ag-neny,l'able N: Concentrations of pollutants in Puget Sound Wle A-1. Summaty of basic analytical...

i

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Po.llutants 0.1 Concern in Puget Sound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . - .........- .... .- - . . . . . . - . . . . .- -. . . . . . . . . - . . - ............. -. . . . . . . . . -. . . . . . . . . . . . . - ...... . . - . . . . . . . . . -. . . . . . . .

PTI Environmental Services, Bellevue, WA

Prepared for:

Environmenral Procect ion ag-neny, Seat*, WA -. ----.-.-.A

Apr 91

- -

pu31-211953

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,. . . . . . . . . . . . . . . . . . . . . - . . . . . . . . .

Estuary Program - . . . .. .... - ,

.-...... , .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . .

POLLUTANTS OF CONCERN IN PUGET SOUND

.....................................................................

.....

April 1001

REPRODULEDBY

....

U.S. DEPARTMENTOF COMMERCE NATIONAL TECHNICAL

3 PD91-211953! 1

i . - : - . ... . .... . ..+%" Pollutants of Conccrn in PuqoL sound b - A p r i l I991

I -.- -----..-r. hr(ormin' o,#anlznuon Nan. and M6r .s~ I I& PIOII~IIT~I~IWP~IUntl No.

T I Environmcntal Scrviccs i . --- . . . 15375 SE 30th place ! 11: contracacl or ~ t . ~ t c o )NO.

Bcllcvue, WA 98007 68-DO-00851"' --11=)

12. swnlo,lng OrganualUn Ham. IM Ad4rarr

I I* TI*. O) 8l.m rl P*r,m Wr.*

U.S. Environmental Protection Agency Of Eice of Pugat Sound, Region 10 -- . .1200 Sixth Avo. Scattlo, WA 98101 i ", .

ID. S Y P D I ~ ~ ~ ~ I . Ynot..

This report replaces and updates information originally compiled for the 1986, informati-port i s available only in hard cpqy, not in a spreadsheet format as in 1986.

The report contains the following informatiofitor 64 pollutants:

Table I Regulatory status and analytical consiclerationa

Table If ' Criteria, guidelines and regulatory action lovels

Table 111 Sources of pollutants Table IV Concentrations of pollutants in Puget Sound.

The report also contains a narrative section on each pollutant, describing exposure routes and risks, sources and fate in the environment, and other information.

The information contained in this report is useful to permit writers and reviewers, resource managers, writers and reviewers of environmental

&E%$s%%#.and others.

DO NOT PRINT.THESE INSTRUCTIONS AS A PAGE IN A REPORT

E - INSTRUCTIONS ..-....-..... . . .

Opnona) Perm 272. R a m 0ocume.IaUon Paw I& basad on Ou8deluar for Fotmal m d Ptoduclcon 01 Sclantollc and Tmhn~esl R~pons. ANSI WO.l&1974avaolab~ from ~ ~ a n ~ n N a l # o ~ lSwneams Inrl~tute. 1100 Otoadmy, New ~orh. New York lIW18. Each sipa,ato~r ~oun$.repw--(or erampla each mlume In a mulllvoluma wl-man havo ilru~taqueRawR Docvmentat~on Pege.

I. R a n Numbar. lndlvtdualhl bound report shall carv a unaoua alphanumetic daaignallon assiglll( by ihs peIfmdng o r e .&don or provlded bm me r w n w n u orgenllallon on accordanu mlh Iun.nwn Nollonal Slandate ANSI 239.23-1974. Tachmul nepan Number (STUN). For raglsuellon 01 rapan cads. mntacr NTIS Rapatt Number Clealmgnouse. SplmN~eId. VA 22161. Use UyperCaM IeMm. A~ablc numsralr. stashas. and hypnens onov. ar in !he lallomng oramplas. FASEOINS-75/87 and fPAI RO-78/09.

Z Leavs.bfenk

3. Rociplenl'~ Accaaalon Number. Rereluod lor ura by each rewtt mclolant.

41 TUIe and SubUUs. TIlb should indieole dearly and bnaW tho wblect coverage Q l 1M repoll. %ulpcdinsbrubtille to lhe w n UUa. When a nwnir prepared in more than one volume. repeat the pnmsry ltllo. add volumo numbur and lnclvdo rubtttte lor tho ~LcIIIE voIoma.

5. Rapan Oat0 Each repor( sh8ll cotw a date ~ndlcaun~ was SeIeeled (e.8..r l loss1 monlh and v~rr.lndoca~o rho bas16 on *n#ch 41

dale 01 ir~ue, dale 01 dppr~lal, dale 01 praparalaon, date punlomsdl.

6. Sponsoring Agency Coda. Leave blank.

7. Aulltor(s). Oka name($) m conventtonal otdar (s.g.. John n. 00%oar I. Roben Doel. Lsrf aulhrr'r allihal~an d 11 dnnotr fmm the pedormiua owntrstan.

8. Parlonnsns Olernlrellon napor( Number. Insert 11 psrlonlng or~nolslion wnsltcr toassign lhas numb#*

9. PddOImln# 01gan126110n Nrma a110 Malllng Mdrau. Oke nemc %lrasl. cw,rl*la. md ZlPcWe Llsl no mare lhsn hm lauels a1 an otganlull0nal hlrnrchy. OlYp14 the name of lha oganlrarlon araclly as 11 should appear in Oovetnmot8l ondsrsr such as Oovalnmtnl Reports Announcemanls & Index (ORA & 11.

la ProlsctlTarkNon Unit Number. Use tha prolecl. task m d work unml numbors under whlch the report was preparea. . 12. C~ntra:tIO~nt Number. In:ar( conlrad or grant numbar under whlch report was prepared.

12 Sponsoring Agancy Nma a d Mailing Address, Include ZIP code. Cils marn s~onsors.

la. F/Oa 01 R~DOI~ and mnod Covand. Slate inlartm. nnal. ate.. and. ifaontlcabk ~nclustvedatar.

I& Pallormln# Oganltallon Ooda Lelva Olsnk.

1V. S~pplammUwNoleu Ulter infonnallan not inclwdad abownara bul usarul. such a r Pm~andin coop.rrl@n will Tmnslstlon of. . Pmson(ad 11 wnlarance of , To ba publlshad #n... When a town 3s revlred, Include a rlslsmonl whathe. the n w report tupeISMas 01 rupplemanlr Ills oldar awn.

16. Abrlracl. lnoluda e brlei (2M)vrordr or Ins) Ienual summaw of Uu most alenitlcant informalion contelned m tho report. 11 rha rawn Eonlalns a rlgninmnl Mbnowaphy or i l a r a t u ~ SUW~Y.nlonuon 11 hero.

17. Oocumanl AneWrl& (0). Ouodotolu Satact lrom the Tnesaurueof Englnoerlne and SclanllncT1m8 the pramr eumowed lams lh l t idenulu ma nulor concept of the Ieaalnh and are SuloCIonlty ~pecific end pmcfse to be used an mdax snlnas tor calaloging.

(b). Idontlbn and OPan.€ndM Terms. Use tdenllnen lor prolecl names. code names. oqulpmonl daslgnators. elc. Urn open onded urmr wrlnan in daxnoror form lot tnme sub~ec~o far wh~chno doscn~tor OXISIS.

(el. COSATI Fbldl~roclp. Vleld end Proup asa~pnmmu are lo be Iabn lmm the 1964 C08ATl Sublm CaIegaw Urt. Slrm ~1. malorlhl of documenla are mullldlscwlmay m nature, lne Drtmav FieMIO~oup arugnmoent(s) w11 be the spwnc dlsclplinr. m a 01 hUml) endeavor. or Vvn of of1~6I~al obl%t The apPllcotlon(s) will be cross.fofenncod with secondary Pletdioroue afllgnmonll that wlll Iollow the pnmsw poslIng(s).

1% Olll1lbuIloII Slatament Danou puMlc raleasabill~. lor oxomDle "Ratease unllmKM". or llmllallon lor reasons olhor than tecurlhl CIIO any rvallablliw lo 118s ~vbllc. well* address. Ordm number an6 mace. 11 hnmm

18. & 20. Se~urlhlClassl~collon.EnlerU.8 llacurlty Classlfic~tton In accord~nco ~ 4 t hUS. Swurlw R08ula11ons 0.0.. UNCVLSSIFIED).

21. Number 01 Paces. lnsM lha tote1 number 01 pagar, lnclualne lnlroduclow pacer. bul crcludlng dlsrnbullon 11st. i t any

22. Pllca. Enta PIlce In papsr cow (PC) andlor mlfroncw (Mn lr known.

--- --

POLLUTANTS OF CONCERN IN PUGET SOUND *.---

Prepared for U.S. Enviroomencal Proteelion AgencyOMWof Puget Sound Region 10 Seanls, Washington

BPA Contract 68D80085 PTIContract C744-15

April 1991

- .

CONTENTS

em LIST OF FIGURES v

LIST OF TABLES v

LIST OF ACRONYMS vi

ACKNOWLEDOMENTS vii

EXECUTIVE SUMMARY viil

1, INTRODUCTION I

BACKGROUND I

SELECTION OF THE POLLUTANTS OF CONCERN 2

2. POLLUTANTS OF CONCERN TABLES 9

TABLE I. REGULATORY STATUS AND ANALYTlCAL CONSIDERATIONS FOR POLLUTANTS OF CONCERN 9

TABLE I!: CRITERIA, GUIDELINES, AND REGULATORY ACTlON LEVELS FOR POLLUTANTS OF CONCERN 16

TABLE Ilk S0URCE.S OF POLLUTANTS 30

TABLE IV: CONCENTRATlONS OF POLLUTANTS IN PUGm SOUND 37

3. DESCRWITON OF POLLUTANTS OF CONCERN IN PUGET SOUND 46

INORGANIC CHEMICALS 46

Anlimony 46 Arsenic 47 Cadmium 50 Chromium 51 Copper 52 cyanides 54 Lead 55 Mercury 56 Nickel 58

ii

Silver Zinc

ORGANOTMS 62

NONIONIC ORGANIC COMPOUNDS -AROMATIC HYDROCARBONS 63

Polycyclic Aromatic Hydrocarbon Compounds Methylnaphbalenm and Melhylphenanthrenes

N O m N I C ORGANIC COMPOUNDS -CHLORINATED AROMATIC HYDROCARBONS 66

Dichlorobenlrnes 66 Hexachlorobenzene 67 Polychlorina~ Dibenzofurans 68 Polychlorinateo Dibcnm-p'dioxins 69 Polychlorinated Biphenyls 71

71 NONIONIC ORGANIC COMPOUNDS -MlSCELLANEOUS EXTRACTABLE COMPOUNDS 72

N-Nilrosodiphenylamine 73 Methylethyl Ketone 73

74Bis(2.ethyl)haylphlhato Hexachlorobutadiene 75 Dibcnzofuran 76

NONIONIC ORGANIC COMPOUNDS -PESTICIDES 76

Aldrin and Dielddn 76 DDT, DDE, and DDD 78 +fucschlorocyclohexane 79

VOLATILE NONIONIC ORGANIC COMPOUNDS 80

Benzene 80 Chloroform 82 Ethylbenzene 83 Toluene a4 Total Xylenes 85

IONIZABLE ORGANIC COMPOUNDS 86

Phonol 86 4-Methylphenol (4-Cresol) 87 Pentachlorophonol 88 Mono- and Dichlorodehydroabietic Acids 90 2-Methoxyphenol 91 Chlorinated Guaiawls 91

iii

Trichlonwlhenc Tetrachlorocchene

REFERENCES

APPENDIX A: SUPPLEMENTAL INFORMATlON

LIST OF FIGURES Eaee

Figure A-1. Graphical risk characterization for arsenic jn seafood A-5

Figure A-2. Graphical risk characrerization for mercury in seafood A-6

Figure A-3. Graphid risk charackrization for carcinogenic PAH in seafood A-7

Figure A-4. Graphical risk characterization for PCBs in seafood A-8

LIST OF TABLES

Table 1. Inorganic contaminants of porenlial concern in Puget Sound 3

'Ihble 2. Organic contaminants of potential concern in Pugel Sound 4

Table I: Regulatory status and analytical considerations for pollutants of concern

nb le 1k Criwria, guidelines, and repulatory action levels for pollutants of concern

l'able N: Concentrations of pollutants in Puget Sound

W l e A-1. Summaty of basic analytical techniques for organic compound analyses A-1

Table A-2. Reference dose (RtD) vaIuss for ppdodty pollutants A-2

Table A-3. Carcinogenic priority pollutants ranked by potency factors A-3

AET CFR CLP corps CSO DW &logyEHW EPA FDA HCB HCBD HCH HPAH

LPAH

MCLGs MCLS MEK MeV0 NOAA NURP PCBs PCDDs PCDFs PCP PNBts PPM PPB PSDDA PSBP RfD QAlWSEDQUAL SLCs TBT 2,3,7.8-TCDD TPPS

LIST OF ACRONYMS

apparent effects threshold Code of Federal Regulations Conmct Laboratory Program U.S. Army Cops of Engineers combined sewer overflow dangerous waste Washington Department of Ecology extremely hazardous vmle U.S. Environmenlal Proteclion Agency U.S. Food and Dmg Administralion hexachlorobenzc~e hexachlorobutadiene hexachlorocyclohexane high molecular weight polycyclic aromatic hydro- c&ns low molecular weight polycyclic aromatic hydrocarbons maximum cantaminant Level goals maximum contaminant levels Methylethyl ketone Municipality of Metropolitan SeatUe National Oceanic and Atmospheric Administration National Utban Runoff Program polychlorinated biphenyls dibonz@pdioxhc polychlorinated dlbenmhrans pentachlorophenol probable no-alfoct levels pans per million pwa per bUon Puget Sound Dredged Disposal Analysis Puget Sound Esluary Program reference dose quality a~suranea and qualily control sediment quality database ~rebnlnglevel cancenharions viburyltin 2,3.7,8-tauachlodlbell~~pdi~n Toxicant Preueatment Planning S ~ d y

ACKNOWLEDGMENTS

This document replaces and provides updated information originally compiled for the 1986 Po//wanr 4f Concern Ma~rLr,which was prepared by Tetra Tech, Inc. for the U.S. Environmental Protection Agency (EPA) in partial fulfillment of Contract No. 68-03-1977.The cunent document was prepared by I T 1 Environmental Services in partial fulfillment of EPA Contract No. 68D8W85. Ms. Sally HanR of EPA was the Project Officer and Dr.John Armstrong of EPA was the Project Monitor for this document.

Primary authors of this repon were Ms. Kimbcrly Henson, Ms. Teresa Michelsen, Mr. Wayne Clark, Ms. Lorraine Read, and Ms. Jennifer Sampson.

EXECUTIVE SUMMARY

Recent studies by federal, slate, and local agencies have identified adverse biological conditions associared with contaminants in some areas of Puger Sound. Permit writers, resource managers, reviewers of environmental impaet statements. and others involved in environmental decision-making are f a d with the task of assessing a wide variety of information lo deal with the pollution problems. To addross the netds of this diverse group of data users, information on each of 64 po:lutants is sumlnarized in the following tables:

Table I: Regulatory Slatus and Analytical Considerations for Pollutants of Concern

Table Ik Criteria. Guidelines, and Regulatory Action Levels for Pollumu of Concern

Table m: Sources of Pollutanu Table IV: Concentrations of Pollutants in Puget Sound.

In addition, chmcteristics of these pollutants are summarized in Ule text of the report. A general description of the polluulnts is provided as well as a brief comment on exposure routes and risk and sources and fate in the environment (including soil, submerged sediment, air, and water).

viii

INTRODUCTION

1. INTRODUCTION

Background information on the dcvclopment of this repon and criteria used to select pollutants of concern are described in the following sections. Explana- tions of ealumn headings for each of four lables of information on these pollulanrs of concern and examples of how to interpret the data for one chemical fi.e.. benzo(a)pynnel are provided in Chapter 2 (Pollurms of Concern Tables). More detailed text descriptions of each pollutant of concern are provided in Chapter 3 (Descripdon of P o l l m s of Concern in Plcger Sound).

BACKGROUND

Recent studies by federal, state, and local agencies have found that significant adverse biological conditions are associated with contaminated sediments in some areas of Puget Sound (i.a, Commencement Bay,Elliolt Bay. Eagle Harbor, Sinclair Inlet, Event Harbor, and Ule Duwamish River). These studies have been ~erformcd by or for the U.S. Environmental Protection Agency @PA), ~ a s h b ~ t o n~ e p h n e n t o fEcology (~colog~), ~ational~ceanicand~tmospheric AdminisIration (NOAA). U.S. Army Corps of Engineers (Corps) SeatUe District, and Municipality of Mevopolitan Seatlle (Metro). A limiled number of pollutants of concern were listed ss part of an EPA Region 10project to quantify chemical loadings into Puget Sound (Jones & S t o h 1983). This list was circulated for review to the Technical Advisory Committee and the Management Committee of the Puget Sound Estuary Program (PSEP). Review comments from Ecology suggested dovsiopmont of a broader list of pollutants. This broader list was developed Into ihc Users Manualjbr rhe PoNw~t4f Concenl Ma& VSEP 1986). The objective of lhis rsport is lo update, expand. and reorganize tho 1986 manual b a d on the nsults of a survey of users condueled in January 1990. Ins~ructionson the use of elecwnic spreadsheet tables and diskenes containing these tables wen provided with the 1986 manual but have been deleted for lhis mpott because most usera preferred using writen copies of the lables (see Chapter 2, POIIWMISof Concern Tabfa).

The information summarized in the pollutant tables and the subsequent dascdpdve text in Chapter 3 can ba used as a durance for pernit wd(cra, reviewers, and Inspectom when evalualing discharges &om new or axisling lndustrlal and municipal facilltia; an aid for the design and execution of field investigations and monitoring efforls; and a resource for agency personnel in evaluatfng envlmnmenlat conditions and polenllalImpacts of pollurants on Pugel Sound. Examples of m t Puget Sound studies that have been used to update

INTRODUCTION

this rcpon include urban bay investigations wmplcted by EPA in 1988 for Elliott Bay and Everett Harbor. scdimcnl dam from the 1989 and 1990 Pugct Sound Ambient Monitoring Program. and class I1 inspection suwcys of industrial and municipal cfllucnts conducted by Ecology between 1987-1990.

SELECTION OF THE POLLUTANTS OF CONCERN

In 1986, an initial list of over I00 inorganic and organic contaminants of potential concem in Pugct Sound lTables I and 2) w s compiled for possiblc inclusion in thc poUulank of concern list. Thlhese contaminants were chosen fmm I) EPA's list of priority pollulank, 2) lisk compiled specifically for Pugct Sound (c.g., Konasewich ct al. 1982: Quinlan et al. 1985; Jones & Stokes 1983). 3) PSEP and Pugct Sound Dredged Disposal Analysis (PSDDA) workshops held to esrablish p r d u r c s for cnvironmenlal analysis of inorganic and organic conlaminants (PSEP 1989a,b), and 4) from field investigations in Pugct Sound (c.g.. Gahler ct a!. 1982; Malins ct al. 1980: Romberg ct al. 1984; TCM Tech 1985a). Expens in s p i l i c fields of chcmical rcscarch also providcd advicc during preparation of the initial list.

In addition to the individual compounds initially wnsidercd. three groups of compounds wcrc recommended: high molecular woight polycyclic aromatic hydrocarbons WPAH), low molecular wcight polycyclic aromatic hydrocarbons (LPAH), and lcnal polychlorinated biphenyls (PCBs) (mlhcr than individual Aroclors or PCB congeners). 'Ihe 1986 pollulanls of concern list included 52 conlaminants or groups of wnlaminants sclccted from this initial list of 100 chemicals.

