Understanding Variation in Partition Coefficient, Kd, Values Volume II

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ABSTRACT This two-volume report describes the conceptualization, measurement, and use of the partition (or distribution) coefficient, K d, parameter, and the geochemical aqueous solution and sorbent properties that are most important in controlling adsorption/retardation behavior of selected contaminants. The report is provided for technical staff from EPA and other organizations who are responsible for prioritizing site remediation and waste management decisions. Volume I discusses the technical issues associated with the measurement of K d values and its use in formulating the retardation factor, R f. The K d concept and methods for measurement of K d values are discussed in detail in Volume I. Particular attention is directed at providing an understanding of: (1) the use of K d values in formulating R f, (2) the difference between the original thermodynamic K d parameter derived from ion-exchange literature and its “empiricized” use in contaminant transport codes, and (3) the explicit and implicit assumptions underlying the use of the K d parameter in contaminant transport codes. A conceptual overview of chemical reaction models and their use in addressing technical defensibility issues associated with data from K d studies is presented. The capabilities of EPA’s geochemical reaction model MINTEQA2 and its different conceptual adsorption models are also reviewed. Volume II provides a “thumb-nail sketch” of the key geochemical processes affecting the sorption of selected inorganic contaminants, and a summary of K d values given in the literature for these contaminants under oxidizing conditions. The contaminants chosen for the first phase of this project include chromium, cadmium, cesium, lead, plutonium, radon, strontium, thorium, tritium ( 3 H), and uranium. Important aqueous speciation, (co)precipitation/dissolution, and adsorption reactions are discussed for each contaminant. References to related key experimental and review articles for further reading are also listed. vii
CONTENTS NOTICE .................................................................... ii FOREWORD ................................................................ iii ACKNOWLEDGMENTS .......................................................v FUTURE UPDATES .......................................................... vi ABSTRACT ................................................................ vii LIST OF FIGURES .......................................................... xiii LIST OF TABLES ............................................................xv 1.0 Introduction ............................................................. 1.1 2.0 The K d Model ........................................................... 2.1 3.0 Methods, Issues, and Criteria for Measuring K d Values ........................... 3.1 Page 3.1 Laboratory Batch Methods .............................................. 3.1 3.2 Laboratory Flow-Through Method ........................................ 3.1 3.3 Other Methods ....................................................... 3.2 3.4 Issues ............................................................... 3.2 4.0 Application of Chemical Reaction Models ..................................... 4.1 5.0 Contaminant Geochemistry and K d Values .................................... 5.1 5.1 General ............................................................. 5.1 5.2 Cadmium Geochemistry and K d Values .................................... 5.5 5.2.1 Overview: Important Aqueous- and Solid-Phase Parameters Controlling Retardation ............................................ 5.5 5.2.2 General Geochemistry ............................................. 5.5 5.2.3 Aqueous Speciation ............................................... 5.6 5.2.4 Dissolution/Precipitation/Coprecipitation .............................. 5.8 5.2.5 Sorption/Desorption ............................................... 5.9 5.2.6 Partition Coefficient, K d , Values .................................... 5.10 5.2.6.1 General Availability of K d Values .............................. 5.10 5.2.6.2 Look-Up Tables ............................................ 5.11 5.2.6.2.1 Limits of K d Values with Aluminum/Iron-Oxide Concentrations ..... 5.11 5.2.6.2.2 Limits of K d Values with Respect to CEC ....................... 5.12 5.2.6.2.3 Limits of K d Values with Respect to Clay Concentrations .......... 5.12 5.2.6.2.4 Limits of K d Values with Respect to Concentration of Organic Matter ............................................ 5.12 5.2.6.2.5 Limits of K d Values with Respect to Dissolved Calcium, viii
Page 1 and 2: United States Office of Air and Rad
Page 3 and 4: NOTICE The following two-volume rep
Page 5 and 6: This publication is the result of a
Page 7: TO COMMENT ON THIS GUIDE OR PROVIDE
Page 11 and 12: 5.6 Plutonium Geochemistry and K d
Page 13 and 14: Appendix C - Partition Coefficients
Page 15 and 16: Figure E.1. Variation of K d for Cr
Page 17 and 18: Table 5.16. Uranium(VI) aqueous spe
Page 19 and 20: Table H.4. Look-up table for estima
Page 21 and 22: 1.0 Introduction The objective of t
Page 23 and 24: eviewed. The main focus of Volume I
Page 25 and 26: 2.0 The Kd Model The simplest and m
Page 27 and 28: no longer be used to perform the in
Page 29 and 30: of the velocity of the contaminant
Page 31 and 32: An increasing body of evidence indi
Page 33 and 34: contaminants of interest and the as
Page 35 and 36: dissolved gases and complexing liga
Page 37 and 38: Element Table 5.2. Concentrations o
Page 39 and 40: 5.6
Page 41 and 42: 5.8
Page 43 and 44: 5.2.4 Dissolution/Precipitation/Cop
Page 45 and 46: 1980). In contrast, zinc almost com
Page 47 and 48: 5.2.6.2.2 Limits of K d Values with
Page 49 and 50: 5.3 Cesium Geochemistry and K d Val
Page 51 and 52: Cesium may also adsorb to iron oxid
Page 53 and 54: Table 5.5. Estimated range of K d v
Page 55 and 56: ore processing, plating operations,
Page 57 and 58: elow the isoelectric point, the min
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Among all available data for Cr(VI)
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5.5 Lead Geochemistry and K d Value
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on dissolution/precipitation of lea
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Percent Distribution 100 80 60 40 2
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A number of studies have confirmed
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Solid organic matter such as humic
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Plutonium is produced by fissioning
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The pe is related to Eh by the equa
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Table 5.10. Plutonium aqueous speci
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5.6.5 Sorption/Desorption Plutonium
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conditions depended on the colloida
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5.6.6.2.2 Limits of K d Values with
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present in vadose zone pore water w
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There is little tendency for stront
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strontium partitions from the disso
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greater than about 10 -4 M, humic s
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Table 5.13. Look-up table for estim
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1976; Cotton and Wilkinson, 1980).
