GEOLOGICAL SURVEY

SELECTED TRACE-ELEMENT AND . ORGANIC CONTAMINANTS IN 0' STREAMBED SEDIMENTS OF THE BASIN, AUGUST 1992

(~c~ By James M. Gerhart and INTRODUCTION l0 R L Joe/ D. Blomquist This report pre ellls th e re ult of a '-\'\o q s -lf d. lo; Background ABSTRACT urvey of contaminants in strea mbed edi­ melll in selected stream of th e Potomac This report describes the occur­ The U.S. Geo logica l Survey ( SGS) is implementing th e ational Water­ Ri ver Ba in. The report focuses on five rence and distribution of five selected Quality A ssessment ( AWQA) program elec ted contaminants, including two trace contaminants in streambed sediments to de cribe and xplain water-quality co n­ element - lead and mercury-and three at 22 strea m sites in the Potomac ditions and trend s of th e Nation' urface­ organic compound hl01·dane, total River Basin. Lead, mercury, and total wa ter and grou nd-water resources DDT (dichl orodiphenyltrichloroeth ane). DDT (dichlorodiphenyltrichloro­ (Gilliom and oth ers. 1995). One of the ethane) were detected at all sites, and fir. t area s to be studied as part or th e full­ Streambed-sediment samples were co ll ected and chlordane and total PCB's (polychlori­ sca le A WQA program i. th e Potomac composited from a variety of depositional settings nated biphenyls) were detected at Ri ver Basin. where water-quality within stream reaches that averaged 300 feet in length at each sampling site. most sites. At six sites, streambed­ sa mpling ac ti vities for th e study sediment concentrations of contami­ were begun in 1992. A major goal nants were detected at levels with the of th e Potomac Ri ver Bas in tu dy i potential to cause frequent adverse to describe th e cc urrencc and dis­ effects on aquatic organisms that live tribution of a wide vari ety of ph y. i­ in the sediments. Chlordane was ca l, chemica l, and bi ologica l wa ter­ detected at these high levels at sam­ quality charac teri . ti c of trea ms pling sites on the Anacostia Ri ver, the and ground wa ter in th e bas in. North Branch Potomac River, Bu ll Some of th e chemica l com- Run , and ; mercury pound of interes t in th e WQA was detected at these levels at sites program. in cluding many trace cle­ on the and the South ments and syntheti c organic com­ Fork ; and total pound . . do not eas ily dis. ol e in PCB's were detected at these levels strea mwa ter. but in tead tend to at the site on the Sou th Fork Shenan­ accum ul ate in trcambed s diments doah Ri ver. The highest concentra­ and aq uati c biologica l ti ss ues. When th ese co mp unds accumulate tions of all five contaminants generally in ufficiently high co ncentrati ons occurred at sampling sites down­ in sediment or ti ue , they can ac t stream from areas with industrial as contam inant th at ca n adver. ely plants, urban centers, or orchard and affect th e hea lth of aqu ati c orga n- ag ri cultural activity. The occurrence i m . To addre th e occurrence of these contaminants in streambed and distribution of selec ted trace­ sediments of the Potomac River Basin element and orga nic contaminant · is of concern because the co ntami­ in strea ms in th e Potomac Ri ver nants (1) are environ mentally persis­ Ba in, a survey of contaminants in tent, (2) are avai lable fo r downstream streambed sediments and aquatic transport during high streamflow peri ­ b. ·ca l ti sues wa s conducted in ods, and (3) have the potential to cause adverse effects on the health of aquatic organisms and humans th rough bioaccumulation . MAY 2 8 1996

SR lfBRAR Y Figure 1. Streambed sediments were sam­ pled in August 1992 at 22 stream sites in the 14,670-square-mile Potomac River Basin.

Physiographic Provi nces

Appalachian Plateau

Great Valley subprovince D Blu eRidge and total PCB ' (polyc h Iori nated Piedmont bi phenyls). Lead, mercury, • Triassic Lowlands subprovi nce chl ordane, and total PCB 's were 0 10 20 30 40 50 MILES selected becau e these com- D Coastal Plain 0 10 20 30 40 50 KILOMETERS pounds have been designated as 17 "toxics of concern" by the • Location and number of sampling site Program (Che apeake Bay Program, 199 I a); total DDT wa elected becau e of nati onal concern regarding its environ­ (3) What are some of the importan t environ­ Potomac Ri ver Basin (fig. I). mental effect during the Ia t several mental implications of the occurrence of At each of the 22 sampling sites, decade . The report de cribes the re ult these contaminant s in streambed sed i­ fine-grained streambed sediment were of treambed- edi ment ampling at 22 men ts? coll ected and compo ited from a vari ety tream site throughout the Potomac of depositi onal setting within stream River Ba in in Augu t I 992, and addre - Streambed-Sediment Sampling reaches th at averaged about 300 feet in e the fo llowing questi ons about the and Analysis length . Samples were coll ected from the occurrence and di stribution of the five The sampling site that were selected top I inch of fine-grain ed sediments u ing contami nant in streambed sediments of for a sessin g the occurrence and di stribu­ a scoop in wadeabl e streams or a dredge the ba in : ti on of contaminants in streambed sedi ­ in deeper streams; sampling equipment ( 1) Which stream ite have streambed sedi ­ ments in the Potomac Ri ver Ba in cover a was con tructed fro m inert materi als. All ments with elevated concentrations of range of phy iographic ettings (fig. I), sites were sampled during low streamflow th ese contaminant s? tream izes (table I), and land u es. conditions when no fine-grained sedi ­ (2) What i the re lation between elevated con ­ Drain age areas for the 22 sites generall y ments were in suspension in the water centrations of these contam inant in range from about 20 to I 2,000 square column. Each ample was sieved into treambed ed iments and potenti al mile (tabl e I), and incl ude parts of the 7 subsamples in the field fo r laboratory up. tream contam inant sources? physiographic provinces and subprovince analy i . and parts of th e fo ur States in the 2 Contaminants in Streambed Sediments Table 1. Streambed-sediment sampling sites in the Potomac River Basin, August 1992 Drainage Sampling area, in site square number Station number Station name miles 1 01595000 North Branch Potomac River at Steyer, Md. 73.0 2 01596500 near Barton, Md. 49.1 3 01600000 North Branch Potomac River at Pinto, Md. 596 4 01603000 North Branch Potomac River at Cumberland, Md. 875 5 01608000 South Fork South Branch Potomac River near Moorefield, W. Va. 283 6 01611500 near Great Cacapon, W. Va. 677 7 01614500 at Fairview, Md. 494 8 01616500 near Martinsburg, W. Va. 272 9 01617800 Marsh Run at Grimes, Md. 18.9 10 01618000 Potomac River at Sheperdstown, W. Va. 5,936 11 01625000 near Grottoes, Va. 375 12 01627500 South River near Harriston, Va. 212 13 01631020 South Fork Shenandoah River below Cabin Run at Front Royal, Va. 1,647 14 01634000 North Fork Shenandoah River near Strasburg, Va. 768 15 01636500 Shenandoah River at Millville, W.Va. 3,040 16 01639000 at Bridgeport, Md. 173 17 01644000 Goose Creek near Leesburg, Va. 332 18 01651010 near Bladensburg, Md. 130 19 01652589 Potomac River below Oxon Creek at Alexandria, Va. 11 ,880 20 01654000 Accotink Creek near Annandale, Va. 23.5 21 01657000 Bull Run near Manassas, Va. 147 22 01661050 St. Clement Creek near Clements Md. 18.5

