Concentrações de cádmio (Cd), chumbo (Pb) e mercúrio (Hg) foram determinadas em amostras de água (teores dissolvidos e particulados), sedimento de fundo, peixes e bivalves, coletados em seis bacias hidrográficas do Estado de São Paulo: Alto Paranapanema, Peixe, Aguapeí, São José dos Dourados, Mogi-Guaçu e Piracicaba, as quais apresentam diferentes características quanto ao uso e ocupação da terra. Dentre estas bacias, as dos rios Piracicaba e Mogi-Guaçu apresentam maiores densidades demográficas e industrialização, o que gera, conseqüentemente, maior degradação da qualidade das águas, enfatizando a necessidade de estudos freqüentes nesses sistemas. As amostragens de água e sedimento foram feitas bimestralmente durante o ano de 2001. Os peixes e bivalves foram amostrados no mesmo ano em dois períodos: seca e cheia. As concentrações de Cd e Pb foram determinadas por espectrometria de absorção atômica com atomização eletrotérmica, e as de Hg por espectrometria de fluorescência atômica. Os teores de Cd e Pb na fração trocável do sedimento também foram determinados. Os resultados obtidos mostraram baixas concentrações dos metais Cd e Pb na coluna d’água, tanto nas formas dissolvidas quanto particuladas, no entanto, tais concentrações foram maiores nas bacias dos rios Piracicaba e Mogi-Guaçu. No sedimento de fundo e nos bivalves, as maiores concentrações de Pb foram observadas no rio Mogi-Guaçu, embora este elemento tenha ocorrido em pequenas quantidades na fração trocável do sedimento (<1%). O Cd ocorreu em maiores teores no sedimento e no material particulado do rio Piracicaba. Por outro lado, as maiores concentrações de Pb nos bivalves foram detectadas no rio Mogi-Guaçu. Na fração trocável do sedimento, o Cd ocorreu em altas proporções (até 76%), principalmente, nos rios Itapetininga (Bacia do Alto Paranapanema), Piracicaba e Mogi-Guaçu. Em algumas amostras de água e sedimento de fundo ocorreram quantidades relativamente elevadas de Hg. Por outro lado, nos bivalves os teores do elemento foram sempre baixos. No entanto, nenhuma tendência significativa de distribuição espacial ou temporal de Hg ocorreu nas amostras. Portanto, acredita-se que os altos teores registrados para algumas amostras foram resultantes de fontes de origem difusa não-pontual, como deposição atmosférica e fontes originárias da agricultura. Nos peixes, as concentrações de Cd e Pb foram sempre inferiores aos limites de detecção (0,005 e 0,08 µg/g peso seco, respectivamente). Por outro lado, peixes carnívoros coletados no reservatório de Jurumirim (bacia do Alto Paranapanema) apresentaram altas concentrações de Hg (média: 1,14 +/- 0,54 µg/g peso úmido) e metilmercúrio (média: 1,04 +/- 0,51 µg/g peso úmido). Este último, representou em média 92% do mercúrio total determinado no músculo dos peixes. Tais concentrações foram maiores que o máximo permitido pela legislação brasileira para peixes predadores (1 µg/g peso úmido) e, provavelmente, foram resultante de altos teores de metilmercúrio produzido no reservatório devido aos processos de produção e liberação de mercúrio a partir da vegetação e solos inundados. Portanto, concluiu-se que os peixes do reservatório de Jurumirim estavam contaminados com Hg, recomendando-se que novos estudos sejam realizados para se identificar as fontes e processos responsáveis por tais contaminações. As bacias dos rios do Peixe, Aguapeí, Alto Paranapanema e São José dos Dourados apresentaram baixas quantidades de todos os elementos estudados. Por outro lado, foram observadas concentrações relativamente elevadas de Cd no rio Piracicaba, e Pb e Cd no rio Mogi-Guaçu, os quais devem ser periodicamente avaliados. / Concentrations of cadmium (Cd), lead (Pb), and mercury (Hg) were determined in water (dissolved and particulate), bottom sediment, fish, and bivalves sampled in six watersheds located in the State of São Paulo (Southeast, Brazil): the Alto Paranapanema, the Peixe, the Aguapeí, the São José dos Dourados, the Mogi-Guaçu, and the Piracicaba. These watersheds show different levels of land-use. Among these basins, the Piracicaba and the Mogi-Guaçu River Basins show highest population and industrialization rates. Such features lead, consequently, to a higher degradation of water, thus decreasing its quality. These facts emphasize the need of new and frequent studies in those systems. Water and sediment samplings were carried out bimonthly during 2001. Fish and bivalves samples were collected twice a year: at the end of the rainy and dry season. Cd and Pb concentrations were determined through electrotermal atomic absorption spectrometry, whereas Hg through atomic fluorescence spectrometry. In addition, exchangeable