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Table 5.14. Thorium aqueous species
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Figure 5.5 changes slightly in the
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to less than 10 -9 mol/l (0.0002 mg
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Based on the assumptions and limita
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5.10 Tritium Geochemistry And K d V
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Uranium(VI) species dominate in oxi
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most natural waters. For waters ass
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U(IV) mineral, is a primary mineral
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Percent Distribution 100 80 60 40 2
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5.11.6 Partition Coefficient, K d ,
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strong anionic carbonato complexes.
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Elemen t Table 5.18. Selected chemi
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Another objective of this report is
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6.0 REFERENCES Adriano, D. C. 1992.
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Billon, A. 1982. “Fixation D’el
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Chisholm-Brause, C., S. D. Conradso
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EPA/DOE/NRC (Cooperative Effort by
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Griffin, R. A., and N. F. Shimp. 19
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+ Keeney-Kennicutt, W. L., and J. W
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McBride, M. B. 1980. “Chemisorpti
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Östhols, E. 1995. “Thorium Sorpt
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Rhoads, K., B. N. Bjornstad, R. E.
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Schwertmann, U., and R. M. Taylor.
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Tanner, A. B., 1980. “Radon Migra
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Zimdahl, R. L., and J. J. Hassett.
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APPENDIX A Acronyms, Abbreviations,
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PC Personal computers operating und
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A.3.0 List of Symbols and Notation
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APPENDIX B Definitions
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Cation Exchange - reversible adsorp
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subbituminous coal. Marl - an earth
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APPENDIX C Partition Coefficients F
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Mean Standard Error Table C.1. Desc
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Figure C.1. Relation between cadmiu
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Cd K d (ml/g) Clay Cont. (wt%) pH C
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APPENDIX D Partition Coefficients F
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Two separate data sets were compile
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The soil-only data set was frequent
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The high correlations between mica
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D.2.4 Cesium Adsorption onto Mica-L
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Table D.7. Approximate upper limits
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Table D.8. Freundlich equations ide
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Table D.9. Descriptive statistics o
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D.2.6 Approach to Selecting K d Val
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Mica Concentration in Clay Fraction
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Cesium Kd (ml/g) 15200 8440 143 73
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Cesium Kd (ml/g) Clay (wt.%) Mica (
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Cesium Kd (ml/g) Clay (wt.%) Mica (
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D.4.0 Data Set for Soils Table D.14
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Cesium K d (ml/g) Clay (wt%) Mica (
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Li, Y., L. Burkhardt, M. Buchholtz,
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APPENDIX E Partition Coefficients F
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Windsor, and Olivier soils with pH
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Table E.1. Summary of K d values fo
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E.2.0 Approach The approach used to
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Table E.3. Estimated range of K d v
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Table E.4. Data from Rai et al. (19
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E.4.0 References Davis, J. A. and J
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APPENDIX F Partition Coefficients F
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(CEC) of the soils. Such an anomaly
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Table F.1. Summary of K d values fo
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Figure F.2. Variation of K d as a f
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F.4.0 References Abd-Elfattah, A.,
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APPENDIX G Partition Coefficients F
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influenced significantly by the typ
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The Pu(IV) and Pu(V) adsorption dat
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that Pu(IV) adsorption on soils wou
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Table G.1. Plutonium adsorption dat
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KD PH CEC EC DCARB Figure G.1. Scat
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Figure G.2. Variation of K d for pl
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Delegard, C. H. , G. S. Barney, and
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Seattle, Washington, pp. 291-497. B
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H.1.0 Background Appendix H Partiti
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H.2.0 Approach and Regression Model
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strontium K d values, which are cle
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Table H.3. Simple and multiple regr
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Table H.4. Look-up table for estima
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H.3.0 K d Data Set for Soils Table
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Sr K d (ml/g) Clay Content (%) pH C
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H.4.0 K d Data Set for Pure Mineral
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H.5.0 References Adeleye, S. A., P.
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Satmark, B., and Y. Albinsson. 1991
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I.1.0 BACKGROUND Appendix I Partiti
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Table I.2. Correlation coefficients
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The regression equation between the
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I.3.0 K d Data Set for Soils Figure
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I.5.0 References Ames, L. L., and D
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APPENDIX J Partition Coefficients F
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J.2.1 Sources of Error and Variabil
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Erikson et al. (1993) determined th
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26.1 wt.% plagioclase feldspar, and
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Kd (ml/g) 100,000 10,000 1,000 100
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Sheppard and Thibault (1988) invest
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Warnecke et al. (1986) present an o
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Borovec (1981) investigated the ads
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Table J.2. Uranium K d values liste
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J.3.0 Approach in Developing K d Lo
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at any pH. These estimated K d valu
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The minimum and maximum K d values
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ehavior associated with disposal of
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accompanied by unreacted zeolite. T
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pH Table J.5. Uranium K d values se
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pH U Kd (ml/g) Clay Cont. (wt.%) CE
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pH U Kd (ml/g) 6.90 1,739,87 7 6.90
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J.6.0 References Ames, L. L., J. E.
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Erikson, R. L., C. J. Hostetler, R.
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Lindenmeier, C. W., R. J. Serne, J.
Page 339 and 340:
Sheppard, M. I., and D. H. Thibault
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Zachara, J. M., C. C. Ainsworth, J.
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