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1.
J Hazard Mater ; 467: 133646, 2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38330651

RESUMO

The exposure of terrestrial organisms to soils freshly contaminated by polycyclic aromatic compounds (PACs, including PAHs and polar-PACs) is known to cause significant toxicity effects. However, historically contaminated soils, such as former coking plant soils, usually induce a limited toxic impact, due to the "aging" phenomenon which is the result of several processes causing a reduction of PAC availability over time. For a better understanding of these behaviors, this study aimed to compare the toxic responses of terrestrial organisms exposed to aged contaminated soils and their counterparts submitted to a moderate heating process applied to increase PAC availability. Two aged "raw" soils (limited PAC availability) were selected for their representativeness of former industrial soils in terms of PAC contamination. These soils were submitted either to moderate heating (expected PAC availability increase) or solvent-extraction (expected PAC removal). Physico-chemical parameters, contamination levels and availability were determined for these three soil modalities. Additionally, standardized limit bioassays on plants and earthworms were performed to assess soil ecotoxicity. The findings demonstrated that historically contaminated soils exposed to moderate heating induced the highest ecotoxic responses from terrestrial organisms. Heating increased PAC (bio)availability, without modifying any other soil physico-chemical properties. These results pointed out the importance of considering the contamination availability parameter in risk evaluation and also provide a possible tool for protective long-term risk assessment.


Assuntos
Coque , Hidrocarbonetos Policíclicos Aromáticos , Compostos Policíclicos , Poluição Ambiental , Hidrocarbonetos Policíclicos Aromáticos/análise , Solo/química
2.
J Contam Hydrol ; 262: 104319, 2024 03.
Artigo em Inglês | MEDLINE | ID: mdl-38359773

RESUMO

Light-Non-Aqueous phase liquids (LNAPLs) are important soil contamination sources, and groundwater fluctuations may significantly affect their migration and release. However, the risk assessment remains complex due to the continuous three-phase fluid redistribution caused by water table level variations. Hence, monitoring methods must be improved to integrate better the LNAPL multi-compound and multi-phase aspects tied to the groundwater level dynamics. For this purpose, a lysimetric contaminated soil column (2 m3) combining in-situ monitoring (electrical permittivity, soil moisture, temperature, pH, Eh), direct water and gas sampling and analyses (GC/MS-TQD, µGC) in monitoring well, gas collection chambers, and suction probes) were developed. This experiment assesses in an integrated way how controlled rainfalls and water table fluctuation patterns may affect LNAPL vertical soil saturation distribution and release. Coupling these methods permitted the investigation of the effects of rainwater infiltration and water table level fluctuation on contaminated soil oxygen turnover, LNAPL contaminants' soil distribution and remobilization towards the dissolved and the gaseous phase, and the estimate of the LNAPL source attenuation rate. Hence, 7.5% of the contamination was remobilized towards the dissolved and gaseous phase after 120 days. During the experiment, groundwater level variations were responsible for the free LNAPL soil spreading and trapping, modifying dissolved LNAPL concentrations. Nevertheless, part of the dissolved contamination was rapidly biodegraded, leaving only the most bio-resistant components in water. This result highlights the importance of developing new experimental devices designed to assess the effect of climate-related parameters on LNAPL fate at contaminated sites.


Assuntos
Água Subterrânea , Solo , Poluição Ambiental , Gases , Água
3.
Environ Pollut ; 335: 122330, 2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37572846

RESUMO

An experimental approach mimicking the land-sea continuum in microcosms was developed in order to determine the effect of the terrigenous inputs by soil runoff on the microbial functional potential in hydrocarbon (HC) contaminated marine coastal sediment. We hypothesized that the coalescent event increases the functional potential of microbial communities in marine coastal sediments, influencing the fate of HC in marine coastal ecosystems. The microbial functional potential including the HC degradation ability was assessed by DNA-array to compare the sediment receiving or not terrigenous inputs. The removal of HC and the functional gene richness in sediment was unchanged with the terrigenous inputs. However, the gene variants (GVs) composition was modified indicating functional redundancy. In addition, functional indicators including GVs related to sulfite reduction, denitrification and polyaromatic degradation were identified in higher proportion in sediment receiving terrigenous inputs. The terrigenous inputs modified the functional co-occurrence networks, showing a reorganization of the GVs associations with an increase of the network complexity. Different keystone GVs ensuring similar functions were identified in networks with or without terrigenous inputs, further confirming functional redundancy. We argue that functional redundancy maintains the structure of microbial community in hydrocarbon-contaminated land-sea continuum mixing zone. Our results provide helpful functional information for the monitoring and management of coastal environment affected by human land-based activities.