M l v e additional conlaminants or groups of contaminants havc been addcd to Ulc text and tables to accommodate responses fmm tho h o n t suwcy of thc 1986 manual uscrs. These new mamlnanrs wcre mmmendcd bnsed on worker safety, mtmcnt plant aporalion, toxicity, and water quality considcr- atlons. The following four BPA priority pollurnts wcre addcd: bis(2-ethyl). hexylph~hala~e, In addition, the following bemnc, toluene, and toul xylcnw. eight groups of poilulank that arc no1 EPA priorily pollurnla wcre added:

Mono- and di.chlorodehydmabictic acids (rcsin acids found in pulp mill discharga)

TABLE 1. INOROANIC CONTAMINANTS OF POTENTIAL CONCERN IN PUGET SOUND

Antimony Silvor

Arsenic Load Zinc

Cadmium Mercurv Cyanide

Chromium Nickel Organolins

. ,. . ..- . ... . . . . . . . . . . . . . .. . . .. . . .. . . , . . . . . . . . . . .,

TABLE 2. ORGANIC CONTAMINANTS OF POTENTIAL CONCERN IN PUOET SOUND

Phenols

HSL 4-MolhylphBnOl

HSL' 2.M0thvlOhe~Ol 34 2.4~Olmerhvphenol

Subslltutsd Phenols

24 2~Chlorophonol 21 2.4.8-lrichlorophenol 57 2.Nltrophonol

31 2.4~D1cnloro~honol HSL 2.4.6-Tr~chlorophenol 59 2.4-Oinitrophenol

22 4.Chlor~3.meIhylphonol 64 Pentachlorophenol 80 4.8.Din1tro.o.crorol

Mlscallanaous Organlc Aclds l~ualacolrlrssln acldsl

2.Melhoxvphonol lgua~acoll 4.5,8~Tr1chloroouaiacol actdsMonochlorodehvdroab~ot~c

3.4.5~Tr1chloroguaiocol Tetrachloro~uaiacoI Olchlorodehvdroabiotic acids

LPAH Cornpounda

55 Naphthalono 1 Acenaphthons 81 Phenanthrono

77 Aconophthvlono 80 Fluoreno 78 Anthracene

Alkylaled LPAH Cornpounda

Z~Melhvlnaph~halOnO 1.Mothvlnaphlhaleno 1.2.3~Mothvlphonanthrenos

HPAH Compounds

39 Fluoranthono 74 Bonzotblfluoranthene 83 lndonoll.2.3~cdl~vrene

84 Pvreno 76 Bonzolkllluoranlhono 82 Mbenzola,hlenthracane

72 0enzola)enthfaceno 73 Banzo1e)pyrono 70 Bonzot~.h.l)porylono

78 Chrvseno

Chlorlnatsd Arornetlc Hvdrooerbons

28 1.3.Dlchlorobonzono 8 1.2.4.Trichlorobonzeno

27 1 A.D~chlorobonrano 20 2.Chlaronaphlhalono

25 1,2.0lch1orobenzon0 9 Hexachtorobenzene IHCBI

4

Chlorlnatad Allphetic Hydrocarbons

12 Hexachloroolhana 52 Haxachlarobutadiene L

ij PhthaIaIes

71 O~mothvlphthalate 68 0i.nbufylphlhatate 89 0i.n.octylphthlate

I 54 lsophorono HSL Oibenzoluran Polvchlorlnared Oibenrodioxins

HSL Benzyl alcohol Polychlorinated dibonzofurans

HSL Benroic acid

Organonltrogan Compounds

82 N.Nitr060diphOnylaminO 9 lH l - Carbozole

Pasdoldaa

93 D,P'.OOE 90 Ololdrin 102 o-HCH

94 p.p'-000 91 o.chtordano 103 @HCH

92 pep'-DOT 98 Endrln 104 A-HCH

89 Aldrln 100 Heptachlor 10s pHCH (llndanel

PCBs

Total PCBs'

Volatlle Halogenatad Alksnar

46 Chloromethane 23 Chloroform 32 1.2~Oichloropro~ane

48 8romomothano 10 1.Z~Dlchloroethano 61 Chlorodlbromomelhane

18 Chloroolhsne 11 1 ,l,l-Tr~ehloroelhano 14 1.1.2~Trlchloroethan~

44 Olohloromathane 6 Carbon tutraohlorlde 47 Bromolorm

13 1.1 '-Dlchtoroolhons 48 8romocllchloromothans 16 1,1,2.2-Tevachloroethano

- -Volatlla Halopanatad Alkanaa

88

29

V~nylchloride

1.1 '.Oichloraelhene

33 Cis-1.3.dichloropropene 87

Trans.l.3-dichloropropene 8 5

Trichloroetheno

Tettachloroethone

30 Trans.l,2.dlchlomothene

Volatlta Aromatlo and Chlorlnalad Aromallc Hydrocarbons

4 Benzene 3 8 Ethvlbenzene HSL Total xvlenes

86 Toluene HSL Styrene 7 Chlorobenzene ,.

Indicates EPA priority pollutant number.

' EPA hazardous subetanco list IHSLl compound.

( Total PCBs includes monochlorobiphonyls throuoh docachlorobiphenyls.

r Chlorinated guaiacols (associated with bleached discharges of pulp mills)

r Three of the most toxic PCB congeners that elicit adverse biological effects similar to those of 2,3,7,8-lemchloradibcnzodioxin

r Polychlorinated dibenzofurans

r Polychlorinated dibenzodioxins (in addition lo 2,3,7,8-tetrachloro- dibenzcdioxin)

r Methylethyl ketone (MEK)

Methylnaphthalenes (I-methyl and 2-methyl isomers)

r Methylaled phenanthrenes.

Pollutants that are not included in this report but have been recommended for routine monitoring based on a recently completed pesticide reconnaissance survey (FSEP 1991) include: diazinon in water and sediment (an organophosphate insecticide oRen used for conuol of fmit, vegetable, and ornamental foliage pests), diuron in water (a uracil herbicide used for sterilizing soils), and endo- sulfan I in sediment (a chlorinated pesticide used for control of foliar feeding insects on a wide variety of plants). These three pesticides wem detected in samples of sediment or waters in drainage basins of Puget Sound at levels that could cause biological effects (PSEP 1991). The reconnaissance survey was completed afler the pollumt rables had been completed. Eight other pesticides were detecled in samples collected during this reconnaissance survey but at concentrations that are of less concern. The detected pesticides are pan of a broad gmup of organophosphate, chlorinated, polar phosphorous, carbarnam, and urea pastieides, and chlorinated and iriazine herbicides that were Lested for in these samplw. Thwc compounds had been Identifled as of potential concern in Puget Sound based on an earlier review of contemporary pesticide usage (PSEP 1988).

Contaminants selected as pollulanls of concern for Ulis report meet all of the fouowing general criteria: 1) high toxicity (measund in laboratory studla), 2) high penlstence in the environment, 3) high bioaccumulation potential. In addition, pollutanls of concern meet one or more of the following speciflc criteria for Fuget Sound: 4) high measured wator column or effluent concenuation, 5) sxistence of known sources, 6) high conetnIration relative lo sediments from Puget Sound referencs anas, andlor 7)widc-spnad dlsvtbution in PugM Sound. The last two criteria were evaluated using data from we^ 1.000 sediment samples that have been inconmrated Into BPA's sediment quallty datab~sa (SBDQUAL) for Puget Sound. Some exmmoly toxic chemicals that are supported by few environmental data in Puget Sound are nevenheless included as pollutants of

INTRODUCTION

concern because of sufficient public or agency concern over their potential impacts. For example, available data on chlorinated diknzodioxins, chlorinated dibenzofurans, and chlorinated guaiacofs arcsummanrod even lhough information is available on thcir disrribulion in only a few areas of Paget Sound. Inclusion of those chemicals with few data indicates gaps in present knowledge of toxic pollutants in Pugct Sound.

POLLUTANTS OF CONCERN TABLES: Table I

2. POLLUTANTS OF CONCERN TABLES

The following four pollutants of concern tables are provided in this chapter:

RibIe I: Regulatory Status and Analytical Considerations for Pollutants of Concern

Table If: Criteria. Ouldeline-s, and Regulatory Action Levels for Pollutan(s of Concern

mble Ill Sources of Pollutanls Table IV: Concentrations of Pollutants in Puget Sound.

The information provided in each column of the tables, in addition to associaled references, is also described.

TABLE I. REQULATORY STATUS AND ANALYTICAL CONSIDERATIONS FOR POLLIITANTS OF CONCERN ,

The regulatory status of each contaminant and general analytical considerations are reviewed in lkble I.

Column 1-BPA Identified 65 categories of priority p o l l u ~ t s (lncludlng 126 speciflc chemical substance8 to be the focus lor regulalIon under the Clem Water Act). Because of their slaws as prtorily pollutants (Identified by P, T, and N in column I), thsse chemicals are most frequently analyzed by conmct' laboratories wclpating in BPA Superfund work.

TheUst of pollulants is found in the Code of Federal Regulalions (CFR)Tilk 40, Part 401.15. The complete Ust of inorganic and organic chemicals analyzed by ihe BPA Contract Laboratory Program (CLP) is found In U.S. EPA (1990a,b).

Column8 2.3, and 4-Analytical mahods for water, sediment, and Ussue m p l a r am listed in columns 2,3, and 4. PSBP has mmmendad guldellnes for analysis of many toxic pollu~anls, includirrg most EPA-designated prlorlty pollutants. For some pollutants, existing BPA methods were adopted by PSEP

POLLUTANTS OF CONCERN TABLES: Tahte I

(c.g., metals in water). At least onc class of pollutants on the pollutants of concern list (La, organctin complexes) involves analytical proccdurcs that are not routinely available.

Soums of information for columns 2.3, and 4 include PSEP (1989a.b) and U.S. EPA (1983a, 1984a, 1990a,b).

Columns 8, 6, 7, 8, 9, and 10-Limits of detection and practical quantification limits for analysis of pallutants will vary depending on the method u d and the lcvd of Interfercnws present. Columns 5-10 provide both limits of detection md practical quantification limits for water, scdimenl, and tissue. If PSEP protocols are available for these values, the PSEP-recommorided limits arc provided in the table and arc enclosed in boxes. Protocols dedicated to analysis of individual contaminants or groups of contaminants may yield lower limits of detection. Individual project goals must be considered when choosing target limits of detection.

Limlts of detection for water samples are listed in column 5 and ace from PSEP (1989a) for inorganic chemicals and Metro (1981) for organic chemicals. Practical quantification limits for warer samples are listed in column 6. These wcre oblAinsd from EPA CLP guidelinas for multimedia analysis of inorganic pollutants (U.S. BPA 19%) and organic pollutanls (U.S. EPA 1990b).

Limits of detacllon for sediments am provided in column 7 and are in accordance with those recommended by PSEP (l989a.b). Practical quantification limits for sediments arc listed in column 8 and are nlso consistent with PSEP rocommendations (PSEP 1989a,b). Although quantification limits for motals are not spbciflwlly idsnUfled In PSEP (1989a), Ule values In column 8 am consistent wllh a PSEP rrcommendadon that metals quantification limita be approximately 3.3 times the Umit of dctcctlon.

Limb of detection em pmvided for ~Issuasamples in column 9. Column 10 provides practical quantiflcatfon limits for Ussue mplas. Thew levels am in accordance with those recommended by PSEP (1989a,b).

Example-Benzo(a)pne Is an EPA pdodty pollutant that has analytical methods available for water, sediment, and Ussue samples. The water method for banzo(a)pyrene la a standard BPA procedure used in the analysis of wator and wastewater samples. A PSEP protocol for water has not ye1 been devolopcd for

POLLUTANTS OF CONCERN TABLES: Tabla I

benzo(a)pyrcne; however, sediment and tissue guidelines for analysis are available for benm(a)pyrcne through PSEP (1989a.b). These guidelines allow the use of various analytical techniquesaccording to a consistent set of qualily a s s u m e and quality control (QAIQO procedures.

In water. the practical quantification limit for bcnzo(a)pyrene is 10 pglL (i.e., 10 ppb) for routine analyses of 1-liter samples by EPA CLP methods. Limits of dctectlon (i.e., 1 pglL) can be oblained lhrough special analytical semi- requests. Practical quantification timils and limits of detection are also available for be.nzo(a)pyrene in sediment samples. The limit of detection of 10 &kg dry weight for sediments shown in Table I for benzo(a)pyrene is within the limit of dctection range of < I lo SO &kg possible by different analytical procedures. The use of limits of detection rather than quantification limits are recommended for malyses of benzo(a)pyrene in tissue samples (i.e., 20 &kg wet weight) becauss of the potenlial use of tissue data in risk assessment.

TABLE L REGUATORYSTATUS AND ANALMICAL ~ ~FOR POU-UrANTSOF CONCERN 3!

51 2 S 4 5 6 7 10

POLLUTANTS OF CONCERN 'CABLES: Table 11

TABLE II: CRITERIA, GUIDELINES. AND REQULATOAY ACTION LEVELS FOR POLLUTANTS OF CONCERN

Crileria, guidelines, and regulatory action levels in drinking water, ambient water. shellfish and fish tissue, and sediment are summarized for pollutants of wnccrn in 'IBble IT.

Column 1-Available goals, standards, or proposed standards for drinking water are included in column 1 and defined in footnote b of Table 11. These values are provided for comparison with ambient water quality criteria provided in other wlumns of the tablo. Under the Safs Drinking Waler Act, EPA promulgatu maximum wntaminant level goals (MCLGs) for drinking water. Thase MCLGs an, nonenforceable health goals. Primary MCLOs are set at a level at which no known or anticipated adverse effcels on human health oecur. allowingan adequate marginof safety. Maximum contaminant levels (MCIs) are enforceable slandards lhat are set as close lo MCLGs as feasible. MCLs may be set higher than MCLQs afier considering factors such as available treatment technologies and w s effecUvencss. If MCLO or MCL values are not available for a pollutant, secondary MCIXis are provided as available. mess secondary values address aesthetic qualilies such as taste and odor. Finally, other values in Bible I! that are proposed or are not yet available in final form are qualified by a "P"wde.

Primaty and secondary drinking water iegulations are found in 40 CFR Pam 141 and 143, respectively. Proposed and recently finalized MCLs and MCLOs were pubUshcd in the Federal Register (U.S. EPA 1985a) and updated 23 March 1988.

Column8 2, 3, 4, and @-Ambient water quality criteria documents are published and updated psdodldy by EPA. These criteria reflect the latest scientific knowledge on identifiable eItecls of pollutanls on public health, freshwater and saltwawr aquatic life, and recreation. The available acuuf and chronic criteria are summarlzed and presented for hushwater and saltwater aquatic Ufe in columns 2-5. Dashes indlcate that no criteria or toxicity thresholds are available in the water quality eriteda documents.

18

.~ . . ... - . . . A. . . -

POLLUTANTS OF CONCERN TABLES: Tablo ll

The ambicnt water quality criteria documents arc published and updated by EPA. D a a in Table I1 were obtained from thc Gold Book (U.S.EPA 1986a) and from the water quality criteria documcnts announced in the Federal Rcgister (U.S. EPA 1985b).

Columns 6 and 7-Human health cffccts presented in the ambicnt water quality documents are surnmarizod in columns 6 and 7. Values in column 6 (cancer risk) reflect estimates of ambient water concentrations of known or suspected carcinogens chat represent a one in one million ( 1 incremental~ cancer risk. The 10d incrcmcntal cancer risk was chosen for use in the table bccauso it rcpresenu the middle range of valucs presented by EPA in the water quality criteria documcnts. The cancer risk conccntralion for carcinogcns and no- effect (toxicity) concentrations for noncarcinogens were estimated by extrapolation from animal toxicity or human epidemiological studies using thc following assumplionr a 70-kg man as the exposcd individual and an average daily consumption of freshwafcf and atsarinc fish and shellfish products equal to 6.5 grams per day. Criteria based on these assumptions arc cstimated to be protective of an adult male who experiences average exposure conditions. The ambient water quality documents provide a wealth of information on contaminants. The values provided in columns 6 and 7 merely summarize the informalion contained in Ihe water quality documents and arc not meant to replace Qem. Dashes indicate that no human health data arc available in the watcr quality documents.

Columns 8 and 9-The U.S. Food and Drug Administration (FDA)has established action levels for a limited number of contaminants in seafood (i.e., fish and shellfish). Thwc levels are listed in cclumn 8. These administralivo guidelines, when exceeded, may trigger FDA to investigate the arcs where the seafood was raised or caught. A range of legal limits for seafood established by olher countries is provided in column 9. Dashes indicate chat no values were available.

The FDA action levels have been compiled from FDA documena (U.S. FDA 1982, 1984). Nauen (1983) compiled a summary of legal llmia for other countries for Ihe Food and Agdculeral Organlmtlon of tho United Nations.

Columns 10 and 11-EPA has derived a measure of toxicological potency from the doso-response relationship for a chemical of concern using a data set for

4 POLLUTANTS OF CONCERN

TABLES: Table 11

the most sensitive species. Noncarcinogens are charactedzed by a rcfcrcncc dose (XID) value, which is lhe highest avcmge daily exposure over a lifctimc that would not be expected to cause adverse effects. Carcinogens are characterized by a carcinogenic potency factor, which is a mcasurc of the cancer-causing potential of a subsmw. Both RFDs and carcinogenic porcncy fac~ors are provided in 'kble 11, columns 10 and 11, respectively. Dashcs indicate that neither an RfD nor a carcinogenic polency factor is available.

Columns 12. 13, and 14-Expected (mean) eqiilibrium panitioning values and lower and upper 95 percent confidence interval values have been determineil for sediments for selected nonionic organic chemicals and arc provided in columns 12, 13, and 14. The values were obtained fmm Zarba (Mwch 1989, personal communication) and are normalized lo organic carbon.

Column 18-Some interim guidelines were recently developed for assasing sedin~ent quality. From a national dalsbase. the Battclle Marine Research Laboratory and the Criteria and Standards Division of EPA developed what werc originally termed probable no-effects levels (PNELs) and are now termed screening level concentrations (SLCs). To develop these guidclincs, the prcscncc of a given benthic spocias is correlated to sediment contaminanl conccntralions to determine the minimum concentralion for a given chemical compound that was not exceeded in 90 percant of the samples containing the species. This process is canied out for numerous species to determine an SLC (Battcllc 1985a; 1986). Fourteen SLC values (normalized to organic carbon content) an.available for organic compounds in marine sediments and are lisled in column 15. Dashes indicate that no SLC values were available.

The source of Ihe SLC values in Table 11is a final report to EPA by Battelle (NORet al. 1987).

Column 18-Chemical crlteda for marine sedimcnt quallly standards have recently bean proposed by Ecology (1990; WAC 173-204-320). Values shown In column 16 for inofgenic and ionizable organic chemicals are oxpressed as pglkg dry woight, Compondlng chemical cdtcrfa for nonionic organic chemicclls (in parenthem) am expressed as &kg organic carbon. Dashcs indicate Lat no marfne Jediment quality standards were available.

POLLUTANTS OF CONCERN TABLES: Tabla ll

Columns 17, 18. 18, and 20-Othcr inlcrim guidelines, called apparent effects threshold (AETj values, have been developed for federal and Washington state agencies (U.S. EPA 1988; Ecology 1990). AET values wore derived using chemical and biological data from seveal Puget Sound investigations. The AET values in columns 17, 18, and 19 are based on toxicity data from the amphipod bioassay, the oyster larvae bioassay, and the Microtox* bioassay, respectively. AET values in column 20 rue based on effects as measured by abundances of benthic infitma. The AET values are defined as the concentration above which statistically significant biological effects (PcO.05) always occur in the databases of sediment samples used to create the values. Dashes indicate that AET values have not been established, usually because insuRcient data are available.

The data used in developing AET values are from Battelle (1985b), Chan el al. (1985a.b), Osbom et al. (1985), Barrick et al. (1988). Romberg el al. (1984). Tetra Tech (198Sb), Beller el al. (1988), Pastorok et al. (1988). and U.S. Navy (1985).

Column 21-Exceedance of criteria established in Ecology's Dangerous Waste Regulations (Ecology 1984 (revised 1990); Chapter 173-303 WAC] generally depends on tho volume of waste generated as well as the chemical and physical characteristics of the waste. Although the numeric criteda are not easily adapted to tabular format. WAC 173-303-9903 (Ecology 1984) designates a discarded chemical product as either a dangerous waste OW)or an extremely hazardous waste (EHW)and also provides the reason for the designation. Reponable quantities for the discarded chemicals are determined in aceordance with their toxic constituents, as established in WAC 173-303.081 and 173-303- 084. The infomatfon from WAC 173-303-9903 has been provided in column 21 where data are available. Chemicals that are not spec1flee:ly listed or designated may still be classifled as EHW or DW by the regulations. Dashes indicate that the chemical is not specifically listed in the regulations.

The infomation in column 21 was compiled from the state Dangerous Waste Regulalions [WAC 173-303-9903, ac amended by WSR 90-20-101 (17 October 1990)J (Ecology 19&4). Thm regulations incorporate, by reference, the National Institute for Occupational Safety and Health's Regisrry of Toxic Wecrs sf Chemical Substances and EPA's spill table (40 CPR 302.4). llolh the registry and lhe spill table are references for determining toxic categories for conaituents in a waste.

. . . . . ... ... .

POI.!.UTANTS OF CONCERN TABLES: Table 11

Additional data summaries of lifetime cancer risk vs. chemical wwntmtion provided in Appendix A have been updatcd from Tetra Tech (1986a.b) using information from U.S. EPA (1990~).

Example-No EPA drinking b te r standards or ambient water quality criteria have been set for bfazo(a)pyrene. Some information is available lor HPAH compounds, a gmup of organic chemicals on EPA's priority pollutant list that includes benzo(a)pyrene. These data include water concentrations described in EPA water quality criteria documents as apparent threshold levels lor acute or chronic toxic effeets on marine organisms (300 pglL) and an estimate of the 104 incremental caneer risk (31.1 nglL) to humans by consumption of contaminated seafood. Thc chemical criterion lor the benm(a)pyrene marine sediment standard in Puget Sound is 99.000 &kg organic carbon. Additional levels of concern for benzo(a)pyrcne in sediments are available for diarent biological effects indica- tors based on Puger Sound field investigations; resulting AET values range from 1.600 to 3,600 pglkg dry weight. The state dangerous waste regulations classify bcnzo(a)pynne as a persistent hydrocarbon that has been suficienlly designated as a carcinogen (Category P.+; sea Table 11) for reponable quantity purposes. Benzo(a)pyrene is a persistent HPAH mmpound for which there is sufficient animal or human data to establish the compound as a carcinogen. Thcrc are no FDA or other legal limits lor benzo(a)pyrene in tissue samples.

