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Contaminants can exist in a wide range of states in aqueous environments, especially in surface waters. They can be freely dissolved or associated with dissolved or particulate organic matter depending on their chemical and physical characteristics. The freely dissolved fraction represents the most bioavailable fraction to an organism. These freely dissolved contaminants can cross biomembranes, potentially exerting toxic effects. Passive sampling devices (PSDs) have been developed to aid in sampling many of these contaminants by having the ability to distinguish between the freely dissolved and bound fraction of a contaminant. A new PSD, the Lipid-Free Tube (LFT) sampler was developed in response to some of the shortcomings of other current PSD that sample hydrophobic organic contaminants (HOCs). The device and laboratory methods were original modeled after a widely utilized PSD, the semipermeable membrane device (SPMD), and then improved upon. The effectiveness, efficiency, and sensitivity of not only the PSD itself, but also the laboratory methods were investigated. One requirement during LFT development was to ensure LFTs could be coupled with biological analyses without deleterious results. In an embryonic zebrafish developmental toxicity assay, embryos exposed to un-fortified LFT extracts did not show significant adverse biological response as compared to controls. Also, LFT technology lends itself to easy application in monitoring pesticides at remote sampling sites. LFTs were utilized during a series of training exchanges between Oregon State University and the Centre de Recherches en Ecotoxicologie pour le Sahel (CERES)/LOCUSTOX laboratory in Dakar, Senegal that sought to build "in country" analytical capacity. Application of LFTs as biological surrogates for predicting potential human health risk endpoints, such as those in a public health assessment was also investigated. LFT mass and accumulated contaminant masses were used directly, representing the amount of contaminants an organism would be exposed to through partitioning assuming steady state without metabolism. These exposure concentrations allow for calculating potential health risks in a human health risk model. LFT prove to be a robust tool not only for assessing bioavailable water concentrations of HOCs, but also potentially providing many insights into the toxicological significance of aquatic contaminants and mixtures. / Graduation date: 2010

<p>Predmet&nbsp; istraživanja&nbsp; ove&nbsp; doktorske&nbsp; disertacije&nbsp; je&nbsp; procena&nbsp; potencijalno&nbsp; biodostupne&nbsp; frakcije odabranih&nbsp; prioritetnih&nbsp; organskih&nbsp; polutanata&nbsp;&nbsp; (pentahlorbenzena,&nbsp; heksahlorbenzena,&nbsp; lindana, trifluralina, 4-oktilfenola i 4-nonilfenola) u sedimentu, ispitivanje biodegradacionog potencijala ovih&nbsp; jedinjenja&nbsp; u&nbsp; sedimentu&nbsp; u&nbsp; različitim&nbsp; uslovima,&nbsp; kao&nbsp; i&nbsp; procena&nbsp; potencijala&nbsp; stabilizacije<br />sedimenta&nbsp; dodatkom&nbsp; ugljeničnih&nbsp; sorpcionih&nbsp; agenasa.