Cd and Pb were determined in sediment. The results showed low concentrations of Cd and Pb in water (dissolved and particulate). However, these concentrations were higher in the Piracicaba and the Mogi-Guaçu River Basins. Pb concentrations in sediment and bivalves were the highest in the Mogi-Guaçu River, even so this element occurred in low levels in the exchangeable fraction of sediment (< 1%). The highest Cd concentrations in sediment and particulate suspended matter were related to the Piracicaba River, although the highest levels for bivalves occurred in the Mogi-Guaçu River. High Cd concentrations in the exchangeable fraction of sediment (up to 76%) were observed, mainly in the Itapetininga (the Alto Paranapanema Basin), the Piracicaba, and the Mogi-Guaçu River. High concentrations of Hg were detected in some water and sediment samples, whereas in bivalves Hg was always in low levels. However, no significant tendency of temporal and/or spatial distribution was observed for Hg, so it is belived that the high levels reported for some samples were a result from diffuse non-point source pollution, such as atmospheric deposition and residues from agricultural practices. Cd and Pb concentrations in fish were always lower than the detection limit (0.005 and 0.08 µg/g dry wt, respectively). On the other hand, high concentrations of Hg (1.14 +/- 0,54 µg/g wet wt) and methylmercury (1.04 +/- 0.51 µg/g wet wt), which represented 92% of the total mercury, were found in carnivorous fish samples from the Jurumirim Reservoir (the Alto Paranapanema Basin). These concentrations were higher than the maximum limit permitted by Brazillian legislation for predatory fish (1 µg/g wet wt) and, probably, were a result from high methylmercury levels produced and released in the reservoir supported by inundated soil and vegetation. Hence, we concluded that carnivorous fish from the Jurumirim Reservoir were contamined with Hg, therefore new research sould be carried out in that area in order to identify the sources and processes responsible for high levels of mercury. The Peixe, the Aguapeí, the Alto Paranapanema, and the São José dos Dourados River Basins showed relatively low concentrations of all elements studied. Conversely, high Cd concentrations were determined in the Piracicaba River, and Pb and Cd in the Mogi-Guaçu River, pointing out that these areas should be frequently monitored.

Made available in DSpace on 2014-12-17T15:03:31Z (GMT). No. of bitstreams: 1 AndreaSO_DISSERT.pdf: 3016196 bytes, checksum: 4f0e4a29dd071bcc197364fd98cce054 (MD5) Previous issue date: 2012-08-31 / The accelerated growth of urban regions have produced relevant effects on water resources. Urban regions need an adequate institutional structure that can be able to face environmental demands and the adverse effects of land use on water resources. This study aims at analysing land use effects on heavy metals concentration in sediments and water, as well as making a comparative analysis involving water physical-chemical parameters. Applied methodology included both in loco water parameters measurement and water and bed sediment sampling at 8 sections along the fluvial system. Sample analysis was performed in laboratory in order to measure heavy metal concentrations. It was measured metal concentrations of Al, Cu, Pb, Cd, Fe, Ni and Zn. Once the samples were subjected to acid digestion (method 3050B), concentration values were measured by using atomic absorption spectrometry by flame (ICP-FLAA). The analysis results were compared with normative reference, these standards is intended to assess the risks of toxic substances in sediment and water management programs. The normative reference used in this work were: a) Ontario Ministry of the Environment and Energy (OMEE, 1993) b) Normative Netherlands (VROM, 2000); c) Normative Canadian (CCME, 1999); d) United States Environmental Protection Agency (USEPA, 1977), e) CONAMA Resolution No. 344/2004; f) CONAMA Resolution No. 357/2005. The high concentrations of iron (38,750 mg.g-1), Lead (1100 mg.g-1), Nickel (100 &#956;g.g-1) and zinc (180 &#956;g.g-1) detected sediments confirm the state of degradation of the aquatic system. Iron concentrations (1.08 mg.L-1), Aluminum (0.6 mg.L-1) and phosphorus (0.05 mg.L-1) present in the water are outside the established standards for human consumption / A expans?o acelerada dos centros urbanos tem produzido impactos importantes nos recursos h?dricos. As regi?es urbanas carecem de estrutura pol?tico-institucional capaz de suprir as demandas ambientais e os efeitos produzidos pelo uso e ocupa??o do solo nos recursos h?dricos. Este trabalho tem como objetivo analisar