20

. . . -.. - . *-

- - - - - - - - -

-Em- -

- - - - (50m aXLWO w.w %am (50m- - - - 410 2100 500 a10 -- - - - lam >:*.can S0.w nw >t*.w- - - - 6x00 Q100 sea sea *.la0- - - - 4 1 0 m -.OW ldOo.C40 1.Om.OOO 4lO.W

- -

TABLE Il. (Coosinued)

-( W o r n

1100.000) DWD-o.m.004 fl10.004 Pm.P..

Il1o.w W.P..

i2m.aw W.P..

(go.ooo) W.P..

mooo) OW..

mow) MWAP..

l0l.W -

TA6UII. (CQ)o

POLLUTANTS OF CONCERN TABLES: Tablo Ill

TABLE Ill: SOURCES OF POLLUTANTS

Major known sources of wntamination around Puget Sound are listed in Table Ill. Municipal and industrial discharges are the two main categories of point sources. Additional information of pollutant sources is summarized in Chapter 3, Descriprlon of Pol!urants of Concern in hrger Sortnd.

Column I-For municipal discharges, chemicals are classified according to their frequency of detection (i.e.. deteeted in >25 percenl of samples analyzed, detected in s 2 5 percent of samples. or not detected). When results for fewer than five samples are available, no estimate of the frequency of detection is given. Dashes indicate that insufficient information (i.e., fewer than five samples) is available to categorize L e chemical.

The municipal discharge data used to categorize the pollutants are from Maro's Toxicant Prelreatment Planning Study (TPPS) (Cooley et al. 1984) and 'Barrick (1982). Supporting data were obtained from the cily of Everett wastewater trealment plant (Baird, C.E.. 1 August 1985, personal communication) and Class I1 inspection surveys (Andreasson 1990a,b; Hallinan 1988; Heffner 1988, 1990c, Reif 1988a; Zinner 1991).

Column 2-The types of industries from which release of each chemical has been documenled is coded in the industrial (point source) wiumn of Table 111 (column 2). Each induslry is given a separate descriptor code (e.g., ship building and repair is designated by the letter S). Dashes indicate that insamcienr data are available to categorize the sources of these pollutants.

Industrial sources of pollulants were determined using data from industrial reports prepared by Ecology's Water Quality Investigation Section (Joy 1987; Norton el al. 1987; Stinson and Norton 1987b). and from Class I1 industrial surveys, including recent reports by Hallinan (1989; 1990a,b), Hallinan and Ruiz (1990), Heffner (l989a,b; 1990a,b), and Relf (198813, 1990). Information from older Class I1 industrial surveys was abstracted from the Commencement Bay remedial inve~ligation (Tetra Teeh 1985b) and feasibility study (Tetra Tech 1986~). Additional data were included from Norton (5 February 1986, personal communication), Oalvin and Mwre (1982), Martin and Pavlou (1985), Palmork et at. (1973), Sittig (1980), Stranks (1976), and Young et (11. (1979).

POLLUTANTS OF CONCERN TABLES: Table Ill

Column 3-Data generated from combined sewer overflow (CSO) ampling are included In column 3. Chemicals found in CSOs are classified according to their frequency of detection (i.e.. the same as municipal discharges). Dashes indicate that insufficient information is available lo categorize the chemical. The Metro TPPS (Cmley el al. 1984) was Ule source of information on pollutants in CSOs.

Column 4-Nonpoint sources are difficult to identify and quantify. Nonpoint sources listed in Table 111 include agricultural, urban, and industrial runoffs and groundwater seeps. The urban runoff designation includes those chemicals detected in > 10 percent of thc samples analyzed for the National Urban Runoff Program (NURP)(U.S. EPA 1983b). The 10 percent criterion. used in the NURP summary report, was also used in Table 111. Dashes indicate that insufficient information is available to categorize the type of source.

Urban runoff data are primarily from NURP !US. EPA 1983b) and are considered representative of Puget Sound's urban runoff. The NURP study included analyses of runoff from Bellevue, Washington. Also accommodated in thc table are urban and industrial tunoff and groundwater data gathered by Ecology and other investigators, as summatized in Tetra Tech (1985b) and in recent repons by Johnson and Norton (19891, Joy (1987), Norton (1988; 1990a,b), SUnson and Norton (1987a,b), and Stinson et al. (1987).

Column 5-Occasionally, product spills (e.g., ore and oil) occur in Puget Sound that release chemicals into the environment. The types of spills lhat have occurred in Puget Sound where chemicals are expected to be found are indicated In column 5. Dashes indicate lhat there are insufficient data to categorize the typ of spill. Sounmr of information used to categorize pollutant spills include Nonon (1985b), Sitllg (1980), and Tetra Teeh (1985b).

Example-Benur(a)pyrene has been detected in >2S percent of available municipal effluent and CSO samplas from Puget Sound. There are insufficient data to document the prasenee of benzo(a)pyrene in discharges from industrial point sources in Pl~get Sound, although there are a number of industrial processes that are expected to generate benzo(a)pyrene (e.g., combustion of fossil fuel, primary prduclion of fenous and nonferrous metals, and wocd treatment with creosote). There are also insufficient published data from Puget Sound or NVRP (U.S. EPA 1983b) to document the presence of bcnzo(a)pyrene in discharges

. . . . . .. . . . . . .. ... . . , .. .

POLLUTANTS OF CONCERN TABLES: Table Ill

from nonpoint sources in Pugct Sound, although benzo(a)pyrenc has been reported as a component of stomwater runoff in research studios conducled in LakeWashington, southern California, Narragansett Bay, and Europe. Benzo(a)- pyrcnc is an expected component of most oil spills.

* 32

. TABLE111. SOURCESOF POLLUTANTS

Mmq &sac Qda*m QrcmUn

cwmf CVaides Lead

Merruy Na.4 Sh*r

TABLE Ill. (Conchred)

~ r m a h e d h B a c h K * a n i s ~ b y 0 1 m ~ i n t h e ~ .

POLLUTANTSOFCONCERN TABLES: Table IV

TABLE IV: CONCENTRATIONS OF POLLUTANTS IN PUGET SOUND

Concentrations of chemicals in sediment, fish and shellfish tissue, and water samples from Puget Sound are summarized in Table IV. The summary for sediments includes substantial data for reference areas chosen by different investiaators a? regions removed from known sources of contamination in Pugcl ~ound;as well as for nonreference areas (e.g.. u a a n embayments and the central basin). Data for tissue and water samples are more limited. Additional informalion on the general environmental distribution of each pollutant is presented in Chapter 3, Descrlptfon of Pollrcronts @Concern in P~cget Sorrd.

Columns 1 through 16-A computerized database was used to calculate minimum, median. 90th percentile, and maximum concentrations found in sediment samples @en from reference and nonreference areas and urban bays in Puget Sound. Detection frequencies for sediment samples were also calculated. All sediment analyses conducted in Puget Sound have not been incorporated into the database, but the data for some chemicals represent nearly 1,000 samples from nonreference stations and 150 samples from reference stations in Puget Sound. This database is continuing to be expanded. In all cases, the highest detected value is used as the maximum. The minimum is either the lowest detected value or the lowest detection limit for undetected values (whichever is smaller). These criteria were used because detection limits can vary substantially for different samples and smdies. Dashes indicate that insufficient data are available lo calculale concentWions, or that no data are available for that chemical.

The sediment chemistry database compiled for Pugel Sound (U.S. EPA 1988) Includes data from Chan et al. (1985a,b), Battelle (1986). Beller el al. (1988), Pastorok et al. (1988), Romberg et al. (1984). PSAMP (1990a,b), PSDDA (1988, 1989) Tetra Tech (1985b. 1986d. 1990), Trial and Michaud (1985). and U.S. Navy (1985), Crecelius el al. (1989). PTI (1990).

Columns 16,17,18 and 19-Minimum and maximum concentralions of chemicals found in fish muscle tissue are provided in columns 16 and 17 of mble IV. Minimum and maxin~um concentrations of chemicals in shellfish tissue are provided in columns 17 and 18. The data arc not presently available in a form that readily allows campulatlon of the medians and prcentlles provided for the sediments. Liver or hepatopancreas tissues are not included. However. limited chlorinated dioxin and furan data for fish tissues include whole fish

POLLUTANTS OF CONCERN TABLES: Tabla IV

samples reported by Terpening (4 OctobEr 1989, personal communication). Dashes indicate insufficient data am availabls

The summary mges of wncenmtions in 'lhble 1V are intended to provide an indication of the magnitude of contamination in fish and shellfish tissues from Puget Sound. More detailed summaries by specificarcas of Puget Sound and by species are provided in PSEP (1988b) and Faigenblum (1988). Mean values are also provided in these repom, although not all of the data provided in the ranges in Table 1V are included in those references.

Tissue dam were compiled from Bcller et al. (1988). CH2M Hill (1989). Clark (1983). Crecelius et al. (1989), Faigenblum (l988), Goldberg el al. (1983). Landoll et al. (1987), Malins et al. (1980), Norton (5 February 1986, personal communication), Pastorok el al. (1988), PSEP (1988b), PTI (1990). Sherwood el al. (1980). T m Tech (1985b). Yake et al. (1984) and Terpening (4 October 1989, personal communication).

Columns 20 and 21 -information for concentrations of pollulanlr in waters from reference areas has not yet been included in Table IV. Thus, columns 22 and 23 contain dashes indicating the lack of data.

i i

. . 1Columns 22 and 23-Minimum and maximum concentrations found in nonreferenee Puget Sound waters are provided in columns 20 and 21 of Table IV. The data are not presenlly in a form that allows computation of medians and

;

percentiles provided for the samples. Blank spaces indicate that insufkient data are available. !

1

Receiving wat& dam were compiled from water quality surveys by Ecology (Bernhardl 1982; Johnson and Prescott 1982a,b,c.d; Norton 1985a,b), EPA (Osbom 1980a,b), and Metro (Romberg et al. 1984).

r I

Example-Benzo(a)pyrene is found in sedimats from nonreferencc and j reference areas and from urban bays. Based on the current database, concenlra-

i Uons of benzo(a)pyrene in sediments of Puget Sound -nge from <1 to IKJ,000

I 1figlkg dry weight, although most oonccntrations (eves m nonrafarencc areas) are 1c240 &kg dry weight. Benzo(a)pyrene has been detected in shellfish tissue (maximum 240 pglkg wet weight), but not in muscle tissue of fish. Water iwnccnmtions of benzo(a)pyrcne in Puget Sound arc typically undetected (i.e.,

I < I fi$/L). 1

. TABLE N.CONCENTRATIONS OF POLLWANTS IN PUGETSOUND

urm U1.l 9 0

2n72 W.10 140

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arm w.10 zm Z s n WfO 110

BllO W.lO 20

IS42 VOlO 61

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DESCRIPTIONS OF POLLUTANTS

3. DESCRIPTION OF POLLUTANTS OF CONCERN IN PUGET SOUND

In this chapter, chemical characteristics, common uses. exposure routes. health effects, sources, and environmental rate are discussed for each pollutant of concern in Puget Sound when that information is available. Most of the information provided is generally a ~ ~ a b l e fmm repons published by (he Agency for Toxic Substances and Disease Control Regisy (a unit of the U.S. Public Health Service), Howard (1989, 1990). and Casarett and Doull(1986).

INORGANIC CHEMICALS

Descriptions are provided in this section for the 12 inorganic chemicals listed in Table I (see Chapter I), including cyanides and organotin. Three inorganic chemicals that have been designated priorily pollutants by EPA in 40 CFR 401.15 (i.e., beryllium. thallium, and selenium) were not recommended by Puget Sound expens during development of the pollulants of concern for this repon. Although toxic, beryllium and thallium have not been found in Puget Sound in concentra-tions that exceed reference tevels. Selenium was found in elevated concentrations in only one Puget Sound study. Specval interferences occurring in connection with the particular inswmental analyses used were considered the probable cause of the elevated resuits (PSEP 1989a).

Antimony

Antimony is a natural element that is found in over L O O mineral specie& Antimony is not an abundant element and is usually found as a sulfide rather than in the pure form. The brittle character of antimony improves the hardness and lowers the melting point of certain alloys. Antimony compounds are widely used for the production of flame retardants, fireworks, matches, ammunition, and storage batteries.

Exposure Routes and Risks-The greatest exposure to antimony for humans occurs in connection with selected oecupalions (e.g., mining, industrial proccsslng of antimony-containing ores, and commercial uses of antimony

. . . .. ... , , . . . . . . ..


uioxide). Humans may ingest antimony in small amouncs in water and food. Inhalation is also an exposure route, especially in the vicinity of smelling facilities and municipal incinerators. Howcver, environmenlal exposures from all media appear to be minw sources of antimony for humans.

Although antimony is toxic to mammals. including humans, few epidcmiolog- icd studies of antimony have been conducted due lo the lack of rceognizable public heallh problems associated wirh overall low levels of exposure lo antimony. Limited information is available concerning loxicity to freshwater organisms, but there is almosl no information concerning the acute or chronic toxicity of antimony to saltwater organisms.

Sources and Fate-Antimony may enter aquatic systems from the natural weathering of rocks, in soil ~ n o f f , in effluents from manufacturing facilities, and from municipal dischargw. Smelting operations, fossil fuel combustion, and municipal incineration contribute to atmospheric antimony. Industries involved in the manulacture of alloys, paints, laquers, glazes, glass, and pottery and in the produclion of organic chemicals are sour= of antimony. Other sources include copper smelters, chloralkali plants, and smelter slag. The semiconductor industry also uses antimony in the production of infrared detectors and diodes. Antimony has been detected, onen at very high levels, in 74 percent of sediment samples taken from nonreference areas in Puget Sound (Table IV). The highest levels of antlmony in Puget Sound [several thousand pans per million (ppm)] are associated with copper smelter wastes (Tetra Tech 1985b).

Solubilities of antimony compounds range from insoluble to fully soluble. Inorganic antimony compounds may be only slightly water soluble or may decompose in aqueous media. C d n compounds undergo hydrolysis or oxidation and are not envimnmentally persistent. However, antimony associated with smelter waslea in Puget Sound is expected to be highly persistent @Ira Tach 1985k 1986~).

Arsenlc

Arsenic is a naturally occurring element not commonly found in its pure state. Amnic generally combines with one or more other elements. For example, arsenic commonly combines with oxygen, chlorine, or sulfur lo form the inorganic spacia, while arsenic can also combine wilh carbon and hydrogen to form the organic species. Arsenic exists in a variety of chemical forms in marine and estuarine ecosystems, including inorganic s p i e s , methylaled forms, arseno-lipids (fats),arseno-sugars. and other biochemical forms. Data for told

47

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DESCRIPTIONS OF POLLWANTS

arsenic are diflicult to interpret in relation to effects in a particular environment because of the multiplicity of organic and inorganic chemical species involved.

Exposure Routes and Rlsks-All humans are exposed to low levels of arsenic because of its wide distfibution in the environment. The Pacific Nonh- west, in particular, contains natuurally high levels of arsenic because of the erosion of rocks that are enriched in arsenic. Greater than average exposure may occur in certain occupations (e.g., metal smelling. wood preservation, and pesticide application) or because of proximity to natural mineral deposits, chemical wane disposal sit=, or induslrial sources.

Most humans are exposed to arsenic by ingesting food containing arsenic; drinking water and air provide lower amounts. Although some arsenic may be absorbed by the sun. skin absorption is a much less important exposure route than ingestion.

In general. the toxicity of arsenic is a function of its chemical and physical form. Organic arsenic is less loxic lhan inorganic arsenic. Therefore, because organic arscnic predominates over inorganic arsenic in most fish, macroalgae. mussels, and shrimp, health concerns from consumption of arsenic-conlaminated tissucs are generally low. Arsenic compounds that are more soluble tend to have more acute toxicity. For example, arsenic (111) compounds are generally more

: toxic than arsenic (V) compounds. Inorganic arsenic has been recognizal as a human poison since ancient times; ingestion of large doses causes death. Ingestion of lower dose-s produees a variety of systemic effects. Animal studies suggest felal effects, but this area has not been well studied in humans. Mottled

! pigmentation and small lesions on the sltin are the most common indication of chronic oral exposure to inorganic arsenic. There is clear evidence that such loaions can develop into skin cancer. Although inhalation exposure causes much milder systemic effect$, thwc is growing concern over the lhrcat of lung cancer, especially with occupational exposure.

Inorganic arsenic is a recognized human carcinogen. However, there are few human studies of carcinogenicity and toxicity of arsenic that have included diffcrent arsenic forms. An additional complicating factor is the limited utilQ of anlmal sludles as predictors of human efkts because of the greater sensitivity w arsenic by humans. While there is evidence that exposure to low lcvels of arsenic has beneficial health effects in some species (e.g., rats, goats, chicks, and minlplgs) (U.S. EPA 1984d), the beneficial daily dose is quite small (La, i0- 50 pglday). This amount is normally supplied in a human diet that does not include seafood, which may Increase the daily intake to 200 pglday (Casarett and Doull 1986).

48


Toxicity and olher effects of arsenic on aquatic life are significantly modified by changes in water temperature, pH, organic content, phosphate concentrations. suspended solids. and presence of other substances and toxicants, as well as with arsenic speciation and dutation of exposure. Large interspecies differences in toxicity are recorded even among species that are closely relared Mxonomically (U.S. FWS 1988).

Sources and Fate-Combustion of fossil fuels is a major source of arsenic in the atmosphere. Tobacco smoke is another source. No arsenic is currently produced in the United Slates except as a by-product of other operations, such as the smelting of copper, l a d , zinc, gold, and silver ores. However, arsenic is imported for use in wood preservatives, pesticides. and herbicides. Use of arsenic-containing pesticides has declined in recent years because of the development of less broadly toxic substitutes. Arsenic is also used as an alloy additive to lead and copper and in the manuliwture of low-melting glasses. ,Although relatively small, use of arsenic in transformers is increasing. Consumer products that once contained arsenic (e.g.. paints, dyes, and rat poisons) are no longer in general use; therefore, exposure from these sources is minimal.

A former copper smelter plant located in Tacoma may have conlributed as much as 25 percent of Ule tolal amount of anthmpogenic arsenic in the world (Phillips 1990). In the United States, arsenic trioxide was produced only at this smelter, which closed in January 1986. Allhough 90 percent of United Slates surface waters contain less than 10 parts per billion @pb) arsenic, higher concen- IraUons have been reported in the Puget Sound area (up to 3,800 ppb) because of smelting operations and natural sourccs of arsenic (Crecelius et al. 1975).

Arsenic may be released lo the atmosphere as a gas vapor or adsorbed lo paniculate matter. However, most arsenic in the air is adsortred to particulate matter. It may be transported to other media by wet or dry deposition; photolysis is not considered an imponant fate process for arsenic compounds.

Arsenic in surface water can undergo a complex pattern of transformations. Arsenic is extremely mobile in aquatic systems and, as a result, rivers ace a major source of arsenic to Puget Sound and oceans. Sorption to clays, iron oxides, manganese compaunds, and organic materials is an imponant fate of arsenic in surface waters. However, as waters become more alkaline or sallne, arsenic is less likely to be adsorbed. Arsenic in water and soil may be reduced and methylated by fungi, yeanu, algae, and bacteria, and these forms may volatilize and escape into the alr. The rare of volatilization may vary considerably, depending on soil conditions (aerobic or anaerobic), pH, and h e presence or absence of microbes.


Plants may awumulale arsenic via mot uplakc from soil solution, and cenain species may accumulate subskantial arsenic levels. Bioconcentration of arscnic also occurs in aquatic organisms, primarily in algae and lower invenebmtcs. However, biomagnification in aquatic food chains does not appear significant, although some fish and invertebrates wnlain high levels of arsenic compounds that are relatively inen toxicologically. In Puget Sound, higher wncenlrations of arsenic are accumulated by invertebrates and musscls located near pollumt sources, but there is no evidence for increased accumulation of arsenic in Puget Sound fish near industrial sourax relative to reference conditions or for biomag- nilication of arsenic in the food chain (Ginn and Bamck 1988).

Cadmlum

Cadmium is a naturally occurring element usually encountered in combina- tion with other elements such as oxygen, chlorine, or sulfur. Cadmium compounds are all stable solids that do not evaporate.

Exposure Routes and Rlsks-For humans who are not subject to occupational exposure to cadmium. the primary exposure route is ingestion of food conlaining cadmium. Contamination of topsoil through the application of phosphate fertilizers or sewage sludge increasw cadmium levels in foods. Another source of cadmium is tobacco smoke. Smokers have approximately twice as much cadmium in their bodies as nonsmokers. U.S. EPA (1990~) has designated cadmium a probable human carcinogen by the inhalation route.

