Document 9JxBLxmLqjRyBrNELEpKzM9gD

9/2 V75 H. S. Bergen w V.'. R^Kichard `\\r ... // - x; / ' A '! > ! A i' IV R-r"'E. Keller D/ Wood The attached rerror z is a crie_ r' from a study by Tr>.Er_ed Lee and his A group for the Certs of Engineers, ',/ Please treat a s' confidential. For { .{/' A PCEs it concludes that' organic con- b1' \ \ A/ j tent cf a sci-lMs the e p terrain ing ^ 2' Vii ' I'-"A 'V' e",* /' factor in .the adscilJtTon cf rCBs, The higher the organic content, the gore tenacious the FCBs. A* , *1 *<\\A/y v ...A / <A V ' I, r' y -- / (\ I j * DEPOSITION | EXHIBIT g EaPagporgp i 90 uiiiurr> WATER_PCB-00055921 HYDROCARBON PESTICIDES AMD OTHER ORGANIC CONTAMINANTS . INTRODUCTION Two of the groups of compounds present in dredged sediments which are of concern because of their potential environmental impact on water quality are the chlorinated hydrocarbon pesticides and chlorinated biphenyl compounds (PCB's). Because cf the potential significance of these compounds it was felt that sene studies should be conducted in order to determine whether there is any release cf these compounds to the water column at dredged material disposal sites. This section of the report presents the results of the studies that have been conducted on the release of chi or in.! :ted hydrocarbon oesticices and PCB.'s from dredged sediments. The purpose of mas pnase ox ne project as to evaluate the validity of the elutriate zeel (now required by the US EPA and the Co rps o f En -- n <= ers) E. 3 a TPS :>d of estimating the rslscss of erga nic cont amin arre s fro: : o -f> ial to -lul-U;d T Y rat ei' c olumn . Speci f ica iiy 5 X. L i vrhe pr.pri ther1 c. is si gnifican t re lea se OX hyd rccci"bon --n . staci des and Tr>wni'D2 t s 1 is ted 1S73 US E?A Proposed Cra. tera.a49 and, a. x so, to i.dent.ify the factors `which could affect the release of these compounds a r cm t h e s e d ime n t s. The z-elease cf chlorinated hydrocarbons was net investi gated until the latter phase of this study period. There fore, this aspect of the project did not progress to the sam.e extent as the study of the release cf other contaminants during the Elutriate Test. It should also be noted that ana loses of organic ccmocuncs in sediments recuire much longe: neraoos ox tnan analyses ox n u l r a e n l s ana muuiir, 182 WATER PCB-00055922 heavy metals. Therefore, the number of samples that could be processed for pesticides during this test was greatly reduced. LITERATURE REVIEW** . The presence of potentially toxic organic compounds, notably chlorinated hydrocarbon pesticides and PCB's, in many sediments has led to some concern that these materials say be released mhen dredged sediments are disposed of in open mater. The S sPA c. n g Armsy Corps of En.gi neers developed the Elutriate Te (Keeley and En ^ e ) to cet ermine if a dredged sedimenl culd have an adverse effect on mater quality upon disposal in open mater. A description of the Elutriate Test and modifications required for determination of organic compound release, is given in Appendix I. The purpose cf this phase of the study is to evaluate the validity and practi cality of the Elutriate Test for determining organic contanina: release, and to identify factors mhich significantly affect the test. - - - 'rA*'* gei]p,c Ane i vsi s Criteria Eulk analysis had been used by the US E?A to determine if a dredged sediment could be dumped in open water. The US ERA dredged material cisnosal criteria mhich are related demand, total volatile solids, and hexane-extractable oil and grease. The problems mith these criteria have been " 2 .. discussed by Lee and Plumb. The oil and grease criterion has also been discussed by Lee e_t al. 6 2 In brief, the attempt to use sanitary wastewafer parameters to evaluate nature;! 