, March 2006.

Fanghänel, T., and J.I. Kim, 1998.  "Spectroscopic evaluation of thermodynamics of trivalent actinides in brines."  Journal of Alloys and Compounds 271-273:728-737.

Fanghänel, T., V. Neck, and J.I. Kim, 1995.  "Thermodynamics of neptunium(V) in concentrated salt solutions: II. Ion interaction (Pitzer) Parameters for Np(V) hydrolysis species and carbonate complexes."  Radiochimica Acta 69:169-176.

Felmy, A.R., and J.H. Weare, 1986.  "The prediction of borate mineral equilibria in natural waters: Application to Searles Lake, California."  Geochimica et Cosmochimica Acta 50:2771-2783.

Felmy, A.R., D. Rai and M.J. Mason, 1991.  "The solubility of hydrous thorium(IV) oxide in chloride media: development of an aqueous ion-interaction model."  Radiochimica Acta 55:177-185.

Harvie, C.E., 1981.  "Theoretical Investigations in Geochemistry and Atom Surface Scattering."  PhD Dissertation, University of California, San Diego.
Harvie, C.E., N. Møller, and J.H. Weare, 1984.  "The prediction of mineral solubilities in natural waters:  The Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C."  Geochimica et Cosmochimica Acta 48:723-751.
IEEE (Institute of Electrical and Electronics Engineers) 1986.  IEEE Standard for Software Verification and Validation Plans, pp. 1012 - 1986, New York, New York:  IEEE Press.

Ismail, A.E., H. Deng, J.-H. Jang and T.J. Wolery, 2009.  Verification of FMT Database and Conversion to EQ3/6 Format.  Sandia National Laboratories, Carlsbad, New Mexico, January 13, 2009, ERMS 550689.

Jenne, E.A., 1981.  Geochemical Modeling:  A Review.  PNL-3574, Battelle Pacific Northwest Laboratory), Richland, Washington.

Lide, D.R., Ed., 1999.  CRC Handbook of Chemistry and Physics.  CRC Press, New York.

Novak, C.F., 1997.  "Calculation of Actinide Solubilities in WIPP SPC and ERDA6 Brines Under MgO Backfill Scenarios Containing Either Nesquehonite or Hydromagnesite as the Mg-CO3- Solubility-Limiting Phase.  Memorandum to R.V. Bynum, April 21, 1997.  WPO 38628, Sandia National Laboratories, Albuquerque, New Mexico.

Novak, C.F., I. Al Mahamid, K.A. Becraft, S.A. Carpenter, N. Hakem, and T. Prussin, 1996.  "Measurement and Thermodynamic Modeling of Np(V) Solubility in Dilute through Concentrated K2CO3 Media."  SAND96-1604J, Sandia National Laboratory, Albuquerque, New Mexico.

Novak, C.F., N.J. Dhooge, H.W. Papenguth, and R.F. Weiner, 1995.  "Systems Prioritization Method  -  Iteration 2 Baseline Position Paper:  Actinide Source Term."  Sandia National Laboratory, Albuquerque, New Mexico, dated March 31, 1995.

Pitzer, K.S., 1975.  Thermodynamics of electrolytes.  "V. Effects of higher-order electrostatic terms."  Journal of Solution Chemistry 4:249-265.
Pitzer, K.S., 1991.  "Ion interaction approach: theory and data correlation," Chapter 3 in Activity Coefficients in Electrolyte Solutions.  Ed. K.S. Pitzer.  CRC Press, 2[nd] Edition.

Plummer, L.N., D.L. Parkhurst, G.W. Fleming and S.A. Dunkle, 1988.  A Computer Program Incorporating Pitzer's Equations for Calculation of Geochemical Reactions in Brines.  U.S. Geological Survey, Water-Resources Investigations Report 88-4153, Reston, Virginia.
Rai, D., A.R. Felmy, S.M. Sterner, D.A. Moore and M.J. Mason, 1997.  "The solubility of Th(IV) and U(IV) hydrous oxides in concentrated NaCl and MgCl2 solutions."  Radiochimica Acta 79:239-247.
SC&A (S. Cohen and Associates) 2008.  "Review of MgO-Related Uncertainties in the Waste Isolation Pilot Plant."  SC&A, Inc., Vienna, Virginia.

Shock, E.L. and H.C. Helgeson, 1988.  "Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C."  Geochimica Cosmochimica Acta 52: 2009-2016.

Shock, E.L., H.C. Helgeson, and D.A. Sverjensky, 1989.  "Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species."  Geochimica et Cosmochimica Acta 53:2157-2183.

Shoemaker, P.E., 2011. Requested EQ3NR files. Letter to J.A. Schramke, July 21, 2011.

SNL (Sandia National Laboratories) 1996.  "Quality Assurance Document for EQ3/6 (Version 7.2a,b)."  Sandia National Laboratories.  Sandia WIPP Central Files ERMS #24125.