Cadmium is not known to have any beneficial health effects, but can cause a number of adverse effects on humans and other organisms, including death. Although high-level exposures are ram, there is great concern regarding the eflects of low-level, long-tenn exposure. Soluble cadmium compounds have grater toxicity than insoluble cadmium compounds becsuse they are more readily absorbed by the body. Typical levels of cadmium exposure through ingestion of food and waler or through inhalation of air (approximately 0 . W mglkg per day) are not a mlljor health concern. However, cadmium is metabolized by humans very slowly and even low doses can result in the accumulation of toxic levels if the oxposum conUnues for a long pedod of Ume. Because of the ssvere effects of cadmlum exposum, then Is pending federal legislation proposing a ban on the usc of cadmium in pigments and on other nonessential uses.

Sources and Fate-Most cadmlum in the United Scales is obtained as a by- product from the smelling of zlnc, lead, or copper ores. Cadmium is used

2


primarily in metal plating and the manufacture of pigments, batteries, and plastics. Cadmium is not onen encountered at levels of concern in water, although it can leach into water from pipes and solder or may enter water from chemical waste disposal sites. The largest source of cadmium to the general environment is the combustion of fossil fuels (such as coal or oil) or the incincra- ;lion of municipal waste materials.

Cadmium in lhe atmosphere is persistent and easily respirable. It can be transpaned to soil and water through wet or dry deposition. Cadmium in surface water is relatively mobile. Because cadmium exists only in the 2+ oxidation slate, aqueous cadmium is no1 strongly influenced by the oxidizing or reducing potential of water. Sorption by clays and iron oxides is imporIan1 for reducing cadmium in water. Cadmium is not reduced or methylated by microorganisms.

Cadmium is readily accumulated by all organisms, through both food and water. Cadmium accumulates in freshwater and marine organisms at concenua- lions hundreds to thousands of limes higher than the concentrations found in ambient water (Callahan et al. 1979). Aquatic bioconcentration is greatest for invertebrates such ar molluscs and crustaceans (bioconcentration factors range up to 250,000), followed by fish and aquatic plants. Bioconcentration factors may range up to 1.000 for aquatic plants and up to 3,000 for fish (Callahan et al. 1979). Typical concentrations of cadmium in organisms from nonpolluted areas range from I lo 10 pglkg in fish and from 100 to 1,000 &kg in shellfish (U.S. EPA 1981; Casarelt and DouIl 1986). These values are similar to those documented in Puget Sound (Table IV). The highest concentration of cadmium in Puget Sound sediments is associated with smelter wastes in Commencement Bay (Tetra Tech 1985b).

Chromium is a lusuous metal found in crystal or powder form. It is a natural element occurring pdmarily as the mineral chromite. Since 1961, all chromium orap haw been imported by the U.S rather than mined. Chromium is widcly distributed in the environment and occurs in four different oxidation states. Only two of he,%forms, trivalent chromium [Cr Qlf)] and hexavalent chromium [Cr (VO]. are environmenlally impanant. Trivalent chromium is more common and slllble lhan hexavalent chromium, which is ihe more toxic and commercially imponsnt form. In additlon, hexavalent chromium is a strong oxidizing agent.


Exposure Routes end Risks-The primary routes of exposure to chromium lor humans are inhalation. ingestion, and dermal contact. Although the general public is wntinuoudy e x p o d m trace amounts of chromium, occupational cxposurc is the major human health concern.

Chromium is an essential nutrient in trace amounts. but excess hexavalent chromium causcs kidney damage, binh defects, and genetic mutations in animals and humans. The advene health effects of excess trivalent chromium are similar, but much higher concentrations are required to produce these effects (U.S. EPA 1986a). Therefore, analysis for total chromium in environmental samples may not be sufficient to establish toxicity. It is not known whethw trivalenichromium i s a carcinogen. Although no data are available conccming the acute toxicity of trivalent chromium to saltwater organisms, hexavalcnt chmmium is highly toxic to aquatic organisms. .... . . . .

Sources and Fate-Chromium is widely used in electroplating and metal finishing, in painls and fungicides, as a catalyst, and as a component of wood prcservalives. Chmmlum can be found in emissions from copper smelters and coal wmbustion and in slag used as fill and sandblast grit. The two major sources of hexavalent chromium are cooling towers and chrome plating wastes. Allhough chromium has been detected in flsh. water, and sediments lhroughout Puget Sound CIgble IV), data are lacking on the relative amounls of uivalent and hexavalent chromium. However, most chromium in Puget Sound appears to be associated wilh natural saurccs (Barrick et al. 1988).

The dominant fate process for chromium in the aquatic environment varies wilh the species of ahromium. While vivalent chromium rapidly adsorbs to paniculate material, h~xavalent chromium does not. Hexavalent chromium is accumulated by marine animals, b u ~ the bivalent form is not accumulated to a significant degree. Ultimately, the fate of both forms of chmmium depends on a number of factors including pH, dimlvcd organic carbon icvels, sediment organic matler content, and physical properties of sediments.

Copper

Copper is a metal that occurs naturally in rock, soil, water, sediment, and air, as well a8 in planu and animals. It is an essential element for all living organisms. Copper compounds occur bolh naturally and anthropogenidly. Copper is mined extensiveiy and i s extremely mallcable.

1

DE3CRIPl'IONS OF POLLUTANTS

-Exposure Routes end Risks-Because copper is common in the environ-

merit, humans may be exposed through inhalation, ingestion, and dermal contact. However, exposure lo humans is likely lo be limiled because copper binds strongly to dust and din or becomes embedded in other materials. Such copper is not easily absorbed. Copper found in hazardous waste sites is usually in this particulate form. Soluble copper compounds used most commonly in agriculture may poso a greater health concern because they may be taken up by plants and animals or released into rivers and lakes. The risks from the transport of soluble copper compounds to surfam water and groundwater may be lessened becsua they are rapidly adsorbed to panicles.

Humans normally consume approximately 1 mg of copper per day. Although : a large single d o a of copper may cause kidney and liver damage or death, the

i body has effective melanisms for blocking the envy of excess copper. Infants* and small children are more sensitive to Copper than adults, although there is no evidence regarding human reproductive or felal effects from excessive exposure to copper. Copper is not a known carcinogen based on animal studies to date.

I t There is little information regarding copper toxicity in humans, and the cffects

of inhalation and dermal wntact have not been well studied. However, copper can be highly toxic to aquatic organisms at concentrations that are only somewhat higher than nuvit~onal doses. Because copper is highly toxic to marine plant$, copper-containing pain& and preservatives have been widely used to control algal growth on boata and piers.

t

i Sources and Fate-Copper is used primarily as an alloy in the manufacture

of wim, sheet mctal, pipe, and other metal products, especially brass and bronze. Copper is also uJed in agricultum to treat plant diseases such as mildew. Other uses include water treatment (as an algicide) and preservative treatments for wood, leather, and fabrics. Consequenlly, copper may be found in the eftluents of industdes associated with those uses.

Several processes determine the fate of copper in water including sorption, complex formalion, andbioaccumulation. In addition, the fate of copper is highly depeltdent on pH, biological activity, and the presence of competing heavy metals. The bioconmtration factor of coppar In fish is 10-100, which is relatively low compared with other species that easily bioaccumulate. For example, bioconocn-muon factors in oysters may reach -30,000 (Callahan el al. 1979: U.S. EPA 1984b). The absenw of substantial bioaccumulation of copper by Puget Sound fish relative to levels of sediment conlaminallon in some &as of the sound is eonsistonr with h e considerable ability of marine flsh to regulate levels of most metals in musclc tissue (Ginn and Barrlck 1988).

DESCRIPTIONS 01: POLLUTANTS

Cyanldea

Cyanides are a diverse group of organic and inorganic compounds. Hydro- gen cyanide is the best known and most toxic of the cyanides. It occurs rarely in nature and is usually prepaced commercially from ammonia and methane. Cyanide ions can react with a variety of metals to form insoluble mela1 cyanides. Iron cyanides (ferricyanides and ferrocyanides) have a variety of industrial uses.

Exposure Routes and Risks-Cyanide is readily absorbed by humans through the skin and all mucous membranes. Inhalation is also an exposure route, although alkali salts of cyanide are toxic only if ingested. In general, an organism exposed to cyanide will either quickly metabolize the substance or be . killed. In the case of hydrogen cyanide, death is caused through interference with the enzymes associated with cellular oxidation. Death occurs within minutes to several hours aner exposure lo even small amounts of sodium or potassium cyanide, depending on the exposure route. DeaL is more rapid afier inhalation of cyanide fumes.

Sources and Fate-Cyanide is found in cenain rat and pest poisons, silver and metal polishes, photographic solutions, and fumigants. It may be found in the eftluents of copper smelters and metal manuhctudng facilities.

The data on fate of cyanides in the aquatic environment are inconclusive and should be interpreted with caution. Volatilization and biodegradation appear to be the dominant processes affecting aquatic cyanide. Cyanides are sorbed by organic materials and, lo a lesser extent, clay m i n d s . Hydrogen cyanide is not strongly partitioned into benthic or suspended sediments, primarily due to its high water solubility. However, the simple metal cyanides am insoluble and probably accumulate in sediments. Complex metal cyanides arc msponed in solution &rough the water column. Changes in the eoncentration ratio of metals to cyanide can alter the behavior of the metal-cyanido compounds. If the metals become mom prevalent, formation of the simple metal cyanides is favor&, if the cyanide becomas more prevalent, the complexed forms occur. lmn cyanides do not release cyanide without exposure to ultraviolet light; thus, sunlight can cause mobilization of cyanide in water containing iron cyanides.

There is litlle potential for bioaccumulalion of cyanides; hydrogen cyanide is either melabollzed or is fatal to organisms. Metal cyanides are less toxic and may have a greater tendency to bioaccumulate. Cyanidesmi biodegraded at low concentrations by almost all organisms.

I


Lead is a naturally occurring heavy metal that is a major constituent of more than 200 minerals, the mast common of which is galena. The metal is bluish- white. very soft, highly malleable, ductile. a poor conductor of electricity, and very resistant to corrosion.

Expo8ure Routes and Risks-Humans accumulate lead by ingestion of food, water, and soil; through exposure to other sources such as ink and paint: and by inhalation of atmospheric lead. Controversy exists over the relative importance of these sources and their contribution to the toxic effects of lead in humans.

Exposure to lead has been linked to a wide range of offects in humans, . including neurological disorders and impairment of blood synthesis. Considerable research has been conducted on lead levels in human tissues and on correlations between levels of lead in children and impaired intellectual development. Cenain lead compounds (i.e., lead acetate and lead sulfate) have been designated probable human carcinogens by U.S. EPA (1990~) based on animal tests.

Little mearch has been conducted on the effects of lead on aquatic organisms, parlicularly marine organisms. Acute toxicity to lead has been documented for 13 saltwater specics a eoncentrations in water that range from 315 to 27,000 ppb (U.S. EPA 1986a). Chronic effects have been documented for mysids and some sp ies of macroalgae. In addition, lead can suppress reproduction in marine polychaeta.

Sources and Fate -The primary sources of lead to the environment include discarded batteries, leaded gasoline spills or leaks, motor vehicle emissions. paints, inks, dyes, and the emissions and slag of copper smelters. LRad is also used in some chemical processes and is present in solder and plumbing. Because lead is ubiquitous in urban arms, urban runoff is a common source of lead pollution. Concenlrations of lead in sediments from urban bays of Puget Sound can be as much as 10limes higher than those found in reference areas of Puget Sound and, in isolated cases, may be as much as 1,000 limes higher (Tetra Tech 1985b, Beller el al. 1988, Pastorok et al. 1988).

The late of lead is influenced by the patlicular oxidation stare g.e., Pb (O), Pb GI), or Pb QV)]. Lcad exists principally as Pb GI)in most waters, and adsorption to sediments and suspended sediments is the predominant fate. LEad tends to form complexes with organic materials in water. Benthic microorgan-


isms can methylate inorganic lead lo form a more volatile and toxic form. Bioaccumulation occurs with weakly sorbed lead. although biomagnificstion is not generally significant. Bioconcentration factors tend to decrease as the trophic level increases.

Mercury

Mercury is a naturally oocumng element used in its pure form in many consumer products (e.g., thermometers and barometers). It is also found in compounds with other chemicals such as chlorine. Organic mercury (e.g.. methyl mercury) can become highly concentrated in the flesh of camivorour freshwater and saltwater fish (e.g., concentrations in pike and swordfish have exceeded 1 pg/g in tissue) (U.S. EPA 1984~). Therefore. olhewise low levels of mercury contamination in oceans and lakes can lead to contamination of these fish that may be toxic to humans. Mercury that is released to the environment remains there indefinitely and its form (inorganic or organic) may change over lime.

Exposure Routes and Rlsks-Because mercury occurs naturally, exposure to low levels from all media is continuous. Cenain segments of the general population are exposed to higher levels of mersury through the consumption of larne amounts of fish that accumulate mercury. Inhalation of mercury associated wi& occupational exposure also is a source of higher levels of mercury. Ooeupa-lions posing greater lhan normal risks of exposure include health-related, chemical, metallurgical, electrical, automotive, and building industries.

Mercury easily enters the body via inhalation and ingestion, and some mercury may be absorbed through the skin. In panicular. methyl mercury is readily accumulated by flsh, which has led to major concerns for human health from the consumption of mercury-contaminated fish. Mercury that has entered Iho body may take months to be eliminated. Long-term exposure to either organic or inorganic mercury can irreversibly damage the brain, kidneys, and developing fetuses. l l ~ eform of mercury and the route of exposure influence the severity of health eftects (ATSDR 1989a). For example, ingestion of organic mercury in contaminated flsh or grain causes greater damage to the brain and to developing fetuses Ihan to the kidneys. Inhaled inorganic mercury vapor tends to cause greater harm to the brain. Inorganic mercury ingested in contaminated food or water tends to cause greater harm to the kidneys. Short-term exposure causes similar eMcts, although full recovery is more likely. Mercury has not been proven carcinogenic. Effects of mercury reponed in studies of aquntic

DESCRIPTIONSOF POLLUTANTS

organisms included increased mortality. reduced growth and reproduction, and skeletal abnormalities. Mercury is considered the most toxic of the heavy meials to aquatic organisms.

Source8 and Fate-Mercury in the environment has both natural and anthropogenic sources. The maor source of atmospheric mercury is global degassing of mineral mercury from Ihe soil and water, at a rate of approximately 30,000 melric tons per year (U.S. EPA 1984~). Subsequent deposition of atmospheiic mercury in the ocean (approximately 11,000 meuic tons per year) is the predominant source to the marine environment land runoff accounts for less than half this amount. Releases of mercury to the air by human activities are estimated at 2.000-10.000 melric tons per yw, mostly from the mining and smelting of mercury ores. industrial procesw, and combustion of fossil fuels (mpeciallycoal). Other sources of emissions may include chloralkali manufacluring facilities, copper and zinc smelting operations, paint application, and waste oil combustion. Of these. fosstl fuel combustion is the largest source.

Weatheringof mercury-Mng minerals in mks releases approximately 800 metric tons of mercury per year to surface waten. Mercury is also released lo surface waters in effluents from numerous industrial sources including mining operations, ore processing, chloralkali production, metallurgy and elecuoplating, leather lanning, and the manufacture of chemicals. ink, paper. pharmaceuticals, and textiles. Mercury was used in marine paint to control mildew and barnacles before the 19708, contributing to conlamination of sediment near marinas and ship repair Bcilities. Mercury is releasad to cultivated soils through Ute direct application of inorganic and organic fertilizers (e.g., sewage sludge and compost), lime, and funglcidss. Additional relfmx occur through the disposal of indusvial and domestic producls (e.g., thermometers, electrical switches, batteries) as solid wastes in landfills. In Puget Sound, a major historical source of mercury has been a chloralkali plant in Eellingham (Bothner 1973).

The global cycling of mercury is characterized by degassing from soils and surface waters, fouowed by atmospheric uanspon, deposition to land and su&w walen, and sorption to mil and sediments. The atmosphere is Ihe smallest environmental rese~oir for mercury, containing only about 1,000 metric tons. Mercury is removed from Ute atmosphere through wet and dry deposition and by the sorption of mercury vapor to soil and surface waters. Transport and partitioning of mercury in surface waters and soils is a hnction of Ihe particular form of mercury. Volatile forms evaporate to the atmosphere, while solid forms panilion to sedimenrr or suspended sediments or are transpotled in the water column, depending on solubility. Nonvolatile forms of mercury sorb lo soil and sediment. Bacteria common to most waters are capable of converting virlually

57


any mercury compound to .-xic methyl mercury, which has significance in bioawumulation.

Nickel

Nickel is a natural element chat forms compounds with sulfur and oxygen. Nickel is silvery-white, hard, malleable, ductile, somewhat ferromagnetic, and a fair conductor of heat and elecwicity. The commonly occurring oxidation states of nickel are Ni (0). Ni 0,and Ni (In). In addition to natural sources, nickel is produced either as a by-product from copper refining or is recycled or reclaimed from secondary sources.

Expoaure Routes and Risks-Occupational inhalation of nickel, especially in the nickel-refining industry, presents the most serious exposure risk to humans. However, humans may also be exposed to nickel by ingation or dermal contact because nickel is present naturally in the environment. Dietary nickel levels have been estimated to range from 100 to 300 &day and aversge 165 pglday (Casarett and Doull 1986).

There is gmwlng evidence that nickel may be an essential trace element for mammals. Howevcr, nickel is not well absorbed by the body and is excreted almost completely withii 5 days. Dermal exposure may aim cause allergic reactions. There is limited evidencs of Ute carcinogenicity of nickel and certain nickel compounds in humans. However. &ere is sufficient evidence indicating carcinogenic effects to workers exposed to nickel sulphide fumes and dust at nickel-refining facilities. R e d u d larval survival and growth were reported in studies of aquatic organisms exposed to high levels of nickel. Nickel is apparent-ly quite toxic to fre&water algae at concenmlions of approximately 50 pglL; acute toxicity to saltwater species may w u r as low as 150 pglL (e.g., juvenile mysld) (U.S. EPA 1986a).

Souroes and Fare-Nickel m u m naturally and enters the environment through natural weathering processes. Nickel is also released as industrial effluent or as atmospheric emissions fmm iu use in electroplating, in metallic alloys, as a catalyst for various organic p m s o s , in batteries, and in enamels, earamics, and glass, Nickel is widely used to produce slainless steel, coins, nickel steel for armor plate, and as a catalyst for hydrogenating vegetable oils. Nickel has also been found in tho effluents of copper smelters, chloralMi plants, pulp mills, and dry-cleaning facilities.


Nickel has been found at somewhat elevated concentrations in some sediments from nonreferenee areas of Puget Sound (Table IV). However, the mean concenvaUon of nickel is vinually identical in reference and nonreference areas of the sound, suggesting a predominantly natural source.

Nickel can be extremely mobile in aquatic systems because many nickel compounds are highly soluble in water. However, in unpolluted environments, nickel is primarily associated with suspended particles and organic material or is coprecipilated with hydrous iron and manganese oxides. Photolysis and volatil-ization are not imponant fate processes for nickel. Although nickel is bioaccumv- lated, the bioconcentration factors suggest that partitioning into biota is not an important fate process.

Silver

Silver is an element that occurs naturally as a son metal. A common anthropogenic source of silver is the disposal of photographic wastcs in municipal wastewater ueatment systems. Silver from photographic proecsses is usually released as soluble silver thiosulhte, which is convened to insoluble forms during wastewater treatment. Environmentally imponant forms of silver include silver nitrate and silver sulfide, which are the forms usually found at hazardous waste sites.

Exposure Router, and Rlsks-In the aquatic environment, silver is one of the most toxic metals to organisms, especially invertebrates and fish (U.S. EPA 1980). The loxicity of silver to aquatic organisms ranks second only to mercury among the heavy metals mble n). Most people are exposed to very low levels of silver, primarily through food and drinking water, which come at least in pact from naturally wcuning silver in soil and water. Occupational exposure is another source, specially in medicine, jewelry-making, soldering, and photography. Silver may also enter the body by inhalation or dermal contact; however, these are much less imponant routes of exposure to silver than ingastion. Most of the silver that is consumed or inhaled leaves the body within 1 week. Little information is available about the fate of silver in the body resulting from dermal contact.

Greying of the skin and other body Ussues is a well-known and permanent result of long-term exposure lo silver compounds. Generally, many exposures to silver are required to produce this effect. inhalation of dust containing relatively high levels of siIver compounds (e.g., silver nilrate or silver oxide) may cause breathing problems. lung and throat irrilation, and stomach pain. Dermal


exposure has caused mild allergic reactions in some people. Higher occupational exposures may cause kidney problems, bul existing studies arc inwnclusive. There are no other reponed health effects of silver exposure.