Assuntos
Microbiota , Humanos , Solo , Sedimentos Geológicos/química , Hidrocarbonetos
5.
ACS Omega ; 7(27): 23653-23661, 2022 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-35847320

RESUMO

The characterization of organic compounds in polluted matrices by eco-friendly three-dimensional (3D) fluorescence spectroscopy coupled with chemometric algorithms constitutes a powerful alternative to the separation techniques conventionally used. However, the systematic presence of Rayleigh and Raman scattering signals in the excitation-emission matrices (EEMs) complicates the spectral decomposition via PARAllel FACtor analysis (PARAFAC) due to the nontrilinear structure of these signals. Likewise, the specific problem of selectivity in spectroscopy for unexpected chemical components in a complex sample may render its chemical interpretation difficult at first glance. The relevant chemical information can then be complicated to extract, especially if the raw data is noisy. There are several strategies to overcome these drawbacks, but weaknesses remain. As a consequence, a new alternative method is proposed to handle these interferences, the noise, and the rank deficiencies in the data and applied for the characterization of polycyclic aromatic compound (PAC) mixtures. It is based on effective truncated singular-value decomposition (MT-SVD) that does not require any prior knowledge of the raw data. The algorithm provides a valuable estimation of the global rank to choose on complex samples where selectivity problems are observed. It is a real alternative compared to other existing methods applied to the fluorescence matrix to filter the signal from noise or light scattering effects. The first exploratory results of the proposed algorithm are promising to handle matrix rank deficiencies as well as the effects of noise and light scattering on complex PAC mixtures.

6.
Sci Rep ; 12(1): 7245, 2022 05 04.
Artigo em Inglês | MEDLINE | ID: mdl-35508504

RESUMO

Natural attenuation, involving microbial adaptation, helps mitigating the effect of oil contamination of surface soils. We hypothesized that in soils under fluctuating conditions and receiving oil from seeps, aerobic and anaerobic bacteria as well as fungi could coexist to efficiently degrade hydrocarbons and prevent the spread of pollution. Microbial community diversity was studied in soil longitudinal and depth gradients contaminated with petroleum seeps for at least a century. Hydrocarbon contamination was high just next to the petroleum seeps but this level drastically lowered from 2 m distance and beyond. Fungal abundance and alpha-diversity indices were constant along the gradients. Bacterial abundance was constant but alpha-diversity indices were lower next to the oil seeps. Hydrocarbon contamination was the main driver of microbial community assemblage. 281 bacterial OTUs were identified as indicator taxa, tolerant to hydrocarbon, potentially involved in hydrocarbon-degradation or benefiting from the degradation by-products. These taxa belonging to lineages of aerobic and anaerobic bacteria, have specific functional traits indicating the development of a complex community adapted to the biodegradation of petroleum hydrocarbons and to fluctuating conditions. Fungi are less impacted by oil contamination but few taxa should contribute to the metabolic complementary within the microbial consortia forming an efficient barrier against petroleum dissemination.


Assuntos
Petróleo , Poluentes do Solo , Anaerobiose , Bactérias/genética , Bactérias/metabolismo , Biodegradação Ambiental , Hidrocarbonetos/metabolismo , Petróleo/metabolismo , Solo , Microbiologia do Solo , Poluentes do Solo/metabolismo
7.
Sci Total Environ ; 806(Pt 1): 150412, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34562757

RESUMO

The intergovernmental panel on climate change (IPCC) predicts significant changes in precipitation patterns, an increase in temperature, and groundwater level variations by 2100. These changes are expected to alter light non-aqueous phase liquid (LNAPL) impacts since groundwater level fluctuations and temperature are known to influence both the mobility and release of LNAPL compounds to air and groundwater. Knowledge of these potential effects is currently dispersed in the literature, hindering a clear vision of the processes at play. This review aims to synthesize and discuss the possible effects of the increase in temperature and groundwater level fluctuations on the behavior of LNAPL and its components in a climate change context. In summary, a higher amplitude of groundwater table variations and higher temperatures will probably increase biodegradation processes, the LNAPL mobility, and spreading across the smear zone, favoring the release of LNAPL compounds to the atmosphere and groundwater but decreasing the LNAPL mass and its longevity. Outcomes will, nevertheless, vary greatly across arid, cold, or humid coastal environments, where different effects of climate change are expected. The effects of the climate change factors linked to soil heterogeneities, local conditions, and weathering processes will govern LNAPL behavior and need to be further clarified.