amples for trace-e lement ana lys i Nati onal Wat er-Quality Laborat ory in for a va ri ety of 1 urposes (tabl e 2). The were sieved through a 63 -micrometer Arvada, olo. Ch lord ane. total Dl T. and uses f many of th ese cont aminants ha e nylon filter, digested to complete di sso lu­ total P B's were determined by dual ca p­ been regul ated r bann cl in the last sever­ ti on. and analyz d fo r 45 trace e l eme nt ~ . illary-column gas chroma tography with al decade because of an incrca ·eel a1 arc­ Lead wa.· determined by inducti ely cou­ eleCll·o n-ca pture detection (Foreman and ne. of th e ad erse effect th ey can have pl ed pia ma-atomic em iss ion . pec trome­ oth er . 1995). on animal and human health. ome of try (Briggs, 1990). and mercury was th eir adver e effect on human hea lth are determined by cold apor-a tomic abso rp ­ li. ted in table 2. ti on ·pectrophotometry (O'Leary and oth ­ OCCURRENCE AND The unit of streambed-sediment con­ ers. 1990). Samp les for rganic-com­ DISTRIBUTION OF centration u. ed in thi report are part per pound analys is were sieved through a 2- SELECTED CONTAMINANTS million (ppm) fo r trace element s and parts millimeter stain less-s teel sieve and ana­ per bi llion (ppb) for organi compounds. lyzed for 40 organochl orine compounds. The occurrence of th e fi ve selec ted Pans per million are equivalent to mil­ 80 s · mi vo latile orga ni c compound s. and co nt aminant in strea mbed sediment of ligram per kilogram of dry sediment, and all P 8 co ngeners b th e M eth ods th e Potomac Ri ver Bas in generally co rre­ part per billion are equi va lent to micro­ Deve lopment Program of th e U late with th eir u e in th e basin by man gram per kilogram of dry sediment. Streambed-sediment concentrations of th e three orga nic compounds (chlord ane. tout! DDT. and total P B · ) are th e sum of th e concen trati ons of several related com- pounds. hl ord ane concentrati on is th e sum of cis-chlord ane, tran -chlord ane. oxychlord ane, ci:-nonac hlor, and trans­ nonachlor concentrati ons. Total DDT con entrati on i th e Lllll of o, p'-DDT. p.p'-DDT. o,p'-DDE, p,p'-DDE. o.p'­ DDD. and p.p'-DDD concentrati on . Tota l PCB c nce ntration is th e sum of th e concentrati ons of all th e P B co ngener · that were detected. The laboratory con­ sidered th e concentrati ons of indi vidual chl ord ane and DDT compound to be c. ti­ matcs if th e co ncentrati on. detected were lc s th an th e labora tory"s re1 orting limits. In thi s repo rt . th e sums of concentrati ons

Contaminants in Streambed Sediments 3 Table 2. Summary of Information on five selected contaminants sampled in streambed sediments, Potomac River Basin, August 1992 NO, not detected

Lead Batteries; pipes U..ln pelnta, gasoline, Damage to nervous system, 1S 31 110 4.0 end plumbing; ..tiNd ehot now llmJIMI, kidneys, brain; fatigue; vehicle emissions; anemia; paralysis; fetal brain paint lngracllants; damage; possible cancer. solder; corrosion of brass; natural mineral deposita.

Manufacture of DilciWge8 to--and Damage to kidneys and 0.09 14.S 0.02 paint, paper, and air now regulated. nervous system. vinyl chloride; batteries; Ingredients In fungicides; natural mineral

Possible cancer; dizziness; 1.0 headache; fatigue; and ants. conwlslons.

4 Total DDT Insecticide used to Banned In 1972. Possible cancer; damage to 0.09 1.13 23.9 1.0.2.0 control mosquitoes nervous system, liver, and spiders on a kidneys, skin. wide variety of crops and fruits.

TotaiPCB'a Used In electrical Banned In 1979. Possible cancer. NO 3.9 .1·.5 transformers and plasticizers.

1 U.S. Environmental Protection Agency, 1991 ; Chesapeake Bay Program, 1991b. 2 Porta per million = milligrams ol contaminant per kilogram ol dry streambed sediment. 3 Parts per billion = micrograms of contaminant per kilogram of dry streambed sediment. limits for Individual compounds of chlordane and total DDT. Some Individual corr1poo1nds were detected at concentrations less than the reporting limit; these concentrations were I