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SNL (Sandia National Laboratories) 2006a.  "Verification and Validation Plan/Validation Document for EQ3/6 Version 8.0."  Sandia National Laboratories, Albuquerque, New Mexico.  (ERMS# 543603)

SNL (Sandia National Laboratories) 2006b.  "Verification and Validation Plan/Validation Document for EQ3/6 Version 8.01."  Sandia National Laboratories, Albuquerque, New Mexico.  (ERMS# 544574)

SNL (Sandia National Laboratories) 2006c.  "Requirements Document for EQ3/6 (Version 8.0)."  Sandia National Laboratories.  Sandia WIPP Central Files ERMS #543602.

SNL (Sandia National Laboratories) 2006d.  "Quality Assurance Plan for EQ3/6 (Version 8.0)."  Sandia National Laboratories.  Sandia WIPP Central Files ERMS #543601.

SNL (Sandia National Laboratories) 2006e.  "Software Installation and Checkout for EQ3/6, Version 8.0."  Sandia National Laboratories, Albuquerque, New Mexico.  (ERMS# 544310)
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SNL (Sandia National Laboratories) 2011.  "Verification and Validation Plan/Validation Document for EQ3/6 Version 8.0a for Actinide Chemistry, Revision 1."  Document Version 8.2020, Carlsbad, New Mexico, May 12, 2011. (ERMS #555358)

TEA (Trinity Engineering Associates) 2004.  Review of Effects of Supercompacted Waste and Heterogeneous Waste Emplacement on WIPP Repository Performance.  Final Report.  Prepared for U.S. Environmental Protection Agency, Office of Radiation and Indoor Air, Washington, DC, March 17, 2004.

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Wolery, T. J., 1979.  "Calculation of Chemical Equilibrium between Aqueous Solutions and Minerals:  The EQ3/6 Software Package."  UCRL-52658.  Lawrence Livermore National Laboratory, Livermore, California.

Wolery, T.J., 1992a.  "EQ3/6, A Software Package for Geochemical Modeling of Aqueous Systems:  Package Overview and Installation Guide (Version 7.0)."  UCRL-MA- 1 10662-PT-I.  Lawrence Livermore National Laboratory, Livermore, California.

Wolery, T.J., 1992b.  "EQ3, A Computer Program for Geochemical Aqueous Speciation- Solubility Calculations:  Theoretical Manual, User's Guide, and Related Documentation (Version 7.0)."  UCRL-MA-110662-PT-III.  Lawrence Livermore National Laboratory, Livermore, California.

Wolery, T.J., 2008.  "Analysis Plan for EQ3/6 Analytical Studies, Task <IP_ADDRESS>."  AP-140, Rev. 0.  Sandia National Laboratories, Carlsbad, New Mexico.

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Software Package:  User's Guide and Related Documentation (Version 7.0)."  UCRL-MA-110662-PT-I.  Lawrence Livermore National Laboratory, Livermore, California

Wolery, T.J. and S.A. Daveler, 1992b.  "EQPT, A Data File Preprocessor for the EQ3/6 Software Package:  User's Guide and Related Documentation (Version 7.0)."  UCRL-MA-110662-PT-II.  Lawrence Livermore National Laboratory, Livermore, California.

Wolery, T.J. and S.A. Daveler, 1992c.  "EQ6, A Computer Program for Reaction Path Modeling of Aqueous Geochemical Systems:  Theoretical Manual, User's Guide, and Related Documentation (Version 7.0)."  UCRL-MA-110662-PT-IV.  Lawrence Livermore National Laboratory, Livermore, California.
Wolery, T.J. and R.L. Jarek, 2003.  "Software User's Manual for EQ3/6, Version 8.0."  U.S. Department of Energy, Office of Civilian Radioactive Waste Management, Las Vegas, Nevada.  Software Document Number 108 13-UM-8.0-00.

Xiong, Y., 2005.  Release of FMT_050405.CHEMDAT.  E-mail to J.F. Kanney and J.J. Long, April 5, 2005.  Sandia National Laboratories, Carlsbad, New Mexico, ERMS 539304.

Xiong, Y., L.H. Brush, A.E. Ismail and J.J. Long, 2009.  Uncertainty Analysis of Actinide Solubilities for the WIPP CRA-2009 PABC.  Sandia National Laboratories, Carlsbad, New Mexico, ERMS 552500.

 ATTACHMENT A:  DATABASE MIGRATION

The FMT database used in the PABC09 actinide solubility calculations was FMT_050405.CHEMDAT (Brush et al. 2009, Xiong 2005).  Ismail et al. (2009) describes the conversion of the FMT database FMT_050405.CHEMDAT to a format compatible with EQ3/6 (data0.fmt.R0).  The data included in the EQ3/6 database includes atomic weights for the elements in the database; log K data for aqueous species, gases and solid phases; and Pitzer parameters.

