A D

TECHNICAL REPORT 88-10

OCTANO. WATER PARTITION COEFFICIENTS OF

SURFACE AND GROUND WATER CONTAMINANTS FOUND AT MILITARY INSTALLATIONS

(0 MICHAEL A. MAJOR, Ph.D.00

co NOVEMBER 1989

N DI

U S ARMY BIOMEDICAL RESEARCH & DEVELOPMENT LABORATORY

Fort Detrick.1 Frederick, MD 21701-5010

I Approved for public release;I distribution unlimited.

U S ARMY MEDICAL RESEARCH & DEVELOPMENT COMMAND *

Fort Detrickrederick, MD 21701-5012

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The findings in this report are not to be construed as an officialDepartment of the Army position unless so designated by other authorizeddocuments.

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Destroy this report when it is no longer needed. Do not return tt to theoriginator.

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6a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATIONU.S. Army Biomedical Research (If appic.ble)and Development Laboratory SGRD-UBG-E

6c. ADDRESS (City, State, and ZIP Code) 7b. ADDRESS (City, State, and ZIP Code)Fort DerickFrederick, MD 21701-5010

8a. NAME OF FUNDING ISPONSORING " O8b. OFFICE SYMBOL 9. PROCUREMENT INSTRLIMENT IDENTIFICATION NUMBERORGANIZATION U.S. Army Medical (If applicable)

Research and Development Comman_

8c. ADDRESS(City, State, and ZIP Code) 10. SOURCE OF FUNDING NUMBERSFort Detrick PROGRAM PROJECT TASK WORK UNITFrederick, MD 21701-1010 ELEMENT NO. NU. NO. ACCESSION NO.

1I1. TITLE (Include Security Classification)Octanol/Water Partition Coefficients of Installation Surface and Ground WaterContaminants

12 PERSONAL AUTH OR(). . .. ..Michael A. Major, Ph.D.

13a. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Year, Month, Day) 15. PAGE COUNTTechnical I FROM Jun 88 TO Oct 89 1989 November

16. SUPPLEMENTARY NOTATION

17. COSATI CODES 18. SUJECT TERMS (Continue on reverie if necessary and identify by block number)FIELD GROUP SUB-GROUP Octanol/water partition coefficients

Kow

Log P.

11% ABSTRACT (Continue on reverse if necessary and Identify by block number)

-'An octanol/water partition coefficient .(Kow) is the ratio of the concentrations ofa solute in the two phases that are created when water containing the solute is extractedwith octanol. "Kow, values are of considerable use in an estimating other equilibriumconstants needed for predicting the fate of chemicals in the environment. This paperreports Kow' values for a number of compounds, some of which are unique to the military.The values have been selected from government reports and the open literature or determinedin the U.S. Army Biomedical Research and Development Laboratory.

20. DISTRIBUTION /AVAILABILITY OF ABSTRACT 21. ABSTRACT SECURITY CLASSIFICATIONM UNCLASSIFIEDAUNLIMITED 0 SAME AS RPT. [ DTIC USERS Unclassified

22a. NAME OF RESPONSIBLE INDIVIDUAL 22b. TELEPHONE (Include Area Code) 22c. OFFICE SYMBOLMichael A. Major, Ph.D. 301/663-2538 SGRD-UBG-E

DD Form 1473. JUN SE Previous editions are obsolete. 5ECURITY CLASSIFICATION OF THIS PAGE

TABLE OF CONTENTS

" EXECUTIVE SUMMARY .......................................... 1

INTRODUCTION ................................................... 1

DERIVATIVES OF METHYLPHOSPHONIC ACID ........................... 2

METHYLMERCURIES AND DIMETHYLMERCURY ............................ 4

COMPOUNDS OF ARSENIC ........................................... 5

ELEMENTAL METALS .................... .......................... 5

OTHER COMPOUNDS FOR WHICH KOW IS NOT APPLICABLE ................ 6

TABLE OF LOGKow VALUES ......................................... 6

REFERENCES ..................................................... 13

APPENDIX A ..................................................... 16

DISTRIBUTION LIST ................................................ 17

Ao-aesion For

VTIS GRA&fDTIC TAB [UnainiouncodJust i£1 Iclit, ion - .

By . .

Distriblil

Avllr.AbliitY CodOs

EXECUTIVE SUMMARY

This report summarizes the octanol/water partition coefficients (Kow)for a variety of substances frequently encountered as environmental pollutantsthat are unique to or of particular interest to the military. Sources of thedata are experimental values published in the open literature or in governmentreports, and values determined experimentally in this Laboratory. The purposeof the report is to contribute to the establishment of a Kgw data base to beused in predictive models of transport and transformation in the environment;it will aid in the assessment of possible ecological and health impacts due topast or present military activities.