os efeitos do uso e ocupa??o do solo na concentra??o de metais pesados em sedimento e na ?gua. A metodologia utilizada incluiu a coleta de amostras da ?gua e sedimento do leito em 8 se??es ao longo da calha fluvial. As amostras foram submetidas ? an?lise laboratorial para detectar a concentra??o de metais pesados na ?gua e sedimento, al?m de f?sforo total na ?gua. Foram analisadas as concentra??es de Al, Cu, Pb, Cd, Fe, Ni e Zn. Ap?s serem submetidas ? digest?o ?cida (m?todo 3050B), as concentra??es foram medidas por espectrometria de emiss?o at?mica por chama (ICP-FLAA). Os resultados das an?lises foram comparados com normativas de refer?ncia, sendo que essas normas tem o intuito de avaliar os riscos de subst?ncias t?xicas no sedimento e na ?gua em programas de gest?o. As normativas de refer?ncia utilizadas neste trabalho foram: a) Ontario Ministry of the Environment and Energy (OMEE,1993); b) Ministery of Housing Spatial Planning and Environment. (VROM, 2000); c) Canadian Council of Ministers of the Environment (CCME, 1999); d) United States Environmental Protection Agency (USEPA, 1977); e) Resolu??o Conama n? 344/2004; f) Resolu??o Conama n? 357/2005. As altas concentra??es de Ferro (38750 &#956;g.g-1), Chumbo (1100 &#956;g.g-1), N?quel (100 &#956;g.g-1) e Zinco (180 &#956;g.g-1) detectados nos sedimentos, confirmam o estado de degrada??o do sistema aqu?tico por metais pesados. As concentra??es de Ferro (1,08 mg.L-1), Alum?nio (0,6 mg.L-1) e F?sforo (0,05 mg.L-1) presentes na ?gua, encontram-se fora dos padr?es estabelecidos para ?gua de consumo humano

Concentrações de cádmio (Cd), chumbo (Pb) e mercúrio (Hg) foram determinadas em amostras de água (teores dissolvidos e particulados), sedimento de fundo, peixes e bivalves, coletados em seis bacias hidrográficas do Estado de São Paulo: Alto Paranapanema, Peixe, Aguapeí, São José dos Dourados, Mogi-Guaçu e Piracicaba, as quais apresentam diferentes características quanto ao uso e ocupação da terra. Dentre estas bacias, as dos rios Piracicaba e Mogi-Guaçu apresentam maiores densidades demográficas e industrialização, o que gera, conseqüentemente, maior degradação da qualidade das águas, enfatizando a necessidade de estudos freqüentes nesses sistemas. As amostragens de água e sedimento foram feitas bimestralmente durante o ano de 2001. Os peixes e bivalves foram amostrados no mesmo ano em dois períodos: seca e cheia. As concentrações de Cd e Pb foram determinadas por espectrometria de absorção atômica com atomização eletrotérmica, e as de Hg por espectrometria de fluorescência atômica. Os teores de Cd e Pb na fração trocável do sedimento também foram determinados. Os resultados obtidos mostraram baixas concentrações dos metais Cd e Pb na coluna d’água, tanto nas formas dissolvidas quanto particuladas, no entanto, tais concentrações foram maiores nas bacias dos rios Piracicaba e Mogi-Guaçu. No sedimento de fundo e nos bivalves, as maiores concentrações de Pb foram observadas no rio Mogi-Guaçu, embora este elemento tenha ocorrido em pequenas quantidades na fração trocável do sedimento (<1%). O Cd ocorreu em maiores teores no sedimento e no material particulado do rio Piracicaba. Por outro lado, as maiores concentrações de Pb nos bivalves foram detectadas no rio Mogi-Guaçu. Na fração trocável do sedimento, o Cd ocorreu em altas proporções (até 76%), principalmente, nos rios Itapetininga (Bacia do Alto Paranapanema), Piracicaba e Mogi-Guaçu. Em algumas amostras de água e sedimento de fundo ocorreram quantidades relativamente elevadas de Hg. Por outro lado, nos bivalves os teores do elemento foram sempre baixos. No entanto, nenhuma tendência significativa de distribuição espacial ou temporal de Hg ocorreu nas amostras. Portanto, acredita-se que os altos teores registrados para algumas amostras foram resultantes de fontes de origem difusa não-pontual, como deposição atmosférica e fontes originárias da agricultura. Nos peixes, as concentrações de Cd e Pb foram sempre inferiores aos limites de detecção (0,005 e 0,08 µg/g peso seco, respectivamente). Por outro lado, peixes carnívoros coletados no reservatório de Jurumirim (bacia do Alto Paranapanema) apresentaram altas concentrações de Hg (média: 1,14 +/- 0,54 µg/g peso úmido) e metilmercúrio (média: 1,04 +/- 0,51 µg/g peso úmido). Este último, representou em média 92% do mercúrio total determinado no músculo dos peixes. Tais concentrações foram maiores que o máximo permitido pela legislação brasileira para peixes predadores (1 µg/g peso úmido) e, provavelmente, foram resultante de altos teores de metilmercúrio produzido no reservatório devido aos processos de produção e liberação de mercúrio a partir da