Sources and Fate-Dixharges of photographic materials into wastewater is the major source of silver released into the environment. It is also released as a by-product from the mining of copper, lead, zinc, and gold ores. Direct mining of silver is another large source. Hazardous waste sites are source8 of silver compounds, and silver is released naturally through the weathering of silver- bearing rocks and soil.

Other important sources of silver include the manufacture of electrical contacts, silver paints, and baltcries, as well as steel refining, cement manuhcturing, fossil fuel consumption, municipal waste incineration. and cloud seeding. Ore smelting and fossil fuel consumption processes emit fine panicles of silver to the atmosphere. Sources of elevated dietary silver include seafood from areas near sewage outfalls or industrial sources and crops grown in areas with high ambient levels of silver in the air or soil.

Silver is capable of Wing Imsponed Long dislances in air and water. It is stable and remains in the environment until it is mined, but may change forms depending on environmental conditions. Sorption and precipitation are the dominant processes controlling partitioning in water and movement in soil. Silver may leach from soil into groundwater. Silver is bioconcentrated to a moderate extent in fish and inven~hrates. There appears to be HtUe potential for silver biomagnificalion in tested aquatic food chains (Callahan et al. 1979).

Zinc

Zinc is found naturally in air, soil, and water and is present in all foods. It is an essential nutrient for all organisms in trace amounts. As a refined metal. zinc is used in its pure form, as an alloy with other metals, and in compounds with chemicals.

Exposure Routes end Rlsks-Zincenters the body easily through ingestion and inhalation. Dermal absorption is a relatively small exposure mute for zinc. Most zinc not needed by the body is excreted. Higher than avem8e exposure lo zinc can oceur from drinking water that has been stored in galvanized metal containen, from souras contaminated with indusuial zinc wastes, and from the air at galvanizing, smelting, welding, or brass foundry operations. Higher levels

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of exposure can also result from use of diclary supplements and by injection of certain drugs (e.g.. insulin) that contain zinc salts. t

Gastrointestinal problems can occur after ingestion of excess zinc; severity of the problems can increase with long-term ingestion. Excess zinc may also interfere with the body's ability to absorb and use other essential minerals such as copper and imn. Inhalation of zinc may cause metal fume fever, a temporary syndrome. Zinc is not known to cause cancer or birth defects. Insufficient levels of zinc have also been associated with adverse health effects. Significant decreases in reproduction and growth have been reported in fathead minnows, guppies, and polychaetes after exposure to zinc.

Sources and Fate-Zinc is used most commonly as a protective coating for other metals. In addition, it is used in alloys such as bronze and brass, for electrical uses, and in organic chemical extractions and reductions. Zinc chloride is a primary ingredient in smoke bombs. Salts of zinc are used as solubilizing agents in many dmgs (e.g., insulin). Zinc and copper alloys are used in coinage.

Zinc is released to the air as dust and fumes from zinc production facilities, lead smelters, brass works. automobile emissions, fuel combustion, incineration, and soil erosion. Refuse incineration, coal combustion, smelter operations. and metallurgical industries are major sources of zinc in air. Zinc releases to air account for only a small portion of the total environmental release. Erosion of soil particles containing zinc is the largest overall source of zinc to ihe aquatic environment but the effect on water quality at any one location is likely minor (ATSDR 1989b). More conmtrated sources of zinc to aquatic environments include uhan runoff, mine drainage, and municipal and industrial effluents. Mew cortoslon and lire abrasion also contribute to urban mnoff. Indusldes lhat directly discharge zinc to water include iron and sleel, zinc smelting, plastics, and elwmplating. Municipal wastewaters are major contributors of zinc in sstuarine environments.

Adsorption lo scdimenls is the dominant fate of zinc in the aquatic environment. Zinc partltlons to sediments or suspended solids in surfam watcrs throt~gh adsorption onto hydrous iron and manganese oxides, clay minerals, and organic material. The tendency of zinc lo be adsorbcd is affected by the nature and concentralion of lhe sorbent, and by Ute pH and salinity of the water. Zinc tends to sorb more readily at higher pH levels and desorption of zinc from sediments occurs ac salinity incream. Zinc does not volatiiiut significantly from water. Although bioaccu~nulated by all organisms, zinc probably does not biomagnify in lhe food chain (Callahan et ai. 1979; Oinn and Barrick 1988).

. . . . . . . . . .. ... . . , .. . .. .


ORGANOTINS

Use of organotins (including melhyltins, butyltins. and clhyltins) as the active biocide in antifouling paints for ships and marine slmclures has increased dramalically over the past two decades. Organolins, especially lribu~yltin (TBT). have been targeted for environmental concern. In 1988. Congress passed tho Organotin Antifouling Paint Control Act lo restrict the use of organotins. Analysis of organotins is made more difficult because they behave as both metals and organic compounds, and their aquatic chemistry is not completely underslood.

Expoeure Routes and Risks-The primary risk of exposure lo organotins is from leaching of paint into ambient water. where the organotins are adsorb& to suspended or benthic sediments. Organotins are bioaccumulaled by aquatic organisms exposed to contaminated sediments, but no action levels or other maximum acceptable concentrstion in tissue has been established.

Organolins are very loxic to marine organisms and TBT is lhe most toxic of the organotins. TBT is acutely toxic, by deign, to aqualic life at concenlrations exceeding 0.5 &L, wilh acute lethal concenlrations reported for embryo, larval, and post-larval clams, mussels, and oysters at wnccntra~ions of approximately 0.6-4.0 pg/L (Center for Lake Superior Environmental Studies 1988). TBT bioconcentdon factors for mussels and oysters have been reported in the range of 6.800 to 11,400 (Center for Lake Superior Environmental Studies 1988).

Sources and Fata-Bemuse of their use in antifouling paints, primary sources of organotins are marinas, small boat harbors, vessel repair facilities, and berthing areas. Organotins have been used as agricultural fungicides to control plant diseasss, as in~eclicides,and as biocides in pulp mills, breweries, textile mills, and leather-prowssing facilities. Organolins arc also used lo stabilize polyvinyl chloride.

The fate of organolins. like other toxic organic compounds, is determlned by physical, chemical, and biolqical processu. Phololysis and biological degrada- lion act to modi&TBT In water. The adsorption of TBT to suspended particulate maredal and sediments mults in TBT concentrations that are appmximately 3 orders of magnllude hlgher than those found in water.

Among pathways avallable for degrading TBT in water, aerobic melabolism appears Ihe most imponant. Many groups of plants and animals appear cnpable of readily degrading TBT. Rapid half-lives of 4-14 days have been repfted in algae. TBT appears lo be degraded by progressive debulylation to dibulyltin.

62

. . .. . . . , . . . .. . . . .


monobutyltin, and inorganic tin (Center for Lake Superior Environmental Studies 1988). The intermediate products appear to be less toxic than TBT.

m e metabolism of TBT in aquatic life and humans appears only slightly slower than microbial metabolism. TBT is bioconcentrated by fish and invene- bmes to approximately 3,000 limes the ambient water concentration. The contribution of dietary accumulation to lhe tow body burden is much less than lhal from bioconcentration. Biomagnification is unlikely because TBT is eliminated (La, depurated) at all trophic levels, including fish and humans. However, definitive tests are necessary to resolve many remaining questions of the environmental effeca and fate of organotins.

NONlONlC ORQANIC COMPOUNDS - AROMATIC HYDROCARBONS

In this seclion, chaiacleristics of polycyclic aromatic hydrocabon (PAH) compounds and related aromatic hydrocarbon compounds are sum~narized. Characteristics of additional nonionic organic compounds (compounds that do not dissociate in water) are summarized in subsequent sections.

Polycycllc Aromstlc Hydrocarbon Compounds

PAH compounds are a gmup of chemicals formed most commonly during incomplete combuslion of organic materials (e.g.. coal, oil and gas, garbage, and wood). HPAH compounds (compounds having 2 4 aromatic rings) are present in high concentration in lhese combustion products. LPAH compounds (3 or fewer mmalic rings) turd to be found in high concentration in unwmbusted fossil fuels. PAH compounds are ubiquitous in h e environment and natural sourees of these compounds include forest Ores and volcanoes, as well as oil soaps and erosion of coal beds. In Pugel Sound, major sources of PAH com-

Then are no uses for moal individual PAX compounds except as research chemicals. However, PAH compounds OCCUT in several imporrant mixtures, including creosote, which is comprised of greater than 85 percent PAH compounds. Because they have many of the same sourm, individual PAH compounds are not dislinguished in Ulis discussion. Information for individual PAH compounds is included in Appendix A, primarily because of differing degrees of loxlcily and perslslcnce. LPAH compounds include acenaphthene, acenaph- Ihylcne, anlhracene, fluorene, and phenanthrene. HPAH compounds include

83

-.. . . . --- .. .. . . .


nuoranthene, pyrene, bent(a)anLracenc. benm(b)fluoranthene. benzo(k)nuoranthene. benm(g.h.i)pyrene, benzo(a)pyrene, chryscne, dibenz(a.h)anthraccnc, and indeno(l,2,3-cdl~rene.

Exposure Routes and Rlsks-Because PAH compounds are found throughout Ute envlronmenl, humans may be exposed to PAH compounds by inhalation, ingestion, and dermal contact. Inhalation is by far the most common exposure route.

Although PAH compounds may have similar toxicological effects and environmental fates. the health effecls of individual PAH compounds are not identical. Reliable health-based studies exist only for a few compounds; potential health effects of the remaining compounds must be inferred from available information. PAH compounds enter the body easily. and the rate of absorption is increased when the PAH compounds are prosent in oily mixtures. Animal studies indicate that most PAH compounds are metabolized within a few days. Several PAH compounds [i.e., bendafanthracene, benzo(a)pyrene, benzo@)fluoranthene, benzo(k)fluoranthene, chrysene, dibcnz(a.h)anthracene, and indeno- (l.2,3-cd)pyrene] have been identified as animal carcinogens.

Although there is no available information regarding cancer in humans following inhalation exposure lo individual PAH compounds, epidemiologic studies show increased mortality from lung cancer in humans exposed to coke- oven emissions, roofing-tar emissions, and cigarette smoke. Because each of these sources conlains various mixtures of individual PAH compounds as well as other potentially carcinogenic chemicals, the contribution of any individual PAH to the tolal ovcinogenicity of these mixtures in humans has not been evaluated. Despite UIW limitations, the shldles provide qualitative evidence of the ptential for mixtures containing PAH compounds to cause cancer in humans. Adverse Immunological, mproductive, and genetic effects have been shown in studies on mice. No information is available regarding similar effects on humans.

Sources and Fate-The primary source of PAH compounds in the air is the burning of wood and he1 for residential heating. Other common sources are vehicle exhaust, asphalt roads, eoal Lar and coal tar production, agricultural burning, hazardous waste sites, tobacco smoke, creosote-treated wood, coking plants, coalgaalfication, smokehouses, aluminum pmduction, and municipal waste inclnmtors. PAH compounds we also found in most foods (e.g., cereals, grains, vegetables, f ~ l t s , and meals). Most of the PAH compounds in surface waters and soils are belleMd to nsult from almosphedc depsition. For any given body of water, the major source of PAH compounds could vary depending on the pmx-

84

DESCRIPTIONS 01: POLLUTANTS

imity of other sources such as municipal wastewater treatment plants and wood treatment facilities. Most nonreference area sediments in Puget Sound havc significantly elevated PAX levels compared with refcrence areas (Table IV). Sources of PAX compounds in the marine environment include wood treatment facilities, docks and pilings, coal incineration and handling facilities. pulp mills. organic chemical plants (e.g., manukclure of dyes, plastics, and pesticides), and urban runoff from automobile emissions. The composition of PAH emissions to the atmosphere varies with lhe combustion source [e.g.. emissions from residential wood combustion contain more acenaphlhylene U l a n other PAH compounds. while auto emissions contain more benzo(g,h.i)perylene and pyrene].

In surface waters. PAH compounds may volatilize. photooxidize, biodegrade, adsorb to sediments, or bioaccumulatc in aquatic organisms (with bioconcentration factors ranging from LOO to 2.000). In sediments. PAX compounds can biode-grade or bioaccumulate in aquatic organisms. In soils. PAX compounds can bio-degrade or bioaccumulate in plants, and lhcy may also enter groundwater ;uld be transported within an aquifer.

PAH compounds attach to dust and other airborne panicles and are capable of being transported long distances, hence their detection in relatively uncontami- nated areas. PAX compounds photooxidize and react in the almosphere with other pollutants. Atmospheric half-lives are generally lcss than 30 days.

The PAX compounds are classified in the pollutant tables according to low or high molecular weight. PAH compounds within each weight classification generally share similar environmental fates. Tmspoa and pdtioning characteristics are also roughly conelated to molecular weights of PAH compounds, in la~gepart because lhe solubility of PAH compounds tends lo decrease with increasing molecular weight. HPAH compounds havc stronger adsarption tendencies and less significant volatilization, and some HPAH compounds are carcinogens. LPAH compounds show moderate adsalption tendencies, more significant volaIllizarion, and greater microbial degradation. No LPAH are established carcinogens.

Methylnaphthalene8 and Methylphenanthrenar,

Melhylnaphlhalenes are alkylated forms of naphthalene and are genorslly found with other PAH compounds. Melhylphenanlhrcnes are analogous forms of phenanlhmnes. Both of lhase melhylattxl groups of compounds areof\endewred in Puget Sound sediments (TernTech l985b; Barrick and Prahl 1987; CH2M Will 1989) and originate primarily as fossil fuel products including oil and coal (Banick 1982; Barrick el al. 1984). Because of their similarities in chemical


structure and spatial distribution, they have similar or identical sources, cffects, and fates as hose dwcribed in the section on PAH compounds.

NONlONlC ORQANIC COMPOUNDS - CHLORINATED AROMATIC HYDROCARBONS

In the next sections, characterislics are described for the most common chlorinated benzenes, polychlorinated dibenwfurans and dibenzodioxins, and PCBs, which are all different types of chlorinated aromatic hydrocarbons.

Dlchloroberlzsnee

Dichlorobenzenu are anthropogenically produced chemicals that are not known to occur naturally. They exist primarily in the vapor slate and are ubiquitous in the environment. In general. Uley have low water solubilities and low flammabilitiw and are chemically unreactive.

Exposure Routes and Rlske-The general population is exposed to dichlorobenzenes through the consumption of contaminated drinking water and food @adcularly flsh; allhough dichlorobenzenes bioaecumulate toonly low ppb levels in fish) and through inhalation of contaminated air. Data suggest that inhalation may be a greater source of exposure than other routes with respect to occupational exposure, and is a much more significant souree of exposure than the dermal mute.

Afier absorption by the body, dichlorobenzenw are rapidly distributed to fat, liver, lung, hean, braln, &id muscle tissue. T h w chemicalsare eliminated from the body within 5-6 days. Epidemiological studies are insufficient tocharacterize human effects of exposure to dichlorobsnzenes. Studies of acute and chronic toxicity of dichlorabcnzene isomers indicate that the compounds have similar catget organa and effects. There is no evidenee that dichlombenzenes are carcinogens.

Souroee end Fate-Dlchlorobenzenes am usod in a number of organic chemical syntheses and in solvents, electrical equipment insulators, pesllcldes. herbicides, and fungioides. Chemical waste dump leacham and direct manufac- tudng affluentsare the major sources of dichlombenmnes.

66

.. . . .. . . . . . . . . . . .. . .. . . . - . . . . . .. - .... .....


Sorption. bioaccumulation, and volatilizstion are expected to be competing fate proccssu of dichlombenzenes due to their lipophilic nature,'relatively low vapor pressure, and low water solubility relative to polar organic compounds. However, dichlombentenes are relatively soluble compared with other nonpolar organic compounds, such as HPAH (Howard 1989). The rate at which each of mese competing procwes occur will determine the predominant fate, especially in water. Adsomon to sediments is likely due lo the low water solubility. Dichlorobenmes may be released directly to the atmosphere and soil in wnnec- Uon with their use as fumigants. Their detection in groundwater near hazardous waste disposal anas indicates that leaching occurs. Experimental bioconcenm- lion factor values suggest that significant bioconcenlration does not occur, although high bioconcentration factors were reported in a study of guppies. The data suggest that bioaccumulation occurs in both animals and humans and that dichlorobenzenes are biologidly persistent. Volatilization from soil surfaces may be an important fate process. Dicltlorobenzenes may be slowly biodegraded in soil under aerobic conditions. Chemical transformation by hydrolysis, oxidation, or direct photolysis is not an importar. fate process.

Hexachlorobenzene

Hexachlorobenzene (HCB) is a solid white cryslalline compound, formed as a by-product during the manufacture of chemicals used as solvents, other chlodnsconralning wmpounds, and pesticides. HCB is the most persistent of the chlorinated benzenes in the environment. It has a half-life ranging from 3 to 6 years In soil and approximately 30 days in water in one test (ATSDR 1990a; n b a k et al. 1981). HCB is not venj water soluble and sorbs strongly to sediments. There are no currant commercial usas of HCB in the United Slates. HCB was used as a pesticide until 1985, when the last regismtion of HCB as a pesticide was voluntarily canceled.

Exposure Routes and Rlsks-Pmximity lo industrial sources or hazardous wasls sites provides pdmary enposure routes for HCB. HCB may be msponed to !he air by dust panicles. Dermal contact is a major source of exposun. HCB exposun may alsooccur by ingestion of certain foods (e.g., dairy products, meat, and poulq). More HCB is absorbed If it is consumed in cambinallon with fat or 011.

HCB i s rapidly transported lo tissue in the body after exposure and tends to accumulate In lht Ussue. Most HCB leaves the body, but small amounls may remaln for years. especially in the fat tissue. Specific effects of HCB exposure via inhalalion md dermal eonmct are not yet known. However, sWn disorders

67


have been rrponed in humans following digestion of HCB. There is also evidence that HCB is ~ O X ~ Cto nursing mammals exposed through maternal milk. There is sufficient evidence that HCB is a liver and thyroid carcinogen in test animals and that HCB is considered a probable human carcinogen.

Sources and Fate-There are cunently no dwumentcd producers of HCB in the United States. and imponation of this compound has also ceased. However, HCB may still enter the environment as a by-product of the manufacture of chlorinated solvents, other chlorinated compounds, and several pesticides. In addition, an utimated 3,500-1 1,500 kg of HCB was inadvextently produced during the manuhcture of chlorinated solvents in 1984 (Carpenter et al. 1986). HCB can also be produced during combustion pmcesses such as the incineration of municipal wastes. Total releases from this source are estimated to range from 57 to 454 kg per year (Carpenter et al. 1986). HCB was also used in the production of pyrotechnic materials (e.g.. smoke bombs), aluminum. graphite electrodes, and dyes and as a component in wood preservatives. Direct discharges from manu&ctudng facilities are the primary sources of HCB in water and sediments; effluents from sewage lreatment plants present a significant, but lesser, conlribu- tion.

HCB is one of the most persistent pollutants. It bioaccumulates in the environment, in animals, and in humans. Low levels of HCB have been found in almost all humans tested, most likely as a result of ingestion of HCB in foods. Environmental HCB is generally found tightly bound to soil and sediments. However, bacause of the low water solubility of HCB, it is not usually found in water (HCB was found in less than 1 percent of the groundwater samples taken from more lhan 862 hazardous waste sites) (Carpenter et al. 1986). Because HCB is not generally found in the atmosphere, photodegradation may be the praccss that limiu atmospheric leveh of HCB. Biodegradation appears to beslow in oxygenated waters. Leaching of HCB from soils is not significant, although biodegradation removes HCB from soils over a period of years. Isensee el al. (1976) did not nport any degradation in soils after 1 yr of incubation under either aerobic or anaerobic conditions; however, Fathepure et al. (1988) have more neenlly reponed anaerobic microbial dechlorination of such highly chlorinated aromatic compounds.

Polychlorinated Dlbenzofurans

Polychlorinated dibenzofurans (PCDFs) are members of a gmup of widespread Ad environmentally stable halogenated tricyclic aromatichydrocarbons. PCDFs are not intentionally produced, but rather enter the environment as trace


impurities in PCBs and chlorinated phenols and as a result of combustion processes. PCDR are smcturally similar lo PCBs and polychlorinated dibcnmp' dioxins PCDDs), with similar signs and symptoms of toxicity. Public concern over PCDFSis related largely to heir prevalence in the envir&nmcnt and to their similarities to PCDDs, rather lhan to reported health effects.

Exposure Routes and Rlsks-PCDFs have been detected in fly ash and in flue gas from municipal and industrial incinerators. Residues of PCDFs have been found in human breast milk. The most toxic PCDF congeners are 2,3.7.8- tetcachlorodlbcnzofuran. 1.2.3.7,8-penenlachlorodiknmfuran, and 2,3.4.7.8-pentachlorodibenzofuran. PCDFs arc severely toxic to animals and humans in acute concentrations, multing in retarded growth, birth defects, liver damage, and skin lesions. Data on Long-Wm exposure to PCDFs are not available. PCDFs arc not known carcinogens.

