RESUMO
Herein, efficient degradation of hexabromocyclododecane (HBCD) and Lindane, a persistent organic pollutant using guar gum based calcium oxide doped silicon dioxide (GG-CaO@SiO2) has been reported. The nanocomposite was prepared by waste egg shell (CaO) and rice husk (SiO2) was well characterized. The maximum degradation of HBCD and Lindane were observed at 8 mg catalyst loading, neutral pH, and 2 mg L-1 of pollutant amount. The photocatalytic performance of GG-CaO@SiO2 for HBCD and Lindane photodegradation was evaluated, and it was found that the rate constant increased in the order of GG-CaO@SiO2 > CaO@SiO2 > GG. The polymeric GG-CaO@SiO2 nanocomposite showed maximum removal of both pollutants due to higher surface area (70 m2 g-1) and synergistic interactions among GG moieties. It achieved HBCD and Lindane elimination rates of 94 % and 90 % by photo-adsorptive degradation within 150 min. Meanwhile, the leaching of HBCD from expanded polystyrene (EPS) materials (0.14 ± 0.05 ppm) underwater with different time intervals and degradation of leachate HBCD were also assessed. The eradication of the pollutant manifested first-order kinetics, with the Langmuir adsorption. LC-MS analysis confirmed that GG-CaO@SiO2 effectively breaks down complex structure toxic pollutants into safer metabolites under natural sunlight exposure. The polymeric GG-CaO@SiO2 nanocomposite showed notable reusability up to ten cycle promotes sustainability.
Assuntos
Galactanos , Hexaclorocicloexano , Mananas , Nanocompostos , Gomas Vegetais , Gomas Vegetais/química , Mananas/química , Nanocompostos/química , Galactanos/química , Hexaclorocicloexano/química , Dióxido de Silício/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Compostos de Cálcio/química , Óxidos/química , Fotólise , Adsorção , Resíduos , Catálise , Concentração de Íons de Hidrogênio , Hidrocarbonetos BromadosRESUMO
Hexachlorocyclohexane (HCH) isomers are persistent organic pollutants (POPs) with high toxicity, lipid solubility, chemical stability. Despite the current ban on usage of Lindane, residual contamination cannot be ignored, and HCH are frequently detected in groundwater and threaten human health. Cultures capable of degrading α-HCH, ß-HCH, γ-HCH, and δ-HCH individually have been enriched in anoxic aqueous conditions. Compound-Specific Isotope Analysis (CSIA) was applied to examine the transformation mechanisms of different HCH isomers by the four enrichment cultures. 16S rRNA sequencing techniques were employed to examine the community composition of the enrichment cultures and detect changes in these communities resulting from adding individual HCH isomers. The results indicated that the ability of the enrichment cultures for dichloroelimination of HCH isomers was inconsistent. During dichloroelimination, different bond cleavage mode of ß- and δ-HCH led to distinct isotopic effects. HCH isomers had significant impact on the microbial community, while different microbial communities showed comparable isotopic effects during the transformation of a specific HCH isomer. In addition, bacteria in the phyla Proteobacteria and Firmicutes were proposed as the dominant dechlorinators. This study provides a novel perspective on the mode of bond cleavage during HCH dichloroelimination and the effect of HCH on microbial communities, which could potentially support the evaluation of HCH transformation by CSIA and their effects on the microecosystems of groundwater.
Assuntos
Hexaclorocicloexano , Microbiota , Humanos , Hexaclorocicloexano/química , Biodegradação Ambiental , Isótopos de Carbono/análise , Anaerobiose , RNA Ribossômico 16S/genética , RNA Ribossômico 16S/metabolismo , BiotransformaçãoRESUMO
The hexachlorocyclohexane isomers (HCH) are long-banned pesticides. Even though their use has been prohibited for decades, their presence in the environment is still reported worldwide. Wetland + is a registered trademark of the remedial treatment technology consisting of an aerobic sedimentary tank, a permeable reactive barrier, a biosorption system, and an aerobic wetland. This proven method combines a reductive treatment known from PRBs with the natural wetland self-cleaning processes. The average efficiency of the system is 96.8% for chlorobenzenes (ClB) and 81.7% for HCH, during the first 12 months of the system operation. The presence of the genes encoding enzymes involved in the degradation of the HCH compounds indicates that the removal of HCH and ClB occurs not only by chemical removal but also through aerobic and anaerobic combining biodegradation. Changes in abundance and the composition of the diatom community were found to be suitable indicators of the water quality and of the impact of the Wetland + operation on the water ecosystem. The system's annual operation exhibited a markedly higher number of diatom species in the closing profiles of the Ostrovský Creek, the Wetland + effluent recipient.