JETRODUCTION

The ecological and health effects of chemical pollutants disseminated inassociation with the production and use of munitions and chemical agents arean important concern of the U.S. Army Medical Research and DevelopmentCommand. The problem is complex from a chemical standpoint because of thelarge variety of toxic chemicals associated with their manufacture. Thesituation is further complicated by the physical and chemical transformationsthese compounds undergo in storage, during use and in the environment.Moreover, much of the current contamination was generated by a succession ofgovernment and corporate laboratories; proper containment procedures were yetto be developed and records were sometimes inadequate.

Octanol/water partition coefficients (KowS) are of considerable use forderiving other equjlibrium copstants needed to predict the fate of chemicalsin the environment . Valuzvs of Kow can bs estimated by a variety ofcalculations but are more accurately der ved experti ntally. The earliestexperimental method relied on establishing an equilibrium of solute betweenthe immiscible distribution solvents octanol and water. In this Oshake flask"method, octanol and water containing the solute are vigorously shaken untilequilibrium is achieved and the two phases allowed to separate; theconcentration of the solute in the octanol divided by that in water is theKow. This method, although still the standard, is time-consuming and presentsproblems whenever very large or very small Kows are encountered. A moreconvenient method3 has been developed that relies on the relationship betweena compound's octanol/water partition coefficient and its retention tine inreverse phase high-performance liquid chromatography (HPLC). In this methodthe known log Kow values for a series of standards are plotted against thelogarithms of their corrected HPLC retention times, and the slopes of suchrelationships are determined by linear regression. Kow values for compoundssimilar to the standards can then be accurately estimated from their retentiontimes by interpolation. While this solves many of the problems associatedwith the shake flask method, it is only accurate when the compounds used asstandards and the unknowns contain similar functional groups and have similar

' i i I I i i I I I I 1 1

polarity. Compounds with very high Kow values require a special modificationof the shake flask method. In this technique the combined octanol/waterphases are carefully layered to avoid emulsicn, the solute added and themixture slowly stirred for several days to achieve equilibrium. The phasesare then analyzed and the Kow determined as in the shake flask procedure.

Regressions have been established between Kow and solubility, adsorptionon soil and uptake by aqueous organisms1 . Due to the utility of Kow as apredictive tool, values for many compounds have been determined, and aconvenient listing of these was provided a decade ago by Hansch and Leo2 . Inaddition, relatively accurate estimates of Kow can often be obtained bycalculations that utilize fragment analyses and by regression equations thatrelate Kew to the partition coefficient of solutes between water and othersolvents .

The listing we provide here is in response to a U.S. Army Toxic andHazardous Materials Agency (USATHAMA) request for Kow values for the compoundsfound in Appendix A. The reported values are experimentally derived butestimation methods have been used to pick best values among widely differingpublished Kows. Laboratory determinations of Kow were performed in-house bythe NPLC retention time method of Harnisch3 when literature results were notavailable. Kow determinations for compounds with known values were alsoperformed for standardization, and as a check on the accuracy of thelaboratory procedures.

To assist the reader in identifying the compounds of interest, chemicalstructures are provided and related compounds are handled as subgroups.Compounds not found in water in the form listed, such as lewisite, andcompounds that are ions under normal conditions (pH values between 5 and 9) donot have meaningful Kow values. These compounds are identified in the text.

DERIVATIVES OF METHYLPHOSPHONIC ACID

Owing to changes in the rules of nomenclature one may experience someambiguity as to the s~ructure of these compounds. Under olderrules of nomenclature , ethyl methylphosphonate and ethyl methylphosphonicacid would denote the monoethyl ester and the "secondary phosphonic" (really aphosphinic) acid shown here.

0_jCH 3-P-0-CH2-CH. *4

OH OHEthyl half ester Secondary phosphonic acid

Under current rules5 the latter compounds are named phosphinic acids,and the terms ethyl methylphosphonate and ethyl methylphosphonic acid nowdesignate the same compound.

2_ _

CH3-P-0- CH2-C.L

OHEthyl methylphosphonate/Ethyl methylphosphonic acid

Similar nomenclature applies to isopropyl methylphosphonate (isopropylmethyiphosphonic acid).