'maters ar.d sediments, for vdsich they are not This liter etr.re review n, as seen cesig_nec o supplement thx literature reviev; on this topic by Lee ar.d Plumb. ^ i.e; 00104 4 WATER_PCB-00055923 necessarily valid, has led to the problems discussed in the above papers. - Because bulk analysis of a sediment does not truly evaluate the potential for release of a compound into solution, the Elutriate Test was developed. A number of studies lend support to this belief. Boucher and Lee91 found that 70 percent of lindane sorbed on natural aquifer sands v:as leached by three washes with distilled water, but less than 20 percent of sorbed dieldrin Was released. Huang and Liao 92 found that about 25 percent of dieldrin sorbed on pure r.cntjiiorillonite could be leached into distilled water, but that very little BDT or heptachlor could be leached. Nissenbaum et alf0o3 und no correlatio n between the organic matter in a sediment and that in the interstitial water. > C T 0C Q M P -f" v-* ^ r: c V? 0m S. "t s"i Both natural and synthetic organic compounds may be significant in natural water for a number cf reasons. The classical reason for concern about organics is that they can increase biological oxygen demand, resulting in oxygen .U L . :n and rossible resultant damage to ac-uatic life. Another possible effect of organics release is the chelation of heavy metals, which would lead to higher metal concentra tions in the water than would be expected frcm the solubility c: the tietal. : G C ZL C. lC( organic material in natural water (Buce et_ cfl.Oy4il ) th There is evidence that seme chelated metals are less toxic to organisms (Steem.an-Kielsen and V.'ium-Andersen s and that chelated Hiicrcnutrients such as iron are more available to algae for growth (Siegel . . . . Natural organic matter may promote biological activity i.n ways other than chelation of trace metals. Seme algae require organic micrcnutrients such as Bn 2 ?c-n grew-th, and sere invertebrate larvae develop better in c:r W 'T .O S"> t' v; 1E - uukm WATER PCB-00055924 than another, a phenomenon which has been attributed to the organic content of the water (Raymont 97 ). Humic material has been found to stimulate grov.-th of marine dincflagel- lates in synthetic culture mediums (Prakash and Rashid 99). This effect seems to have been due to mere than chelation of metals, since the chelator EDTA was already present in the culture media. ' - Perhaps the ;atest reason for concern about organic compounds in natural waters is-that some of them are toxic :o aquat: . vj CL. i . w: organisms. For example, some steroids are toxic to minnows (Miller and Munma 99 ). Petroleum deposited in sediments can be taken up by benthic organisms, although there does not appear to be any concentration in the food chain (Scarratt and Zitko 100 ), V.r petroleum fractions are more toxic than others, Aromatic and light hydrocarbons are the most toxic, while weath ere d petroleum is rlatively harmless (Nelson-Smith ) . An order possible efface of oil is the concentration of pesticides, cither m surrace shiicr-xms (.DDuucce et aa. l.9^) or in sediments (Hartung and Klinger 1UZ ). Pthalate esters, commonly used as plasticizers, can interfere'with regroduci `.on or iron, They hav'e'been identified in a number of spec _es of fish from North American waters (Mayer et al^99 ) The group of compounds that has received perhaps the greatest attention recently is the chlorinated hydrocarbons, which include polychlorinated biphenyls (FCB's) and the pesti cides DDT, cldr-in, enersn, and lindane. These compounds are significant not only because of their toxicities in water, but also because they accumulate in organisms at concentrations much higher than those in the surrounding water (Hannon et_ al. ~ ). It has long been thought that this concentration was due to magnification 'within a food webj however, it has recently been suggested that the concentration is cue to partitions between lipids in an organism UIIKM V.\ 185 WATER PCB-00055925 surrounding water (Hamelink et_ al. ^ . Algae (Hamelink et al. ), crustaceans (namelmk et al. ; Johnson et _al. ), and oysters (Westlake and Gunther ) are all capable of' accumulating DDT directly from 'water. While accumulation, from v?ater may be important for invertebrates at lower trophic levels, there is evidence that food web magnification is the more inocrtant mechanism for some fish in higher trophic * 10 8 levels (Kacek and Korn ). The reports on the occurrence of chlorinated hydro carbons and other compounds in organisms are too numerous to be covered here; however, mention of a few of these demonstrates the range of their occurrence. PCB's have been found in fish from the Milwaukee River in Wisconsin (Veith ar.d Lee 109 ) and in zooolanktcn from the Atlantic . .