  Atomic Weights

Atomic weights are included in the EQ3/6 database to allow the conversion of input concentration units, for example mg/L, to units of molality (moles/kg solvent H2O) used in EQ3/6 calculations.  The source of the atomic weights cited in data0.fmt.R0 was "99lid via data0.ymp.R5." Neither data0.ymp.R5 nor data0.fmt.R0 provides information regarding this reference, although it is likely Lide (1999).  Information regarding the "99lid" reference should be included in the EQ3/6 database.

Atomic weights are included in data0.fmt.R0 for the elements listed in Table A-1.  FMT_050405.CHEMDAT provides atomic weight data for the elements in Table A-1 and for PosIon, NegIon, oxalate [C2O4[2-]], acetate [C2H3O2[-]], perchlorate [ClO4], lactate [C3H5O3[-]], EDTA [C10H12O8N2[4][-]] and citrate [C6H5O7[3-]].  PosIon and NegIon are pseudo-species included in the FMT database to permit charge balancing of the modeled solutions.  The pseudo-elements Null- and Null+ were included in data0.fmt.R0 with atomic weights of 1  10[-38] g/mole and the aqueous species NegIon and PosIon were assumed to be composed of the fictitious elements Null- and Null+, respectively.  Oxalate, acetate, perchlorate, lactate, EDTA and citrate were included in data0.fmt.R0 as auxiliary basis species.  Because molecular weights of the auxiliary basis species are calculated by EQ3/6 using chemical formulas and the atomic weights provided for the elements in Table A-1, molecular weights for oxalate, acetate, perchlorate, lactate, EDTA and citrate are not included in data0.fmt.R0.

                 Table A-1.	Elements Included in Data0.fmt.R0
Oxygen
Chloride
Neptunium
Americium
Hydrogen
Phosphorus
Boron
Potassium
Sulfur
Bromine
Magnesium
Thorium
Carbon
Nitrogen
Null-
Calcium
Sodium
Null+

The atomic weights listed for hydrogen, chlorine, boron and phosphorus in data0.fmt.R0 differ slightly from the values in FMT_050405.CHEMDAT because of an additional significant figure in the data0.fmt.R0 database.  The atomic weight of 32.06 g/mole for sulfur listed in FMT_050405.CHEMDAT differs slightly from the value of 32.066 g/mole included in data0.fmt.R0.  The atomic weights listed in data0.fmt.R0 are correct, based on a comparison to Lide (1999).

The atomic weight data in FMT_050405.CHEMDAT have had no effect on past WIPP PA calculations because all data were input in units of molarity (moles/L).  Similarly, the atomic weight data in data0.fmt.R0 are unlikely to affect future WIPP PA calculations performed using EQ3/6, because input data are likely to be in units of molarity or molality (moles/kg solvent H2O), which will not require use of the atomic weight data to obtain the molality units used in the EQ3/6 calculations.

 Strict Basis Species

EQ3/6 divides aqueous species in the database into three categories: strict basis species, auxiliary basis species and other aqueous species.  Each strict basis species represents a chemical element, with the exception of the O2(g) species that serves as the redox species.  The strict basis species included in data0.fmt.R0 are listed in Table A-2.  The information included in the EQ3/6 database for each strict basis species are the charge and the elemental composition of the species.  These data, which are checked by EQ3/6 during preprocessing, were visually examined and found to be complete and accurate.

                Table A-2.	Strict Basis Species in Data0.fmt.R0
H2O
Cl[-]
NpO2[+]
Am[3+]
H[+]
HPO4[2-]
B(OH)4[-]
K[+]
SO4[2-]
Br-
Mg[2+]
Th[4+]
HCO3[-]
NO3[-]
NegIon
Ca[2+]
Na[+]
PosIon

 Auxiliary Basis Species

Each auxiliary basis species represents an aqueous species that can be modeled to persist in solution without reacting to form its constituent elements.  Data included in data0.fmt.R0 for the auxiliary basis species include the charge, elemental composition, the identity and stoichiometry of the dissociation reaction, the associated log K for the reaction and the source of the log K data.

Oxalate is an example of an auxiliary basis species included in WIPP PA calculations.  Oxalate can react to form bicarbonate [HCO3[-]]:

                     C2O4[2-] + H2O + (1/2) O2(g)  2 HCO3[-]

Because WIPP PA calculations include the assumption that the organic ligands, including oxalate, acetate, citrate, EDTA and lactate, are neither consumed nor produced during the 10,000 year regulatory time period, the organic ligands are included as auxiliary basis species in data0.fmt.R0.  Because organic ligands are not modeled to be either consumed or produced, no log K data are required or provided for the organic ligands in the data0.fmt.R0 database.

The other species included as auxiliary basis species in data0.fmt.R0 are O2(aq), H2(aq), NH3(aq) and perchlorate.  The species O2(aq), H2(aq) and NH3(aq) are not included in the FMT_050405.CHEMDAT database, but were added to data0.fmt.R0.  Ismail et al. (2009) stated that the log K data for O2(aq) and H2(aq), originally derived from data reported by Shock et al. (1989), were obtained from data0.ymp.R5.  However, the cited reference in the data0.fmt.R0 database for these species is data0.ypf.R1.  The log K data for O2(aq) and H2(aq) are the same in all three databases (data0.fmt.R0, data0.ymp.R5 and data0.ypf.R1).  Citations for the original data source (Shock et al. 1989) should be included in data0.fmt.R0.