Assuntos
Ecossistema , Hexaclorocicloexano , Hexaclorocicloexano/química , Hexaclorocicloexano/metabolismo , Áreas Alagadas , Biodegradação Ambiental , BiodiversidadeRESUMO
This review elucidates different bioremediation approaches used for degradation of HCH from contaminated sites. It highlights the significance of degradative pathways, microbial diversity and impact of different environmental factors for developing viable bioremediation strategies. The application of innovative biotechnological approaches and a thorough understanding of HCH biodegradation pathways show great promise for the creation of long-term solutions to HCH pollution and the restoration of polluted soil ecosystems. Bioremediation technologies viz. biostimulation, bioaugmentation, phytoremediation have been considered till date for treating HCH-contaminated sites. Different bacterial and fungal strains have been reported for degradation of HCH residues. However, these methods are limited to γ-HCH degradation, at laboratory scale and achieving lower success rate for large scale demonstration trials. This review presents a theoretical background for degradation of different HCH isomers in soil through plants, microbes and through their cooperative interactions. This work briefly overviews the substantial contamination of the environment by HCH residues, along with spontaneous evolution of degradation pathways through various HCH degrading microbes. Bioremediation mechanism and pathways of HCH degradation through plants and microbes have been discussed thoroughly. Through molecular and genetic investigations, the complex metabolic pathways used by these microbes, including reductive dechlorination, hydrolysis, and ring cleavage, has been clarified. This study seeks to give a thorough summary of recent discoveries and developments in bioremediation methods for soil HCH degradation. Numerous microbial consortia, including fungi, plants, and bacteria have been recognised as important participants in the transformation of HCH.
Assuntos
Hexaclorocicloexano , Poluentes do Solo , Humanos , Hexaclorocicloexano/química , Hexaclorocicloexano/metabolismo , Biodegradação Ambiental , Solo , Ecossistema , Bactérias/genética , Bactérias/metabolismo , Fungos/genética , Fungos/metabolismo , Poluentes do Solo/metabolismoRESUMO
During production of γ-hexachlorocyclohexane (γ-HCH), thousands of tons of other isomers were synthesized as byproducts, and after dumping represent sources of contamination for the environment. Several microbes have the potential for aerobic and anaerobic degradation of HCHs, and zero-valent iron is an effective remediation agent for abiotic dechlorination of HCHs, whereas the combination of the processes has not yet been explored. In this study, a sequence of anoxic/oxic chemico-biological treatments for the degradation of HCHs in a real extremely contaminated soil (10-30 g/kg) was applied. Approximately 1500 kg of the soil was employed, and various combinations of reducing and oxygen-releasing chemicals were used for setting up the aerobic and anaerobic phases. The best results were obtained with mZVI/nZVI, grass cuttings, and oxygen-releasing compounds. In this case, 80 % removal of HCHs was achieved in 129 days, and 98 % degradation was achieved after 1106 days. The analysis of HCHs and their transformation products proved active degradation when slight accumulation of the transformation product during the anaerobic phase was followed by aerobic degradation. The results document that switching between aerobic and anaerobic phases, together with the addition of grass, also created suitable conditions for the biodegradation of HCHs and monochlorobenzene/benzene by microbes.