&nbsp; U&nbsp; cilju&nbsp; razvoja&nbsp; metoda&nbsp; za&nbsp; određivanje biodostupnosti odabranih organskih polutanata ispitivane su i&nbsp; optimizovane metode vi&scaron;estepene i jednostepene parcijalne ekstrakcije primenom sledećih hemijskih agenasa:&nbsp; Tenaks&nbsp; smole, XAD-4&nbsp; smole&nbsp; i&nbsp; rastvora&nbsp; ciklodekstrina&nbsp; (2-hidroksipropil-&beta;-ciklodekstrina,&nbsp; &beta;-ciklodekstrina&nbsp; i&nbsp; metil-&beta;-ciklodekstrina).&nbsp; Optimalni&nbsp; agens&nbsp; za&nbsp; procenu&nbsp; biodostupne&nbsp; frakcije&nbsp; odabranih&nbsp; organskih zagađujućih&nbsp; materija&nbsp; sa&nbsp; sedimenta&nbsp; XAD-4&nbsp; smola,&nbsp; a&nbsp; optimalno&nbsp; vreme&nbsp; ekstrakcije&nbsp; primenom jednostepenih&nbsp; ekstrakcija&nbsp; je&nbsp; oko&nbsp; 8&nbsp; h.&nbsp; Procena&nbsp; biodegradacionog&nbsp; potencijala&nbsp; odabranih prioritetnih&nbsp; organskih&nbsp; zagađujućih&nbsp; materija&nbsp; u&nbsp; sedimentu&nbsp; ispitana&nbsp; je&nbsp; u&nbsp; različitim&nbsp; aerobnim&nbsp; i anaerobnim uslovima uz optimizaciju uslova putem biostimulacije i bioaugmentacije. Pokazano je&nbsp; da&nbsp; svih&nbsp; &scaron;est&nbsp; odabranih&nbsp; jedinjenja&nbsp; poseduju&nbsp; značajan&nbsp; potencijal&nbsp; biodegradacije&nbsp; u&nbsp; anaerobnoj sredini&nbsp; pri&nbsp; čemu&nbsp; u&nbsp; slučaju&nbsp; lindana&nbsp; i&nbsp; trifluralina&nbsp; dolazi&nbsp; do&nbsp; potpunog&nbsp; uklanjanja&nbsp; biodostupne količine&nbsp; jedinjenja&nbsp; primenom&nbsp; sva&nbsp; četiri&nbsp; ispitana&nbsp; inokuluma.&nbsp; Aerobni&nbsp; potencijal&nbsp; u&nbsp; ispitanim uslovima&nbsp; pokazali&nbsp; su&nbsp; samo&nbsp; alkil&nbsp; fenoli,&nbsp; gde&nbsp; je&nbsp; takođe&nbsp; uklonjena&nbsp; skoro&nbsp; celokupna&nbsp; količinabiodostupne&nbsp; frakcije&nbsp; jedinjenja&nbsp; u&nbsp; sedimentu&nbsp; (78-85%).&nbsp; Potencijal&nbsp; remedijacije&nbsp; sedimenta dodatkom&nbsp; ugljeničnih&nbsp; materijala&nbsp; ispitan&nbsp; je&nbsp; sa&nbsp; aspekta&nbsp; odabira&nbsp; ugljeničnih&nbsp; sorpcionih&nbsp; agenasa (aktivni&nbsp; ugalj,&nbsp; biougalj&nbsp; i&nbsp; humus);&nbsp; određivanja&nbsp; optimalne&nbsp; količine&nbsp; materijala;&nbsp; isptivanja dugoročnih i kratkoročnih efekata dodatka ovih agenasa na biodostupnost organskih zagađujućih materija&nbsp; kako&nbsp; bi&nbsp; se&nbsp; ispitao&nbsp; efekat&nbsp; starenja &nbsp; i&nbsp; toksičnosti&nbsp; dobijenih&nbsp; sme&scaron;a.&nbsp; Rezultati&nbsp; stabilizacije zagađujućih&nbsp; supstanci&nbsp; u&nbsp; sedimentu&nbsp; pokazuju&nbsp; da:&nbsp; (1)&nbsp; povećanje&nbsp; doze&nbsp; sva&nbsp; tri&nbsp; sorpciona&nbsp; agensa dovodi&nbsp; do&nbsp; povećanja&nbsp; efikasnosti&nbsp; imobilizacije&nbsp; i&nbsp; smanjenja&nbsp; biodostupne&nbsp; frakcije&nbsp; odabranih organskih jedinjenja; (2) starenjem sme&scaron;a sedimenta i&nbsp; sorbenata u toku prvih 90 dana dolazi do daljeg smanjenja biodostupne frakcije svih jedinjenja, nakon čega se biodostupna koncentracija ispitivanih&nbsp; jedinjenja&nbsp; primenom&nbsp; aktivnog&nbsp; uglja&nbsp; ne&nbsp; menja,&nbsp; dok&nbsp; primenom&nbsp; biouglja&nbsp; i&nbsp; humusa&nbsp; dolazi&nbsp; do&nbsp; porasta&nbsp; biodostupne&nbsp; frakcije&nbsp; jedinjenja.