Sources end Fate-PCDFs enter the environment as contaminants in a number of chemical products, including herbicides, polychlorinated phenols, HCB. PCBs, and thermal insulation materials. PCDFs are also formed from the combustion of chlorinated material and can be found in incinerator fly ash. PCDFs may be found at wood treatment facilities, at sites of transformer fires. near incinerators, and at other facilities where l h w products are used or burned.

PCDFs are very persistent in sediments and have been found lo bioaccu- mutate in seal, nsh, turtle, and human fat tissue. PCDFs are generally quite soluble in organic solvents, but water solubility decreases with chlorinauon.

PCDDs [including 2,3,7,8-te1rachlorodibenm~p'dim;in(2,3,7,8-TCDD)] belong lo a class of compounds commonly referred to as chlorinated dioxins. According to the position and number of chlorine atoms, it is possible to form 75 different congeners of chlorinatfd dioxins. Dioxins arc fairly slable in lhe presence of heat, acids, and alkalies. Of the dioxins, 2,3,7,8-TCDD is regarded as the mcst toxic, and it is widely distributed in theenvironment. PCDDs are not produced intanlionally and have no known uw. They are produced as unwanted by-producw of the manufaemre of chlorophcnols and their derivallves, including chlorophenoxy hehicides, germicides, and wood pr~somtives. The production and use of 2,4,5-uichlorophenoxyacetic acid and 2,4,5-Lrichlomphenol as defoliants ha^ been a mrijor source of PCDDs. Although this production was


discontinued in the United Slates in 1979, prerent sources of exposure exist from remaining $tore& improper disposal methods, and hazardous waste sites.

Exposure Routes end Rlsks-Consumers may be exposed lhrough ingestion of contaminated food (e.g., fish, cow's milk), inhalation of conlamhat- ed dust or air, or dennal contact with contaminated plants, wood. and paper produw. Apan from certain industrial efIluents and lcachates from chemical dump sites, no 2,3,7,8-TCDD has ever been reported in drinking water. Therefore, it is expected that exposure through consumption of drinking water is negligible, In mammals, 2.3.7,s-TCDD is readily absorbed through the gastrointestinal tract. Although exposure from dermal contact and inhalation has also been reported, it has b a n predicted Ihat ingestion of conlaminated food accounts for 98 percent of the daily human uplakcof PCDDs (Syracuse Research Corpora-tion 1989). Occupational exposure occurs during the bleaching process in pulp and paper mills, at certain hamdous waste sites, at municipal and industrial incinerators, and at chlorophenoI production facilities. Accidenlal releases may occur through msformer fires.

Some PCDDs (including 2,3.7,8-TCDD) are among the mosl toxic come pounds known. PCDDs have been proven toxic to unborn animals, and they reduce fertility in some species. Although 2,3,7.8-TCDD is highly toxic to all species that have been tested, there are large differences in sensitivity among species. Health effects similar lo those caused by exposure to 2,3,7,8-TCDD are expected for other PCDDs, although higher dosu are requirad. The symptoms of loxicity in humans after exposure to 2,3,7.8-TCDD include altered liver function and fat metabolism, pathologic changes in the blood, and skin lesions. Some of lhesc symptoms may be attributed to other chemicals of which PCDDs are minor conlaminants. Based on animal studies, EPA (1990~) has determined that 2.3,7,8-TCDD is a probable human carcinogen.

Souross and Fate-The primary soums of PCDD contamination are associated with the industrial manufacture of chlorophenols and lheir derivativu and with the subquent disposal of wastes fmm these industries. Municipal incineration tacllities may also emit PCDDs. Thedatado not indicate the relative imponanrm of lhesc sources in contributing to environmental emissions. Curnnt data indicate that ihe maximum levels of PCDDs arelikely to be found in soil and drainage sediment samples near chlorophenol manu~acluring hcilities and chemical waste dimsal slw. There am few studies of atmos~heric PCDD levels. In the United S&W,the highest PCDD levels have been reported at hazardous waste sites and in flsh and wlldllfe tissue rmm areas contaminated with 2,3,7,8-TCDD (Syracuse Research Corporation 1989).

70


PCDDs are persistent contaminants that are not likely to undergo chemical or biological transformation in air, water, or soil. The role of photochemical msformation in determining the fate of l h w chemicals in various ambient media i s unknown, but PCDDs are sumptible to photochemical reactions in the presence of organic acids. In water, a substantial proponion of PCDDs may be present sorbed h?sedimentsor in biota. Allhough very persistent. 2,3,7,8-TCDD may be removed from waler through volatilization and photolysis. In air. PCDDs are expected lo be present as a vapor and s o M to panicles. PCDDs in soils are most likely transported lo the atmosphere by contaminated dust particles and direct volatilization from the surface and lransported to surface water by erosion. PCDDs are resismt to photochemical degradation and biodegradation in soil. Several bioconcenuation factors have been I@prted for 2.3.7.8-TCDD, but none fan be. considered definitive values. Experimental bimcentration factors for aquatic organisms range from 2,000 to 39,000 (U.S. EPA 1985c; Syracuse Re.?earch Corporation 1989). with EPA's best estimateestablished at 5,000 (U.S. EPA 1985~).

Polyohlorlnated Biphenyls

PCBs are cnvironmmntally persistent campounds that have a strong tendency to accumulate in aquatic sediments and in tissues of aquatic organisms. There are 209 PCB congeners (Mullin et al. 1984). Various mix~res of these compounds were marketed in the past and can sometimes be identified in the environment. However, the compunds do not all degrade at the same rate, confounding attempts to identify original sources of contamination.

Exposure Routes and Risks-PCBs enter the body through ingestion of contaminated food, inhalation of conlaminated air, and dermal contact. The most common mute of exposure is through the consumption of fish and shellfish from PCB-contaminated water. Exposure from consumption of contaminated drinking water is minimal.

Although he effecis of PCBs have been diminishing since manufamring of the chemicals ceased in 1977,it is exwted that there arecontinued health effects in cornarton with cenain o&upalions. Studies performed on humans show that irritations such aa acneUke lesions and rashes can occur in PCB-exposed workers. PCBs are also classified by U.S. EPA (1990~)as probable human carcinogens. The sublethal toxic effects of PCBs are well documented for phytoplankton, mammals, and birds (Camenand Doull 1986).


Sources and Fates-PCBs have bem used primarily as coolants and lubricants in transformers. capacitors, and other electrical equipment. Sources of PCBs include transformer leaks or spills, old hydraulic fluids, lubricants, pesticides, and surface coatings. ~ow&er, manufacturing of PCBs was banned in the United Slates in 1977 because of human health hazards resulting from high PCB levels in fish and shellfish, environmental persistence. and bioaccumulation levels. Importation of PCBs was banned by the federal Toxic Substances Control Act in 1979. Although there are no new indusVial (point) sources oPPCBs, many of the transformers and capacitors that contain PCBs are still in service. These products present ongoing risks of exposure through illegal or inadequate disposal methods and accidental release (e.g., transformer explosions and fires). PCBs have been found in high concentrations in small areas of urban bays in Puget Sound (Malins el al. 1982; Tetra Tech 1985b;Chan et al. 1985a.b; Stinson et al. 1987; Beller et al. 1988). However, PCBs are widely dislributed and occur in most sediment and tissue samples taken from the sound.

PCBs are relatively insoluble in water compared with many other organic compounds and are highly soluble in solvents. PCBs also resist hydrolysis and oxidation. These factors make them highly persistent in the environment and susceptible to bioconcentration. However, eontaminants similar to PCDFs may account for some of the harmful effects attributed to PCBs. There is ample evidence that PCBs bioaccumulate in the food chain; the degree of bioaccumulation may depend on fat content, the cctanol-water partitioning coeflicients, and the stmcmre of PCBs, rather lhan on Le quantity of PCBs ingested. Additional factors are the sim and age of the aquatic organism and water temperature. The degree of chlorination affects metabolism, bioconcentration, degradation, adsorption, and volatilization of PCBs. Generally, metabolization, degradation, and volatilization decrease with chlorination, while bicconcenVation and adsorption increase. Sorption to sediments is an imponant fate process for PCBs that depends on salinity, sediment organic content, and sediment size. If anaerobic degradation of PCBs in sediments occurs, it is a very slow process.

NONlONlCOROANlCCOMPOUNDS-MISCELLANEOUSEXTRACTABLE COMPOUNDS

In the next rrect~ons, the characteristics are described for several nonionic organic compounds that do not Ill within the classes of compounds discussed in previous sections. These eompounds include N-nitrosodiphenylamlne, MEK, bis(2-ethylhexyl)phthalate, hexachlorobutadiene, and dibenzobran.

. . . . . ... . .. . . . . . ..


N~Nlrrosodlphenylamlne

N-Ni(ros0diphenylamine is an EPA-designated priority pollutant from the class of chemicals known as nitrosamines. It may w u r naturally during the metabolism of nitrates and mines. There is little published information on this chemical, and relatively little is known of its aquatic fate and environmental and human health efkts.

Exposure Routes and Risks-Humans are primarily exposed to N-nitrosodiphenylamine through dermal contact with subber and vinyl products. Ingestion is a secondary source. Although lhere is sufficient evidence of carcinogenicity in animals, N-nitrosodiphenylmine has only a suspected human carcinogen.

Sources and Fate -N-Nitrosodiphenylamine is used in the vulcanization of rubber, as a chemical intermediate in the production of dyes and pharmaceuticals. and as an antioxidant. N-Nitrosodiphenylamine is more stable than most nitro- gamines, but it is sensitive to light and undergoes photolytic degradation. When heated to decomposition, it emits toxic fumes of nitrogen oxides. Photolyric degradation and aptton to sediment a p p to be the most imponant tate

Methylethyl Ketone

MEK, also known as 2-bumone, is used as asolvent in lacquers, adhesives, rubber cements, inks, paint removers, and cleaning solutions. MEK is also present in vehicle exhaust.

Exposure Routes and Risks-Primary human exposure roules include inhalation of contaminated workroom air,.vehicle exhaust, and other forins of air pollution. There am limited data available indicdng lhat MBK is a natural component of some foods, so ingestion is also a source of exposure.

Sources and Fate-MEK is discharged into water as wastewler effluent and enters the atm0Sphere from induslrial emissions. It is slrongly associated with photochemical smog events, although it is usually absent from ambient air. It is formed by the natural photooxidation of hydrocarbons emitted from automo-

73


bilw and other induswial sources. MEK may be a natural component of cenain foods. MEK is removed from water generally by evaporation or slow biodegradation. It will not hydrolyze under normal conditions. Although it will not indirectly photooxidize in surfam waters, it may be subject to direct photolysis. It doad not significantly adwstt to sediments or bioconcentrate in aquatic organisms. MEK will partially evaporate from near-surface soils and leach into groundwater; it is subject to slow biodegradation in both soil and groundwater. MBK exists primarily in the gas phase in the atmosphere and will photodcgrade at a modem rate or will be removed by rain.

Bls(2-ethyllhexylphthalete

Bis(2-eUtyl)hexylphthalale is a colorless liquid that is insoluble in water. miscible with mineral oil, and soluble in most organic solvents. It is used in large quantities as a plaslicizer for polyvinyl chloride and other polymers. Because of ils use as a plasticizer, it is a common laboratory contaminant. Bis(2-ethyl)hexylphrhale is also used as a replacement for PCBs in dielectric fluids for electtical capacitors. It may also be naturally produced by plants and animals.

Exposure Routes and Rlsks-Exposure lo bis(2-ethy1)hexylphthalate occurs from inhalation of contaminated air. consumption of wntaminated food (especially fish, milk, and cheese) and water, and dermal contact with products containing bir(2-ethy1)hexylphthalate. Although occupational exposure during Ute production of plastics is the source of the greatest concentrations of bis(2- elhyl)hexylphthalate, the most widespread exposure mulls from its use in plastic products.

Although there are no data available to evaluate the carcinogenicity of bis(2- ethy1)hexylphthalate in humans, it has reponally caused cancer in tcst animals ( W e l t rmd Doull1986) and has beenclassifiedas a probable human carcinogen based on lhe-se mulls (U.S. BPA 1990~). However, other authors mhnical Ruourea~, Inc. 1989) have concluded that them is inconclusive evidence of carcinogenicity in animals. There have also been limited reports in the early 1970s of chronic reproductive effects in aquatic organisms oxposed to low concenlrations of bh(2-ethyl)hexylphthalate (Casarett and Doull 1986).

Sources and Fate-Bis(2-cthyl)hexylphlhate is widely distributed in the environment as a mult of its use as a plasticizer. Disposal of plastic products in landfills, as well as incineration, rcleases bis(2-elhyl)hcxylphLalate into the

74

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DESCRIITONS OF POLLUTANTS

environment. Other sources arc h e treated wastcwater from coal mining operations, aluminum forming, foundries. and water-based ink and dye manuhcturing facilities. In 1980, three firms were reported to be producing bis(2- ethy1)hexylphthalate in the United SIaIes ( U S I ' 1981).

Bis(2-ehy1)hexylphthalaS biodegrades in water and has been shown lo bioconcentnte in aquatic organisms. Bis(Z-ethy1)hexylphthalafe strongly sorbs to sediment due to its low water solubility and is relatively persistent in the environment. Evaporation and hydrolysis are not imponant fate processes for aquatic bis(2-elhy1)hexylphthalale. Atmospheric bis(2-ethy1)hexylphthalatc will be carried long distances and may bc returned to soil by wet deposition. Bis(2- cthyl)hexylphthalate in wil neither evaporates nor leaches into groundwater. It may biodegrade under aerobic conditions. It is unknown whether photolysis or photooxidation are imponant atmospheric processes.

Hexachlorobutadiene

Hexachlorobutadiene (HCBD) is used in me chemical industry as a solvent for natural and synthetic rubber and other polymers. as welt as in heal transfer liquid. transformer liquid. and hydraulic fluid. HCBD is a by-product of the manufacture of telrachloroethene, frichloroethene, and tetrachloromethane.

Exposure Routes and Rlsks-The primary route and highest level of exposure to HCBD is associaled with the inhalation of workplace air, although the general public can be exposed throtcgh the ingesuon of conlaminated drinking water. Although sudies exln for freshwater organisms, no data are available concerning the chronic toxicity of HCBD or any other chlorinated buladienes to saltwafer aquatie life. Acute toxicity may occur as low as 32 9glL (EPA 1984~). There are also vey few dam available reporting the effecu of HCBL) on humans.

Sources and Fate-HCBD has been found in drinking water supplies, in aquatic organisms, and in aquatic sedimcils. It has been found in the effluent of chemical produyrs and in wastewater discharges. HCBD has been detected at elevated coneenvetions in sediments from the Hylehm Waterway in Commence- ment Bay (Tetra Tech 1985b), and was also founa in elevated concentrations in some ffrh tissue samples from the same area. Historical discharges from chemical manl;facuring plants along the waterway are probable s o u r w of this contaminant.

76

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HCBD is expected to evaporate rapidly from soils and may biodegrade under aerobic conditions. No teaching from soil is expacled because of strong sorption tendencies, although leaching is more likely in sandy soils. HCBD will volatilize rapidly from water and has a half-life fmm months to years in fhe atmosphere. m water, sorption to sediments and suspended sediments is also likely due to the high log K.,, value of HCBD (3.74 to 4.28) (Callahan et al. 1979; Veith et al 1979).

Dibenzofuran

Little information has been published about the sources, effects and fate of dibenrahrmn. Dibenwfum has been documented at wood treatment facilities in Puget Sound (Barrick et al. 1986; CHZM Hill 1989) and has been detected at elevated cancentrations in many wntaminated sediments and fish tissues (Tetra Tech 1985b; Beller et al. 1988: Pastorok ct al. 1988). It is present in the fly ash from municipal incinerators and is a component of insecticides. No information was found regarding the toxic effects of exposure to dibenwfuran on aquatic organisms. The environmental distribution of dibenzofuran in Puget Sound is cornfared with that of LPAH mmpwnds, indicating that dibenzofuran and ammalic hydrocarbons have similar sourecs in the sound (Tetra Tech 1985k Banick et al., 1988).

NONlONlC ORGANIC COMPOUNDS - PESTICIDES

In this d o n , fhe characteristics of three major groups of chlorinated perticides are summarized. alddn and dieldrin; DDT and its major breakdown products, DDD and DDR and hexachlorocyclohexane (HCH),which is also known as Undane. These and numemus other pesueide~ of potential concern in Puget Sound are dsscribed in detail in PSEP (1988). Three of these pesticides of potential concern (diazinon, diumn, and endosullan I) have recently been recommended for routlne monitoring in Puget Sound (PSEP 1991) but were tdenclflcdafler lablar for this report had been wmplated (madditional discussion in the Selecrlon of the PoIIu!ms @ C o r n section of Chapter 1).

Aldrln and Dleldrln

Alddn and dleldrin are two closely-related chemicals that are used primarily as insecticides. Beeause of thelrchemieal and toxioologia~I similwitiss, they are considered together by regulatory bodles. Alddn has been used as a soil Insecticide to wntrol mot worms, beetles, and termites. Dielddn has been used

78

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for the treatment of wood, soil, and seeds; to eontrol mosguitoes and tsetse flies; as a sheep dip; and for mothproofing. All uses of aldrin and dieldrin on food crops were banned in 1975.

Exposure Routes and Risks -In the past, the most common exposure route for humans was ingestion of plants grown in treated soil and animal products exposed to ihe chemicals. The risk of exposure from these routes has been reduced since agricultural uses of aldrin and dieldrin were banned. The most likely current source of exposure for humans is through inhalation of indoor air

. in wood nmcturw treated with excessive amounts of aldrin or dieldrin. Some

..risk of exposure may remain through new applications of individually owned stockpiles of the chemicals or as a result of improper or illegal disposal mcthods.

Although aldrin and dieldrin are clearly toxic to humans, the severity of health efleets depends on the concentration and length of exposure. Brief exposure to high levels of the chemicals may cause headaches, dizziness, nausea. convulsions, and death (at extremely high doses). Although human studies of the carcinogenicity of aldrin and dieldrin are largely inconclusive, EPA has classified these two chemicals as probable human carcinogens based on the results of animal tats (EPA 1990c).

Sources end Fete-Although the chemicals were banned in 1975 for general agricultural use, they were available ancr 1975 to control term: aand for molhprooflng. However, even these uses have been prohibited or voluntarily discontinued. There should ba no new sourca of the chemicals, although emissions may result from treated wood and from new applicauons of old stocks. Most of the alddn and dieldrin levels recorded for Puget Sound air. water, and soil were reponed prior to 1976 and may be overestimated (TeIra Tech 1985b).

Aldrin is readily convenal to dieldrin in d l media. Dieldrin is fairly persistent and is resistant lo biodegradation. Dieldrin readily bioaceumulata and biomagnifiw thmugh the food chain. Rapid volatilization is the principal removal mechanism of aldrin from soil and waler.. Dieldrin sorbs UghUy lo sou and Jcdlment and volalilim more slowly. Allhough surface runoff of dieldrin is a m@or palhway of loss from treated soil, leaching from soil to groundwater appears minimal.

I

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DESCRIF'TIONS OF POLLUTANTS

DDT, ODE, and DDD

DDT is primarily composed of three compounds that are white, crystalline. tasteless, and almost odorless solids. DDT does not occur naturally. It has been one of the most widely uxd insecticides. DDE and DDD arc breakdown products of DDT and also oecur as conlaminanls of technical gradc DDT. DDT was banned from general agricultural use in the United States in 1972, but it is still produced and exported for use in other areas of the world.

Exposure Routes and Rtsks-DDT, DDE, and DDD enter the body primarily by ingestion. although exposure is possible through inhalation. Dermal exposure is not significant because the compounds are absorbed very'poarly through the sldn. Under eenain conditions, DDT, DDE, and DDD may remain in soil for long periods of lime and be transfcmed to crops gmwn in the soil; imported foods are a continuing source of exposure. In 1981, ingestion of DDT and DDE in food was estimated at 2.24 fig per day (Gmrell et al. 1986). Other primary sources of exposure may be through occupational involvement at hazardous waste sites.

D M ; DDD, and DDE are stored most readily in fat tissues and are eliminated very slowly. Breast-fed children are a group at special risk because DDT in maternal milk is found in higher conmnmtions than in cow's milk or other food. D M has rcpofiedly caused rashes and irrilalion of the cyes, nose, and throat. Acute wposure at high doses primarily affects the nervous system. In addition, synergistic and anlagonistic effecls of DDT have been shown in animal tests. DDT administered to animals along with known carcinogens resulted in both greater and lwser tumor production than when the carcinogens were tested without DDT. Although no studies wlst that indicate a definite link hetween DDT and Nmors in animals by the inhalation route, or with tumors in humans by cithar the inhalation or ingeslion route, U.S. EPA (1990~)has classined the compounds as probable human carcinogens.