01

CH,-P-O-CH (CN~ 2OH

Isopropyl methylphosphonate/Isopropyl methyiphosphonic acid

Apparently USATHAMA (Appendix A) used the suffix *ate" to indicate thesalt form and the "acidn ending to indicate an undisassociated Lowry-Bronstedacid. The question of whether these compounds exist in the ionized orun-ionized form is importAnt, fo'r if they are ionized they will remain almostexclusively in the aqueous phase and will not have a demonstrable Kow. Acidstrength of organic acids decreases with increasing length of the attachedhydrocarbon chains. Therefore, since thie pK of the largest phosphonic acidon our list (isopiopyl methylphosphonic acidl is lower than 5, it follows thatit and the other phosphonic acids would be almost completely ionized undernormal environmental conditions.

a DExp~riments in our laboratory6 using the titration method of Rosenblattan avis have demonstrated a pKa for isopropyl methylphosphonate of 2.41.

Kosolapoff4 reports a pKal for niethyiphosphonic acid of 2.35. We thereforeconsider both ethyl methylphosphonate and isopropyl methylphosphonate to havevanishingly small Kows at ambient pH.

Dimahylmethyiphosphonate has a log Kow of -0.61 according to

II

O-CH3

Dimethyl methylphoe honate

Disopropyl methy~phosphonate (DIMP)_has 1log Kgw values reported as 1.03by Orikorian and Chorn and 1.35 by Brueggeiiarin . de relationship betweenthe log Kow values reported by Krikorian and Chain for a series ofphosphg9nates and the number of carbon atoms in these molecules, appears to belinear . Regression of the data indicates an anomaly in the fit of DIMP, suchthat Krikorian and Chorn's value for log Kow is probably too low. Inclusionof Brueggemann's result in th~is relationship yields a much better fit and istherefore considered the more accurate value.

3

0

ii CH3) F-P-O-CH- (CH3) 2CH3-'-O- C(C ) i

O-CH (C 3) CH3

Diisopropyl methylphosphonate GB

GB (isopropyl methylphosphonofluoridate) is a quick-acting nerve agent.It could not be tested in our laboratory, and Kow values were not available inthe literacure. Rosenthal et al. reported chloroform/water, benzene/water,carbon tetrachloride/water and h ane/water partition coefficients of 31.2,2.08, 0.84 and 0.20 respectively . Such values an sometimes be used toestimate Kow through solvent regression equations . However, the results ofsuch calculations were so divergent in the present instance that a crediblevalue for Kow could not be deterT!ned. It is known, however, that GB isvolatile and hydrolyzes in water and should therefore not pose a long-termenvironmental hazard.

METHYLMERCURIES AND DIMETHYLMERCURY

/• Determination of the Kow for metallic mercury and for methylmercurycompounds presents several interesting problems. Mercury may be found inoxidation states 0, 1,1 and +2. Mercury mlal (oxidation state O) has limitedsolubility in water1' and high volatility . Shoichi and Sokichi report Kowvalues for metallic mercury of from 3.80 to 4.80, with values decreasing as afunction of temperature in the range of 278 to 308 K. Mercury +1 and +2 saltsmay be methylated abiotically or microbially. In the methylated mol ules thecovalent bond between carbon and mercury resists hydrolytic cleavage" °. Kowvalues for mixed methylmercuric hydroxide and methylmercuric chloride are aresult of equilibrium between the two species. The Kow of the mixture in anaqY9ous medium appears to depend on salinity (chloride concentration) andpH

Dimethylmercury is a product of a microbial disproportionation reactionin which two methylmercury cations conignse to yield un-Ionizeddimethylmercury and ionized mercury +2 .

2 CH3-Hg ----- ) (CH3)2-Hg * Hg+

Dimethylmercury is nearly insoluble in water and it has a high vaporpressure. These properties combine to give the compound a short residencetime in aqueous systems and tend to makq accurate determination of Kow byconventional methods difficult. Wasik" was able to overcome these problemswith an elegant method that determined the octanol/water partition coefficientand the Henry's ltw constant simultaneously. This system yielded the log Kowvalue for dimethylmercury of 2.26 at 200 C.

CH3-Hg-CH 3

Dimethylmercury

4

COMPOUNDS OF ARSENIC

The compounds of arsenic for which Kow values were requested are2-chlorovinylarsonic acid, 2-chlorovinylarsonous acid, dimethylarsenic acid,lewisite, lewisite oxide and methylarsonic acid.