vegetação e solos inundados. Portanto, concluiu-se que os peixes do reservatório de Jurumirim estavam contaminados com Hg, recomendando-se que novos estudos sejam realizados para se identificar as fontes e processos responsáveis por tais contaminações. As bacias dos rios do Peixe, Aguapeí, Alto Paranapanema e São José dos Dourados apresentaram baixas quantidades de todos os elementos estudados. Por outro lado, foram observadas concentrações relativamente elevadas de Cd no rio Piracicaba, e Pb e Cd no rio Mogi-Guaçu, os quais devem ser periodicamente avaliados. / Concentrations of cadmium (Cd), lead (Pb), and mercury (Hg) were determined in water (dissolved and particulate), bottom sediment, fish, and bivalves sampled in six watersheds located in the State of São Paulo (Southeast, Brazil): the Alto Paranapanema, the Peixe, the Aguapeí, the São José dos Dourados, the Mogi-Guaçu, and the Piracicaba. These watersheds show different levels of land-use. Among these basins, the Piracicaba and the Mogi-Guaçu River Basins show highest population and industrialization rates. Such features lead, consequently, to a higher degradation of water, thus decreasing its quality. These facts emphasize the need of new and frequent studies in those systems. Water and sediment samplings were carried out bimonthly during 2001. Fish and bivalves samples were collected twice a year: at the end of the rainy and dry season. Cd and Pb concentrations were determined through electrotermal atomic absorption spectrometry, whereas Hg through atomic fluorescence spectrometry. In addition, exchangeable Cd and Pb were determined in sediment. The results showed low concentrations of Cd and Pb in water (dissolved and particulate). However, these concentrations were higher in the Piracicaba and the Mogi-Guaçu River Basins. Pb concentrations in sediment and bivalves were the highest in the Mogi-Guaçu River, even so this element occurred in low levels in the exchangeable fraction of sediment (< 1%). The highest Cd concentrations in sediment and particulate suspended matter were related to the Piracicaba River, although the highest levels for bivalves occurred in the Mogi-Guaçu River. High Cd concentrations in the exchangeable fraction of sediment (up to 76%) were observed, mainly in the Itapetininga (the Alto Paranapanema Basin), the Piracicaba, and the Mogi-Guaçu River. High concentrations of Hg were detected in some water and sediment samples, whereas in bivalves Hg was always in low levels. However, no significant tendency of temporal and/or spatial distribution was observed for Hg, so it is belived that the high levels reported for some samples were a result from diffuse non-point source pollution, such as atmospheric deposition and residues from agricultural practices. Cd and Pb concentrations in fish were always lower than the detection limit (0.005 and 0.08 µg/g dry wt, respectively). On the other hand, high concentrations of Hg (1.14 +/- 0,54 µg/g wet wt) and methylmercury (1.04 +/- 0.51 µg/g wet wt), which represented 92% of the total mercury, were found in carnivorous fish samples from the Jurumirim Reservoir (the Alto Paranapanema Basin). These concentrations were higher than the maximum limit permitted by Brazillian legislation for predatory fish (1 µg/g wet wt) and, probably, were a result from high methylmercury levels produced and released in the reservoir supported by inundated soil and vegetation. Hence, we concluded that carnivorous fish from the Jurumirim Reservoir were contamined with Hg, therefore new research sould be carried out in that area in order to identify the sources and processes responsible for high levels of mercury. The Peixe, the Aguapeí, the Alto Paranapanema, and the São José dos Dourados River Basins showed relatively low concentrations of all elements studied. Conversely, high Cd concentrations were determined in the Piracicaba River, and Pb and Cd in the Mogi-Guaçu River, pointing out that these areas should be frequently monitored.