of related compound s for chlord ane and minant concentrati ons in streambed sedi ­ thi s report to es timate th e potential for total DDT include th ese es timated con­ ments to observed adverse effects on adverse effects on aq uati c orga ni sm. centrati ons. aq uati c rgani sms for a large number or posed by th e measured contaminant con­ On th e basis of ana lysis f reference studies in e. tu aries and bays or orth centrati on · in th e streambed-sediment standard s and duplica te samples, th e labo­ A meri ca. Two concentrati ons were sa mples. It should be noted th at th ese ratory analyses indica te a fa ir degree or defin ed- Effec ts Range- Low (ERL) and guidelines ca n only serve as informa l pre­ reproducibility. Determ inati ons of lead Effects Range-M edian (ERM)- which liminary screening tools for strea mbed and m rcury in reference samples : h w a divide th e range or contaminant concen­ sed iments in freshwater strea ms. and do 5.8-pcrccnt standard dev iation for both trati ons and thei r potential effects on not replace the need for tox icity tes ting to clements. The standard deviation of th e aq uati c orga ni sm into th ree ban Is determine specific adverse effec ts on analyses of laborat ry reference amplcs (table 3). Sediment concentrati ons in th e aq uati c orga nism . . for chlord ane and DDT compounds fiL t band (less than th e ERL va lue for th e Trace Elements ranges from II to 23 percent. The stan­ ind ica ted contaminant) rarely ca use da rd de iation or th e analyses or refer­ adverse effccL· on organi sms th at live in The concentrations of lead and mer­ ence sa mples for tota l P 8 's is abo ut 7 th e sediments. concentrations in th e mid­ cury discussed in thi s report repre ent th e percent. dle band (between th e ERLand ERM va l­ sum or th e naturally occurring elements Beca use or th e man y complex factors ues) occas iona lly ca use adverse effects, contained in th e mineral grains of th e sed­ involved in bioaccumulation processes, and conce ntrations in th e third band iments and the element att ached to th e contaminant concentrations in streambed (grea ter th an th e ERM va lue) frequently mineral grains a a re ult or contamina­ sediment s ca nn ot be used as di rec t mea ­ ca use adverse effects. tion from human activities. To obtain an sur s of th e potential or th e co nt aminant s Long and Morga n's ( 1990) ERLand es timate of the proportion of the lead and to cause adverse effects on human hea lth. ERM va lues for chlord ane were not mercury due to contaminati on, th e propor­ Howe cr, it is pos.· iblc to relate sed iment updated by Long and oth ers ( 1995); co n­ tion contained in the mineral grains was concentrati ons to th e potential for ad crsc seq uentl y, th e ch lordane guidelines pre­ determi ned from compari sons to worl d­ cf"fec ts on th e hea lth of aq uati c orga nisms sented in tab le 3 probab ly shou ld be wide averages of elementa l concentrati ons th at li ve in th e~ ·climents. Long and oth ­ applied with more ca uti on than th e guide­ in th e Ea rth 's cru st, or average cru stal ers ( 1995) and ong. and M orga n ( 1990) lines for lead, mercury. total DDT, and abundances. Fyfe ( 1974) computed th e es tab lished sediment-quality guidelines total PCB's. T he edimcnt-quality guide­ average cru stal abu ndances or lea d and useful for thi s purpo. c by relating conta- lines for all fi ve contaminants arc used in mercury to be 13 ppm and 0.08 ppm,

4 Contaminants in Streambed Sediments Contaminant ERL- ERM

218 ppm1 Lead Occasional Mercury adverse l 0 .71 ppm effects 2 Chlordane on 16.0ppb aquatic Total DDT organisms Total PCB's

' Long ond others (1995) ' Long and Morgan ( 1990)

wh ich th e potential ex ists for occasional 140 adve rse effec ts on aq uati c orga ni sms th at li e in th e sed imen ts. 120 Lead a. , Three of th e four , itcs where lead a>c concentration in strea mbed sed iment s ~ ,g 100 g)E exceeded th e RL va lue ar~ ncar Wa sh­ ~ ~ 80 ington, D. .- site I on th e nacos ti a .!: C/) ct:: Ri ve r. site 19 on th e Pot omac Ri ve r. and 0"' ~ ~ 60 . ite 20 on Accotink reck; th e fourth site c.,"'·-:. i. itc 4 on th e onh Branch Potoma §i 40 Ri ver (fi o. 2b). The hi ghes t I ad co ncen­ u:.O tration ( II 0 ppm) was detected in s di­ m~ 20 _J ment from . ite 18 on the A nacos tia Ri ver, j ust northea t of Washington , D.C.. wh ich drains an intensi ely deve loped urban area. Strea mbed sediment at site

Potential frequency of occurrence 19 on th e Potomac River cl own trea m ol adverse effects on aqua t• c from Wa hington, D.C .. had a lead con­ orgamsms as a result of lead concentrat•ons •n bo ttom sed• ments centrati on of 5 1 ppm; th e strea mbed sedi­ (l ong and others. t 995): ments at thi s site repre cnt a compos ite of Mop Bar graph materi als cl eri ved from I 1.880 . quare • Frequent • miles of P tomac Ri ver Bas in drainage • Occasional area . The lowe t lead concen trati on ( 15 • Rare • ppm) was detec ted in trcambccl sedi­ • Not detected ND ments from site 9 on Marsh Run. which Not analyzed NA drains a sma ll, relati vely unpopul ated and highly agri cultural wa tershed.

Figure 2. Lead concentrati ons in streambed sediments at all sites exceeded the average crustal Mercury abundance value for lead; concentrations at four sites exceeded the Effects Range-Low (ERL) The median mercury concentrati on in value. Th e four sites where lead concentrations in streambed sediments exceeded the ERL strea mbed-sed iment sa mples collec ted at value are near urban areas in Washington, D.C. (si tes 18-20), and Cumberland, Md . (site 4). sa mpling sites where mercury was ana­ lyzed was 0.09 ppm (a bout the sa me as respec tively. In th e discuss ions of lead had lead concentrations that exccccl ccl th c th e a crage cru tal abundance of mercury and mercury concentrations in strea mbed average cru stal abu ndance of lead of 13 of 0.08 ppm). but th e range of concentra­ sediments that follow, th ese average ppm. indica ting th at th e occurrence of ti ons wa large. with a maximum va lu e of cru stal ab undances of lead and mercury lead in th ese strea mbed sediments may be 14.5 ppm (fi g. 3a), more than 150 times arc used to provide a frame of reference related to contamination by human ac ti vi­ grea ter th an the median. trca mbecl sedi­ for th e pr portion of lead and mercury ti es (fi g. 2a) . one of th e sites had a lead ments at six of th e site. had mercury con­ th at might be related to c ntamination. co nce ntration th at exceeded th e ERM centrati ons greater than twice the average va lue of 2 18 ppm for lead. However, cru stal abundance va lue, indicating proba­ Lead strea mbed sediment at 4 or 2 1 ·ites had ble mercury c nt aminati n. Of th ese six lead concentration. th at exceeded the Strea mbed-sed iment sample collec t­ sites, two had mercu ry co ncentrations th at ERL va lue of 46.7 ppm , th e level above eel at all sites where lea d was ana lyzed exceeded th e ERM va lue of 0.7 1 ppm for