Assuntos
Hexaclorocicloexano , Poluentes do Solo , Hexaclorocicloexano/química , Descontaminação , Biodegradação Ambiental , Poluentes do Solo/metabolismo , Solo/química , OxigênioRESUMO
This study proposed the fluidization-like dielectric barrier discharge (DBD) plasma for the remediation of lindane contaminated soil and integrated physical and chemical reaction pathway. Soil particle distribution within the reactor was simulated with Euler-Euler and Gidaspow drag models, and a bipolar pulsed power supply was applied to energize the DBD reactor after full fluidized. The effect of soil particles movement on electric features was discussed in terms of voltage waveforms and Lissajous figures. Lindane degradation was found to be related to electrics parameters and soil properties. Soil samples before and after treatment were analyzed by XRD and SEM methods. A 95.98% lindane decomposition and 0.66 mgLindane/h average reaction rate were obtained with 3 wt% CaO injection by pulse power drove fluidization-like DBD after 32 min treatment. Ozone was proved to play a major role during lindane degrading by plasma. The reaction potential pathway of lindane decomposition contains 4 steps, including dehydrogen, dehydrochlorination, and dechlorination, respectively.
Assuntos
Recuperação e Remediação Ambiental , Poluentes do Solo , Hexaclorocicloexano/química , Poluentes do Solo/química , Solo , Poluição AmbientalRESUMO
Dehydrochlorination is one of the main (thus far discovered) processes for aerobic microbial transformation of hexachlorocyclohexane (HCH) which is mainly catalyzed by LinA enzymes. In order to gain a better understanding of the reaction mechanisms, multi-element compound-specific stable isotope analysis was applied for evaluating α- and γ-HCH transformations catalyzed by LinA1 and LinA2 enzymes. The isotopic fractionation (εE) values for particular elements of (+)α-HCH (εC = -10.8 ± 1.0, εCl = -4.2 ± 0.5, εH = -154 ± 16) were distinct from the values for (-)α-HCH (εC = -4.1 ± 0.7, εCl = -1.6 ± 0.2, εH = -68 ± 10), whereas the dual-isotope fractionation patterns were almost identical for both enantiomers (ΛC-Cl = 2.4 ± 0.4 and 2.5 ± 0.2, ΛH-C = 12.9 ± 2.4 and 14.9 ± 1.1). The εE of γ-HCH transformation by LinA1 and LinA2 were -7.8 ± 1.0 and -7.5 ± 0.8 (εC), -2.7 ± 0.3 and -2.5 ± 0.4 (εCl), -170 ± 25 and -150 ± 13 (εH), respectively. Similar ΛC-Cl values (2.7 ± 0.2 and 2.9 ± 0.2) were observed as well as similar ΛH-C values (20.1 ± 2.0 and 18.4 ± 1.9), indicating a similar reaction mechanism by both enzymes during γ-HCH transformation. This is the first data set on 3D isotope fractionation of α- and γ-HCH enzymatic dehydrochlorination, which gave a more precise characterization of the bond cleavages, highlighting the potential of multi-element compound-specific stable isotope analysis to characterize different transformation processes (e.g., dehydrochlorination and reductive dehalogenation).
Assuntos
Hexaclorocicloexano , Isótopos , Hexaclorocicloexano/química , Isomerismo , Estereoisomerismo , Isótopos de Carbono , Biodegradação AmbientalRESUMO
Lindane is a persistent organic pollutant that has attracted worldwide attention because of its threat to human health and environmental security. A horizontal planetary mechanochemical method was developed for rapid and efficient degradation of lindane in soil in an alkaline environment. Under the condition of a very low reagent-to-soil ratio (R = 2%), ball-to-powder ratio (CR = 6:1), rotation speed (r = 300 rpm) and high soil single treatment capacity (SC = 60 g), the lindane in four typical soils (~ 100 mg/kg) can be degraded up to 96.30% in 10 min. This method can also remediate high-concentration lindane-contaminated soil (833 ± 26 mg/kg). The experimental results and theoretical calculations proved that the stepwise dechlorination and final carbonization of lindane in soil are mainly attributed to the combined action of mechanical energy and alkalinity. The bimolecular elimination (E2) reaction was the first step of lindane destruction. Subsequently, the unimolecular elimination (E1) reaction tended to occur with the weakening of alkalinity. Then, benzene was obtained through stepwise hydrogenolysis reaction. The last was the generation of carbon substances by fragmentation or condensation of benzene rings. This work proposes a practical remediation technology for organic contaminated soil and improves the understanding of the degradation pathways of lindane in soil in alkali-assisted mechanochemical system.