<p>Od primenjenih elektrokinetičkih tehnika:<br />konvencionalna, elektrodijalitička (uz primenu CEM), zatim tretman<br />uz izmenu polariteta na elektrodama, primena pomeranja anode ka<br />katodi, bipolarnih elektroda kao i povećane dužine katodnog prostora,<br />na uzorku Ni zagađenog kaolina (model matriks) najveću efikasnost<br />uklanjanja Ni pokazale su primena pomeranja anode ka katodi (51%<br />odnosno 82% bez uračunavanja katodnog regiona kaolina) i primena<br />bipolarnih elektroda uz povećani katodni prostor (45%).<br />Primenom bipolarnih elektroda uz povećan katodni prostor kao<br />unapređene EK tehnike preči&scaron;ćavanja sedimenta sa visokim ANC<br />postignute su efikasnosti od 44% za uklanjanje Ni odnosno 36%,<br />42% i 43% za uklanjanje Ni, Cd i Pb u sme&scaron;i, redom. Ove efikasnosti<br />su približno dvostruko veće u odnosu na efikasnosti konvencionalnih<br />tretmana, a uviđa se neznatni uticaj prisustva Cd i Pb na efikasnost<br />uklanjanja Ni. Procena rizika na osnovu različitih kriterijuma utvrdila<br />je da je sediment zagađen Ni nakon tretmana siguran za okolinu.<br />Sediment zagađen Ni, Cd i Pb je prema sadržaju Ni i Pb siguran po<br />okolinu, ali se poređenjem različitih kriterijuma procene rizika koji su<br />kori&scaron;ćeni u toku rada dobijaju informacije koje se u manjoj ili većoj<br />meri potvrđuju &scaron;to ukazuje na neophodnost postojanja jedinstvenih i<br />sveobuhvatnih kriterijuma procene rizika. Navedeno potvrđuje da je<br />primena bipolarnih elektroda uz povećan katodni prostor efikasna<br />tehnika preči&scaron;ćavanja sedimenta koji je zagađen Ni i Pb pri<br />koncentracijama koje su navedene u radu.<br />Primenom pomeranja anode ka katodi uz povećan katodni<br />prostor kao unapređene EK tehnike preči&scaron;ćavanja sedimenta sa<br />niskim ANC postignute su efikasnosti od 25% za uklanjanje Ni<br />odnosno 17%, 24% i 62% za uklanjanje Ni, Cd i Pb u sme&scaron;i, redom.<br />Ove efikasnosti su približne za Ni odnosno dvostruko i trostruko veće<br />za Cd i Pb, redom u odnosu na efikasnosti konvencionalnih tretmana.<br />Može se utvrditi da je efikasnost unapređenog procesa značajno<br />povećana, ali poređenjem krajnih koncentracija metala u sedimentu<br />nakon tretmana sa kriterijumima procene rizika, utvrđeno je da jedino<br />prema sadržaju Pb sediment se može smatrati sigurnim po akvatičnu<br />sredinu dok prema sadržaju ostalih metala spada u visoko rizičnu<br />klasu (&gt;50%).</p> / <p> As the result of applying electrokinetic techniques:<br /> conventional, electrodialytic, treatment with electrode polarity<br /> exchange, moving anode, using bipolar electrodes and increased<br /> cathodic compartment length, on Ni contaminated kaolin (model<br /> matrix) the most efficient were moving anode technique (51% or<br /> 82% without calculating the cathode region of kaolin) and using<br /> bipolar electrodes and increased cathodic compartment length (45%).<br /> Using bipolar electrodes and increased cathodic compartment<br /> length as enhanced EK technique for remediation of sediment with<br /> high ANC resulted in 44% of Ni removal and 36%, 42% i 43% for<br /> removal of Ni, Cd and Pb, respectively. This technique nearly<br /> doubled efficiency after conventional treatment and there is slight<br /> influence of Cd and Pb on Ni removal. Risk assessment based on<br /> different criteria determine that Ni contaminated sediment is safe for<br /> the environment after EK treatment. According to Dutch standards it<br /> is classified as Class 1/2. Ni, Cd and Pb contaminated sediment is<br /> safe for the environment according to Ni and Pb content after EK<br /> treatment according to Dutch standards but comparing the risk<br /> assessment arise from different criteria in some cases it do not<br /> provide the same information. This indicates that it is of great<br /> importance to develop unique risk assessment criteria. According to<br /> the results using bipolar electrodes and increased cathodic<br /> compartment is efficient EK remediation technique of Ni and Pb<br /> contaminated sediment at the concentrations used for these<br /> investigations.<br /> Using the moving anode technique and increased cathodic<br /> compartment length as enhanced EK technique for remediation of<br /> sediment with low ANC resulted in 25% of Ni removal and 17%,<br /> 24% and 62% for removal of Ni, Cd and Pb, respectively. It can be</p> <p> concluded that efficiencies after enhanced technique compare to<br /> conventional treatments are significantly increased but the final metal<br /> concentrations (except Pb) in sediment after treatment according to<br /> risk assessment criteria are highly hazardous for the environment<br /> (&gt;50%).</p>