&nbsp; Testovi&nbsp; fitotoksičnosti&nbsp; su&nbsp; pokazali&nbsp; da&nbsp; je&nbsp; <em>Zea mays&nbsp; </em>akumulirao&nbsp; značajno&nbsp; veće&nbsp; količine&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; iz&nbsp; netretiranog&nbsp; sedimenta&nbsp; u poređenju sa&nbsp; <em>Cucurbita pepo</em>&nbsp; i&nbsp;<em> Lactuca sativa. </em>Toksičnost sme&scaron;a sedimenta sa aktivnim ugljom i humusom&nbsp; procenjena&nbsp; na&nbsp; osnovu&nbsp; inhibicije&nbsp; luminiscencije&nbsp; na&nbsp; <em>Vibrio&nbsp; fischeri</em>&nbsp; kao&nbsp; i&nbsp; ispitivanjem <em>Zea&nbsp; mays&nbsp; </em>germinacije&nbsp; i&nbsp; produkcije&nbsp; biomase&nbsp; je&nbsp; pokazala&nbsp; značajno&nbsp; smanjenje&nbsp; u&nbsp; odnosu&nbsp; na netretirani&nbsp; sediment.&nbsp; Akumulacija&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; u&nbsp; biomasi&nbsp; <em>Zea&nbsp; mays&nbsp; </em>u&nbsp; netretiranom sedimentu je bila značajno veća u odnosu na sve sme&scaron;e sedimenta i aktivnog uglja i humusa. Sva tri&nbsp; sorbenta&nbsp; pokazala&nbsp; su&nbsp; veliki&nbsp; remedijacioni&nbsp; potencijal&nbsp; za&nbsp; sediment&nbsp; zagađen&nbsp; organskim zagađujućim supstancama, ali je aktivni ugalj pokazao najbolje performance.</p> / <p>The&nbsp; aim&nbsp; of&nbsp; the&nbsp; research&nbsp; in&nbsp; this&nbsp; PhD&nbsp; dissertation&nbsp; is&nbsp; the&nbsp; assessment&nbsp; of&nbsp; the&nbsp; potentially biodegradable&nbsp; fraction&nbsp; of&nbsp; selected&nbsp; organic&nbsp; pollutants&nbsp;&nbsp; (pentachlorbenzene,&nbsp; hexachlorobenzene, lindane,&nbsp; trifluraline,&nbsp; 4-octylphenol&nbsp; and&nbsp;&nbsp;&nbsp; 4-nonylphenol)&nbsp; in&nbsp; the&nbsp; sediment,&nbsp; estimation&nbsp; of&nbsp; the biodegradation potential of these compounds in sediment in different conditions, as well as the assessment&nbsp; of&nbsp; the&nbsp; stabilization&nbsp; potential&nbsp; sediment&nbsp; by&nbsp; the&nbsp; sediment&nbsp; amendment&nbsp; with&nbsp; of&nbsp; carbon rich sorption agents. In order to develop and optimise&nbsp; methods for the bioavailability assessment of&nbsp; the&nbsp; selected&nbsp; organic&nbsp; pollutants,&nbsp; methods&nbsp; of&nbsp; multistage&nbsp; and&nbsp; single-step&nbsp; non&nbsp; exhaustive extraction&nbsp; were&nbsp; studied&nbsp; using&nbsp; the&nbsp; following&nbsp; chemical&nbsp; agents:&nbsp; Tenax&nbsp; resin,&nbsp; XAD -4&nbsp; resin&nbsp; and&nbsp; a cyclodextrin&nbsp; solution&nbsp; (2-hydroxypropyl- &beta;-cyclodextrin,&nbsp; &beta;-cyclodextrin&nbsp; and&nbsp; methyl-&beta;-cyclodextrin).&nbsp; Results&nbsp; showed&nbsp; that&nbsp; optimal&nbsp; agent&nbsp; for&nbsp; estimating&nbsp; the&nbsp; bioavailable&nbsp; fraction&nbsp; of selected organic pollutants from the sediment is XAD-4 resins, and that the optimum extraction time using single-step extraction is about 8 h. The assessment of the biodegradation potential of selected&nbsp; priority&nbsp; organic&nbsp; pollutants&nbsp; in&nbsp; the&nbsp; sediment&nbsp; was&nbsp; examined&nbsp; in&nbsp;&nbsp; various&nbsp; aerobic&nbsp; and anaerobic&nbsp; conditions,&nbsp; with&nbsp; the&nbsp; optimization&nbsp; of&nbsp; conditions&nbsp; through&nbsp; biostimulation&nbsp; and bioaugmentation.