Contaminants in Streambed Sediments 5 "0 Q) "Ea r------*~ 0. River, and site 4 on th e orth Branch ~ ~ 0. Potomac River; all three ite are down­ Mercury c (I) a. ERM ~[ 0. stream from major urban area . 13 .E. 0. S diment from site 19 on the Potoma u (/) g ~ 0. River downsu·eam from Washington, u E 5'0 D.C., had a mercury concentration of 0.17 ~ ~ Q) ppm, about twice th e median concen u·a­ ::;: tion for th e 2 1 sampled ite . Site 5 9, 16, and 22, wh ich had the lowe t mercury concentrations-le than 0.05 ppm­ drain relatively undeveloped areas th at are mainly characterized by fore t and farm ­

Streambed-sediment sampling site number land.

Pot'ential frequency of occurrence Organic Compounds of adverse effects on aquatic orgamsms as a result of mercury Unlike lead and mercury and other concentrat•ons 10 bottom sed1ments (Long and others, t995) trace elemen ts that occur in strea mbed Bar graph sediments, and which can be derived from Froquont II natural mineral source a well a co nt a­ Occasional mination from human activitie , th e Rare II occurrence of chl ordan e, total DDT, and Not detected ND total PCB 's in strea mbed sediment can Not analyzed NA onl y result from contamination from human acti itie . In the following di. cus­ Fi gu re 3. Mercury concentrations in streambed sediments at many sites generally were at or sions of th e concentrations of these three near the average crustal abundance value for mercury; concentrations exceeded the Effects organic compounds, strea mbed sediment. Range-Median (ERM) value at two sites and the Effects Range-Low (ERL) value at four other at ampling sites where th e compounds sites. The six sites where mercury concentrations in streambed sediments exceeded the ERL were detec ted are co nsidered to be conta­ or ERM values are in the Shenandoah River Basin (sites 12, 13, and 15) and urban areas in minated to some degree. Washington, D.C. (sites 18 and 19) , and Cumberland, Md. (site 4) . mercury, th e level above whi ch th e poten ­ Three oth er sites th at had mercury Chlordane ti al ex ists for freq uent adver e effec ts n concemrations th at exceeded th e ERL At the 13 sites where chlordane was aquatic orga ni sms that li ve in th e sedi­ aluc for mercury are site 18 on th e detec ted in strea mbed sediment s, th e co n- ment s. Anacostia River, site 19 on the Potomac The 1wo sites where mercury concen­ t4 r------'"""':'--..., trati ons in strea mbed sed iments exceeded Chlordane a. a:: t2 th e ERM aluc for mercury-site 12 on .0 Ec: th e South Ri ver and site 13 on th e South roo Fork , h nandoah Ri ver-are loca ted in ~~ 10 .!: ~ th e Shenandoah Ri ver Bas in (fi g. 3b). g ~ 8 The hi ghes t concentration of mercury was "" t:: ~a."' "' 14.5 ppm in strea mbed cd im nt s at site ~ .!:_ 61---11------1 ... c: (/) 12 on th e South Ri er, fol lowed by 0.86 8~ ~ .£: 4 ppm at site 13 on th e outh Fork ro-o -oG> Shenandoah Ri vcr an I 0.46 ppm at site 15 ~ (/) :c0 on th e henand oah River. Since 1979, (.) th e Water ontrol Board (now th Virginia Department of "Iwironmcntal Qu ality) has condu cted several . urvcys Potent•al frequency of occurrence for mercury in streambed sediment. nca r of adverse effects on aquat•c organisms as a result of chlordane sites 12 and 13 (C.T. Mizell, Virginia concen trat•ons in bottom sedime nts l cpartmcnt of nvironm mal Quality, (Long and Morgan. t990) wriucn commun ., 1995). Th ir . urveys Bar graph Frequent also have detec ted 111 rcury in strea mbed Ill sediment s at co ncentrations that exceeded Occasional th e RM aluc for mer ury. although th e Rare - Not detected ND co n ·entrations in th eir surveys arc not as Not analyzed NA high as th e co ncentrations in th e 1992 ·ur cy. The irginia Department or nvironmcntal Quality is continuing to Fig ure 4. Chlordane concentrations in streambed sedi ments were detected at 13 si tes; concentra­ monitor mercury co ntaminati on at th ese ti ons at 4 sites exceeded the Effects Range-Median (ERM) value. Seven of the 13 sites where sites through periodic collec ti on and chlordane was detected in streambed sediments are located in the Great Valley (sites 7, 8, 11 -15) ; 4 ana lys is or fi sh ti ss ues . are in the Washington , D.C., area (sites 18-21 ), and 2 are in th e Cumberland, Md ., area (sites 3-4) .