Bources and Fate -Although there aresignlflcanlly fewer sources of DDT, DDE, and DDD in the envlronrnent, the products wem used so extensively in thc past that they n m still found in vimally all air, waIer, and soil samples. Levels in most air and water samples are low, and exposure by these pathways is not of gmt concern. New rcleases of the compounds in the United States are expected lo be negligible. In 1985, there were two producers of DDT for export in the United Stales (HSDB 1988). These facilities may have relead small amounts of DDT via lbgitive or nonconlrolled emissions. Studies of peat lands located in the middte latitudcsof the United Slates Indicate that there are continuing sourcos

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of the compounds; the cause has been attributed lo atmospheric transport from areas where DDT is still in use. Other studics have shown that levels of DDT and i e metabolites have been decreasing eonsisrenlly in ail media and in food samples.

AtmosphericDDT is subjcct to photodegradation and wet and dry deposition. D M preferentially binds to soil and sediment, where it may be subjecl lo photodegradation near the su&ce and biodegradation with depth. Under cemh conditions, DDT may persist for long periods of time or may be convened to DDE, which persists even longer. DDT, DDE,and DDD are only slightly soluble in water; thcrcfore. loss of these compounds in ~ n o f f is primarily due lo uanspon of h e panicles to which they cue bound. Volatilization of D M and DDE accounts for subslantial losses from soil and water. It is estimated that DDT evaporates from water within 50 hours. Laboratory studies of the aidwater panition coefficient of DDE indicate that it volatilizes from marine water LO to 20 times fastar lhan from fresh water (Allas et al. 1982). DDT, DDE, and DDD are highly fat-soluble compounds with long half-lives, resulting in bioaccumulation and biom&nification that increase with advances up the food chain.

pHexachlorocyclohexane

HCH isomers were developed in 1942 as simple and effective penicides. Of its iaomcrs, y H C H is the most effective and is marketed as lindane. yHCH is uJbd primarily as a peslicidal wtment for wood, as a seed treatment, and as a fumigant. It has not been produced commercially in the United Slates since 1983; however, it is still imported and distribu~ed domestically. In Puget Sound, r-

k HCH is used primarily in urban areas (PSEP 1988). Its use as an insecticide is declining because of its environmental persistence and tendency to bioaccumulate.

i

i

j Exposure Routes and Rlsks-The primary routes of human exposuro are

ingestion, inhalation, and dermal contact. Occupalional exposure was a signln- cant aoum prior to 1977, when EPA began regulating y-HCH. Theprimary risk

78 t

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of exposure to the general population is through the consumption of foods contaminated with pesticide residues.

There is limited evidence of the carcinogenicity of y-HCH in test animals, although other isomers of HCH have been linked with cancer in test animals. Evidence regarding carcinogenicity of y-HCH in humans is inconclusive. Acute toxicity has been associated wilh rHCH concentrations in the range of 5-28 pglL for marine shrimp and killifish (PSEP 1988).

Source8 and Fate-y-HCH :s present in agricultural ~ n o f f from areas where pesticides were used that contained y-HCH. Other sourccs are the effluents of industries using y-HCH, such as wood and seed treatment plants. yHCH has been found infrequently in surface sediments in Everett Harbor (Pastorok el al. 1988). Of the pesticides and herbicides found in Puget Sound. y-HCH is of secondary concern based on its nstrictcd usc and relatively low mobility (PSEP 1988). The use of y-HCH in the Puget Sound basin has been estimated to range from 0 to 1,300 poundslyear. Total use in the Puget Sound basin is estimated to be 2,640 poundslyear.

y-HCH is environmentally persistent. The fate of yHCH in aquatic systems is determined by its bicavailability to transformation pr6cesse-s. Although sorption to suspanded sediinent and biota is not extensive, sorption is probably an imponant process for transponing yHCH to anaerobic sediments where transformations occur. Hydmlysis, oxidation, and photolysis are not imponant processes in aquatic environments. However, bioaccumulation aocurs in aquatic organisms.

VOLATILE NONlONlC ORGANIC COMPOUNDS

In lhis seciion, the characteristics of lhe following volatile organic wm-pounds are described: benzene, chloroform, ethylbenzene, toluene, tri- and tetrachloroethene, and total xylenes.

Benzene

Benzene is a natural product of volcanoes, forest lires, and crude oil seeps and is present in many plants and animals. Benzene is also a major industrial chemical manu%ctured from coal and Iar. Benzene is used to make other chemicals (prlmarlly elhylbenzene, cumene, and cyclohexane), as well as some types of plastics, detergents, and pesticides. 11is a component of gasoline, glum

... . .. . . . . . .. ,

DESCRIPTIONS OF POLLUTAW

and adhesives, household cleaning products. paint strippers, some an produ;ts, and tobacco smoke. As a pure chemical, benzene is a cleat and colorless liquid. Benzene has been found at337 of the 1,177 NPL hazardous waste sites (ATSDR 1989~).

Exposure Route8 and Rlsks-Occupational exposure accounts for the highest levels of benzene found in humans, particularly in rubber manufacturing facilities, oil refineries, and chemical plants and at gasoline retail stations. Benzene evaporates quickly, making inhalation by far the most likely exposure mute for humans. The most widespread exposure to the general public is from inhdation of tobacco smoke and vehic:e exhaust. Small amounts of benzene may also be found in some foods and in contaminated drinking water. Dermal expo-sure is possible Lhrough eontact with benzene-containing products (e.g., gasoline).

Benzene is harmful to human health, although the degree of harm depends to a great extent on the length and ammlnt of exposure. Shon-tenn exposure of humans and animals to high levels c:f benzene generally causes drowsiness. dizziness, and headaches; death from such exposure has also been reponed. Long-term exposuro to various levels of benzene has caused leukemia and subsequent deathof wurkers exposed for periods from 5 lo 30'years. Long-lerm exposure to benzene may affect normal blood production, possibly resulting in severe anemia and internal bleeding. Overwhelming evidence exists that benzene is a human carcinogen. Human and animal studis also indicate that benzene is harmful to the immune system and has been linked with genetic changes. Reproductive effects have been reponed in animal shldies, atlhough human studies have been too limited to form a cleat link wth benzene. There is general agreement among investigators that benzene metabolites, rather than benzene itself, are the primary toxic agents.

Source8 and Fate-Environmentdl sourw of bonzeno may be both anthropogenic and natural. The most significant source results from the combustion of gasoline. Other minor sources include septic m k effluent, slmctural fires, off- gasslng from panicle baard, clgirella smoke, and pofdC42 natural food sources. Annual benzeneemisdons from anthropogenic sources are approximalsly 236,030 mevic tons (ATSDR 1989~). However. envimnmenlal levels are low due to emcient environmental removal processes.

Chemical degradation reactions, primarily the reaction with the hydmxyl radical, limit the atmospheric persistence of benzene to only a few days (and possibly only a few hours if the concentration of hydroxyi radicals is suMciently

81


high). Biodegradation, principally aerobic, is the most important envimnmental fate mechanism for benzene associated with water, soil, and sediment.

Chloroform

Chloroform is a colorless, clear, dense, volatile liquid that is produced by both direct and indirect processes, It is ubiquitous in the environment. Chloro- form is widely used as a procws ingredienl in the manufachlre of fluorocarbon refrigerants and propellants, fire extinguishes, electronic circuitry, and plastics. Chlorofonn is also used in aneslherics and pharmaceuticals, fumigants and insecticides, solvents, and sweeteners and as a chemical intermediate.

Exposure Routes and Rlskr-The major route for human exposure to chloroform is from ingestion of contaminated drinking water and inhalation of contaminated air, especially in induslrial areas. A less important route of exposure is ingestion of contaminated faod. Chloroform is absorbcd almost completdy through the gastrointestinal tract and tends lo accumulate in fat and liver tissues. Regardless of the mode of entry into the body, chloroform is metabolized and excreted unchanged through the lungs.

Neurological, hepatic, renal, and cardiac effects have been associated with exposure to chloroform and have been documented in both humans and animals. Animal studies suggest that chloroform is carcinogenic and may be teratogenic. Human dam regarding the eIfects of acute and chronic oral exposure to ohloro- form are insufllcient, and animal tests did not clearly establish a no-effects level of exposure for toxicity.

Sources and Fate-Chloroform is likely to enter the environment in industrial effluents (e.g., pulp mill discharges), as well as from its indirect prcduction in the chlorination of drinking water, municipal sewage, and cooling water.

The primary fate of chloroform is vol~tilization to tho atmosphere. Chloro-form mav be m s w n e d long dislances in the atmosuhere and wlll react in the gas ph& with phoiochemicaliy produced hydroxyl dicals. Chloroform releases to land that do not evaporate will leach into groundwater, where they may reside for Long periods of lime; near-surface rcIews are expected to evaporate rapidly. SorpUon to soil or sediment is not considered a significant fate pmcess. Chloroform may be subject to significant biodegradation based on laboratory

. . . . .. . . . .

? :

Ab ..

7 .

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i r F

DESCRlPTIONS OF POLLUTANTS

tests, although the data are conflicting. Chloroform shows little or no tendency to bioconcenvate in tests of freshwater fish.

Ethylbenzene

Ethylbenzene is a ~01orless liquid that smells like gasoline, evaponles at room temperature, and bums easily. Ethylbenzene occurs naturally in coal tar and petroleum and is also found in many manukclured products including paints, inks, and inaficides.

Expowre Routes and Risks-Ethylbenzene enters the body rapidly through the lungs and digestive tract. Envy through the skin after contact with liquids containing ahylbenzene is also an exposure route. Because of iw volatile nature, ethylbenzene is most likely to be inhaled. Ethylbenzene is brokan down into olher chemicals once it enters the body. Levels of ethylbenzene are likely to be higher in all media (apeelally groundwater) near hazardous waste siles and petroleum refineries. Conrumers may be exposed to erhylbenzcne through a wide range of products including pesticides, solvents, carpet glues, varnishes, paints. and tobacco producw. The highest source of exposure to consumers is probably %If-service gasoline stations. Indoor air has a higher average concentration of elhylbenzene (approximately 1 ppb) than ouldoor air baause of the use of household cleaners and paints (Howard 1989; ATSDR 1990b). Occupational exposure occurs in the petroleum industry and in chemical manufacluring, and workers using varnish, spray painw, and adhesives also may be subject to greater exposure.

Exposure M low levels of atmospheric ethylbenzene has caused eye and lhroat lrrllstion in humans. Exposure to higher levels has caused decreased mobility and dizziness. No studies have reporled death in humans, although animal studies suggest that ethylbenzene may be fatal. Short-term exposure to high concantrations of ethylbenzene may cause liver and kidney damage, nervous system changes, and blood changes in animals, although lhere ate conflicting laboratory msulfa. Long-tern exposure data are not available. No conclusions have been established regarding carcinogenic properties of ethylbenzene.

Sources and Pate-Ethylbenzene is most commonly found as a vapor in the air because it volarWzes easlly from water and soil. Atmospheric ethyl- benzone can be removed by wet deposilion or through photooxidation within approximately 2.5 days (Howard 1989). Photolytic Vansformations and biodegradation may also remove ethylbenzene from surfnce water. In soll, elhylbenane

83

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i i

DESCRIPTIONS OF POLLUTArn

is degraded most easily by microorganisms. It docs not readily sob to soils or sediments and can move rapidly into groundwater. Ethylbenzene does not appear to bioaccumulate significantiy in the food chain.

Toluene

Toluene is produd bath naturally and anthmpogenically. It is found primarily in pevoleum products and in solvenls and thinners for paints and lacquers. Toluene is a by-product of the production of styrene.

Exposure Routes and Rlsks-the primary route of exposure to toluene for humans is from inhalation of contaminated air. Exposure levels are increased wirh proximity lo gasoline stations and vehicle exhaust, or in occupational atmospheres where toluenebased solvenls arc used. Exposure to toluene also occurs as the result of intentional sub(itancc abuse. Workers in the chemical, pstroleum, and paint and dye industcia are at greateat &k of exposure. Neurological damage is the primary adverse effect of toluene on both humans and animals. The mccr-causing potential of toluene in rats and mice is still being studied.

Source8 and Fate-'lbluene is deased into the atmosphere principally from the volalilizatian of pelroleurn fielsand toluene-based solvents and Ulinners and from motor vehicle exhaust. Large amounts of toluene are discharged into waterways or spilled onto land during the storage, ttanapon, and disposal of hels and oils. Natural wurm of toluene include volcanoes, forest fires, and crude oils.

If toluene Is released to soil, it volatilizes to the air from near-surface soil and leaches togroundwater. Biodegradation occurs both in soil and groundwater, but ia likely to be slow (especially at high concentrations that may be toxic to micmrganisms). The presence of acclimated microbial populations may speed biodegradation. Toluene does not signiHcantly hydrolyze in soil or water. In water, loluene eoncenuatlons will deer- due to evaporation and blodegrada- tion. Aquatic mmod can bo mpld or may lake s o d wecks depending on Iemperature, mixing conditions, and presence of acclimated microorganisms. 'Kbluene d m not significantly adsorb to sediments or biaconcentrate in aquatic organisma.

. . . . .


Total Xylenes

Total xylem refers to the three isomers of xylene (meta-, ortho-, and para- xylene). This tenn is also sometimes applied to a mixture of xylenes and smaller amounts of otherchemicals (primarily ethylbenzene). Xylenes occur in petroleum and coal and are fanned during forest tires. Xylenes are colorless liquids with a sweet odor that leach into soil, surface water, and groundwater, generally as a rault of petroleum use. transport, and storage. Xylenes are onen a component of solvents and paint thinners and are used asa cleaning agent. Xylenes are also used in the manufacture of ceaain polymers and are ingredients in jet fuel, gasoline, and fabric- and paper-coating materials.

. . Exposure Routes and Rlsks-Occupational inhalation of xylenes is the

most common exposure route for humans, although ingestion of contaminated food and water and dermal contact may be. additional exposure mute.

Short-term exposure by humans to xylenes may cause skin, eye, nose, and throat irritation; impaired memory and reaction time; and stomach, liver, and kidney damage. Exposure to high doses of xylenes within short periods of lime may cause nervous system damage and death. Data are insufticient to prove human carcinogenicity.

Sources and Fate-Primary sour= of xylenes are fugitive industrial emissions and automobile exhaust. Additional sources of exposure are inhalation of tobacco smoke, gasoline, paint, varnish, shellac, and rust preventives. Other potential sourcesinclude hazardous waste sites and accidental releases of materials containing xyleno (e.g.. solvents).

Xylenes may persist in groundwater for several years. Soiplion to soils and sediments occurs, although there is considerable variation and uncertainty in estimates of persistence in thcse media. Xylenes may persist in other aquatic syatems for greater than 6 months before degrading. Limited biodegradation is the only signillrant source of xylene degradation in sub surf act^ soils and most aquatic systems. Because xylcnes evaporate easily, the highest levels are found in the atmosphere. ARcr several days, xylenes in the atmosphere an degraded by photooxidation. Modest bfoaccumulation levels have been shown in fish (e.g., bioconcentration fncton less Ulan 2.2). but food chain biomagnification has not been observed (Howard 1989).

86

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DESCRIi'TIONS OF POLLUTANTS

IONIZABLE OROANIC COMPOUNDS

In the following sections, chmcteristics are summarized for organic compounds that can dissociate in water. These compounds include various phenols, resin acids, and guaiacols.

Phenol

Pure phenol is a colorless or white solid. The commercial product is a liquid. Phenol has a distinct odor that is sweet and acrid. It evaporates more slowly lhan water, is moderately soluble, and is flammable. Phenol is primarily a manufactured chemical, though it also occurs naturally from decomposition of

organic matter. Phenol has been obtained by distillation from petroleum, lhrough synthesis by oxidation of cumene or toluene, and by vapor-phase hydrolysis of chlorobenzene. The largest single use of phenol is as an intermediate in the production of resins, and it is also used as an intermediate in the production of cenain synthetic fiben, as an algicide, as a disinfeclant, and in medicinal preparations.

Exposure Routes and Rlsks-Exposure to phenol for humans is possible through inhalation, ingeaion, and dermal contact. Because phenol is used in many manufacturing processes and in consumer products, exposure can occur both at work and in the home. Phenol is present in many medicinal products (e.g.. ointments, ear and nose drops, cold sore medication, mouthwashes. gargIes, analgesic rubs, and throat lozenges) and is also found in drinking water, air, certain foods, and in wood and tobacco smoke.

The magnilude, frepuency, likelihood, or relative contribution of each exposure route and source to tolal phenol exposure cannot be estimated using cunent data. In general, more phenol will enter the body if large areas of skin wme in contact with dilute solutions of phenol lhan if small areas of the skin wme in contact with concentraled solulions. Afier exposure lo airborne phenol, as much as 50 percent of the phenol that enters the body will enter through the sMn. Most of the phenol entering thc body is excreted within 24 hours.

The severity of efYeets from exposure to phcnol increases as both the level and duration of exposure increases. Ingestion .>f very high concentrations of phenol has resulted in dearh. The effects on hur~ans of inhalation of phenol ant unknown. Tests on animals of inhalation of pher.01 show lung irritation. musele Ucmors, and loss of coordination. Exposure to higher coneenIralions of phenol for a period of weeks has caused severe damage io the hem, kidnoys, liver, and

86

DESCRlPTIONS OF POLLUTANTS

lungs, followed by dcalh in some cases. Reproductive effects of phenol are unknown in humans. although effects have been shown in animal tests. Although phenol applied to the skin of mice has caused cancer, it is not known whether phenol is a human carcinogen. Phenol acted synergistically in tests with known carcinogens, causing more cancer than when thecarcinogens were applied without phenol. Phenol also has beneficial effects; it is an antiseptic and an anesthetic and is used to remove skin blemishes. Studies of effects of phenol exposure on algae and fathead minnows mponed reduced reproduction and growth, while effects on other aquatic organisms included increased enzyme activity in liver and muscle and decreased activity in the brain.

Sources and Fate -Phenol is released primarily to air and water during its manufacore and use. Phenol-formaldehyde resins have major uses in the construction, automotive. and appliance indunries and canbe found in associated effluents. Phenol is found in coal tar and is released in wastewater fro~s the manufacture of plastics, adhesives, iron and steel, aluminum, leather, and ~ b b e r , and in wood treatment plants and p a p pulp mills. Phenol is released during the burning of wood and in vehicle exhaust. Natural sources d phenol in water are animal wastes and decomposition of organic wastes.

Single, small releascs of phenol do not remain in the air; the half-life is generally less &an 1 day. Removal from soil by biodegradation is accomplished wilhin 2-5 days (Howard 1989). Phenol can remain in water for more than 9 days. However, single large discharges or continuous small diharges of phenol may remain in each of thcse media for much longer periods of time. Phenol has not becn found in soil except at hazardous waste si ts , pmbably because it is efficienlly removed from soil at low concentrations. Phenol in soil biodegrades and leaches to groundwater. Volatilization from soil and water is a slow proms and Is not expled to be a source of atmospheric phenol. Sorption to sediments is not an imponant transport mechanism of phenol in water. However, phenol has been detected occasionally in sediments from Puget Sound, including near pulp mills and in some sediments collected in nonurban areas (Tetra Tech 1985b), possibly as the mult of aquaculture applications.

4-Methylphenol is a constituent of pulp mill waste, is found at wood treatment facllilies, and is used in the manukcture of organic chemicals.

.... . .. .. . .... - .


Exposure Routes and Rlsks-Human exposure is primarily through inhalation and dermal conact in occupational environments and source areas. 4-Methylphenol is moderately toxic to benthic organisms.

Sources and Fete-4-Methylphenol is released to lhe atmosphere in vehicle exhaust, during coal tar and petroleum refining and wood pulping, and during its use in manulacluring and inetal refining. 4-Methylphenol is contained in effluents from industries engaged in wwd products manuhcturing, leather tanning, iron and s w l manulacwring, plastics production, textile production, rubber processing, and ~leetronics manultrcturing, and in eMucnts from municipal wastewater treatment facilities. Elevated concentrations of 4-me~hylphenol have been documented in surface sediments near pulp mills in Pugel Sound @tmTech 1985b, Norton el al. 1987, Pastorok el al. 1988).

In the air, 4.mcthylphenol reacts with photochemically produced hydroxyl radicaJs during the day and with nitrate radials at night. It can return to soil through wet deposition, and it can be oxidized by metal cations in rainwater. Biodegradation is e~,pxled to be the dominant fate process. Complete removal fmm soils is possible within 6 days, although the process is slower undu anaerobic conditions (Howard 1989). Disproportionate losses of 4-methylphenol (and phenol) relative to dimethylphenols have been observed in groundwater at a wood treating facility, presumably fmm biodegradation (Goerlia el al. 1985).