Methylarsonic ai d should have an extremely low Kow at pH 7 because ithas a pKa of only 4.l1. The similar compound, 2-chlorovinylarsonlc acid,should hence have a low Ko., as its chlorovinyl group is electronwithdrawing,2 making it an even stronger acid than methylarsonic acid.

o 0I ,

H3C-As- (OH) 2 C I-CH-CH.Au - (OH) 2Methylarsonic acid 2-Chlorovtnylarsonic acid

The Kow of lewisite can??t be determined since this ctna pound is notstable in water. ARMY FM 3-9 reports that "The rate of hydrolysis is rapidfor both vapor and dissolved lewisite and when the humidity is high lewisitehydrolyzes so rapidly that it is difficult to maintain a concentrationsufficient to blister even unprotected skin.0 Lewisite oxide is the speciesformed when lewisite is hydrolyzed and then dried. It, in turn, is nvertedquantitatively to 2-chlorovinylarsonous acid when dissolved in water " . linelatter compound represents the lewisite species actuall found in water; ithas a log Kow of -0.07 as determined in this Laboratory

CI-CH=CH-As=0 CI-CH-CH-As- (C1)2 C2-CH-CH-As-(OH)2

Lewisite oxide Lewisite 2-Chlorovinylarsonous acid

Dimethylarsenic acid correctly denotes the diester of arsenic acid.However esters of ts compound are highly unstable in water and diesters havenever been reportedLO. This terminology has however, been useg incorrectly todenote dimethylarsinic acid (cacodylic acid). Our experiments havedetermined the latter compound to have a log Kow of -1.18.

0 0(CN-O) 2-As-OH (CH 2-As-OH

Dimethylarsenic acid Cacodylic acid

ELEMENTAL METALS

With the exception of mercury, all the native metals listed are mediumto high melting solids. Melting point has a substantial effect on aqueoussolubility, and, as expJcted, the solubility of these elements is low. Kowvalues are not available for any metal except mercury and their determinationis not within the current capability of this laboratory.

V5

.... . .. . . .. __m___mm I

OTHER COMPOUNDS FOR WHICH KOW IS NOT APPLICABLE

Biscarboxymethyl sulfone, biscarboxymethyl sulfoxide and thiodiglycolicacid are putative or known environmental breakdown products of sulfur mustard;they differ only in the oxidation state of their sulfur atoms and are all inthe form of anionic salts at pH'5. They are not susceptible to facile Kowmeasurement.

0'1 0HOOC-CH2-S-CN 2-C00H 0- HOOC-CH 2-S-CHF2 -COOH HOOC-CHS-C-CODH0

Biscarboxymethyl sulfone Biscarboxymethyl sulfoxide Thiodiglycolic acid

Bromide and chloride, being anions, are not susceptible to Kowdetermination Chloroacetic acid and fluoroacetic acid have pKa values of2.87 and 2.570, so that they occur as anions at ambient pH.

CI-CH"2-COOH F-CH2 -COOH

Chloroacetic acid Fluoroacetic acid

2-Diisopropylaminoethylsulfonate denotes the salt form of a sulfonicacid. Sulfonic acids as a class do not have determinable Kow values becausethey are very strong ac~ s. They are reported to be the most water-solubleorganic compounds known .

CH- (CH3) 2I 0N-CH2 -CH'-9LO-

CH- (CH3)2

2-Diisopropylaminoethylsulfonate.

LOG KOW FOR COMPOUNDS FOR WHICH KOW VALUES ARE APPLICABLE (value listed first

is considered most accurate)

COMPOUND Log Kow REFERENCE

C3 6.50 22 De Bruiin et al. 19895.66 23 Geyer et al. 19845.66 2Kenaga 1980a

A 0 5.3 25 USEPA 1986mAl drin

SNH-CH C2.32 26 Rao and Davidson 1983NCH) 2.64 23 Geyer et al. 1984

Atrazine

6

o CH 0CH3-O-P-0-C-CH-C-NH-CH3

o-cH31.03 6 Major 1988

Azodrin

2.01 28 Valvani et al. 19802.12 25 USEPA 1986m2.13 Sangster 1989

Benzene

N 2.01 2 Hansch and Leo 1979Benzothiazole.

3.11 6 Major 1988Bicycloheptadiene

CIt 2.73 29 Davies and Dobbs 1984

ci-Ci 2.73 23 Geyer et al. 1984

CI 2.83 28 Valvani et al. 19802.64 30 Neeley et al. 19742.83 27 Sangster 1989

Carbon tetrachloride

4 Ci

.I.z !en 2.78 33 Kadeg et al. 1986Chlordane

2.84 5. Sangster 19892 .84 28Valvani et al. 1980

S2.98 31 Tewart et al. 1982

~Chlorobenzene_

1.90 29 Davies and Dobbs 1984I -CC!1.96 28 Valvani at al. 1980

: C]1.97 32Mortguchi 1975tChloroform 1.97 27 Sangster 1989

rl i .,.F ..l i , .i, i i i i i ' .. .. ... .. ... .m

CL -- S CH,3.22 9 Brueggemann 1979p-Chlorophenyl methyl sulfide__________________