6 Contaminants in Streambed Sediments 3 0 ~------, ERM • 46.1 ppb Ri er Ba in, had a hi rd ane concentra­ ti on (3.39 ppb) th at wa b 1v cc n th ERL 20 "0 and ERM alu . . ite 4 on th e onh ~ E c Branch Potoma Ri cr had str amb d Total DDT a. ::lg 10 edim nt s with a chi rd an cone ntrati on .~S ~~ 45 ::===:::::======~ th at ex eeded th e - RM va lu ' . _g~ "'"'~a. ~ . s Total DDT g~..,., T tal DDT cone ntrations in str am­ 1-E bed sed iment s at sc en sites ex cede I th e g~ 2 RL va lue of 1.58 ppb fort tal DDT (fig. -"'"' ~ Sa) . The highc t total DDT cone ntrati n in sed iment (23.9 ppb ), although 15 time. grea ter th an th e RL va lu e, was onl y about one-half th e ERM value of 46. 1 ppb for total DDT. Total DDT co n­ Potential frequency of occurrence centrati on. in . trca mb d sediment s at I 0 of adverse effects on aquatic organisms as a result of total DDT of th e 22 itc. were I ss th an I ppb. concentrations rn bottom sedrments (Long and others. t995) Of th e seven site. th at had total DDT Bar graph co ncentrati on exceeding th e ERL va lu ', Frequent II fi e ites ar in th e Grea t Valley- site 7 Occasional on on co hcaguc Creek, site 8 on Rare Ill Opcqu on reck, site II on th e Middle Not detected ND Ri ver, site 14 on the orth Fork Not analyzed NA hcnandoah R i vcr, and sit I 5 on th e Shenandoah Ri cr (fig. 5b). The seco nd hi ohes t total DDT concentrati on detec ted Figure 5. Total DDT was detected in streambed sediments at all sites; conce ntra tions exceeded in strea mbed sediment s was 15 ppb at sit ' the Effects Range-Low (ERL) value at seven sites. Five of th e seven sites where total DDT con· I 5 on th e Shenandoah Ri cr, whi ch drains centrations in streambed sediments exceeded the ERL value are in the Great Vall ey (si tes 7, 8, 11 ,

14, and 15). 200 r------~------~ 180 ~----...f~---.... ERM centrati ons ranged from 1. 67 to 66.6 ppb 160 (ri g. 4a). Four itcs had streambed sedi ­ 140 ment. with chl ord ane concentrati ons th at ~ 120 exceeded th e ERM aluc of 6 ppb for ~ 100 Total PCB's chl ord ane. The oth er nine site where a. 'g c 80 L------..&.----~ chl ord ane was detec ted in strea mbed sedi ­ ~ g 28 .------.., ments had co ncentrati ons less th an th e ~~ E ~ 24 1------+--- ERM va lue, but grea ter th an th e ERL ~~ ~ ~ 20 va lue of 0. 5 ppb . Chl orda ne was not .!: [ 16 detected a1 9 of th e 22 sa mpled sites. Co"'c·- u 12 Chlord ane was detected in strea mbed n. sed iments at it cs 7, 8, and 11 - 15 in th e 8 inten ivcly fanned Grea t Valley; fi ve of 4 th ese sites are in th e Shenandoa h Ri ver Ba. in (fi g. 4b). Site I , 20, and 2 1 on 0 ~~~~~~~~~ strea m · in th e heav ily urban Was hington,

D.C., area had trca mbcd . cdimcnt s with Paten !tal frequency of occurrence chlord ane concentrati ons th at exceeded of adverse effects on aquatic organisms as a result of total PCB th e ERM va lue. The chlord ane concen­ concentrations 10 bottom sediments trati on (66.6 ppb) in strea mbed sediment s (Long and others, t 995) Bar graph at site 18 on th e Anacosti a Ri ver was Frequent II more th an I 0 times grea ter th an th e ERM va lu e. This hi gh chlord an co ncentrati on Occasional in strea mbed sediments at . ite 18 i · cor­ Rare - Not dolected ND roborated by lreambed-. cdiment sampl es Not ana lyzed NA co ll ec ted by Wad e and oth ers ( 1994) at ix sites several miles downstream from site I , where chl ord ane co ncentrati ons in Figure 6. Total PCB's were detected in streambed sediments at 17 si tes; concentrations exceeded . ediments ranged from 28 to 140 ppb. th e Effects Range-Median (ERM) valu e at 1 si te and th e Effects Range-Low (ER L) value at 2 other The sediment s at site 19 on th e Potomac sites. Concentra tions of total PCB's in streambed sediments we re highest at site 13 on the South Fork Shenandoah River, site 18 on the Anacostia River, and site 10 on the Potomac River at Ri ver. which !rains mos t of th e Potomac Shepherdstown , W.Va.

Contaminants in Streambed Sediments 7 nearly all of th e hena ndoah Ri ver Ba in. naco tia River had the hi ghe. t total To tal PCB's The oth er . ite in th e central pa rt of the DDT c ncentrarion in th e Potomac Ri ver Streamb d sediments at on ly one site P tomac Ri ver Basin where the total Basin ; the co n en trati on at thi ite, which had a total PCB concentrati on th at DDT concentrati on in streambed sedi ­ drains a hi ghly urban area, wa. 23.9 ppb. exceeded th e ERM value of 180 ppb for ment. exceeded the ERL va lue is ite 6 on Streambed ·ed iment at five site. in the total P B '. (fig. 6a). Two other site · had the acapon Ri ver, whi ch drain. an area we ternmost part of th e Potomac Ri ver strea mbed ediment with total PCB con­ th at is mostly forested and undeveloped, Bas in had total DDT oncentration. th at centrations that exceeded th e ERL va lue but which ha ome agricultural ac ti vity. were le th an I ppb. of 22.7 ppb but were le . than the ERM The. treambed. ed imen ts at ite 18 on the va lue. Total PCB concentration at the

Chlordane

EXPLANATION

Urban land use (from USGS GIRAS data base)

• Orchard land use (from USGS GIRAS data base)

.A. Site with elevated contaminant levels

[J Industrial discharges greater than or equal to 1 million gallons per day (from U.S. Environmental Protection Agency STORET data base) Contaminants shown in RED were detected in streambed sediments at concentrations that exceeded the Effects Range-Median values. Contaminants shown in were detected in streambed sediments at concentrations that exceeded the Effects Range-Low values by a significant amount, but were less than the Effects Range-Median values.

Figure 7. Mercury and total PCB contamination at sampled si tes probably is related to industri al point sources in upstream areas; chlor­ dane and lead contamination probably is related to urban nonpoint sources, and most total DDT contamination probably is rel ated to orchard and cropland applications.