&nbsp; It&nbsp; has&nbsp; been&nbsp; shown&nbsp; that&nbsp; all&nbsp; six&nbsp; selected&nbsp; compounds&nbsp; possess&nbsp; significant biodegradation&nbsp; potential&nbsp; in&nbsp; the&nbsp; anaerobic&nbsp; environment,&nbsp; where&nbsp; in&nbsp; the&nbsp; case&nbsp; of&nbsp; lindane&nbsp; and trifluraline there is complete removal of the bioavailable amount of the compound&nbsp;&nbsp; using all four inoculum tested. Aerobic potential under the applied conditions has been showen only for alkyl phenols,&nbsp; where&nbsp; almost&nbsp; all&nbsp; of&nbsp; the&nbsp; bioavailable&nbsp; fraction&nbsp; of&nbsp; the&nbsp; compound&nbsp; in&nbsp; the&nbsp; sediment&nbsp; was removed (78-85%). The potential of sediment remediation with the amendment of sediment withcarbon&nbsp; rich&nbsp; materials&nbsp; was&nbsp;&nbsp; examined&nbsp; from&nbsp; the&nbsp; aspect&nbsp; of&nbsp; selecting&nbsp; carbon&nbsp; sorption&nbsp; agents (activated carbon, biochar and humus); estimation the optimal material doses; the long -term and short-term effects of the addition&nbsp; of these agents on the bioavailability of organic pollutants&nbsp; in order to examine the effect of aging and the toxicity of the resulting mixtures. The results of the stabilization of pollutants in the sediment show that: (1)&nbsp; increasing the dose of all three&nbsp;&nbsp; sorption agents&nbsp; leads&nbsp; to&nbsp; an&nbsp; increase&nbsp; in&nbsp; the&nbsp; immobilization&nbsp; efficiency&nbsp; and&nbsp; reduction&nbsp; of&nbsp; the&nbsp; bioavailable fraction of the selected&nbsp; organic compounds; (2) aging of the amended sediment during the first 90 days results in a further reduction of the biodegradable fraction of all compounds, after which the&nbsp; biodegradable&nbsp; concentration&nbsp; of&nbsp; the&nbsp; selected&nbsp; compounds&nbsp; remain&nbsp; the&nbsp; same&nbsp; in&nbsp; the&nbsp; case&nbsp; of activated carbon amendment, while the bioavailable fraction of&nbsp; the compound increases with the use&nbsp; of&nbsp; biohar&nbsp; and&nbsp; humus.&nbsp; Phytotoxicity&nbsp; tests&nbsp; showed&nbsp; that&nbsp; <em>Zea&nbsp; mays&nbsp;</em> accumulated&nbsp; significantly higher amount of selected organic pollutants from unamended sediment, comparing to&nbsp; <em>Cucurbita pepo&nbsp;</em> and <em>Lactuca sativa</em>. Toxicity of activated carbon and humus amended sediment assessed by <em>Vibrio&nbsp; fischeri&nbsp;</em> luminescence&nbsp; inhibition&nbsp; test&nbsp; and&nbsp; by&nbsp; measuring&nbsp; <em>Zea&nbsp; mays&nbsp; </em>germination&nbsp; and biomass yield was significantly reduced in the amended sediment samples. Accumulation of the selected&nbsp; organic&nbsp; pollutants&nbsp; in&nbsp; the&nbsp; <em>Zea&nbsp; mays</em>&nbsp; biomass&nbsp; in&nbsp; the&nbsp; unamended&nbsp; sediment&nbsp; were&nbsp; a significantly&nbsp; higher&nbsp; than&nbsp; in&nbsp; the&nbsp; humus&nbsp; and&nbsp; activated&nbsp; carbon&nbsp; amended&nbsp; sediment.&nbsp; Both&nbsp; sorbents show&nbsp; potential&nbsp; to&nbsp; be&nbsp; used&nbsp; as&nbsp; remediation&nbsp; agents&nbsp; for&nbsp; organically&nbsp; contaminated&nbsp; sediment,&nbsp; but activated carbon exhibited the better performance.</p>