The source of the 25°C log K data for NH3(aq) is cited in data0.fmt.R0 as "DBConversion050405.xls."  Examination of the spreadsheet DBConversion050405_Rev3.xls cited by Ismail et al. (2009) showed that the standard chemical potentials (u[0]/RT) of NH3(aq) and NO3[-] were calculated from the free energy of formation data (ΔGf[0]) in data0.ymp.R5.  These data and standard chemical potential data for O2(g) (zero by convention) and for H[+] and H2O from Harvie et al. (1984) were used to calculate the log K value for the reaction as described below (Section A.4):

                    NH3(aq) + 2 O2(g) = NO3[-] + H[+] + H2O

The accuracy of the log K value for this reaction in data0.fmt.R0 was confirmed by independently performing the calculation.  The source citation should be corrected from ""DBConversion050405.xls" to "DBConversion050405_Rev3.xls" and the original sources of the free energy of formation and standard chemical potential data used in the calculation (Harvie et al. 1984, Shock and Helgeson 1988, Shock et al. 1989) should also be included in the source citation.

The standard chemical potential for perchlorate was included in the FMT database, but the FMT database did not include data for the O2(g) species required to calculate the log K for the reaction:

                          ClO4[-] = Cl[-] + 2 O2(g)

Consequently, the log K data for perchlorate were obtained from data0.ymp.R5.  Examination of data0.ymp.R5 showed that the data were obtained from this source.  However, the original data source for the log K values was not provided; an explanation of the original source of the perchlorate log K data in data0.ymp.R5 should be provided.

 Other Aqueous Species and Solid Phases

Data provided in the EQ3/6 database for aqueous species that are not strict basis species or auxiliary basis species include the charge, elemental composition, the identity and stoichiometry of the dissociation reaction, log K values for the reaction and the source of the log K values.  For solid phases, the data in the EQ3/6 database include the elemental composition, the identity and stoichiometry of the dissolution reaction, log K values for the reaction and the source of the log K values.  A field is also provided for the molar volume (V0PrTr), but because this parameter is unused in WIPP calculations, it was set equal to zero for all solid phases (Ismail et al. 2009).

The data for the aqueous species and solid phases in the FMT database are provided as the standard chemical potential (u[0]/RT) of each aqueous species or solid phase, which can be used to calculate the log K values for the appropriate dissociation or dissolution reaction.  The log K for a reaction can be calculated from the change in the chemical potentials of the reactants and products (Δu[0]r/RT) using the relationship:

                            logK= -Δur0/RT2.30259

Calculation of the log K values for the aqueous species and solids in data0.fmt.R0 from the standard chemical potential data in the FMT_050405.CHEMDAT database was described by Ismail et al. (2009) and documented in the spreadsheet DBConversion050405_Rev3.xls.  The log K values in data0.fmt.R0 were verified by independently performing calculations of the log K values from the standard chemical potential data for the AmEDTA[-] and Th(OH)4(aq) dissociation reactions and the anhydrite [CaSO4(s)], ThO2(am), Am(OH)3(s) and hydromagnesite5425 [Mg5(CO3)4(OH2)::4H2O(s)] dissolution reactions.

Some of the standard chemical potential data in FMT_050405.CHEMDAT were originally calculated from log K values in the literature.  As an additional verification of the conversion of the standard chemical potential data in FMT_050405.CHEMDAT to log K data in data0.fmt.R0, the log K values in the original references were compared to the log K data in the EQ3/6 database for the aqueous species AmCO3[+] (Fanghänel and Kim 1998) and NpO2OH(aq) (Fanghänel et al. 1995) and the solid phase ThO2(am) (Felmy et al. 1991) and found to be equivalent.

FMT_050405.CHEMDAT included an arbitrary standard chemical potential value of 500 for the aqueous species NaOH(aq), HCl(aq), HClO4(aq), PosIon(OH)(aq), HNegIon(aq) and an arbitrary standard chemical potential value of 999.999 for the aqueous species UnuCat#1+, UnuAn#2-, UnuAn#3-, UnuAn#4- and UnuNeu#1(aq).  These data were not included in the data0.fmt.R0 database.  In addition, the FMT_050405.CHEMDAT database incorporated data for uranium and plutonium aqueous and solid species.  Because WIPP PA calculations do not include direct calculations of uranium and plutonium reactions, these data were not included in data0.fmt.R0 (Ismail et al. 2009).  Database entries for CO2("solid",DISABLED), H[+](solid) and OH[-]/H2O(solid) are also present in FMT_050405.CHEMDAT with standard chemical potential values of zero; these phases were not included in data0.fmt.R0.  These omissions were appropriate, as these data are not needed for the EQ3/6 verification calculations or WIPP PA calculations.