Assuntos
Mudança Climática , Água Subterrânea , Biodegradação Ambiental , Solo , Temperatura
8.
Environ Sci Pollut Res Int ; 29(11): 15966-15982, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-34642882

RESUMO

Permanganate is an oxidant usually applied for in situ soil remediation due to its persistence underground. It has already shown great efficiency for dense nonaqueous phase liquid (DNAPL) degradation under batch experiment conditions. In the present study, experimental permanganate oxidation of a DNAPL - coal tar - sampled in the groundwater of a former coking plant was carried out in a glass bead column. Several glass bead columns were spiked with coal tar using the drainage-imbibition method to mimic on-site pollution spread at residual saturation as best as possible. The leaching of organic pollutants was monitored as the columns were flushed by successive sequences: successive injections of hot water, permanganate solution for oxidation, and ambient temperature water, completed by two injections of a tracer before and after oxidation. Sixteen conventional US-EPA PAHs and selected polar PACs were analyzed in the DNAPL remaining in the columns at the end of the experiment and in the particles collected at several steps of the flushing sequences. Permanganate oxidation of the pollutants was rapidly limited by interfacial aging of the DNAPL drops. Moreover, at the applied flow rate chosen to be representative of in situ injections and groundwater velocities, the reaction time was not sufficient to reach high degradation yields but induced the formation and the leaching of oxygenated PACs.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Compostos Policíclicos , Poluentes Químicos da Água , Compostos de Manganês , Oxirredução , Óxidos , Hidrocarbonetos Policíclicos Aromáticos/análise
9.
Environ Sci Pollut Res Int ; 27(1): 704-716, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31808080

RESUMO

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (FeVI). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.


Assuntos
Ferro/química , Hidrocarbonetos Policíclicos Aromáticos/análise , Poluentes do Solo/análise , Coque , Óxido Ferroso-Férrico/química , Água Subterrânea , Compostos de Manganês , Modelos Químicos , Oxidantes/química , Oxirredução , Óxidos , Oxigênio , Compostos Policíclicos/análise , Areia , Solo/química
10.
Chemosphere ; 224: 437-444, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30831494

RESUMO

Potassium permanganate and Fenton-like oxidations were applied on two PAH-contaminated soils collected on former coking plant and gas plant sites. The impact of oxidant dose on the polycyclic aromatic compound (PAC) evolution, including 16 US-EPA PAHs, 11 oxygenated- and 4 nitrogen heterocyclic-PACs (O- and N-PACs) was studied for both treatments. The content of extractable organic matter and PACs was determined prior and after oxidation. Overall, permanganate treatment was more efficient than Fenton-like to decrease the PAH content, this latter being limited by the contamination availability. However, permanganate treatment resulted in incomplete PAH degradation, leading to the formation of O-PACs, that was limited with the application of higher dose. It underlines the importance of the dose and the oxidant type in the selection of oxidation parameters for remediation purpose, as improper use of oxidant can lead to the accumulation of oxidation by-products that could be as toxic as the parent compounds.


Assuntos
Recuperação e Remediação Ambiental/métodos , Peróxido de Hidrogênio/química , Ferro/química , Oxidantes/química , Hidrocarbonetos Policíclicos Aromáticos/análise , Permanganato de Potássio/química , Poluentes do Solo/análise , Oxirredução , Solo/química
11.
Environ Sci Pollut Res Int ; 26(2): 1693-1705, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30448950

RESUMO

In industrial sites, historically contaminated by coal tar (abandoned coking and manufactured gas plants), other families of organic pollutants than the 16 PAHs (polycyclic aromatic hydrocarbons) classified by the US-EPA can occur and induce potential risk for groundwater resources. Polar PACs (polycyclic aromatic compounds), especially oxygenated and nitrogenated PACs (O-PACs and N-PACs), are present in the initial pollution and can also be generated over time (i.e., O-PACs). Their aqueous solubilities are much greater than those of the PAHs. For these reasons, we need to increase our knowledge on polar PACs in order to better predict their behavior and the potential on-site risk. Batch leaching tests were carried out under various conditions of temperature, ionic strength, and availability of pollutants to determine the mechanisms and key parameters controlling their release. The results show a release of low-molecular-weight PAHs and polar PACs mainly by dissolution, while higher molecular weight PAHs are mainly released in association with colloids. Aging mainly controls the former mechanism, and ionic strength mainly controls the latter. Temperature increased both dissolution and colloidal mobilization. The Raoult law predicts the PAC equilibrium concentration for soils presenting high pollutant availability, but this law overestimates PAC concentration in aged soils (low pollutant availability). This is mainly due to limitation of PAC diffusion within coal-tar particles with aging. The most soluble PACs (especially polar PACs) are the most sensitive to aging. For better prediction of the PAC behavior in soils and water resources management, aging needs to be taken into account.