0

CL-- SCH3 1.33 9 Brueggemann 1979p-Chlorophenyl methyl sulfoxide__________________

0CL 1)

S-CH 3

01.20 9Brueggemann 1979p-Chlorophenyl methyl sulfone________________

Cl-CHWCH-AS- (OH) 2-0.07 6 Major 1988

2,Chlorovinylarsonous Acid_____________________

CI -0 11 - _ C, 6.96 22 De Bruijn et al. 1989C ~5.69 26 Rao and Da~ldson 1983

5.60 (Mean value) Kadeg et al. 1986Dichlorodiphenyldichloroethylene (DDE)

CC13C1 CH0 - C1 6.91 22 De Bruijn et al. 1989

26 Rao and Davidson 19835.91 Lyman et al. 1982

Dichlorodiphenyltrichloroethane (DDT)

BrCH-CHr-C2CI2.29 25 USEPA 19862.43 34USEPA 1985

I ,2-Dibromo-3-chloropropane

1.8 25 USEPA 1986

1,1-Dichloroethane

CI C._CH2C 1 1.79 3 Veith et al. 1983

1.45 9 Davies and Dobbs 19841.48 2 Hansch and Leo 1979

1 ,2-Dichloroethane_________________________

C12C=CH2

1.84 36 Mabey et al. 19811,1-Dichloroethylene

CICH-CHC1

1.98 37 Gossett et al. 1983trans-i,2-Dichloroethylene

1 5.40 22 De Bruijn et al. 9891 4.32 29 Davies and Dobbs 1984

c 11 6.20 38 Briggs 1981, 3.69 26 Rao and Davidson 1983

cl 5.48 24 Kenaga 19803.50 25 USEPA 1986

Dieldrin

0CH-P-0-CH (CM2) a

O-CH {CN1.35 9 Brueggemann 1979

Diisopropyl methylphosphonate

~CN=-S-S-CH 3

Dimehyl isulide1.77 2 Hansch and Leo 1979Dimethyl disulfide___________________

CH3-Hg-CH 32.26 17 Wasik 1978

Dimethylmercury

0.'1' O°

CH3-P-o-cH 3

O-CH3 -0.61 8 Krtkortan 1987

* @Dimethyl methylphosphonate

9

Li____

US

1.85 6 Major 1988Dithiane (1,4 isomer)

6 5 22 De Bruijn et &l. 19896.34 24 Kenaga 1980

Endrin

CH2-CH 3 3.15 27 Sangster 19893.13 31 Tewari et al. 19823.15 32 Moriguchi 1975

Ethylbenzene

C C l

I I

5.04 23 Geyer et al. 1984

Hexachlorocyclopentadiene

6.51 1 Lyman et al. 1982SIsodrin____________________________

S(CH3-O) :P-S-CH-COO-CH2CH3 2.89 U5 uSEPA 1986

SC6z-COO-CH2-CH 289 2 Hansch and Leo 1979.2:89 26 Rao and Davidson 1983

Malathion_

HgHg 3.8 to 4.2 Shoichi 13 1985

Mercury

(CH3) 2-N-N=O,ra -0.57 2 Hansch and Leo 1979

N-N itrosodimethylaiine'"" 10

S

O-CMOCHCHa31

:3.9 38 Briggs 1981

3.8 26 Rao and Davidson 1983Parathion

CI- -Cl 1.25 39 Callahan et al. 1979H .30 25 USEPA 1986

1.31 27 Sangster 1989Methylene chloride

CH3 -CH-CH 2 -C-CH1.53 6 Major 1988

Methyl isobutyl ketone

1.37 25 USEPA 1986mSulfur mustard

0.oy%- 1 C I -O| 40 O-€ -CHC I

Cl! 3.11 38 Briggs 1981Supona

C12-CC-CI 2

2.60 2 Hansch and Leo 1979

Tetrach1oroethylene

HO-CH2-CH2-S-CH2-CHa-OH

-0.08 6 Major 1988Thiodiglyol

11

0S 0.77 6Major 1988

Thioxane (1,4 Oxathiane)

CH3 .,;327 Sangster 19892.73 25 USEPA 19862.68 28 Valvani et al. 19802.65 31 Tewari et al. 19822.69 23 Gyret al. 19842.69 32 Moriguchi 1975