` 110 v . . Ocean ofr North America (Rxsebrough et_ al. ). Dueldnn ana endrin have been detected in oysters from estuaries of the Gulf of Mexico (Rowe et al ) . DDT and its metabolites, DDD ar.d DDT, have been found in oysters (Rowe et_ al. ~~~ ), crayfish, aquatic insects (Hannon et al. ), freshwater n 1 r? U> <-> '"n z-' "1 .nk*t*-on, a2 nnnd -fr"iisrkh ((Hsar --m-- me"1l n ^ -A`* e 1 ^ ^ ). 1 *) o , (Leshniowsky et al. ^ ) and several stecaes cf algae , (Hall ana. Mc_Car.ty 1~~13; Kang et aJ,L. 1--U' ,) sere. c.nlcranmaated hvdro- carbons from solution, very efficiently. Factors Affecting Exchange Between Sediment and Water1 k number' of factors may affect the exchange of an organic compound between sediment and water. These include: the pH, salinity, temperature, and organic composition cf the receiving 'water; the composition and organic content of the sediment; redox conditions of the water and sediment; the concentration cf the compound in the water and sediment; ' and the chemical nature of the compound. The time cf con tact and the solid-liquid ratio of the sediment and -water are also factors -which could affect exchange, factors are discussed in subsequent sections. 18S WATER_PCB-00055926 pH of Water Luh end Baker*-found that m-amir.opher.ol and 2,4- diamincphencl were sorbed at 'acidic, not basic, pH values by mcntmorillonite and kaolinite. Phenol, m-cresol, 2,4- dichlcrophenol, valeric acid, and n-hexancic acid were not .. 116 sorbed at any pH. Tne sane investigators" found that maximum desorption of pyridine occurred at pH's of 1 and 11; minimum desorption occurred at pH 4.0-5.5. Schnitzer--^ found that sorption of a soil -fulvic acid fraction cn r.on.t- morillonite decreased v;ith decreasing pH. The decrease was greatest between pH 4 and 5, which corresponds to the pH of the fulvic acid carboxylic groups. In general, it appears that greatest d e'serpticn of organic ccmoour.ds from clay minerals occurs at basic pH values at vrhich organic acids are ionized a nd, thus , electrostatically repelled from the negativ e ly charged clays. This effect may be mere noticeable f cr acid s l n fcr bases, since increase; pH generally increases sciu- bility of organic acids but decreases solubility of organic bases. In natural sediments, electrostatic interactions with clay minerals may be largely overshadowed by other factors, such as organic-organic interactions and organic- iron oxide interactions. The effect cf pH on sorption and desorption of neutral . OI organic molecules is not clear. Boucher and Lee-- report that the pH range normally found in an aquifer had no significant effect on the sorption of lindane and dieldrin by unconsolidated aquifer sands. Huang- found that with- 5.n the pH range of 6 to 10, the sorption cf dieldrin by montmcrillonite decreased slightly with increased pH. Howe et al. Ill studied the sorption and release of sediments. They rur.d that after ent of the dielcr been sorbed at pH 7.S to SS..OO, vrh i I e 2 b5 oercent had been .2, cijiC 2b oercen st on 6.7 to 7.1. IS 7 01110.351 WATER PCB-00055927 After1 three days, about 60 percent had been sorbed at all three pH values. A difference v:es again observed after seven days, however, with 2 percent sorbed at pH 7.8 to S.0, 10 percent at pH 3.8 to 4.2, and 23 percent at pH 6.7 to 7.1. Although the effect of pH on sorption and release of neutral organic compounds is probably slight within the pH range usually found in'natural water, the study by Rowe cut al.^^ indicates that it should be further investi gated. - Salinity Salinity and ch< is m salinity ray have an :eci on ; orotion-dasortiion V*. cause ox icn e>:c ngc alteration cf clay crystal structure, and clay particles. V.h ion of organic matt et ai 119 found n;0 difference lenite for the adsc cion ox -athicn, which indica" :het the ionic form of ip . . .. Huang" w determined tie sorption of dielcrin by mcntmoril- lonite at sodium. cnlcrice concentrations of 3.0, 0.3, and 0.03 oercent (reoresenting aourcxi-ate salinities of ` estuarine environments, respectively). Variations in sorption and retention were slight. Greatest sorption and desorption occurred at 3.0 percent sodium chloride, followed by 0.03 percent, and 0.3 percent; thus, it appears that the tendency for sorption of dielcrin by mentmeri llcr.ite is slightly