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THE SALT NORM: a Quantitative Chemical Mineralogical Characterization of Natural Waters

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THE SALT NORM: a Quantitative Chemical Mineralogical Characterization of Natural Waters THE SALT NORM: A Quantitative Chemical Mineralogical Characterization of Natural Waters M.W. Bodine, Jr. and Blair F. Jones U.S. GEOLOGICAL SURVEY Water Resources Investigations Report 86 4086 UNITED STATES DEPARTMENT OF THE INTERIOR DONALD P. HODEL, Secretary GEOLOGICAL SURVEY Dallas L. Peck, Director For additional information Copies of this report can be write to: purchased from: Project Chief Open-File Services Section U.S. Geological Survey Distribution Branch MS 432, National Center U.S. Geological Survey Reston, Virginia 22092 Box 25425, Federal Center Denver, Colorado 80225 CONTENTS Abstract.................................................................. 1 Introduction.............................................................. 2 Acknowledgments......................................................... 3 The SNORM Program......................................................... 3 Solutes................................................................. 4 Carbonate-Bicarbonate Modifications.................................. 6 Carbonate fraction in analyzed (bi)carbonate alkalinity........... 6 Carbonate-bicarbonate assignment to normative salts............... 8 Boron Modifications.................................................. 9 Cation-Anion Charge Balance.......................................... 9 Normative Salts......................................................... 11 Occurrence as Salt Minerals.......................................... 11 Compound Salts....................................................... 12 Salt Stability Criteria.............................................. 13 Salt Composition Modifications....................................... 19 Normative Salt Assemblages.............................................. 20 Eligible Salts....................................................... 20 Number of Salts in the Assemblage.................................... 22 Prohibited Salt Associations......................................... 23 Hydration-Dehydration Equilibria..................................... 24 Simple Salt Assemblages................................................. 26 Interpretation of Salt Norms.............................................. 27 Meteoric Norms.......................................................... 38 Marine Norms............................................................ 39 Diagenetic Norms........................................................ 45 Summary................................................................. 47 References................................................................ 48 Appendix I: Source Codes................................................. 53 Program SNORM........................................................ 53 Subroutine PREP................................................... 58 Subroutine SALWAT................................................. 66 Subroutine LOAD................................................... 70 Subroutine JOIN................................................... 75 Subroutine PICK................................................... 81 Subroutines ARRAY, CONVT, and DGELG............................... 83 Subroutine SWAP................................................... 85 Subroutine PRINT.................................................. 85 NEODAT (data file of constants for SNORM)............................ 96 Appendix II: Structure of SNORM.......................................... 98 -iii- Appendix III: User Procedures and Options................................. 106 Designating and creating input file.................................. 106 Designating output devices........................................... 108 Designating character of output...................................... 109 Designating solute modifications..................................... Ill Appendix IV: Examples of SNORM Output.............................. In pocket Standard format................................................ In pocket Short line-length format........................................ In pocket Appendix V: Phase Relations among Normative Salts......................... 112 Ca-Mg-K-Na sulfate salts............................................. 113 Ca-Mg-Na borate salts................................................ 121 Ca-Mg-Na phosphate and fluoride salts................................ 127 Equilibria involving three anions.................................... 129 FIGURES Diagrams showing: 1. Calculated stability relations among Na2C03-NaHC03-H20 salts..... 16 2. Hydroxyapatite-whitlockite stability relations................... 18 3. Relative proportions of calcium, carbonate species, and sulfate in natural waters and character of precipitated salts............ 