Assuntos
Recuperação e Remediação Ambiental , Poluentes do Solo , Atenção , Benzeno , Hexaclorocicloexano/química , Humanos , Solo/química , Poluentes do Solo/metabolismoRESUMO
Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid-liquid extraction method of HCHs in water. The results showed that there were negligible changes in the δ13C of HCHs after extraction, indicating that liquid-liquid extraction can be used as a pre-concentration method for the determination of δ13C of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the α-HCH oxidation by CaO2/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched δ13C in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (εC) of -1.90 ± 0.10‱ were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.
Assuntos
Carbono , Hexaclorocicloexano , Biodegradação Ambiental , Carbono/análise , Isótopos de Carbono/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hexaclorocicloexano/análise , Hexaclorocicloexano/química , Hexaclorocicloexano/metabolismo , Extração Líquido-Líquido , Água/análiseRESUMO
Lindane and other 1,2,3,4,5,6-hexachlorocyclohexane (HCH) isomers are persistent organic pollutants highly hydrophobic, which hampers their availability and biodegradation. This work aimed at (i) investigating genes encoding enzymes involved in HCH degradation in the bacterium Sphingobium sp. D4, (ii) selecting strains, from a collection of environmental isolates, able to mobilize HCHs from contaminated soil, and (iii) analysing the biodegradation of HCHs by strain D4 in co-culture with HCH-mobilizing strains or when cultivated with root exudates. Fragments of the same size and similar sequence to linA and linB genes were successfully amplified. Two isolates, Streptomyces sp. M7 and Rhodococcus erythropolis ET54b able to produce emulsifiers and to mobilize HCH isomers from soil were selected. Biodegradation of HCH isomers by strain D4 was enhanced when co-inoculated with HCH mobilizing strains or when cultivated with root exudates. The degrader strain D4 was able to decompose very efficiently HCHs isomers, reducing their concentration in soil slurries by more than 95% (from an average initial amount of 50 ± 8 mg HCH kg-1 soil) in 9 days. The combination of HCH-degrading and HCH-mobilizing strains can be considered a promising inoculum for future soil bioremediation studies using bioaugmentation techniques or in combination with plants in rhizodegradation assays.
Assuntos
Poluentes do Solo , Sphingomonadaceae , Biodegradação Ambiental , Técnicas de Cocultura , Exsudatos e Transudatos/química , Exsudatos e Transudatos/metabolismo , Hexaclorocicloexano/química , Solo/química , Poluentes do Solo/metabolismo , Sphingomonadaceae/genética , Sphingomonadaceae/metabolismoRESUMO
The stable isotope fingerprints of hexachlorocyclohexane (HCH) isomers have potential for identifying sources as they are related to the synthesis processes and isotopic compositions of raw materials. However, the isotopic fractionation associated with the synthesis processes has not been investigated. Therefore, photochemical synthesis experiments using benzene and chlorine gas were conducted to characterize the associated isotopic fractionation under different conditions. Different patterns of isotopic fractionation factors (αC, αCl, and αH) were observed in each experiment. The large variability of αH is related to the accumulating secondary hydrogen isotope effects or the rearrangement of C-H bonds at the cyclohexane ring. An increase of δ13C and δ37Cl values of HCH isomers was observed during synthesis, which is related to the C-Cl bond formation in the radical dichlorination forming HCH and the subsequent chlorine substitution forming heptachlorocyclohexanes. The large variability of δ2H values is related to the secondary and primary hydrogen isotope effects. Different δ13C, δ37Cl and δ2H values among HCH isomers were observed, indicating that conformational complexity of HCH caused by arrangement of C-Cl bonds in planar and axial positions also influence the isotope values. The understanding of isotopic fractionation during HCH synthesis can be indicative for source identification in the field.