stronger at marine ana fresh water salt concentrations than at estuarine concentrations. Howe et a_l. studied tne e:sects or salinity (ranging from 9 to 25 parts per thousand) on the sorption and release cf dielcrin and aldrin by estuarine sediments. They found that maximum sorption after one cay occurred in' the ;linitv rente of 13 to 17 carts cer thousand for both dieldrin and aldrin. tnere was no variations in soroti.cn o: alcrin with .nity: minimum 18 8 nnin.152 WATER_PCB-00055928 scrption of dieldrin occurred in the 13 to 17 parts per thousand salinity range. All ox these studies shew sore variations with salinity but the results are contradictory. Further work should be done to establish the effects of salinity and salinity ' changes on leaching and scrotion of organics. Temperature Baker and LuhA^O found that sorption of pyridine on r.cntrnorillcn.ite and kaclinite wes trice as great at 1C o ci . ,. as at IS C . Boucher ar.d Lee determined that vntn.in the temperature range normally found in a VJisccnsin aquifer. tnere was no signiricant temperature exxect cn tr.e uptake lindane and dieldrin bv san' as. r.uan;___1 ] s -. j. u i vu that in the range of 10C to 30C, sorption and desorption of dieicrin by montmorillonite was not significantly axxected by water temperature. Tnese stucxes moicate xha mocraturs rant = > i v f our. .n r.atu .1 rat; temperature does not have a very significant effect cn :r u Li; .on ox organic Organic Content of water Organic material in the receiving water' may have an effect on sorption and desorption o a compound, either by competing tor sorption sirs ; or oy axfectm* rtgor -trhV.e scr ro\ "1 l* u> bn 1iltity :ne ccmocur.as . nuang118 found that the presence of glucose, d. --- J * -- } w a -- -- V-- :cid, and soluble organic ma L i tri j. i domestic sewage had no effect on the uptake of dieldrin, heptachlor, and DDT by r.cntmorillonite and illite. The presence of rhocamine B increased the sorption of parathicn by kaclinite and montmoriilonite and illite, but methylene blue, phenol, and organics f rom natural vrater had no effecL ," ns oi . , ('bang_ _e_ jfL. ~~ ). Boucher and Le; round that naturally occurring organic material in water decreased the sorptic of dieldrin on an aquifer sar.d but had no effect on the uniM-in:-! 1S9 WATER_PCB-00055929 sorption of Undone. Pthalate esters have been found associated with fulvic acTd~exlfFar:ted from soil. The pthalates were strongly bound and could be separated from the fulvic acid only after methylation and adsorption of the fulvic acid on aluminum oxide (Ogner and Schnitzer -1 ). V'ershaw et al. 122 showed that sodium humate increased the solubility of DDT by a factor of 20 to MO, and that humic acid strongly sorbed 2,4,5- T from solution. Pcirrier et al..-1-^'3 found that DDT tended to associate with colored iron-organic colloids (<10 nm diameter), and that DDT was concentrated by the colloids by -a factor of at least ' 16,000. The association of compounds such as DDT with naturally occurring soluble or colloidal organic material cculd be a mechanism for their solubilization and mobil ization; however, it could also lead to their deposition if the organic matter were to become sorbed cr be flocculated by changes in salinity cr redox conditions. From these studies, it is apparent that organics in water can affect the sorption, desorption, and solubility of an organic compound. The effect depends on the type of compound being sorbed, the nature of The organic material in the water, and the characteristics of the sediment. Cr. inisms Organisms in natural water can also affect the uptake and release of organic material. Bacterial floe is able to sorb alcrin from solution with about the same efficiency as natural sediments (Lechnicwsky et al. 112 ). Alga* ; cl Die to sorb chlorinated hydrocarbon pesticides from solution 10 to ICO times more effectively than either bentonite clay 11^ .. (Hill and HcCarty ~~'J ) or natural lake sediment (King et al ) . Thus, 'water disncsal of dredged . sediments con- n a *ru"iG3`i ci "tns pcs"C-Ci1 ry algae These pesticides might then either be passed on to or; .sms feeding on the algae or detosited in the sedi- 1S0 J111! I -15 -1 WATER PCB-00055930 jr.ent upon death of the algae. Composit 5 on cf Sediment Eoth the organic and inorganic composition of a sedi ment could affect its ability to sorb and release organic material. Different pesticides may be associated with different types of particles. For example, Pfister at al. 124 fractionated particulate matter isolated from natural wate and found that lindane v;as associated vrith the heavier xncrganxc xeria. while alcrin and il'j-ii L ended to be associated with the less dense organic fractions, r~'.r and DD .sscciate-d with all fractions. The clay mineral content is likely to be one of the most significant inorganic characteristics cf a sediment. 