The solid phases in FMT_050405.CHEMDAT were compared to the solid phases in data0.fmt.R0.  With the exception of the omissions noted above, all solid phases were transferred from the FMT database to the EQ3/6 database.  The americium(III) aqueous species in the FMT database were compared to the americium(III) species in the EQ3/6 database and it was confirmed that all americium(III) species were transferred.

Data0.fmt.R0 does not contain information regarding the sources of the log K data for aqueous species unless they are auxiliary basis species.  The database also does not provide log K data source information for the solid phases.  The data sources should be added to the database, citing either the references that provided the log K data or the sources of the standard chemical potentials used to calculate the log K values.
 Gas Phase Data

FMT_050405.CHEMDAT does not contain gas phase data.  The gas phases included in the data0.fmt.R0 database include methane [CH4(g)], carbon dioxide [CO2(g)], hydrogen [H2(g)], water [H2O(g)] and oxygen [O2(g)].  Data provided for the gas phases include elemental composition, the gas dissolution reaction in terms of the strict basis species and the corresponding log K values.  The source of the log K data in data0.fmt.R0 for gaseous methane, hydrogen and water was data0.ymp.R5.  The data0.ymp.R5 database provides the original data sources for the gas phases and these sources should be documented in the data0.fmt.R0 database.

Gaseous oxygen [O2(g)] is a strict basis species and its dissolution reaction is provided by the data for O2(aq), which is an auxiliary basis species.  Consequently, the data block for O2(g) in the gas phase section of the database simply equates O2(g) with itself.  The gaseous carbon dioxide log K at 25°C was obtained using a standard chemical potential of -159.092 for gaseous carbon dioxide that was hard-coded in FMT Version 2.4.  Calculation of the log K value for the gaseous carbon dioxide reaction in the database was verified using this standard chemical potential.

 Pitzer Parameters

The Pitzer parameters used to calculate activity coefficients in high-ionic-strength solutions and included in the FMT_050405.CHEMDAT and data0.fmt.R0 databases are:

 The A[φ] Debye-Hückel parameter
 Single electrolyte parameter values for cation-anion (ca) pairs: α1, α2, β[0], β[1], β[2] and C[φ]
 Common-ion two electrolyte parameter values for cation-cation (cc') and anion-anion (aa') pairs: ϴcc' and ϴaa'
 Common-ion two-electrolyte parameter values for each cation-cation-anion (cc'a) and anion-anion-cation triplet (aa'c): Ψcc'a and Ψaa'c
 Neutral ion parameter values for each neutral ion-cation (nc) and neutral ion-anion (na) pair: λnc and λna
 Neutral ion-cation-anion (nca) interaction parameters for each triplet: ξnca

Non-zero Pitzer parameters were extracted from FMT_050405.CHEMDAT (Ismail et al. 2009).  EQ3/6 uses a temperature-dependent model for Pitzer parameters, but all WIPP PA calculations are carried out assuming a temperature of 25°C.  Consequently, only the parameters required for calculating Pitzer parameters at 25°C are nonzero in the data0.fmt.R0 database.

 Debye-Hückel parameter A[φ]

FMT uses a hard-coded Debye-Hückel A[φ] value of 0.39, which is the value cited in Harvie et al. (1984).  However, Plummer et al. (1988) determined that the A[φ] value used by Harvie et al. (1984) was actually 0.392, which is the correct value.  Because the value of 0.39 is used in the FMT calculations, A[φ] was set equal to 0.39 in data0.fmt.R0 to maintain consistency (SNL 2011), but this value should be corrected to 0.392 after the EQ3/6 code validation and verification effort is complete.

 Single Electrolyte Parameters

The single electrolyte Pitzer parameters for cation-anion pairs include α1, α2, β[0], β[1], β[2] and C[φ].  The only conversion of the parameters from FMT_050405.CHEMDAT was for α1 and α2, which are used in the equation to calculate the term B[φ]MX for the electrolyte MX (Pitzer 1991):

     B[φ]MX = β[0]MX + β[1]MX exp(-α1I[1/2]) + β[2]MX exp(-α2I[1/2])

In the FMT database, the entries for the single electrolyte parameters include a code for the α1 and α2 values (Table A-3).