Assuntos
Hexaclorocicloexano , Isótopos , Biodegradação Ambiental , Isótopos de Carbono/análise , Fracionamento Químico , Cloro , Hexaclorocicloexano/química , Hidrogênio , IsomerismoRESUMO
Organochlorines (OCs) are groups of highly toxic pesticides with known immunotoxicity. The present work aimed to study the potential association between serum residues of OCs and the risk of developing systemic lupus erythematosus (SLE) as well as correlating to the clinical-laboratory manifestations in a sample of Egyptian SLE patients. A cross-sectional study was conducted on 132 patients environmentally exposed to OCs. Patients were diagnosed as SLE based on the American College of Rheumatology (ACR) revised criteria. Systemic Lupus Erythematosus Disease Activity Index-2000 (SLEDAI-2K) score was calculated to stratify the disease severity. Blood and urine samples were collected to measure the levels of OCs, serological markers, and urinary protein. The most frequently detected OCs were p,p'-DDE; lindane; and hexachlorobenzene (HCB). The risk of developing SLE was significantly associated with detected p,p'-DDE and HCB (B value 7.704 and 14.33, respectively). Hexachlorobenzene, in addition, was significantly associated with increased SLEDAI-2K score and polycythemia. Lindane was significantly associated with hypocomplementemia, cardiac manifestations of SLE, anemia, and leucopenia. In conclusion, the detected OCs p,p'-DDE and HCB are associated with increased risk of SLE in Egyptian patients and correlates to the manifestations of disease severity.
Assuntos
Diclorodifenil Dicloroetileno/química , Hexaclorobenzeno/química , Hexaclorocicloexano/química , Hidrocarbonetos Clorados , Lúpus Eritematoso Sistêmico , Estudos Transversais , Humanos , Lúpus Eritematoso Sistêmico/induzido quimicamente , Índice de Gravidade de DoençaRESUMO
Phytoremediation and advanced oxidation processes are among the most promising techniques for removing organic pollutants from soils. A field trial was performed for six months to evaluate the effect of nano-Fe3O4 on the degradation of organochlorine pesticide residues including Lindane, p,p'-dichlorodiphenyltrichloroethane (DDT), p,p'-dichlorodiphenyldichloroethylene (DDE), and p,p'-dichlorodiphenyldichloroethane (DDD) in pesticide-contaminated soils in the presence of vetiver in Bac Giang province, Vietnam. Vetiver was planted in three zones with different nano-Fe3O4 concentrations. Soil samples from each zone were periodically collected to determine the remaining concentrations of selected organochlorine pesticides via gas chromatography-electron capture detector. Results indicated that the total DDT concentrations in the examined soil were 1.9-13 times higher than the permissible threshold level (10 µg g-1) established by the national technical regulation on pesticide residues in soil. The (p,p'-DDE + p,p'-DDD)/p,p'-DDT ratios ranged from 13.5 to 114, indicating the absence of recent inputs of technical DDTs at the study area. DDT dechlorination mainly occurred under aerobic pathways to form DDE. Furthermore, DDE degradation in soil was adequately described by the pseudo-first-order kinetics model (R2 > 0.892). In the presence of vetiver, the rate constants of DDE degradation were 0.264, 0.350, and 0.434 month-1 with 0, 25, and 100 mg kg-1 of added nano-Fe3O4, respectively, indicating that the degradation of DDE correlated positively with Fe3O4 concentration in the soil. Additionally, the presence of vetiver and nano-Fe3O4 in the soil increased DDT removal rates, which might be linked to the involvement of Fenton/Fenton-like reactions.