<p>U radu je: 1. Određena efikasnost elektrokinetičkih tretmana (konvencionalni tretman, tretman sa izmenom polariteta, tretman sa dve anode i heksagonalni dvodimenzionalni elektrokinetički tretman) koji izuzimaju dodatak agenasa u tretirani sediment, za uklanjanje metala; 2. Ispitan je uticaj diskontinuiteta napajanja strujom (tokom noći), kao i uticaj oscilacija jačine električne energije pri primeni solarnih panela na efikasnost tretmana; 3. Ispitan je uticaj geohemije sedimenta, fizičko-hemijskih promena u sistemu i karakteristika prisutnog zagađenja (oblici pojavljivanja metala, koncentracije) na efikasnost elektrokinetičkog procesa. 4. Izvr&scaron;ena je procena rizika u sistemu sediment/voda pre, tokom i nakon tretmana; 5. Primenjen je matematički model na dobijene rezultate. Na osnovu određene efikasnosti i procene rizika tretmana elektrokinetičke remedijacije na realan problem Velikog Bačkog kanala zaključeno je, da je najbolja opcija dvoanodni tretman u kome se primenjuju solarne panele (e9). Dobijeni rezultati tretmana ukazuju da diskontinuiteti napajanja strujom (tokom noći), kao i uticaj oscilacija jačine električne energije pri primeni solarnih panela nemaju značajnog uticaja na efikasnost procesa. &Scaron;to se tiče, geohemije sedimenta, pokazalo se da ona ima snažan uticaj i da upravo ona određuje fizičko-hemijske promene koje se događaju u sedimentu tokom sprovođenja tretmana elektrokinetičke remedijacije. Ključ uspeha ovih tretmana sedimenta jeste i zadržavanje metala u frakcijama (karbonatna i reducibilna) koje lak&scaron;e migriraju. Primenom matematičkog modela zaključeno je da se mogu predvideti promene koncentracija metala bez sprovođenja eksperimenata, &scaron;to je od krucijalnog značaja za buduća istraživanja.</p> / <p>This work includes: 1. An investigation into efficiency of various electrokinetic treatments (a conventional treatment, and treatments with changing polarity, two anodes and two-dimensional hexagonal electrodes) without the addition of agents to the treated sediment, for the removal of metals; 2. An investigation of the influence of discontinuous (off during the night) and oscillating power supplies on the application of solar panels and their effect on the efficacy of the treatment; 3. A study on the influence of sediment geochemistry, physico-chemical changes in the system and the characteristics of the pollution present (metals speciation and concentration) on the efficiency of the electrokinetic process; 4. A risk assessment of the sediment/water system before, during and after the treatment; 5. Mathematical modelling of the results obtained. Based on the risk assessment and the efficiency of the electrokinetic treatments in the Veliki Backa canal sediment, it was concluded that the best remediation option was a two anode treatment using solar panels (e9). The investigation into the influence of treatments using discontinuous (off during the night) and oscillating power supplies showed they did not have a significant impact on the efficiency of the process. Sediment geochemistry was shown to have a strong influence, determining the physical and chemical changes that occur in the sediment during the implementation of the electrokinetic remediation. The key to success for these treatments is the retention of metals in the fractions (carbonate and reducible) which more easily migrate. It is concluded that the mathematical model can be applied to successfully predict thechanges in the concentration of metals without experimentation, which is of crucial importance for future studies.</p>

<p>Ekolo&scaron;ki&nbsp; problem&nbsp; svetskih&nbsp; razmera&nbsp; predstavlja&nbsp; zagađenost&nbsp; sedimenta&nbsp; te&scaron;kim&nbsp; metalima, usled negativnih ekolo&scaron;kih efekata metala na životnu sredinu. Mnoge zemlje i regioni, kao i na&scaron;a zemlja&nbsp; suočavaju&nbsp; se&nbsp; sa&nbsp; ovom&nbsp; problematikom,&nbsp; koja&nbsp; je&nbsp; vrlo&nbsp; rasprostranjena&nbsp; usled&nbsp; sve&nbsp; brže urbanizacije&nbsp; i&nbsp; industrijalizacije,&nbsp; a&nbsp; sa&nbsp; sve&nbsp; većom&nbsp; nebrigom&nbsp; usled&nbsp; ispu&scaron;tanja&nbsp; otpadnih&nbsp; voda&nbsp; bez prethodnog&nbsp; preči&scaron;ćavanja&nbsp; u&nbsp; vodotokove.&nbsp; Prilikom&nbsp; promene&nbsp; uslova&nbsp; vodenog&nbsp; ekosistema,&nbsp; može doći do&nbsp; izluživanja&nbsp; metala&nbsp; i &scaron;tetnih efekata na&nbsp; životnu sredinu kao&nbsp; i&nbsp; na zdravlje&nbsp; ljudi. Stoga je remedijacija sedimenata zagađenih metalima ključna aktivnost u okviru procesa potpune sanacije vodenog ekosistema, a ekonomične, efikasne i ekolo&scaron;ki prihvatljive tehnike remedijacije su hitno potrebne&nbsp; i&nbsp; rado&nbsp; primenljive&nbsp; u&nbsp; tretmanu&nbsp; na&nbsp; velikoj&nbsp; skali.&nbsp; Pre&nbsp; primene&nbsp; remedijacione&nbsp; tehnike&nbsp; na velikoj skali, neophodna su ispitivanja pri laboratorijskim uslovima i pilot skali.&nbsp; Na kraju svakog uspe&scaron;nog&nbsp; laboratorijskog&nbsp; ispitivanja&nbsp; nalaze&nbsp; se&nbsp; pilot&nbsp; istraživanja.