           Table A-3.	FMT Database Codes for α1 and α2 Parameters
                             (Babb and Novak 1997)
                                     Code
                            α1 (kg[1/2]/mol[1/2])
                            α2 (kg[1/2]/mol[1/2])
                                  Electrolyte
                                       1
                                      2.0
                                     12.0
                  1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 2:1, 3:1, 4:1
                                       2
                                      1.4
                                     12.0
                                      2:2
                                       3
                                      1.4
                                     50.0
                                 2:3, 2:5, 3:2

Transfer of the single-electrolyte parameters for the selected "Code 1" electrolytes Na[+]  -  Cl[-], K[+]  -  NpO2CO3[-], Na[+]  -  B4O5(OH)4[2][-], Ca[2+]  -  OH[-] and Ca[2+]  -  HCO3[-] was verified by comparing the α1, α2, β[0], β[1], β[2] and C[φ] values in FMT_050405.CHEMDAT to the values in data0.fmt.R0.  As noted in FMT_050405.CHEMDAT and by SNL (2011), Harvie et al. (1984) provides a Na[+]  -  Cl[-] β[1] value of 0.2644, which is included in the FMT database.  The correct value appears to be 0.2664 (Pitzer 1991, SNL 2011), but the β[1] value of 0.2644 was retained in data0.fmt.R0 to maintain consistency with FMT_050405.CHEMDAT.

For all 2:2 electrolytes, the α1 and α2 parameters in data0.fmt.R0 were examined and found to be correct (Table A-3).  Ca[2+]  -  SO4[2-] and Mg[2+]  -  SO4[2-] are the only 2:2 electrolytes in the FMT database with nonzero β[0], β[1], β[2] or C[φ] parameters.  Transfer of the single-electrolyte parameters for the electrolytes Ca[2+]  -  SO4[2-] and Mg[2+]  -  SO4[2-] was verified by comparing the parameter values in the FMT and EQ3/6 databases.

For electrolytes that do not include a univalent cation or anion and that include a cation or anion with a valence of 3 or higher (Code 3), the α1 and α2 parameters in data0.fmt.R0 were verified by comparison of data in data0.fmt.R0 with the values listed in Table A-3.  Transfer of the single-electrolyte parameters for randomly selected "Code 3" electrolytes Mg[2+]  -  NpO2(CO3)3[5-], Am[3+]  -  SO4[2-] and Th[4+]  -  SO4[2-] was verified by comparing the parameter values in the FMT and EQ3/6 databases.

 Common-Ion Two-Electrolyte Parameters

The common-ion two-electrolyte Pitzer parameters for cation-cation and anion-anion pairs are ϴcc' and ϴaa', respectively.  The ϴcc' and ϴaa' values in data0.fmt.R0 were verified by comparing them to the values in FMT_050405.CHEMDAT.  During the verification process, it was noted that reference for the Cl[-]  -  NpO2(CO3)2[3-] ϴaa' (Fanghänel et al. 1995) is missing from data0.fmt.R0.  This source information should be added to the Cl[-]  -  NpO2(CO3)2[3-] ϴaa' data block.

The common-ion two-electrolyte Pitzer parameters for cation-cation-anion and anion-anion-cation triplets are Ψcc'a and Ψaa'c, respectively.  Transfer of these parameters from FMT_050405.CHEMDAT to data0.fmt.R0 was checked for the randomly selected triplets Na[+]  -  K[+]  -  Cl[-], Na[+]  -  H[+]  -  HSO4[-], Ca[2+]  - Mg[2+]  -  SO4[2-], Cl[-]  -  SO4[2-]  -  Mg[2+], Cl[-]  -  B(OH)4[-]  -  Na[+], SO4[2-]  -  OH[-]  -  Na[+] and HCO3[-]  -  ClO4[-]  - Na[+].  Comparison of these Ψcc'a and Ψaa'c values in the two databases indicate that the data were transferred correctly.

 Neutral Ion Parameters

The Pitzer parameters for neutral ion-cation pairs, neutral ion-anion pairs and neutral ion-neutral ion pairs are λnc, λna and λnn, respectively.  Transfer of the λnc and λna parameters from FMT_050405.CHEMDAT to data0.fmt.R0 was verified by comparing λnc and λna values for the randomly selected neutral ion pairs CO2(aq)  -  Ca[2+], B(OH)3(aq)  -  Na[+], Am(OH)3(aq)  -  K[+], CO2(aq)  -  SO4[2-], H3PO4(aq)  -  H2PO4[2-] and NpO2Acetate(aq)  -  Cl[-].  During the review of the λnc parameters, it was noted that the cited source of λnc for B(OH)3(aq)  -  Na[+] is Harvie et al. (1984).  However, the source citation should be changed to the correct citation, which is Felmy and Weare (1986).

Because FMT_050405.CHEMDAT does not include data for O2(aq), the λnc and λna parameters for O2(aq) were obtained from data0.ypf.R1.  These parameters were verified by comparing the values in data0.fmt.R0 and data0.ypf.R1.  Within data0.fmt.R0, the original source of the data (Clegg and Brimblecombe 1990) is also cited.  Pitzer data were not included for H2(aq) because they were not available in data0.ymp.R5.  No λnn parameter values are listed in FMT_050405.CHEMDAT, and λnn values are consequently not included in data0.fmt.R0.