Assuntos
Vetiveria , Recuperação e Remediação Ambiental/métodos , Hidrocarbonetos Clorados/química , Resíduos de Praguicidas/química , Poluentes do Solo/química , Cromatografia Gasosa , DDT/análise , DDT/química , Diclorodifenil Dicloroetileno/análise , Diclorodifenil Dicloroetileno/química , Hexaclorocicloexano/análise , Hexaclorocicloexano/química , Hidrocarbonetos Clorados/análise , Peróxido de Hidrogênio/química , Ferro/química , Nanopartículas de Magnetita/química , Resíduos de Praguicidas/análise , Solo/química , Poluentes do Solo/análise , VietnãRESUMO
Hexachlorocyclohexane (HCH) and mainly the γ-HCH isomer, namely lindane, were extensively produced and used as pesticides. Huge amounts of wastes, solids and liquids, were disposed of in the surroundings of the production sites. The liquid residuum was a complex mixture of chlorinated organic compounds, COCs, from chlorobenzene to heptachlorocyclohexane. This Dense Non-Aqueous Phase Liquid, DNAPL, migrated by density through the subsurface to greater depths, being trapped or adsorbed into the soil in this movement posing a significant risk to the groundwater. Knowledge of the partitioning in water of COCs in DNAPL is a key issue to determine its fate in the environment. However, there are no data in literature for the partitioning and/or solubility of many of the COCs in this DNAPL, such as pentachlorocyclohexene, hexachlorocyclohexene and heptachlorocyclohexane despite them constitute about 13-30% of the mole fraction of the DNAPLs. In this work, the partitioning to water of COCs in free and those adsorbed onto soil has been studied. In addition, measured and predicted aqueous concentrations of each COC in the DNAPL mixture have been compared. To do this, the solubility of a compound that is a solid crystal when pure at Pâ¯=â¯298â¯K and Pâ¯=â¯1â¯atm has been evaluated considering the approach of sub-cooled liquid state of solid organochlorines. Samples were obtained at Sabiñanigo landfills and soils used had several grain sizes. Transformation in alkaline media of COCs had a positive environmental impact.
Assuntos
Hexaclorocicloexano , Hidrocarbonetos Clorados/química , Poluentes do Solo/química , Halogenação , Hexaclorocicloexano/análogos & derivados , Hexaclorocicloexano/química , Solubilidade , Espanha , Instalações de Eliminação de Resíduos , Água/química , Poluentes Químicos da Água/químicaRESUMO
This paper focuses on the removal of lindane from soil washing effluents (SWEs) using combined electrochemical -biological processes. In particular, it has been evaluated the influence of the anodic material used in the electrolysis of the SWE on the biodegradability and toxicity of the effluents. Four anode materials were tested: Boron Doped Diamond (BDD), Carbon Felt (CF), and Mixed Metal Oxides Anodes with iridium and ruthenium (MMO-Ir and MMO-Ru). These materials were tested at different current densities and electric current charges applied. Lindane, TOC, sulphate, and chlorine species concentrations were monitored during electrochemical experiments, showing important differences in their evolution during the treatment. In spite of reaching a good removal of lindane with all the materials tested, results showed that Boron Doped Diamond working at 15 mA cm-2 achieved the best biodegradability results in the electrolyzed effluents, because the ratio BOD5/COD increased from 0.2 to 0.5, followed by Carbon Felt anode. Regarding toxicity, Carbon Felt decreased toxicity by 80%. Opposite to what it was expected, MMO anodes did not achieve biodegradability improvement and they only showed reduction in toxicity at high electrical charges.