&nbsp; Pomoću&nbsp; njih&nbsp; se&nbsp; dobija&nbsp; p ravi odgovor u smislu izbora optimalne tehnologije imajući u vidu investicione i operativne tro&scaron;kove,<br />postignuti rezultat i krajnje ciljeve u pogledu upravljanja postrojenjem i otpadom. U ovom radu ispitan&nbsp; je&nbsp; potencijal&nbsp; primene&nbsp; stabilisanog&nbsp; i&nbsp; zelenom&nbsp; sinte zom&nbsp; produkovanog&nbsp; nano&nbsp; Fe(0)&nbsp; zaremedijaciju&nbsp; sedimenta&nbsp; zagađenog&nbsp; te&scaron;kim&nbsp; metalima.&nbsp; Kao&nbsp; remedijaciona&nbsp; tehnika&nbsp; odabrana&nbsp; je stabilizacija/solidifikacija,&nbsp; koja&nbsp; podrazumeva&nbsp; dodavanje&nbsp; agenasa&nbsp; za&nbsp; imobilizaciju&nbsp; metala&nbsp; u sedimentu&nbsp; sprečavajući&nbsp; time&nbsp; potencijalni&nbsp; rizik&nbsp;&nbsp; od&nbsp; izluživanja&nbsp; metala&nbsp; u&nbsp; životnu&nbsp; sredinu. Konvencionalni&nbsp; materijali&nbsp; poput&nbsp; letećeg&nbsp; pepela,&nbsp; cementa,&nbsp; gline&nbsp; se&nbsp; već&nbsp; odavno&nbsp; koriste&nbsp; u&nbsp; ovu svrhu. Kako u dana&scaron;nje vreme raste potražnja za novim, lako dostupnim agensima za stabilizaciju<br />sedimenta, do&scaron;lo se na ideju o primeni nanomaterijala na bazi gvožđa, tj. nano Fe(0) stabilisanog nativnom glinom&nbsp; i produkovanog redukcijom pomoću organskih&nbsp; molekula prirodno prisutnih u ekstraktu&nbsp; li&scaron;ća&nbsp; hrasta&nbsp; i&nbsp; crnog&nbsp; duda.&nbsp; Nanomaterijali&nbsp; su&nbsp; sintetisani&nbsp; i&nbsp; karakterisani&nbsp; različitim metodama&nbsp; i&nbsp; tehnikama.&nbsp; U&nbsp; nastavaku,&nbsp; u&nbsp; cilju&nbsp; efikasnosti&nbsp; njihove&nbsp; primene&nbsp; za&nbsp; stabilizaciju sedimenta, sprovedeni su ekstrakcioni i dinamički laboratorijski testovi izluživanja. Odabrane su sme&scaron;e sedimenta i nanomaterijala koje su pokazale najbolju efikasnost tr etmana. Nakon toga se ispitivanje&nbsp; nastavilo&nbsp; na&nbsp; pilot&nbsp; skali,&nbsp; gde&nbsp; se&nbsp; pratilo&nbsp; pona&scaron;anje&nbsp; nanomaterijala&nbsp; u&nbsp; zavisnosti&nbsp; od konvencionalnih&nbsp; materijala&nbsp; koji&nbsp; su&nbsp; već&nbsp; u&nbsp; literaturi&nbsp; dokumentovani&nbsp; kao&nbsp; efikasni&nbsp; imobilizacioni agensi. Dodatna potvrda uspe&scaron;nosti tretmana data je analizom i karakterizacijom s/s sme&scaron;a nakon pilot&nbsp; ispitivanja&nbsp; Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; proces&nbsp; se&nbsp; uspe&scaron;no&nbsp; pokazao&nbsp; pri&nbsp; laboratorijskim uslovima,&nbsp; a&nbsp; takođe&nbsp; i&nbsp; prilikom&nbsp; pilot&nbsp; tretmana,&nbsp; odnosno&nbsp; nakon&nbsp; pilot&nbsp; tretmana&nbsp; nije&nbsp; do&scaron;lo&nbsp; do povećanih koncentracija&nbsp; izluživanja metala iz s/s sme&scaron;a, kao ni degradacije sme&scaron;a nakon procesa ovlaživanja&nbsp; tokom&nbsp; &scaron;est&nbsp; meseci.&nbsp; Na&nbsp; osnovu&nbsp; toga,&nbsp; ovako&nbsp; tertirani&nbsp; sediment&nbsp; se&nbsp; može&nbsp; bezbedno odlagati&nbsp; na&nbsp; deponije,&nbsp; ili&nbsp; pak&nbsp; iskoristiti&nbsp; za&nbsp; &bdquo;kontrolisanu&ldquo;&nbsp; upotrebu,&nbsp; izgradnju&nbsp; puteva,kamenoloma, pomoćnih objekata i slično. Rezultati su doprineli u cilju trajnijeg re&scaron;avanja pitanja odlaganja&nbsp; zagađenog&nbsp; (izmuljenog)&nbsp; rečnog&nbsp; sedimenta,&nbsp; pri&nbsp; čemu&nbsp; se&nbsp; u&nbsp; procesu stabilizacije/solidifikacije&nbsp; dobijaju&nbsp; proizvodi&nbsp; sa&nbsp; dodatom&nbsp; vredno&scaron;ću&nbsp; neumanjenog&nbsp; kvaliteta .Nanomaterijali sintetisani u ovom radu na&nbsp; bazi ekstrakta li&scaron;ća biljaka doprinose kako očuvanju životne&nbsp; sredine,&nbsp; tako&nbsp; i&nbsp; ekonomičnosti&nbsp; primene&nbsp; remedijacione&nbsp; tehnike.&nbsp; Zahvaljujući&nbsp; velikoj specifičnoj&nbsp; povr&scaron;ini,&nbsp; malim&nbsp; dimenzijama&nbsp; čestica&nbsp; i&nbsp; velikom&nbsp; kapacitetu&nbsp; za&nbsp; imobilizaciju&nbsp; te&scaron;kih<br />metala predstavljaju efikasnu alternativu komercijalno dostupnim materijalima, &scaron;to ih čini veoma atraktivnim&nbsp; i&nbsp; obećavajućim&nbsp; u&nbsp; budućnosti&nbsp; pri&nbsp; tretmanu&nbsp; rečnog&nbsp; sedimenta&nbsp; zagađenog&nbsp; te&scaron;kim metalima.</p> / <p>The pollution of sediment by heavy metals represents a large environmental problem all<br />over the world.&nbsp; A&nbsp; lot of countries&nbsp; in the region&nbsp; as well as our country deal with this problem, which&nbsp; is&nbsp; widespread&nbsp; because&nbsp; of&nbsp; the&nbsp; fast&nbsp; urbanization&nbsp; and&nbsp; industrialization.&nbsp; There&nbsp; is&nbsp; more&nbsp; and more&nbsp; carelessness&nbsp; about&nbsp; wastewater&nbsp; discharge&nbsp; into&nbsp; water&nbsp; flows&nbsp; without&nbsp; previous&nbsp; purification. When the conditions of the aquatic ecosystem change, metal leaching and harmful effects on the environment&nbsp; and&nbsp; human&nbsp; health&nbsp; can&nbsp; occur.