The neutral ion-cation-anion interaction Pitzer parameter for each triplet is ξnca.  The only ξnca data in FMT_050405.CHEMDAT are for the triplets B(OH)3(aq)  -  Na[+]  -  SO4[2-] and B(OH)3(aq)  -  Na[+]  -  SO4[2-].  Comparison of these ξnca values indicated the data were accurately transferred from FMT_050405.CHEMDAT to data0.fmt.R0.  Because FMT_050405.CHEMDAT does not include data for O2(aq), the ξnca parameters for O2(aq)  -  cation  -  anion triplets were obtained from data0.ypf.R1.  These parameters were verified by comparing the values in data0.fmt.R0 and data0.ypf.R1.  Within data0.fmt.R0, the original source of the data (Clegg and Brimblecombe 1990) is also cited.

 Summary of Database Review Findings

The atomic weight data in the data0.fmt.R0 database are accurate and complete and the aqueous speciation, solid phase solubility and Pitzer parameter data in FMT_050405.CHEMDAT were accurately and completely incorporated in the data0.fmt.R0 database.  However, the database documentation should be corrected and more complete source information should be provided:

 The "99lid" reference for the atomic weight data should be added to the data0.fmt.R0 reference list
 The original source (Shock et al. 1989) of the log K data for the auxiliary basis species O2(aq) and H2(aq) should be included in the data source citations in data0.fmt.R0
 The source citation for the NH3(aq) log K value should be changed from "DBConversion050405.xls" to "DBConversion050405_Rev3.xls" and the original sources of the data used to calculate the log K value (Harvie et al. 1984, Shock and Helgeson 1988, Shock et al. 1989) should be added to the data source citation
 The original source of the perchlorate log K data should be added to the data source citation
 The cited source of the log K data for gaseous methane, hydrogen and water in the data0.fmt.R0 database was data0.ymp.R5; the original sources of the gas phase data should be documented within data0.fmt.R0
 For all aqueous species other than the strict basis species and auxiliary basis species, the log K data sources within data0.fmt.R0 should be provided
 The log K data sources for the solid phases should be provided within data0.fmt.R0
 A reference to Fanghänel et al. (1995) in the Cl[-]  -  NpO2(CO3)2[3-] ϴaa' data block should be provided within data0.fmt.R0
 The source of λnc for B(OH)3(aq)  -  Na[+] in data0.fmt.R0 is incorrectly listed as Harvie et al. (1984); this citation should be corrected to Felmy and Weare (1986)

SNL (2011) identified two parameters in the data0.fmt.R0 database that should be corrected: the A[φ] Debye-Hückel parameter should be changed from 0.30 to 0.392 and the Na[+]  -  Cl[-] β[1] value of 0.2644 should be changed to 0.2664.  Database version data0.fmt.R1 is the same as database version data0.fmt.R0, except these two parameters have been corrected.  This corrected database should be used in future WIPP EQ3/6 calculations after the corrections and additions noted above for data0.fmt.R0 are implemented.


[Federal Register Volume 77, Number 175 (Monday, September 10, 2012)]
[Notices]
[Pages 55513-55514]
[FR Doc No: 2012-22140]

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SECURITIES AND EXCHANGE COMMISSION

[Release No. 34-67776; File No. SR-Phlx-2012-110]

Self-Regulatory Organizations; NASDAQ OMX PHLX LLC; Notice of
Filing and Immediate Effectiveness of a Proposed Rule Change Relating
to the Elimination of a Reversal and Conversion Fee Cap

September 4, 2012.
    Pursuant to Section 19(b)(1) of the Securities Exchange Act of 1934
(``Act''),\1\ and Rule 19b-4 thereunder,\2\ notice is hereby given that
on August 24, 2012, NASDAQ OMX PHLX LLC (``Phlx'' or ``Exchange'')
filed with the Securities and Exchange Commission (``SEC'' or
``Commission'') the proposed rule change as described in Items I, II,
and III below, which Items have been prepared by the Exchange. The
Commission is publishing this notice to solicit comments on the
proposed rule change from interested persons.
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    \1\ 15 U.S.C. 78s(b)(1).
    \2\ 17 CFR 240.19b-4.
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I. Self-Regulatory Organization's Statement of the Terms of Substance
of the Proposed Rule Change

    The Exchange proposes to remove a fee cap on equity options
transactions on certain reversals and conversion strategies.
    The text of the proposed rule change is available on the Exchange's
Web site at http://nasdaqtrader.com/micro.aspx?id=PHLXfilings, at the

principal office of the Exchange, on the Commission's Web site at
http://www.sec.gov, and at the Commission's Public Reference Room.

II. Self-Regulatory Organization's Statement of the Purpose of, and
Statutory Basis for, the Proposed Rule Change

    In its filing with the Commission, the Exchange included statements
concerning the purpose of and basis for the proposed rule change and
discussed any comments it received on the proposed rule change. The
text of these statements may be examined at the places specified in
Item IV below. The Exchange has prepared summaries, set forth in
sections A, B, and C below, of the most significant aspects of such
statements.