8 Contaminants in Streambed Sediments Way nesboro, a. (Brooks. 1977). Historica l rcc rd. indi ·a te th at m r­ cur was u. cd in industrial proc·sses at the plant until 1950. Two sampl ·d site. (fig. 7) downstream from th industrial plan t in Waynesboro- si te I _ on th S uth Ri rat Harri st n. a .. and si te 13 on th e uth l· ork henan loa h Ri er at Front Roya l, Va. - had mercury con · n­ trati ons in streambed sed im ·nt s th at exceeded th e ERM alu for mcrcur . The mercury cone ntrations atth 's' two sites, which were the hi ghes t m 'a. ured in th Pot mac Ri cr Basin , rcn, t th hi s­ tori ca l release of mercury into th e en I ­ other 14 ites where total PCB 's ronment at the industrial plan t in were detec ted, were less th an one­ Wayn sboro. half th e ERL value. PCB 's were not On a broad sca le, it is pos ible to detected in strea mbed sediment s at 4 of relate most of th e hi gh concentrations of nother indu tri al point so urce. th e sampled site . contaminants in streambed sediment. at which is known to have released P B ·s the 22 ampli ng site to three primary into th e environment. is located just The highes t concentration of total so urce of co nt aminati on- industri al upstrea m from site 13 on th e outh Fork PCB 's in streambed sed iments was 468 point . ourccs, urba n nonpoint so urces, hcna ndoa h Ri cr at Front Royal. Va . ppb at site 13 on th e South Fork and orchard and agri cultural nonpoint (fig. 7). Total I B concentra ti on in Shenandoah Ri ver (fig. 6b). The Virginia so urce . In th e following discu. sions. th e streambed sediments at si te 13 was 468 Water Control Board sa mpled streambed upstream pre. cncc of one or more of ppb, which cxc cdcd th e RM va lu e for . cd iment s nea r thi site in 19 and al o these three primary so urces is used to tota l I B"s of 180 ppb. The industrial detected high concentrati ons of total in fer th possible ausc of th e contam i­ plant loca ted ncar the site was losed in PCB 's in th e contaminated sed iments nant concentrati ons th at exceeded ERM 1989 after discovery of th release or (Virginia Water Control Board. 1992). va lu es and mo. t of th e con taminant co n­ P B's into th e South Fork henandoa h The sec nd highc. t concelllrati on of tota l centrati ons th at exceeded ERL va lue (fi g. Ri er ( irginia Water ontrol Board, PCB's in strea mbed sed iments was 13 1 7). Additional sa mpling and detailed 1992). Two oth er ites where total P B 's ppb at site 18 on th Anacostia Ri ver. in ves ti ati on wou ld be necessary to deter­ in stream bed sed iment s exceeded th e ERL which drains a hi ghl y urban and devel­ 0 mine th e spec ifics urccs of contamina­ al uc may be related to indu. tri al sources oped area. The only oth er sit th at had a ti on at each of th ese sam 1 ling sites. of PCB contam inati on. Site 18 on th e total PCB co ncentration in streambed sed­ Anacostia Ri ver drains a high ly urban iments th at exceeded th e RL va lue was Industrial Point Sources area with a major industrial plant in a site I 0 on th e Potomac Ri ver at nearby up. trea m area (fig. 7). itc I 0 on Shepherdstown, W. Va., where th e total A n indu ·trial point sou rce. which is the Potomac Ri er at Shepherdstown, P B concentrati on was I 08 ppb. No known to have released mercury into th e W. Va., has major industri al sources in its P B's were detected in trea mbed sed i­ environment. is loca ted near th e headwa­ upper lrainagc area; however. no major ment. at sites 5, 16, 17, and 22, which ters of th e South Ri ver in th e hcnandoah Ri er Basin. In 1977, mercury was di s­ drain mos tl y farm land and forest areas of Run off from urban areas is a possible source of covered in :oil at an industrialJiant in th e Potomac Ri er Basin. lead and chlordane con tamination in streambed sediments. SOURCES CONTRIBUTING TO CONTAMINATION AT SELECTED SITES T here arc many poss ible point and nonpoint sources of th e fi ve contaminants th at were detec ted in strea mbed sediment s at th e 22 sa mpling sites in th e Potomac Ri ver Bas in . Po ss ible point s urccs in­ clude po rl y co nstru cted landfills, chemi­ ca l spi lls, and di scharge from industri al, municipal, and commercial wa ter-treat­ ment plants. Poss ible nonpoint sources inclu lc atmospheric depos ition and run off from agricultural, urban, and mining areas. It is poss ible th at th e occurrence of a contaminant in strea mbed sed iment. at a sa mpling site is th e res ult of a combina­ ti on of several of th ese source . . discharge point arc located immediately upstream of th e sa mpling site and no kn own PCB point s urces are document ­ ed (fi g. 7). The source of the high total PCB concentrati on at site I 0 is unknown ; further data co llecti on and in ves ti gati on is necessa ry to determine th e source. Urban Nonpoint Sources The pas t u. e of chlord ane for trea t­ ment of termite infes tati on in urban areas is a pr babl e source of th e hi gh chl ord ane concentrati ons meas ured in strea mbed sediments in strea ms th at drain urban areas. The fo ur sites th at have chlord ane co ncentrati ons in strea mbed sediments th at exceeded th e ERM va lue for chl or­ dane all drain maj or urban areas. Site 18 on th e Anacos ti a Ri ver, site Past pesticide application s in orchards are a possible 20 on Accotink Creek, and site 2 1 source of DDT contamination in streambed sed i­ ments. on Bull Run all recei ve drainage remain th ere for long peri od. of time. from urban settings in th e Orchard and Agricultural Nonpoint While present , th ey can be ava ilable Washington. D.C. , metropolitan area. Site Sources under certain environmental conditions to 4 on th e orth Branch Potomac Ri ver cause adver e effec t on aquati c organ­ receives drainage from th e City of Total DDT co ncentrations in ism . . An exa mple of th e environment al umberl and. Mel .. which i. the largest strea mbed ediment exceeded the RL per istcnce of contaminant. in th e city in th e wes tern pan of the Potomac va lue for total DDT at sit es 7, 8. and 15 in Potomac Ri ver Bas in i th e occurrence of Ri ver Bas in (fi g. 7). Urba n nonpoint th e north-central Grea t Valley (fi g. 7). total DDT in strea mbed sediment at all The. c three site. are nca r and downstrea m ~o urccs were identified by Wade and oth ­ ite sa mpled during the 1992 survey, two ers ( 1994) as the probable so urce of high from areas where fruit orchard are mo t decades after th e usc of th e 1 es ti cide wa. chlordan e concentrations in strea mbed preva lent in th e Potomac Ri ver Bas in. In banned in 1972. Anoth er even more co m­ sediment s in th e A mico. ti a Ri ver. and it is ad dition. th e areas drained by th ese three pelling exa mple is th e presence of elevat­ like ly th at similar types of urban source · sites have . ome of th mo t inten ively ed mercury concentrati ons in streambed arc also res ponsible for th e hi gh co ncen­ cropped farml and in th e bas in . The past sediments at ite 12 on th e South Ri ver in trati ons of chlord ane in strea mbed edi­ usc of DDT to control in ec ts in orchard s 1992 . more th an four decades after th e mcnt s at sites 4, 20. and 2 1 in thi s survey. and on cropl and probabl y is th e maj or use of mercury was di sco ntinued in th e source of th e relati ve ly high total DDT nearby indusu·i al pl ant th at released th e The many pas t and pre. ent uses of concentrati ons in strea mbed sediment mercury into th e environment. The lead in urban areas, which include lea ded meas ured at th ese three sites. occurrence of total PCB's and chl ordane fu el for vehicles. batteri es, co nstru ti on in strea mbed sediment at sa mpled ites pipes, plumbing onn ec ti ons, and paint also are exa mples of th e environmenta l ingredient s, probabl y arc th maj or ENVIRONMENTAL per istcnce of cont aminants yea rs aft er source:-. or th e relati ve ly hi gh lead concen­ IMPLICATIONS OF th eir use was bann ed. trati on detec t din strea mbed sediment at CONTAMINANTS IN site 18 on th e nacos ti a Ri ver (fi g. 7). STREAMBED SEDIMENTS Availability for Downstream II sa mpled sit es had lead co ncentrati ons Transport in strea mbed scdim nt s th at exceeded th e The occurrence of lead, mercury, ave rage cru stal abundan ce of lead; th e chlord ane, total DDT, and total PCB ' tn During high streamflow peri ods, maj or reason for thi s 1 r babl y is th e ·trca mbcd sediments throughout th e streambed sediments are mobilized and wi Jcs prca I atmosph ri c depos ition of Potomac Ri ver Bas in ha event! impor­ transported downstrea m. onscquentl y, lea d in dust particles cont aminated by tant implica ti ons for strea m-ecosys tem th e cont aminants stored in th e sediments vehi cl cx hau. t fumes . and human hea lth. Fac tor · such as th e also arc transport ed and redepos ited in !though mos tl y used for agri cultural environmental persistence of th e co ntami­ lownstrca m reaches of th e stream s. purposes, Dl T also was widely used to nant , their a ailability for downstrea m Through thi s frequentl y recurring process, control mosq uitoes in popul ated areas transport , their potential for bi oaccumula­ contaminants are introduced into new until it was ba nned in 1972. Res idual tion in aquati c organi sm , and th eir poss i­ area of th e strea m ecosystem, th ereby concentrations of DDT in urban so ils arc bl e effect: on human hea lth, are briefl y becoming ava ilabl e for ingesti on by a proba bl e so urce of th e relati v ly hi gh di scussed in th e following scc ti ns. grea ter numbers of aquati c orga ni sms. An exa mple of th e transport of contaminants ·onccntrati on of total DDT in strea mbed Environmental Persistence sediments at site 18 on the A nacosti a in ·trea mbed sediment s is th e occurrence Ri cr (fi g. 7). Once th e co ntaminants arc introduced of mercury in th e Shenandoa h Ri er into strea mbed sediments, th ey ca n Bas in . A s noted earlier, th e mercury was