Assuntos
Recuperação e Remediação Ambiental/métodos , Hexaclorocicloexano , Inseticidas , Poluentes do Solo , Poluentes Químicos da Água , Aliivibrio fischeri/efeitos dos fármacos , Boro/química , Carbono/química , Diamante/química , Eletrodos , Eletrólise , Hexaclorocicloexano/química , Hexaclorocicloexano/metabolismo , Hexaclorocicloexano/toxicidade , Inseticidas/química , Inseticidas/metabolismo , Inseticidas/toxicidade , Irídio/química , Óxidos/química , Rutênio/química , Solo , Poluentes do Solo/química , Poluentes do Solo/metabolismo , Poluentes do Solo/toxicidade , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo , Poluentes Químicos da Água/toxicidadeRESUMO
Hexachlorocyclohexane (HCH) isomers constitute a group of persistent organic pollutants. Their mass production and treatment have led to a global environmental problem that continues to this day. The characterization of modes of degradation of HCH by isotope fractionation is a current challenge. Multi isotope fractionation analysis provides a concept to characterize the nature of enzymatic and chemical transformation reactions. The understanding of the kinetic isotope effects (KIE) on bond cleavage reaction contributes to analyses of the mechanism of chemical and enzymatic reactions. Herein, carbon, chlorine, and hydrogen kinetic isotope effects are measured and predicted for the dehydrochlorination reaction of γ-HCH promoted by the hydroxyl ion in aqueous solution. Quantum mechanical (QM) microsolvation with an implicit solvation model and path integral formalism in combination with free-energy perturbation and umbrella sampling (PI-FEP/UM) and quantum mechanical/molecular mechanical QM/MM potentials for including solvent effects as well as calculating isotope effects are used and analyzed with respect to their performance in reproducing measured values. Reaction characterization is discussed based on the magnitudes of obtained isotope effects. The comparative analysis between the chemical dehydrochlorination of γ-HCH in aqueous media and catalyzed reaction by dehydrochlorinase, LinA is presented and discussed. Based on the values of isotope effects, these two processes seem to occur via the same net mechanism.
Assuntos
Proteínas de Bactérias/metabolismo , Isótopos de Carbono/química , Hexaclorocicloexano/química , Liases/metabolismo , Fracionamento Químico , Cloro/química , Teoria da Densidade Funcional , Hidrogênio/química , Hidrólise , Estrutura Molecular , Teoria QuânticaRESUMO
Although persistent organic pollutants (POPs) are currently banned or strictly controlled under the Stockholm Convention on Persistent Organic Pollutants, POPs are still distributed worldwide due to their environmental persistence, atmospheric transport, and bioaccumulation. Herein we investigated the current concentrations of POPs in the sediments from Seto Inland Sea, Japan and sought to clarify the factors currently controlling the POPs concentration of the surface sediments from Seto Inland Sea. The concentrations of hexachlorocyclohexane isomers (HCHs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), and chlordane isomers (CHLs) in sediments from Seto Inland Sea were <0.002-1.20â¯ngâ¯g-1, 0.01-2.51â¯ngâ¯g-1, and 0.01-0.48â¯ngâ¯g-1, respectively. Resuspension increased the concentrations of HCHs, HCB, and DDTs in the surface sediment with the release of historically contaminated pollutants accumulated in a lower layer. We speculate that CHLs in air that were removed by atmospheric deposition affects the concentration of CHLs in surface sediments.
Assuntos
DDT/análise , Sedimentos Geológicos/análise , Hexaclorocicloexano/análise , Poluentes Químicos da Água/análise , Clordano/análise , Clordano/química , DDT/química , Monitoramento Ambiental , Hexaclorocicloexano/química , Japão , Oceanos e Mares , Poluentes Químicos da Água/químicaRESUMO
Perfluoroalkyl substances (PFAS) and organochlorine pesticides (OCPs) in surface sediments were investigated from the Bering Sea, the Chukchi Sea and adjacent Arctic Ocean in 2010. Total concentrations (dry weight) of Σ14PFAS in surface sediments (0.85⯱â¯0.22â¯ngâ¯g-1) of the Bering Sea were lower than that in the Chukchi Sea and adjacent Arctic Ocean (1.27⯱â¯0.53â¯ngâ¯g-1). Perfluoro-butanoic acid (PFBS) and perfluoro-octanoic acid (PFOA) were the dominant PFAS in these areas. The concentrations of Σ15OCPs in the sediment of the Bering Sea (13.00⯱â¯6.17â¯ngâ¯g-1) was slightly higher than that in the Chukchi and Arctic Ocean (12.05⯱â¯2.27â¯ngâ¯g-1). The most abundant OCPs were hexachlorocyclohexane isomers (HCHs) and dichlorodiphenyltrichloroethane (DDT) and its metabolites. The composition patterns of HCHs and DDTs indicated that they were mainly derived from the early residues via river runoff. Increasing trends of PFAS, HCHs and DDTs in surface sediments from the Bering Sea to the Arctic Ocean were found, indicating oceanic transport. In summary, the concentrations of OCPs were orders of magnitude greater than the observed PFAS concentrations, and the concentrations of PFAS and OCPs in surface sediments from the Bering Sea to the Chukchi Sea and adjacent Arctic Ocean are at the low to moderate levels by comparing with other coastal and marine sediments worldwide.
