Investigation of remediation potential of sediment polluted with priority organic pollutants

Abstract

<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>