10 Contaminants in Streambed Sediments 14.50 Figure 8. Several sampling sites with high concentrations of mercury Organisms th at li in th e sedim nts in streambed sediments are downstream from a known source of mer­ • cury contamination in Waynesboro, Va. can ingest th e cont ami nant s and a umulate th min th eir li. sues. The bioa cumulati on of th e ont ·tminants ( ) in the e aquati c organ i. ms has been h wn to ca use ariou. ph siolooical i.!:~ 12 problem and even death r th e rga ni sms 0 46 when cont ami nan t con en trat ions exceed HARPE }-Potorn ERL and ERM JUid lin s (Long and oth ­ I ers. 1995). In add ition, th ese a ·cumulated on entrati ons ca n be passed on to hi gher organi. ms in th e food chain as a result of th e hi gher orga nism. inges ting co nt am in ·lted oroani sms th at li ve in the . ediment s. One example ST \. f th e r lati on of streambed ­ sediment contaminati on to

WASt liN .T N 1).(... th e resulting contami na­ ti on of higher orga nisms is shown in fi gure 9. As part of th e 1992 sur y, ti s. u s from EXPLANATION ca tfl h (yellow bullheads) were col­ • Known source of mercury lec ted at eight of th e . ite. wher trea mbed sed im nt s were co llec ted . .A. Sites with mercury concentration, in parts per million The correlati n coeffi ·ien t ( pearman 's 0. 17 Proportional bar showing mercury concen tration in rh o) between chl ordane concentrati ns in I streambed sediments, in parts per million sed imen ts and chlord ane concentrati ons in ca tfi sh ti ss ues is 0.94, indica ting a strong dire t relati on between th occurrenc of STA th e contaminant in trea mbed ed iments and th e presence of th e contaminant in fish ti s ues.

10 140 released into th e environment along th e South River in Way ne boro, Ya. (fi g. 8). 120 Through decades of down tream tra nsport 8 of mercury-c ntaminated ed iments, mer­ cury has accumulated in high concentra­ 100 tions in strea mbed ediments at site 12 on .£ th e South Ri ver at Harri ton, 16 ri ver 6 miles down trea m from th e indu tri al 80 source; at site 13 on th e outh Fork Shenandoah Ri ver at Front Royal, 11 8 river miles down tream from th e source; 60 and at ite 15 on the Shenandoah Ri ver at 4 Millville, 171 ri ver miles downstrea m from th e source. oncentration of mer- 40 .£ cury in strea mbed ediment at th ese sites Q) c decrease with distan ce downstream from 0 2 th e source in Wayne boro, Ya. It al o is "2 20 :c0 po ssible th at mercury released along the 0 South River has reached th e treambed sediment at . ite 19 on th e Potomac River 0 0 downstream from Wa hington, D.C. 5 7 11 14 16 17 20 21

Potential for Bioaccumulation in Site numbers for sites where both streambed Aquatic Organisms sediments and yellow bullhead tissues were sampled.