Toluene___________________________

CI3C-CH3 2.50 25 USEPA 19862.47 29 Davies and Dobbs 1984

1,1,1-Trichloroethane_____________________

C 12CH-CH2C I

2.38 25 USEPA 19862.29 2 Hansch and Leo 19792.42 35 Veith et al. 1983

C~eCCHCI3.328 Valvani et al. 19803.3-HC 29 Davies and Dobbs 1984

3323 Geyer et al. 19842.29 40 Rogers et al 19802.53 29 Tewari et al. 1982

Trichloroethylene_,

01P- (O-CH3) 3

0.52 2 Hansch and Leo 1979.. mathyl phosphate_____________________

CIZC-CH-0-P- (OCH 3)21.40 2 Hansch and Leo 1979

Vapona

12

I -

REFERENCES:

1. Lyman, W.J., W.F. Reehl, and D.H. Rosenblatt. 1982. Handbook of chemicalproperty estimation methods: environmental behavior of organic compounds.McGraw-Hill Book Co., New York, NY.

2. Hansch, C. and A.J. Leo. 1979. Substltuent constants for correlation

analysis in chemistry and biology. John Wiley and Sons, New York, NY.

3. Harnisch, M., N.J. Mockel, and 6. Schulze. 1983. Relationship betweenlog Kow shake-flask values and capacity factors derived from reversed-phasehigh performance liquid chromatography for n-alkylbenzenes and some referencesubstances. J. Chromatogr. 282:315-332.

4. Kosolapoff, G.M. 1950. Organophosphorus Compounds. John Wiley and Sons,Inc. New York, NY.

6. Fletcher, J.H., C.O. Dermer and R.B. Fox. 1974. Nomenclature of OrganicCompounds Principles and Practice. American Chemical Society, Washington, DC.

6. Mcjor, M. 1988. USABRDL Research Notebook Number 988.

7. Rosenblatt, D.H. and G.T. Davis. 1973. Laboratory Course in OrganicChemistry. Allyn and Bacon Inc. Boston, MA.

S. Krikorian, E.S. and T.A. Chorn. 1987. Determination of octanol/waterpartition coefficients of certain organophosphorus compounds using highperformance liquid chromatography. Quant. Struct. Act. Relat. 6:65-69.

9. Brueggemann, E. 1979. USABRDL Laboratory Research Notebook Number 748.

10. Rosenthal, R.W., R. Proper and J. Epstein. 1965. The distribution ofsome phosphonofluoridates be. -an organic solvents and water. J. Phys. Chem.60: 1596-1598.

11. Military Chemistry and Chemical Compounds, U.S. Army FM 3-9. 1975.

12. Glew, D.N. and D.A. Names. 1971. Aqueous nonelectrolyte solutions. PartX. Mercury solubility in water. Can. J. Chem. 49:3114-3118.

13. Shoichi, 0. and S. Sokichi. 1984. Volatility of mercury In water.J. Hazard. Mater. 8:341-348.

14. Shoichi, 0. anJ S. Sokichi, 1985. The 1-oct:n /-,at partitioncoefficient of mercury. Bull. Chem. Soc. Jpn. 58:3401-3402.

15. Bodek, I.F., W.J. Lyman, W.F. Reehl and D.H. Rosenblatt. 1988.Environmental inorganic chemistry: Properties processes, and estimationmethods. Pergamon Press. Elms Ford, NY.

13

I I_ _ _ _ _

16. Major, t.A., K.A. Bostian, and D.H. Rosenblatt. The octanol/waterpartition coefficient of methylmercuric chloride and methylmercuric hydroxidein pure water and salt solutions. In Draft.

17. Wasik, S.P. 1978. Partition of Organoelements in Octanol/Water/AirSystems. A.C.S. Syrnp. Ser. Organometallics and Organometalloids.Vol. 82:314-326.

18. Levander, O.A. and the National Academy of Sciences Subcommittee onArsenic. 1977. Arsenic. National Academy of Sciences, Washington, DC.

19. Bossle P.C. 1988. Determination of lewisite contamination inenvironmental waters by high performance liquid chromatography. Paperpresented to the Rocky Mountain Conference. July 1988.

20. Albert, A. and E.P. Serjeant. 1958. Ionization constants of acids andbases. John Wiley and Sons. New York, NY.

21. Morrison, T.M. and R.N. Boyd, 1970. Organic chemistry. Allyn and Bacon,Inc. Boston MA.

22. De Bruijn. J., F. Busser, W. Seinen and J. Hermens. 1989. Determinationof octanol/water partition coefficients for hydrophobic organic chemicals withthe "slow-stirring" method. Environ. Toxicol. Chem. 8(6):499-512.

23. Geyer, H., G. Politzki, and Freitag, D. 1984. Prediction ofecotoxicological behavior of chemicals: relationship between N-octanol/waterpartition coefficient and bloaccunulation of organic chemicals by AlgaChlorella. Chemosphere 13(2):269-284.