&nbsp; Therefore,&nbsp; remediation&nbsp; of&nbsp; metal-contaminated sediments&nbsp; is&nbsp; crucial&nbsp; activity&nbsp; in&nbsp; the&nbsp; process&nbsp; of&nbsp; the&nbsp; complete&nbsp; ecosystem&nbsp; remediation.&nbsp; Cost effective, efficient and environmentally friendly remediation techniques are urgently needed and readily applicable in large-scale treatment. Before applying remediation techniques on the largescale,&nbsp; both&nbsp; laboratory&nbsp; and&nbsp; pilot&nbsp; tests&nbsp; are&nbsp; necessary.&nbsp; There&nbsp; are&nbsp; pilot&nbsp; studies&nbsp; at&nbsp; the&nbsp; end&nbsp; of&nbsp; each successful&nbsp; laboratory&nbsp; test.&nbsp; Those&nbsp; studies&nbsp; provide&nbsp; the&nbsp; right&nbsp; answer&nbsp; in&nbsp; terms&nbsp; of&nbsp; choosing&nbsp; the optimal technology, taking into account the investment and operating costs,&nbsp;&nbsp; the achieved resultand&nbsp; the&nbsp; ultimate&nbsp; goals&nbsp; in&nbsp; terms&nbsp; of&nbsp; plant&nbsp; and&nbsp; waste&nbsp; management.&nbsp; In&nbsp; this&nbsp; study,&nbsp; the&nbsp; application<br />potential of stabilized and green&nbsp; -&nbsp; synthesized&nbsp; nano Fe(0) for the remediation of&nbsp; heavy&nbsp; metal&nbsp; -contaminated&nbsp; sediment&nbsp; was&nbsp; investigated.&nbsp; Stabilization&nbsp; /&nbsp; solidification&nbsp; technique&nbsp; was&nbsp; chosen&nbsp; as remediation technique which involves the addition of metal immobilizing agents in the sediment thus preventing the potential risk of metal leaching into the environment. Conventional materials such as fly ash, cement and clay have long been used for this purpose. Nowadays there is need for new, easily accessible agents for the sediment stabilization. Therefore it came up with the idea of&nbsp; using&nbsp; iron-based&nbsp; nanomaterials,&nbsp; ie.&nbsp; nano&nbsp; Fe(0)&nbsp; stabilized&nbsp; by&nbsp; native&nbsp; cla y&nbsp; and&nbsp; produced&nbsp; by reduction&nbsp; using&nbsp; organic&nbsp; molecules&nbsp; naturally&nbsp; present&nbsp; in&nbsp; oak&nbsp; and&nbsp; black&nbsp; mulberry&nbsp; leaf&nbsp; extract. Nanomaterials have been synthesized and characterized by different methods and techniques. In order&nbsp; to&nbsp; be&nbsp; effective&nbsp; in&nbsp; their&nbsp; application&nbsp; for&nbsp; sediment&nbsp; stabilization,&nbsp; extraction&nbsp; and&nbsp; dynamic laboratory leaching tests were performed. Mixtures of sediment and nanomaterials were selected that showed the best treatment efficiency.&nbsp; After that, the examination was continued on a pilot scale, where the behavior of nanomaterials was monitored, depending on conventional materials which&nbsp; have&nbsp; already&nbsp; been&nbsp; documented&nbsp; in&nbsp; the&nbsp; literature&nbsp; as&nbsp; effective&nbsp; immobilizing&nbsp; agents.Additional confirmation of treatment success was given by analysis and characterization of s / s mixtures&nbsp; after&nbsp; pilot&nbsp; testing.&nbsp; According&nbsp; to&nbsp; obtained&nbsp; results,&nbsp; the&nbsp; process&nbsp; was&nbsp; successfully demonstrated&nbsp; under&nbsp; laboratory&nbsp; conditions,&nbsp; and&nbsp; also&nbsp; during&nbsp; the&nbsp; pilot&nbsp; treatment.&nbsp; After&nbsp; the&nbsp; pilot treatment&nbsp; there&nbsp; were&nbsp; no&nbsp; increased&nbsp; concentrations&nbsp; of&nbsp; metal&nbsp; leaching&nbsp; from&nbsp; s/s&nbsp; mixtures,&nbsp; nor mixture degradation after the wetting process for six months. Based on that, the sediment treated in this way&nbsp; can&nbsp; be safely disposed of&nbsp; in&nbsp; landfills, or used&nbsp; for &quot;controlled&quot; use, construction of<br />roads,&nbsp; quarries,&nbsp; auxiliary&nbsp; facilities&nbsp; and&nbsp; etc.&nbsp; The&nbsp; results&nbsp; have&nbsp; contributed&nbsp; to the&nbsp; goal&nbsp; of&nbsp; a&nbsp; more permanent solution to the issue of disposal of polluted (slugged) river sediment, whereby in the process&nbsp; of&nbsp; stabilization/solidification,&nbsp; products&nbsp; with&nbsp; added&nbsp; value&nbsp; of&nbsp; undiminished&nbsp; quality&nbsp; are obtained. The nanomaterials synthesized in this paper on the basis of plant leaf extract contribute to both the preservation of the environment and the economy of remediation techniques. Thanks to their&nbsp; large specific&nbsp; surface area, small particle size and&nbsp; large ca pacity&nbsp; for&nbsp; immobilization of heavy&nbsp; metals,&nbsp; they&nbsp; represent&nbsp; an&nbsp; effective&nbsp; alternative&nbsp; to&nbsp; commercially&nbsp; available&nbsp;&nbsp; materials.&nbsp; It makes&nbsp; them&nbsp; very&nbsp; attractive&nbsp; and&nbsp; promising&nbsp; in&nbsp; the&nbsp; future&nbsp; in&nbsp; the&nbsp; treatment&nbsp; of&nbsp; river&nbsp; sediment contaminated with heavy metals.</p>