The presence of th ese contaminant in streambed sediments can have a signi f­ Figure 9. Chlordane concentrations in catfish tissues are closely correlated with chlordane con­ icant adverse effect on aquatic organisms. centrations in streambed sediments at eight sampling sites where both media were sampled.

Contaminants in Streambed Sediment 11 Possible Effects on Human Health I\III II ~II II ~ 111~1~~11~\~rn~~~l ij~ilifl~~ 1~11 ~I ll ~ I \Ill Long. E. R. , M ac Donald. D.D., mith, .L.. 3 1818 00197652 9 and Calder, F. D., 1995, Incidence of Some of th e poss ible effects of the adver c biologica l effect within ran ges con taminant: on human health are docu­ of chemica l co ncentrati on. in mari ne mented in tab! 2. One way th at human. and e tu arine sedimems: Environmental can be ex posed to th e contaminant. i · M anagement. v. 19, no. I , p. 1-97. through the food chain. The human co n- . umption of fish from strea ms with co nta­ Long. E. R. and M organ, L.G ., 1990. The minated ed iment and th e human con- potent ial for bi ologica l effect. of sedi­ umption of terre ·tri al animfll who 1 rey ment -sorbed co ntam inant tes ted in th e on contaminated fi h can lead to th e ati ona l Statu. and Trends Program: bi oaccumulati n of th e contaminant in .S . ational 0 ean ic and A tmospheric human ti ues. Fish surveys co nducted in Admini. !rati on. Tec hnical Memo OS the Potomac Ri ver Bas in have detec t d OMA 52 . 175 p. unacceptable levels of mercury, chlor­ dan e, and total P B's in fi sh ti s ue in O' Lea ry, R.M .. Crock, J.G., and Kennedy. selec ted tream and . as a result, have K .R .. 1990, Determination of mercury in prompted State regulatory agencie. to geologic material by continuous flow­ iss ue bans or re trictions on th e human co ld vapor-a tomic abso rption spec­ co nsumption of fi sh from certain PCB contamination in the South Fork troph otometry, in Qu ality a surance reache of th e strea m . Shenandoah River has ca used contamination manual for the Branch of Geochemistry, of fish , resulting in restrictions on human con­ U.S . Geologica l Survey: sumption of fish. ACKNOWLEDGMENTS Geologica l Su rvey Open-Fi le Report 90- 668. 184 p. The author are grateful for th e va lu­ Interstate ommiss ion on the Potomac Ri ver Basin Technica l Publica ti on 77-3, ab le ass i tance provided by th e members .S. En ironmental Protection A gency. 1991 , of th e report tea m: Adri enne emura f 77 p. Fact sheet: Nati onal primary drinking th e M etropolitan Washington Council of water standard ·: .S . En ironmental he apeake Bay Program, 1991 a. Chesapeake Government , and John Brakebill. Valeri e Protec ti on Agency, EPA 570/9-9 1- Bay toxics of concern list: .S. Gaine. Cheri e Miller. cott Phillip , and 0 12FS. 8 p. Cel. o Pu ente of th e SGS. Also apprec i­ En ironmental Protecti on Agency. 9 p. ated is th e illustrati on a sistance provided Virginia Water ontrol Boa rd . 1992. Virginia __ 199 1b. Chc,apeakc Bay 10xics of co n­ by Willie aughron and Sara h Kelley of wa ter qua lity assess ment for 1992: cern li. t information sheets: .S. th e USGS, th e editori al assistance provid­ Virginia Water Control Boa rd Environmental Protec ti on gene . ed by Sheryl Protan i of th e U GS. and Information Bulletin #58 . v. 2. 444 p. th e photographs provided by Dav id Usher 11 2 p. of th e US GS , and John Batti. ta, a volun­ Wade, T.L., Velinsky, D.J .. Reinharz. Eli, and Foreman, W.T. . Conn or. B.F., Furlong. .T.. tee r. Strea mbed-. ediment ampling ass is­ Schlckat, .E .. 1994, Tidal river sedi­ Vaught. D.G., and Leslie. M .M .. 1995. tance wa provided by Bruce Bern ard and ment · in th e Washington. D .. area. II. Meth ods of ana lysi by the .S. Janet Deni s of th e U SGS . Finally, Di tribution and so urce of organic con t- Geological Su rvey ational Water­ William Foreman , Edward Furlong, and aminant. , in Estu ari c : tu arine Qu ality Laboratory-Determinati on of Ri chard San zo lone of th e USGS are Re ea rch Federation, vol. 17. no. 2. p. organochl orine pes ti cides and po lychl o­ acknowledged for th eir ·upport in the lab­ 32 1-333. oratory ana lys is of ample and the inter­ rinated biphenyl · in bott om . ed imcnt by pretati on of analyti ca l result ·. dual capi llary-column gas chromatogra­ ph y with electron-capture detecti on: U.S. Geologica l Survey Open-Fi le For further information con tact: REFERENCES Report 95- 140, 78 p. District hi ef Brigg., Pau l, 1990, Elemental ana lys is of geo­ .. Geologica l Survey Fyfe, W. .. 1974, Geochemi stry: Oxford logica l materi al by inducti ve ly co upled 208 arroll Building Uni versity Press, I 09 p. pia ma -atomic emi sion pectrometry, in 8600 LaSa lle Road Qu ality ass urance manu al for th e Branch Tow on, MD 2 1286 Gilliam, R.J ., A lley, W.M .. and Gurtz, M . . , of Geochemi u·y. .S. Geolog ica l Internet: in fo srvrdmdtw .er.usgs.go 1995 , Des ign of th e Nati onal Water­ Survey : .S. Geologica l Survey Open- Qu ality Assess ment Program: Fi le Report 90-668, 184 p. W RIR 95-4267 Occurrence and distri bu ti on of water- quality conditions: .S. Geological Brooks, K.M ., 1977, Critica l areas in th e Survey ircul ar 111 2, 33 p. Potomac Ri ver Basin, A mid- 1977 rev iew of water-pollution co ntrol:

12 Contaminants in Streambed Sediments