24. Kenaga, E.E. 1980. Correlation of bioconcentration factors of chemicalsin aquatic and terrestrial organisms with their physical and chemicalproperties. Environ. Sci. Technol. 14(5):553-556.

25. U.S. Environmental Protection Agency (USEPA). 1986. Superfund publichealth evaluation manual, Prepared for USEPA by ICF Incorporated Washington.DC.

26. Rao, P.S.C. and Davidson, J. M. 1983. Estimation of pesticide retentionAt and transformation parameters required in nonpoint source pollution models.

Overcash, "".R. and J.. Davidson, editor%. Environmental impact of nonpointsource pollution. Ann Arbour Science Publishers, Inc., Ann Arbour, MI.

27. Sangster, J. 1989. Octanol-water partition coefficients of simpleorganic compounds. J. Phys. Ref. Data 18(3):1111-1229.

28. Valvani, S.C., 5.H. Yalkowsky, and T. J. Roseman. 1980. Solubility andpartitioning. IV. Aqueous solubility and octanol/water partition coefficientsof liquid nonelectrolytes. J. Pharm. Sct. 70(5):602-605. t

29. Davies, R.P. and A.J. Dobbs. 1984. The prediction of bioconcentration infish. Water Res. 18(10):1253-1262.

14

i I

30. Neely, W.B. 1974. Partition coefficient to measure bioconcentrationpotential of organic chemicals in fizh. Environ. Sci. Technol. 8:1113.

31. Tewari, Y.B., M.M. Miller, S.P. Wasik, end D.E. Nartire. 1992. Aqueoussolubility and octanol/water partition coefficient of organic compounds at25 degrees centigrade. J. Chem. Eng. Data 27:451-454.

32. Morlguchi, I. 1975. Quantitative structure-activity studies. I.Parameters relation to hydrophobicity. Chem. Pharm. Bull. 23(2):247-257.

33. Kadeg, R.D., Pavlou, S.P., and Duxbury, A.S. 1986. Elaboration ofsediment normalization theory for non polar hydrophobic organic chemicals.U.S. Environmental Protection Agency, Criteria and Standards Division,Washington, DC,

34. U.S. Environmental Protection Agency (USEPA). 1985. Draft HealthAdvisory for 1,2-dlbromo-3-chloropropane (DBCD). Office of Drinking Water.U.S. Environmental Protection Agency. Washington, DC.

35. Veith, G.D., D.J. Call, and L.T. Brooke. 1983. Structure-toxicityrelationships for the fathead minnow, Pimephales Promelas: narcoticindustrial chemicals. Can. J. Fish Aquat. Sci. 40:743-748.

36. Mabey, W.B., J.H. Smith, and R.T. Podoll. 1981. Aquatic fate processdata for organic priority pollutants. USEPA, Monitoring and Data SupportDivision, Washington, D.C. EPA. Report No. EPA-440/4-81-014.

37. Gosett, R.W., D.A. Brown and D. Young. 1983. Prediction thebioaccumulation of organic compounds in marine organisms using octanol/waterpartition coefficients. Mar. Pollut. Bull. 14(10):387-392.

38. Briggs, G.G. 1981. Theoretical and experimental relationships betweensoil adsorption, octanol-water partition coefficients, water solubilitiesbioconcentration factors, and the parachor. J. Agric. Food Chem. 29:1050-1059.

39. Callahan, M.A., M.W. Slimak, N.W. Gabel, I.P. May, C.F. Fowler, J.R.Freed, P.Jennings, R.L. Durfec, F.C. Whitmore, Maestri, W. R. Mabey, 8,R.Holt, and C. Gould. 1979. Water-related environmental fate of 129 prioritypollutants. Vol. I. EPA-440/4-79-029a. Office of Water Planning andStandards, Office of Water Waste Management, U.S. Environmental ProtectionAgency, Washington, DC.

40. Rogers, R.D., J.C. McFarlane and A.J. Cross. 1980. Adsorption anddesorption of benzene in two soils and montmorillonite clay. Environ. Sci.Technol. 14(4):457-460.

15

II)

APPENDIX A: LIST OF SUBSTANCES FOR WHICH Kow VALUES WERE REQUESTED BY THE U.S.ARMY TOXIC AND HAZARDOUS MATERIALS AGENCY.

Aidrin 4'Ars~en ic Dimethyl mercury (sic[)Atrazine DithianeAzodrin Endrin

FBenzene Ethyl benzene (sic!)Benzothiazole Ethyl methyl phosphonate (sic!)Bicycloheptadiene Ethyl methyl phosphonic acid (sic!)