29 4 Diagnostic chart for normative salts............................. 37 V-l. Calculated phase relations in the CaC03-MgC03-Na2 (2HC03 ,C03)-H20 salt system...................................................... 112 V-2. Calculated phase relations in the CaSQ,-MgSO,-K2SO,-Na2SO,-H20 salt system within the 0.726-0.665 water activity interval....... 118 V-3. Calculated phase relations in the CaSO -MgSO.-K^SO.-Na0 SO,-H00 4424242 salt system within the 0845-0.811 water activity interval........ 119 V-4. Calculated phase relations among (bi)carbonate and sulfate nor­ mative salts..................................................... 120 V-5. Calculated relations among (bi)carbonate and sulfate simple-salt components of normative salts.................................... 121 V-6. Calculated phase relations in the CaCl -MgCl -K Cl -Na C1 2-H20 salt system...................................................... 122 V-7. Calculated phase relations in the Ca-Mg-Cl.-CO -H20 salt system.. 122 V-8. Calculated phase relations among sulfate and chloride salts...... 123 V-9. Calculated relations of chloride with (bi)carbonate and sulfate simple salt components........................................... 124 V-10. Calculated phase relations in the Ca-Mg-K-Cl-NO -H20 salt system. 125 V-ll. Calculated relations of nitrate among (bi)carbonate, sulfate, and chloride simple salt components.............................. 126 -iv- V-12. Suggested phase relations in the Ca-Mg-PO^-F-H20 salt system..... 127 V-13. Calculated phase relations among Ca-Mg fluoride salts and coexisting carbonate, sulfate, and chloride salts................ 128 TABLES 1. Solutes in water analyses that SNORM recasts into the normative salt assemblage................................................... 4 2. Abbreviations of normative salts in SNORM and their chemical formulae.......................................................... 5 3. Normative borate salts, their chemical formula with anion charge per formula unit and per boron; and their modified chemical for­ mula with anion anion charge per formula unit and per boron that yields identical borate charge per boron for each................. 10 4. Standard chemical potential values and sources.................... 14 5. Salts excluded from assemblages in SNORM as a function of charge ratios of selected cation and anion groups of solutes...... 21 6. Prohibited associations in normative salt assemblages....... In pocket 7. Water activities (a-a n ) and indicator salts for hydration- **rt \J dehydration equilibria in SNORM................................... 25 8. Major solute concentrations and major-ion normative salts for mean compositions of seawater and world river waters.............. 30 9* Salt norms of representative water samples........................ 32 10. Salinity, major anion concentration, and salt norms for hyper- saline marine liquors from surface evaporation ponds.............. 41 11. Salt norms for selected analyses of groundwaters from the salt lake areas of the Yilgarn Block, Western Australia................ 42 12. Salt norms for representative brines from sabkhas south of the Bardawil Lagoon, north Sinai...................................... 46 II-l. Subprograms in SNORM and their major operational features......... 99 II-2. Solutes and salt components in SNORM data file (NEODAT)........... 103 II-3. Salts in SNORM data file (NEODAT) and their chemical formulae..... 104 II-4. "Base salts" excluded from trial "base salt assemblages" in SNORM as a function of charge ratios of selected cation and anion groups of solutes............................................ 105 II-5. Prohibited "base salt" associations in SNORM's base-salt associations................................................ In pocket III-l. Default concentration units in SNORM output....................... 110 V-l. Calculated water activities for equilibria in the CaSO -MgSO - K0 SO.-Na0 SO -H00 system at 25°C................................... 114 ^4 242 V-2. Stable four-salt sulfate and coexisting chloride salt assem­ blages in the 25°C Ca-Mg-K-Na-S04-Cl-H20 system................... 115 -v- V-3. Stable sulfate salt associations in the 25 C Ca-Mg-K-Na-SO^-Cl- 1^0 system in assemblages with two or more chloride salts......... 116 V-4. Stable four-salt sulfate assemblages in the CaSO^-MgSO^-^SO^- Na2 SO^-H20 system................................................. 117 V-5. Prohibited salt associations involving three or more anions and their permissable isochemical equivalents......................... 129 -vi- ABSTRACT The new computer program SNORM calculates the salt norm from the chemical composition of a natural water. The salt norm is the quantitative ideal equilibrium assemblage that would crystallize if the water evaporated to & dryness at 25 C and 1 bar pressure under atmospheric
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