1?5 . .. . PsCutn " found that the concentration of DDT xn river seci- 77. 3..- S V.*c3 S " n_slv_ correlated.to the amount of fine materia] 19C in the sediment, and Lctse et al.-" found a posiitt:ive corre- tween clay content ana lindane O ^ -tpier-,p bv lake 114 showed that soil with a high :d about twice as much lincann nd parathion as sandy soil. The typo Ec ao. er127 found that the effectiveness cf clays for sorbing alanine, sucre ;e, fructose, succinic acid, and c-xalic acid d- rreasec arc nontmcrillcnite to illite to kaclir.ite. :er and Luh>2 0 sne 1 u u I; _ _ montmoriilonite than by kaolinite. For DDT sorption, the relative capacities decrease in the following crcc-r: m.cnt- morillonite > kaolinite = illite. For heptachlor, the order is montn:orillonxte = kaolinite > illite; for dieidrin the order is illite > mor.tmorillonite > kaolinite (Huang 3 c9 ^ i-\ _ __ j _ C at p5. C ITy for the PCS <; u Hite > m onvroriilon (rt pus e t c 0. 2 fuel oil, ccnsi sorption capacity deecreasc: an . 121 WATER_PCB-00055931 order bentonite > keolinite > illite >' montmorillonite (Keyers end Quinn . In general, for the more polar compounds, sorption capacity decreases with decreasing cation exchange capacity. For clay minerals, cation ex change capacity decreases in the order mcntmorillcnite (0.8 to 0.4 mec/g), illite (0.1 to 0.4 meq/g), kaolinite (0.01 to 0.1 meq/g) (Berner ). There is no apparent correlation of sorption v?ith cation exchange capacity for chlorinated hydrocarbons; for'the fuel oil hydrocarbons there is an inverse correlation. The organic content of a sediment also affects its sorption-desorption characteristics. In sediments con- taming petroleum hydrocarbons, Hartung and Klinger J-u calculated that the partition coefficient between sedi mented oil end the overlying water was one to eight mil lion for DDT in the hydrocarbon phase. Lotse -et el.~ZD found a positive correlation between organic content of lake sediments and lindane sorption capacity. Kang et al however, found tha' par' tially removing organic matter from a lake sedimen' by mane extraction increased the sorption capacity of the sediment for parathion. Rowe 1 et al. '""reported that the initial, uptake of cielcrin and e.ndrin was higher in sediments containing organics, but that after seven cays there was little difference beiV'ScH the amounts sorbed by organic and inorganic sediments. Ct PC] . o sorbed rr.c'jT'B 2 soil ccn'trsiinin^ 3.1 percent cr2c.n2-c- tter than'by pure clay minerals (Haque et al 'Although organic matter in sediment enhances sorp ticn of chlcri; tru e for petroleum ,'drocar'bons. Keyers and Quinn12 9 round, that oxidizing thhee organic matter of a marine sediment with hydrogen pero: 5e aouroxi.natelv doubled the sediment's scrpticn capacity for hydrocarbon i n: result may have been cu< :o otner effects of the oxidation pr*-'\-*r. ocess, hcweve: minnsfi WATER PCB-00055932 Results could be attributed to the solubility of hydro carbons, fats, and humic acids. In 1972, a US Government interdepartmental task force reported that there vrere few data on the removal, dis appearance, and sequestering of PCB's in soils or bottom, sediments of rivers, lakes, estuaries, or the ocean. Available data at that time suggested that sediments may be a major reservoir of FCB residues. Experimental data also indicated transfer of PCB residues from the sedi ment to the overlying vraters. , ' Veith ana Lee ~ reported the occurrence of PCB's in water from the Milwaukee River at concentration levels of 0.1 yg/1. Their study also shewed that many of the PCB's in the water vrere associated with suspended solids in the :r and vrere removed during the water treatment and ril- C. L _ O - i )cess . Haile and Lmeea132 rreeporrec me pres- ence oi rCu 1 s in Lake Ontario vrater and secimant at ccn- cenvr-amcns o d 55 yg/1 and 120 yg/kg, re Their vrater ar. elysis results die not dis dissolved a:'jd carticulate fractions. nacue e' si 12! nvestigated the vrater solubility, acsorptscn orcm aqu of Aroclcr 12 5 u. ( t; s solution, ana vapor phase behavior Aroclors represent a series of comm.ercial formulat Com: ,c-0- * irrap'iiq olubility at room temperature was V = A as - 55 yg/1. Adsorption experiments shew ed m!g l L.:e amount sorbed depends upon the nature of the -.