Assuntos
DDT/análise , Monitoramento Ambiental/métodos , Sedimentos Geológicos/análise , Hexaclorocicloexano/análise , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Poluentes Químicos da Água/análise , Regiões Árticas , China , DDT/química , Sedimentos Geológicos/química , Hexaclorocicloexano/química , Hidrocarbonetos Clorados/química , Oceanos e Mares , Praguicidas/química , Poluentes Químicos da Água/químicaRESUMO
The transformation processes of hexachlorocyclohexane isomers (HCHs) from production sites of Lindane across the landscape and along the food web were studied as an example to understand the fate of POPs in the environment. Therefore, we studied the concentration and isotope composition of HCHs in different matrices in the vicinity of a dumpsite and a chemical plant producing HCHs in India. Carbon isotope compositions (δ13C) of HCHs and the enantiomer fraction (EF) of α-HCH were used as indicators to characterize in situ degradation in soil, groundwater, and sediment as well as along the food web. The HCHs were detected in plants growing on contaminated soil. Elevated concentrations of HCHs were found in a number of crops, which indicates an important transfer pathway of HCHs entering food webs. The EF value of α-HCH and the δ13C signature of HCHs indicated that degradation processes occurred in the rhizosphere or within the plants potentially attenuating the contamination of HCHs. The isotope enrichment of HCHs in dung and milk samples showed that degradation of HCHs may take place in the digestive track of cow and buffalo as well as during their metabolism. The δ13C of HCHs was used to analyze the potential dispersion routes on the landscape scale in order to understand the reactive transport pathways starting at the source of HCHs. In this study, the potential of carbon isotope fractionation and EF for characterizing uptake of HCHs into plants and accumulation in the food web were examined. To the best of our knowledge, this is the first study using the combination of stable isotope fractionation and EF to track the reactive transport processes in a complex environment including the food web.
Assuntos
Monitoramento Ambiental/métodos , Poluentes Ambientais/química , Hexaclorocicloexano/química , Animais , Isótopos de Carbono/análise , Bovinos , Recuperação e Remediação Ambiental , Cadeia Alimentar , Água Subterrânea/química , Índia , Isomerismo , Plantas/química , Solo/química , Instalações de Eliminação de ResíduosRESUMO
In this work, it is evaluated the more critical point of a new electrochemical technology for the removal of organic pollutants based on the regeneration of granular active carbon (GAC) (that can be used efficiently to concentrate aqueous wastes) with methanol and in the electrochemical treatment of methanol with conductive diamond electrochemical oxidation (CDEO). The system proposed was studied with lindane and clopyralid. Results show that it is possible the complete removal of the raw pesticides and intermediates formed by electrolyzing these species in methanol media and that both sodium chloride and sodium hydroxide can be used as supporting electrolyte to increase the conductivity of methanol. The cell voltages obtained are quite similar to those obtained during the electrolysis of aqueous wastes. The electrolysis of these dilute solutions does not generate significant concentrations of intermediates and the depletion of the raw pollutant fits well to a pseudo-first order kinetic model. Oxidants capable to oxidize iodide to iodine are produced during the electrolysis in methanol media and they have an important influence on the degradation of the pollutants. The new technology, based on the concentration of the pollutant before electrolysis, allows to remove completely pollutants from soil and soil washing fluids in a more efficient way, although the concentration of pollutant attained and, hence, the efficiency of the overall removal process depends on the adsorption equilibria of the pollutant in aqueous and methanol media.