Volarilization, bioconcenmtion in fish, and adsorption to sediment are not . important fate proeeszes for 4-me~hylphenol. Photolysis is expected to be significant only in surface waters of oligouophic lakes. 4-Methylphenol is not expected to persist in sediments (Howard 1989). However, persistent high concentrations of 4-methylphenol have bben observed in some Puget Swnd sediments nuu industrial sources. Thw rcsuls can be explained either by large mass loadings of 4-melhylphsnol from lhc source or in siru production of 4-melhylphenol in the sedimena. One untested possibility is lhat 4-melhylphenol could be produced by bacterial conversion of proteins (viap-hydroxyphenylacelate)accumulatingIn the sediments (Balba and Evans 1980).

Psntachlorophenol

Pentachlomphenot (PCP) is one of the most heavily used pesticides in the United Slates. It is used as an industrial wood pn?semaIive, as well as in consumer wood preserving formulalions and i r herbicides and pesticides. PCP does not occur naturally and exists in two forms of differing water solubilities. In ils pure form, PCP exists as colorless crystals. m e impure form of PCP,

88

... .. . DESCRIPTIONSOF

POLLUTANTS

which exists as a dark grey to brown dust in beads or flakes, is the type found at hazardous waste sites.

Exposure Routes end Rlsks-Humans can be exposed to low levels of PCP through inhalation of indoor and outdoor air and through ingestion of conlaminaled food and drinkiag water. Dermal wnlact with treated wood can also result in exposure lo PCP. Occupation and proximity to hazardous waste sites prescnt the greatest risk of exposure to PCP. Occupational lcvels of PCP inhalation in indoor air at wood treatment plants and lumber mills are much higher than for the gcneral public; exposure levels are estimated at 0.9-14 mg per day compared with approximately 0.006 mg per day for the general public. An additional estimated 0.5 mg per day of PCP may be absorbed through the skin of workers who handle treated wood (ATSDR 1989~).

Exposure to high levcls of PCP can cause adverse effects on the liver. kidncys, skin, blood, lungs, nervous system, and gastrointestinal tract. High levels of exposure can also be falal. Longer-vrm exposure to lower levels of PCP can cause damage to thc liver, blood, and nervous system. Animal studies indicate that shon-arm, high-level exposure to PCP can cause similar damage. with the sevcrity of effects ~ncrcasing as the duration of exposure increases. Acute toxicity and increased risk of reproductive failure have been shown in animals exposed to PCP. but there is insuficient evidence of human wcinoge- nicity. Studies of aquatic organisms indicate more severe effects on lish than on other aquatic biota: acute and chronic toxicity to saltwater organisms occur at concenmtions as low as 53 and 34 &L, respeclively (U.S. EPA 1986a). In addition, pen~achlorw~~isole. a degradation product of PCP, has an cvcn grcaar potential lo bioaccumulate than PCP itself (Callahan ct a1. 1919).

Sources and Fete-PCP is releascd directly to air via volatilization from treated wood and evaporation of PCP-treated indurtrial proocss waters from coaling lowers. Eighty preen1 of domestic consumption of PCP is attributed lo the treatment of utility poles (ATSDR 19896). Although generally insignificant, past emissions frorrl production facilities may be more important in Puget Sound because one of the two major historical producers of PCP in the United Slates was located in the Commenccmcnt Bay area. In addition, a number of other chemicals (e.g.. HCB, pentachlorobenzcne, pcnlachloronilrobenm, and benzanchexachloridc isomers) arc known to metabolize lo PCP.

PCP relasscs to watcr occur by direct discharge from source and nonpoint sources, by wet deposition from the atmosphcrc. and by mnoff and leaching from soil. Approximately 90 prcent of wood treatment plans evaporate thcir

88

DESCRIPTIONS OF POLI.UTANTS

wastewaters and consequently they have no dircct discharges to watcr. The remaining 10 percent of these plants discharge to municipal wastewater treamcnt facilities. PCP has been detected in at 10.4 pcrcent of 2,738 hazardous wastes sites sampled for the substance (ATSDR 1989d).

PCP is also registered for use as an insecticide, a fungicide, an herbicide, a molluseicide. an algieide, a disinlec~ant,and as an ingredient in antifouling paint. However, nonwood uses account for no mow than 2 percent of current PCP use (ATSDR 1989d).

PCP is not affected by hydrolysis and oxidation. but is rapidly photolyzed and can bc biotransformed by microorganisms and metabolized by animals and plants. Sorption to soils and scdimena occurs and is more important under acid~c conditionsthan under neutral or ~asic conditions. The compound bioaccumulatcs to modest levels in algae. aquatic invertebrates and fish (ATSDR 1989d), but food chain biomagnilicalion has not been 0bSe~ed.

Mono- and Dlchlorodehydroabletic Acids

Chlorine bleaching processes used in both the ~ l f i t e and krah pulp industries have been demonstrated to result in the formation of chlorinated &in acids such as chlorinakd dehvdroabietic acids. Chlorinated derivatives of dchvdroabietic acid are by far thebredominant chlorinated resin acids reponed in blekhed pulp elfluenu, presumably because its slabilily relative to other resin acids enables it lo survive the suong oxidizing wndlrtons of chlorine bleaching. Dehydroabietic acid, typically the predominant resin acid found in the environment, is derived from abietic acid and is relatively stable as a result of its aromatic ring structure. Chlorinated resin acids, bccause of their unique origin, are powerful geochemical tracers of pulp mills that use chlorine bleaching processes. Chlorinated rcsln acids have been reported in elevated wnocnvationo in sediments near pulp mill discharges In Puget Sound as well as in other parls of the Unllod Statc~ and EYropa (Pastorok ot al. 1988). Dehydroabietic acids are persistent in the envlronmani and toxic to marine organisms. The toxicity of dehydmabietic acid dccreafu markedly at pH greater than 7 because of formation of the sodium salt.

Exposure Router and Rlakr-There are insuMcient data available lo doscrilm routes of vxposure and associated risks of indbidual resln acids to biota.


Sources and Environmental Fete-Dehydroabictic acid is persistent in sediments, wilh a half-life of greater than 20 years estimated in sediments of Lake Superior (PSEP 1988).

2-Methoxyphenol (guaiacol) is a by-product of wood and coal rar deeomposi-tion and is a major constituent of creosote. Guaiawl IS released as a pollutant primarily in pulp mill wasta; it is one of UIC major breakdown products of lignin. which is the primary componcnl of wood. Guaiacol has been detccled infrauent- ly in conlaminated sediments in Evcrctt Harbor. bul has been found in'hiah cocccnlralionsin sediments in other areas of Pugel Sound. the United Smtcs, aid Europe (Pastorok el al. 1988; Tetra Tcch 1985b).

Chlorinated Quslacols

Chlorinated guaiacols are wcll-documented by-products of pulp bleaching proeatsea. The wmpounds are formed when lignin is treated wilh the chlorine bleaching process. Chlorinated guaiamlr arc excellent geochemical tracers of pulp mills because of their unique origin. Baxd on studies showing that unchlorinawd guaiacols dehydroabietic acid, a related compound, is toxic and environmenlally persislcnl, it is expected that chlorinated guaiacols will behave similarly.

Chlorinated guaiawls am moderately toxic to benthic organisms and fish. The most toxic isomer is 3.4,5,6-tstraehloroguaiacol. followed by 3,4,5-tcichlorw guaiawl and 4,5,6-trichlomgua(awl. M-and lotrachlomguaiawl exhibited considerable toxicity in fish laken from a river ncar a pulp mill in Switzerland (LCs0valued wen 0.75 and 0.32 mglL for tri- and tetrachloroguaiawl, respec- tivcly (lauenberger et al. 1985).

Trlchloraethene

Mchlotoothcne (TCE)is used widely aa sdogroasor for metals in the metals and olecuunlca industries. TCE is an intormediato in tho manukcture of polyvinylchlodde snd is also found in the effluent of pulp mllls, chlorslkall plan&, and dry cleanen.


Exposure Routes and Risks-The primary exposun: route for humans is inhalation of contaminated air. followcd by ingestion of contaminated drinking water. Although possibly carcinogenic. TCE is not cons~dered highly toxic to humans or animals.

Sources and Fate-Although it has been detected in both marine and fresh waters. 80 KI 95 percent of TCE evaporaczs to the atnosphere. TCE is most likely to enter the atmosphere from its widespread use as a metal dcgreaser. There are no !mown namm sources of TCE. It has been found in very high concentralions in a few nearshore sediment 'lamples from Hylebas Waterway in Puget Sound (Tefra Tech 1985b). TCE is a volatile compound that moves quickly through groundwater, and it is a common contaminant of grour.dwater in industrial areas. It does not appear to bioeoncentrate in fish tissue. In anaerobic environments. TCE degrades to dichloroethcne and vinyl chloride. Thew breakdown products can be useful in determining the sources, fate, and transpon of TCE to the environment.

Tetrachloroethene

Tetrachloroelhene is s volatile compound used as a mekl degreaser in the metals and electronics industries, in dry cleaning and textile processing, and in the production of fluoromrbons, pcslicides. adhesives, paints, and coatings. There are no known natural sources of letrachloroethene.

Exposure Routes and Rlsks-The primary source of human exposure is inhalation of occuvalional air contaminated by temchlorocthene. Consumption of drinklng watercontaminated by rain or by pips lined with vinyl is another source of lerrachloroothene. Tetrachloroelhene is a carcinogenic compound that oU~crwisais not highly toxic to humans or aquatic organisms. It is moderately toxic to benthic organisms.

Source8 and Fate-Tetraehloroeihene is likely to enter the environment by hgitiva air emissions from dry cleaning and metal degming industries and by aceidantal relearn of products conlaminated with tetrachloroeLcne. Wastewater eflluents Prom maul finishing, laundering, aluminum forming, organic chamid and plmlies manuhcluring, and municipal treatment plants also conlributo to envlronmontal icuachloroethene. Temchlorocthone can also tw found in the effluent of pulp milla and chioralkali plants and in the groundwater nw many industdal areas. Tetrachlorocthene has boen found in highly elevated concentra-

.. .. . . ..

DESCRJPTIONS OF POLLUTANTS

lions in Pugel Sound sediments near a chemical manufacturing facility and in somewhat elevated concenVations in fish tissue from the same vicinity (Tetra Tech 1985b). Telrachloroelhene breaks down in anaerobic environrncnls to trichlorathene, dichloroethene, and vinyl chloride, and the presence of dese breakdown prcducls can be useful in determining the sources. fate, and transport of this chemical.

03

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. . . . . . .

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,, , . .. . . . . . . . . . . . . . . . . , . . . . ...

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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - . . . . . . . . . . . . . -

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107

APPENDIX A:

SUPPLEMENTAL INFORMATION

. . . . . .

TABLE A-1. SUMMARY 01: BASIC ANALYTICAL TECHNIQUES FOR ORGANIC COMPOUND ANALYSES

Analytical Slop Analylical Procdura' -San~ple drying Ccntrilugation or sodium sulfate

Extraction Shakorlrollor; Soxhtct*; aonication

Extract drying Soparatory funnel paniiioning as n c d d to rcmovo walct (pH must bc wnlrolld); sodlum sulfalo for all othcr extractdrying. Kuderna-Danish apparatus (10m.1 mL), rotary cvaporalion (10 2 mL) or wmparablc tcchniquo; purified nitrogcn gas for concontralion lo smallor volumes

Extrael cloanup Rcmoval of dcmonlal sullur (sedimants only; with mcrcury or activated copper

Removal of organic inlcrfcrcnrs with GPC. sizc exclusion chromatography (c.g.. phcnogcl. Scpltadcxo). bondedoctadccyl columns. HPLC, silica gal. or a:umina

Extract analysis GClMS for volatilesand scmlvolatiles; GCIECD for pcs~icides and PCB mixtures

GPC - gel permeation chrom,ttography. HPLC - high pcrforrnance liquid chromalography. GClMS - gas chromatographylmass spwlmmctry, GCIECD - gas ehroma~ogmphyloloctroncaplurc dc~cction. PCB - polychlorlnatd biphenyls.

'Tho stcpsdnscrlbcd gonorally apply l o low pans per billion, broad scan analyses. Some at tho opllons fbr extract clcanup and analysls arc best sultcd for conaln compal~nd groups rathor than for broad scan analyses.

A.1

&eQullml RID ImWkofdavl

114 anllmony 7440-36-0 (a) 0.00004 98 alpha-enaosutlan 115-29-7 O.OOOOE 98 hela-endoaullan 115-29-7 0.00005 127 lhalllum (In soluble salts) 583-88-8 (a) 0.00007 123 mercury 7439-97-6 (a) 0.0003 33 1f-dlchloropropene 10081-02-8 0.0009 98 endiln 72-20-8 0.0003 68 nllrobonzone 98-95-3 0.0005 53 he~achlof~~y~l~penladlene 77-47-4 0.0007 48 Oromomelhane 74-83-9 0.0014 59 2.4-dl17ll~0phefl0l 51-28-5 0.002 120 sllver 7440-22-4 (n) 0.003 31 2.4-d1Chlorophen01 120-83-2 0.003 119 chromlum (Vl) 7440-47-3 (a) 0.005 88 bl~(2-elhylhexyl)phlhalal~ 117-81-7 0.02 7 chloroDenzen0 (08-90-7 0.02 121 cyan;de 57-12-5 (a) 0.02 124 nlckel 7410-02-0 (a) 0.02 64 penla~h10rophenol 87-88-5 0.03 39 lluoranlhene 208-44-0 0.04 42 Ola(2-Ch1010180~10~~l]~Ih~f 39838-32-9 0.04 44 dlchloromolhane (melhylene chlortde) 76-09-02 0.06 25 1 .2-dlch1oi0benzene 98-50-1 0.09 11 1.1 ,I.-lflChlOlO~lhanO 71-55-8 0.08 38 elbylbemone 100-41-4 0.1 64 Isophorone 78-59-1 0.1 86 loluene 108-88-3 0.2 88 phenol 108-95-2 0.8 70 dlethyl phlhalale 04-88-2 0.8 71 almelhyl phlhalale 131-11-3 1 119 chrom~um(111) 7440-47-3 (a) I 88 dl-II-h~lyl phlhalale 87-74-2 10 40 chloromelhane (methyl chloride) 74-87-3 (h) 80 4.8-dlnl~ro-0-oresol 534-82-1 (a) 28 id-dlohlorobenzene 641-73-1 (b) 97 endosullan sullale 1031-07-8 (0) 27 1.4-dlDhloiobon~ene 108-48-7 (0) 2 acroleln 107-82-8 (c) 128 8etenlum 7792-40-2 (0)

(a) CA8 numbers lor these substances vary aependlng on iholr speolllo lorm (9.g.. Inorganic sslte or organlo wmptexes).

(b) Deta lnadequale lor quanlltatlve flak assessmen!. (01 Not deleimlned. Rererenee: U.8.EPA (199Oo), Table A.

--. . . ..- .. ...,.. , . -.A

TABLE A-3. CARCINOQENIC PRIORITY POLLUTANTS RANKED BY POTENCY FACTOR8

& &[email protected] CAS Potencv(gl &ever of Evldence @J

128 2,3.7,8-TCDD (dloxln) 1746-01-8 160000 82 82-07-6 230 (0) A

61 N-nllr080dl~0th~lamln~ 82-67-1 61 (W) 82 89 aldrln 309-00-2 17 82 00 dleldrln 60-67-1 16 82 (c) polychlorinaled blphonp (0) 8.9 82 102 alpha-HCH 310-64-6 6.3 82 100 hoptachlor 76-44-8 4.5 82 $17 beryllium 7440-41 -7 (a) 4.9 (W) 82 88 VIII~I ohlorlde 76-01-4 1.O A 103 bela-HCH 319-05-7 1.8 C 116 araenlc 7440-38-2 (d) 1.8 (W) A

hexaohlorobenzono 118-74-1 1.6 82 106 gamma-HCH 58-89-0 1.3 82-C 91 chlordane 57-74-0 1.3 82 18 ble(2-~hl0~elhyl)elhel 111-44-4 1.1 82 113 toxaphone 8001-35-2 1.1 82 37 1.2-dlpheny~nydrazlne 122-88-7 0.80 B2 38 2A-dl111110101~~~~ 121-14-2 0.68 82

107-13-1 0.54 (W) B1 28 3 , s - d l ~ h l ~ ~ ~ b ~ n t l d l n ~ 01-04-1 0.46 82 92 4.4'-DDT 60-20-3 0.34 82 03 4,4'-ODE 72-66-9 0.34 82 81 4.4'-ODD 72-84-8 0.24 82 16 I,I ,2.2-IeuachI0roeIhano 70-ad-6 0.20 C

carbon telrachlorido 66-23-6 0.13 82 10 1.2-dlchloroelhane 107-06-2 0.001 82 a2 roxaohlorobuladleno 87-68-3 0.078 c I4 1.1.2-lrlah1oroe1hane 70-00-6 0.057 C 86 lelrachloroelhano 127-18-4 0.051 82

71-43-2 0.020 (0) A 12 hexachloroeUtane 87-72-1 0.014 C 21 2C,O-lrlchtorophBn01 88-06-2 0.011 82 44 dlchloromethane 76-08-02 0.0076 (I+w) 82

(molhyleno ohloride) 23 chloroform 87-66-3 0.0061 (W) 02 62 N-n lU0~0d lph0~y l~~ l~0 86-30-6 0.0048 82 I18 ~admlurn(e) ?440-48-0 (a) (el (0) 7a benzo(a1pyrene 60-32-8 (0) 82 11s drom~um(VI) (a) 7440-47-8 (a) (01 (el 20 1.1-dbhloroelhane 76-36-4 (0) C 124 nlokel (subaulllde, rellnery duel) (e) 7440-02-0 (d) (0) (61

A-3

. . . . . . . . . . .

TABLE A-3 (Continued).

(a) From U.S. Envlronmenlal Prolecllon Agency (1SBOc). Table 8. All polency values represent diolary slope factors except (0)- slope calculated from occupallonal exposure. W - slope calculated from human drlnkinp water expobula, and (I) - slope calculated from animal inhalation studies.

(b) A IHuman carclnogen (8ulllclenl evldonce of carclnogenlclty In humans): 8-Probable human carclnogen (81 - llmlled evldence of carclnogenlclly In humans: 82 - sulflcienl evldence of carclnogenlclly In anlmals wilh inadequate or lack 01 evldence In numans): C - Posslble human carcinogen (Ilmlled evldence of carciaogenlcity In animals or lack 01 human dala).

(c) Spec111c Aroclor mlxturee of polyclorinated blpheyls are listed as lndlvldual priorlly pollutanls with ! lndlvldual CA8 numbers.

or organlo complexes). (e) Cnromlum (Vl). cadmlum, and nlckel are no1 Eansldered to be carcinogenic vla dlelary exposure.

A-4

-m=(erw) 1WO 100 10 1 0 1 001 0001

ARSENK

(AFUTOXN B)

CHARCOAC 8)wnfosIEw l e E N z o ( A ) P , R t ~lb

10 7

t : I I I 1 1 I 1 1 1 OOaOOOl 00WD100001 0001 001 0 1 1 10 100 I000 10.000 100.000

CONcENlRATWWI(mghgwa(~r -1mghgrPI.nrPn-tppn

a Fou(aW8spomEperdy b 100sIEdspuysr c 2lperdaya!heUSEPAlin(O005~)

Tim A-1. Gqhical risk chamcterization for arsenic in seafood (PSEP 1988b).

C- RA& (glday) low 1W 10 1 0 1 001 OOOt

I 1 1 I I I I I I 1 om* o.mt 0.01 o t t to 100 IWO 10.000 tm.ow

C ~ ~ T I O N( q k gwet weight) -' I ~ r e t ~ = l p p m

Figure A-2. Graphical risk characterization for mercury in seafood (PSEP 198%).

-ON m=(eMev) 8000 100 10 1 0.1 001 aoo1

I 1 1 I I 1 1 I I I I 1 0.000001a ma0001 aool MI 0.1 I 10 100 1000 10.000 100.000

CONCENTRAllON(mglkgwetwdgM~ 'l~rruwnlpbl.lpprn

-'Q-?-=prw b loosa&L8pryu c 2 L p r d a y ~ * w U S E P A P n r t O 0 0 5 ~ )

PEANUIBU11Lll (AFLAIOXN 81'

tUOlUlllbll AN ~ Z C i A P Y f L t ~I h

O R W X WAII I1 ( fRlmcOROEI lh l lW)C

Figwe A-3. Gaphicat risk chaaerization for carcinogenic PAH in seafood (psEs 198%).

.

. -l3ATE(mw) tom 100 to 1 01 0.01 0001

-------r WnFf (KuTOXlN E)

----- QUflCdAL eROllEDSTEAK ~ e ~ m ) p r = ~ E l

-------WATER ~ O R O E T ~ E N E ) C

I t 8 I I 1 1 I I I 1 I a m ia o o o o t o . ~ ~ ~ a 1 i 10 100 iom ram 1w.ma001 0.01

- - T - ( m o n c e - ~ r-1*mt--1ppa,

a Fargbiospoorapodal 0 IW8elopoyea c 2 ~ ~ ~ a t ~ u . s ~ m ~ o . w ~ ~ ~

Figme A 4 Graphicalrisk-on forPCtk in seafood (PSEP 1928b).

i

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