-.v urzace . Soil with high clay er.d_crger.ic , con-. found to sorb much larger .amounts .than, sa.nd. The' 'study did not identify the nature of the organic content in the soil. . 193 f) u 1 (: '15 7 WATER_PCB-00055933 t Redo:-: Conditions '' Conditions in sediments ere often reducing; thus, metals such as iron can occur in the soluble, reduced form VThen these sediments are brought into contact v?ith oxygenated water, however, the metals are oxidized and precipitated frcm solution. This precipitation can cause flocculation and coprecapitation of other * 13 3 materials, including organics. Sridharan and Lee""' found that flocculation with ferric chloride removed 100 percent of the color from a highly colored lake vrster. They also found that flocculation by iron would at least partially coprecipitate phenol, citric acid, and eyeline from both natural fresh water and dis tillieedd waatteerr.. However, it dide net remove dextrose, kylbenzene sulfonate, or form 5.^ s' iyde. There was positive correlation between the organic content of e v?ater and the amour. t of _oh er.ol precipitated, a negative correlation for citric acid, and no corre lation for glycine. Flocculation with ferric sulfate removed about 10 percent of the soluble COD frcm Hissis- sicoi River water above St. Louis (Dcrnbush and Ryck`134 man ). Other lab studies on coagulation shevred that iron -was not effective in removing 2,4-D organic esters of 2,4-D, 135 . and 2,4-DC? from sclutzcn (Faust and Aly ). Infatuates 135 ............ " with a model sewage plant, Robeck et _al. found that coagulation v.-ith alum removed almost all DDT, 5 0 rercer.t i of the cieldrin, 38 percent of the aldri: out none or lindane or parathion. The lime-soda process followed by flocculation' "wiin-"iron was less efficient; about 50 percent o the DDT and less than 10 meant or me oaeacran were removed. A.s noted previously, pesticides associated v?ith naturally occurring organic matter, such as that respon sible for color, may be removed if the organic matter is precipitated, ' 10U. 0(il(Mrm WATER_PCB-00055934 Another effect of redox conditions is observed in the degradation of organic compounds. Kany naturally occurring lipids, such as sterols, are more readily degraded in aeroba c conditio. ns than m. anaerobic conditions (Turfitt 137 ), The opposite appears to be true for some pesticides, how- j ever. Hill and KcCarty x demonstrated that DDT, lindane, I and aldrin degrade more rapidly under.-anaerobic conditions the n aerobic, and that heptachlor epoxide and dieldrin ware equally persistent in both environments. Thus, if a sedi ment containing DDT.were removed from an anaerobic environ ment and placed in an aerobic one, the persistence of the DDT might be increased. Liouid-Sclid Ratio L-otse et al.' resort that the licuid-solid ratio is the most significant variabl e m TTiC degree ci scrprion or j. mo; _ -i p ^i...ems. Luh and Baker--10 found that fer O. J- -- amount of clav. the amount of eJr jy' ridine desorbed was directly related to the volume of water. Huang and Liao 32 showed that the higher the clay concentration in water, ths greater the amount of pesticide sorbed cr released. The relationship was not linear, however. For every order cf magnitude increase in solids concentration, the amount of terial sorbed or released approximately doubled. Thus, iigher solids concentration will result in a greater change in the aqueous concentration, cf the ccmpounx in Question, lower solids concentration will result in ni it "he ike cr release of a compound per gram cf Tine of Ccm.tact ; t'J w> l. i.iV vU;. o iC ^'s/1 L L.;C -f pesticides occur rapidly and th scrpticn anc aescrpeicn t'' h `t 1 ^ 1 r'V. ^ r = 195 WATER PCB-00055935