A. Self-Regulatory Organization's Statement of the Purpose of, and the
Statutory Basis for, the Proposed Rule Change

1. Purpose
    The purpose of the proposed rule change is to remove a fee cap on
equity options transactions on certain reversals and conversion
strategies. The fee cap was intended to incentivize market participants
by capping option transaction fees related to reversal and conversion
strategies to encourage trading on the Exchange and the Exchange
believes such a fee cap is no longer necessary. Reversals are
established by combining a short stock position with a short put and a
long call position that shares the same strike and expiration.
Conversions are established by combining a long position in the
underlying security with a long put and a short call position that
shares the same strike and expiration.
    The Exchange proposes to eliminate this cap for all market
participants relating to option transaction fees in Multiply Listed
Options (Section II of the Pricing Schedule) of $500 per day for
reversal and conversion strategies executed on the same trading day in
the same options class (``Reversal and Conversion Cap''). The Reversal
and Conversion Cap applies only to executions occurring on either of
the two days preceding the standard options expiration date, which
typically was the third Thursday and Friday of every month.
2. Statutory Basis
    The Exchange believes that its proposal to amend its Pricing
Schedule is consistent with Section 6(b) of the Act \3\ in general, and
furthers the objectives of Section 6(b)(4) of the Act \4\ in
particular, in that it is an equitable allocation of reasonable fees
and other charges among Exchange members and other persons using its
facilities.
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    \3\ 15 U.S.C. 78f(b).
    \4\ 15 U.S.C. 78f(b)(4).
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    The Exchange believes that the proposed elimination of the Reversal
and Conversion Cap is reasonable because the Exchange previously capped
the option transaction fees in Multiply Listed options for reversals
and conversions in an effort to incentivize market participants, but
the Exchange believes such an incentive is no longer necessary. The
Exchange also believes that this proposal is equitable and not unfairly
discriminatory because the Exchange is eliminating the Reversal and
Conversion Cap for all members and the Exchange believes that market
participants will continue to transact in Multiply Listed options for
reversals and conversions.

B. Self-Regulatory Organization's Statement on Burden on Competition

    The Exchange does not believe that the proposed rule change will
impose any burden on competition not necessary or appropriate in
furtherance of the purposes of the Act.

C. Self-Regulatory Organization's Statement on Comments on the Proposed
Rule Change Received From Members, Participants, or Others

    No written comments were either solicited or received.

III. Date of Effectiveness of the Proposed Rule Change and Timing for
Commission Action

    The foregoing rule change has become effective pursuant to Section
19(b)(3)(A)(ii) of the Act.\5\ At any time within 60 days of the filing
of the proposed rule change, the Commission summarily may temporarily
suspend such rule change if it appears to the Commission that such
action is necessary or appropriate in the public interest, for the
protection of investors, or otherwise in furtherance of the purposes of
the Act. If the Commission takes such action, the Commission shall
institute proceedings to determine whether the proposed rule should be
approved or disapproved.
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    \5\ 15 U.S.C. 78s(b)(3)(A)(ii).
---------------------------------------------------------------------------

IV. Solicitation of Comments

    Interested persons are invited to submit written data, views, and
arguments concerning the foregoing, including whether the proposed rule
change is consistent with the Act. Comments may be submitted by any of
the following methods:

Electronic Comments

     Use the Commission's Internet comment form (http://www.sec.gov/rules/sro.shtml); or
     Send an email to<EMAIL_ADDRESS>Please include
File No. SR-Phlx-2012-110 on the subject line.

Paper Comments

     Send paper comments in triplicate to Elizabeth M. Murphy,
Secretary, Securities and Exchange Commission, 100 F Street NE.,
Washington, DC 20549-1090.

All submissions should refer to File No. SR-Phlx-2012-110. This file
number should be included on the subject line if email is used. To help
the Commission process and review your comments more efficiently,
please use only one method. The Commission will post all comments on
the Commission's Internet Web site (http://www.sec.gov/rules/sro.shtml). Copies of the submission, all subsequent amendments, all
written statements with respect to the proposed rule change that are
filed with the Commission, and all written communications relating to
the proposed rule change between the Commission and any person, other
than those that may be withheld from the public in accordance with the
provisions of 5 U.S.C. 552, will be available for Web site viewing and
printing in the Commission's Public Reference Room, 100 F Street NE.,
Washington, DC 20549, on official business days between the hours of
10:00 a.m. and 3:00 p.m. Copies of such filing also will be available
for inspection and copying at the principal office of the Exchange. All
comments received will be posted without change; the Commission does
not edit personal identifying information from submissions. You should
submit only information that you wish to make available publicly. All
submissions should refer to File No. SR-Phlx-2012-110 and should be
submitted on or before October 1, 2012.
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    \6\ 17 CFR 200.30-3(a)(12).

    For the Commission, by the Division of Trading and Markets,
pursuant to delegated authority.\6\
Kevin M. O'Neill,
Deputy Secretary.
[FR Doc. 2012-22140 Filed 9-7-12; 8:45 am]
BILLING CODE 8011-01-P