*Biscarboxymethyl sulfone FluorideBiscarboxymethyl sulfoxide Fluoroacetic acidBromide GB; SarinCadmiurn Hexach lorocyc lopentad jeneCarbon tetrachloride Isodrin

.1Chlordane Isopropyl methyl phosphonicChloride acid (sic!)Chioroacetic acid Isopropyl methyl phosphonate (sic!)Chlorobenzene LeadChloroform Lewisite2-chiorovinyl arsonic acid (sic!) Lewisite oxide2-chiarovinyl arsonous acid (sic!) MalathionAp-Chlorophenyl methyl sulfide Mercuryp-Chlorophenyl methyl Methylene chloride

suifoxide Methyl arsonic acid (sic!)p-Chlorophenyl methyl sulfone Methyl isobutyl ketoneChrom iurn Methyl mercury salts (sic!)Copper Methylphosphoiic acidDDE MustardDDT N-Ni trosodimethylami ne1,2-Dlbromo-3-chloropropane Parathion1,1-Dlchloroethane Sulfur mustard1.2-Dichloroethane Supona1, 1-Dichloroethylene Tetrachloroethylene1,2-Dichloroothylene ThiodiglycolDicyclopentadiene 2,2-Thiodiglycolic acidDiel1dr in Thioxane2-(Diisopropylamino)-n-ethyl Toluene.sulfonate (sic!) 1,1,1-Trichloroethane

2-(Diisopropylamina)-n- 1,1 ,2-Trichloroethanea &A.anaethiol (Sic!) Trichioroethylene

Dllsopropyllrethylphosphonate (sic!) Trimethyl phosphateDimethyl disulfide VaponaDiniethyl methyl phosphonate (sic!)Dimethyl arsenic acid (sic!)

16

DISTRIBUTION LIST

No. of Copies

4 CommanderU.S. Army Medical Research and Development CommandATTN: SGRD-RMI-SFort Detrick, Frederick, MD 21701-5012

2 Commander, U.S. Army Biomedical Research and DevelopmentLaboratory, ATTN: SGRD-UBZ-ILFort Detrick, Frederick, MD 21701-5010

2 Defense Technical Information Center (DTIC)ATTN: DTIC-DDACCameron StationAlexandria, VA 22304-6145

1 CommandantAcademy of Health Sciences, U.S. ArmyATTN: HSHA-DCDFort Sam Houston, TX 78234-5000

ChiefU.S. Army Environmental Hygiene AgencyRegional Oivision, WestFit:sirmaons Army Medical CenterAurora, CO 80045-5000

1 Chief" :U.S. Army Environmental Hygiene Agency

Regional Division, NorthFort George G. Meade, MD 20755-5000

ChiefU.S. Army Environmental Hygiene AgencyRegional Division, SouthBuilding 180Fort McPherson, GA 30330-5000

CommanderU.S. Army Health Services CommuandATTN: IISPA-PFort Sam Houston, TX 78234-5000

e 1CommandantU.S. Army Academy of Health SciencesATTN: Chief, Environmental Quality BranchPreventive Medicine Division (HSHA-IPM)

* Fort Sam Houston, TX 78234-5000

17

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*1 - I Iii L -

U.S. Army EngineersDivision, Huntsville106 Wynn DriveHuntsville, AL 35807-4301

ChiefArmy Environmental OfficeATTN: ENVR-EPThe PentagonRoom 1E669Washington, DC 20310-2600

CommanderU.S. Naval Facilities Engineering CommandEnvironmental Quality Division200 Stovall StreetAlexandria, VA 22332-2300

HeadquartersAir Force Engineering Service CenterATTN: RDVTyndall Air Force Base, FL 32403-6001

ComdanderU.S. Army Materiel CommandATTN: AMSCG5001 Eisenhower AvenueAlexandria, VA 22333-2300

CommanderU.S. Army Environmental Hygiene AgencyATTN: HSDH-AD-LAberdeen Proving Ground, MD 21010-5000

DeanSchool of Medicine

Uniformed Services University of the Health Sciences4301 Jones Bridge RoadBethesda, MD 20014-5000

CommanderU.S. Army Materiel Com.andATTN: AMCEN-A5001 Eisenhower AvenueAlexandria, VA '22333-2300

HQDA(DASG-PSP-E) C5111 Leesburg PikeFalls Church, VA 22041-3258

18

-n

1 HQDA(DAEN-RDM)20 Massachusetts Avenue, NWWashington, DC 20314-5000

1 ComhmanderU.S. Army Toxic and Hazardous Materials AgencyATTN: CETH-TE-D (Mr. Bartell)Aberdeen Proving Ground, MD 21010-5401

19