Assuntos
Alcatrão , Hidrocarbonetos Policíclicos Aromáticos/química , Poluentes do Solo/química , Carvão Mineral , Coloides/química , França , Concentração de Íons de Hidrogênio , Peso Molecular , Concentração Osmolar , Hidrocarbonetos Policíclicos Aromáticos/análise , Solo/química , Poluentes do Solo/análise , Temperatura , Fatores de Tempo
12.
Environ Sci Pollut Res Int ; 25(29): 29556-29571, 2018 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-30136188

RESUMO

PAH biodegradation in plant rhizosphere has been investigated in many studies, but the timescale of degradation and degrading bacteria activity was rarely considered. We explored the impact of plants on the temporal variability of PAH degradation, microbial abundance, activity, and bacterial community structure in a rhizotron experiment. A historically contaminated soil was spiked with PAHs, planted or not with alfalfa, over 22 days with sampling once a week. In both conditions, most of the spiked PAHs were dissipated during the first week, conducting to polar polycyclic aromatic compound production and to decreased richness and diversity of bacterial communities. We showed a rapid impact of the rhizosphere on PAH degradation via the increased activity of PAH-degrading bacteria. After 12 days, PAH degradation was significantly higher in the planted (100% degradation) than in unplanted (70%) soil. Gram-negative (Proteobacteria) PAH-dioxygenase genes and transcripts were higher in planted than unplanted soil and were correlated to the spiked PAH degradation. Conversely, Gram-positive (Actinobacteria) PAH-dioxygenase gene transcription was constant over time in both conditions. At 12 days, plant growth favored the activity of many Gammaproteobacteria (Pseudomonadaceae, Stenotrophomonas, and Acinetobacter) while in unplanted soil Alphaproteobacteria (Sphingomonadaceae, Sphingobium, and Magnetospirillum) and Actinobacteria (Iamia, Geodermatophilaceae, and Solirubrobacterales) were more active.


Assuntos
Medicago sativa/crescimento & desenvolvimento , Hidrocarbonetos Policíclicos Aromáticos/análise , Proteobactérias/crescimento & desenvolvimento , Microbiologia do Solo , Poluentes do Solo/análise , Solo/química , Biodegradação Ambiental , Biodiversidade , França , Medicago sativa/metabolismo , Proteobactérias/classificação , Rizosfera , Fatores de Tempo
13.
Environ Sci Pollut Res Int ; 24(17): 14748-14757, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28470496

RESUMO

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with ß-HCH (45 mg kg-1) and γ-HCH (lindane, 25 mg kg-1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H2O2 alone, H2O2/FeII, Na2S2O8 alone, Na2S2O8/FeII, and KMnO4. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H2O2 improved the oxidation efficiency while in Na2S2O8 system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by FeII-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 µm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO4 > Na2S2O8/FeII > Na2S2O8 whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO4 at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.


Assuntos
Hexaclorocicloexano/química , Poluentes do Solo/química , Peróxido de Hidrogênio , Oxirredução , Solo
14.
Environ Sci Pollut Res Int ; 24(12): 11265-11278, 2017 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-28299567

RESUMO

Thermal treatments prior or during chemical oxidation of aged polycyclic aromatic hydrocarbon (PAH)-contaminated soils have already shown their ability to increase oxidation effectiveness. However, they were never compared on the same soil. Furthermore, oxygenated polycyclic aromatic hydrocarbons (O-PACs), by-products of PAH oxidation which may be more toxic and mobile than the parent PAHs, were very little monitored. In this study, two aged PAH-contaminated soils were heated prior (60 or 90 °C under Ar for 1 week) or during oxidation (60 °C for 1 week) with permanganate and persulfate, and 11 O-PACs were monitored in addition to the 16 US Environmental Protection Agency (US EPA) PAHs. Oxidant doses were based on the stoichiometric oxidant demand of the extractable organic fraction of soils by using organic solvents, which is more representative of the actual contamination than only the 16 US EPA PAHs. Higher temperatures actually resulted in more pollutant degradation. Two treatments were about three times more effective than the others: soil heating to 60 °C during persulfate oxidation and soil preheating to 90 °C followed by permanganate oxidation. The results of this study showed that persulfate effectiveness was largely due to its thermal activation, whereas permanganate was more sensitive to PAH availability than persulfate. The technical feasibility of these two treatments will soon be field-tested in the unsaturated zone of one of the studied aged PAH-contaminated soils.


Assuntos
Temperatura Alta , Hidrocarbonetos Policíclicos Aromáticos/química , Poluentes do Solo/química , Solo , Poluição Ambiental
15.
Pharmacoepidemiol Drug Saf ; 26(7): 731-741, 2017 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-28176407

RESUMO

PURPOSE: Scarce studies analyzing adverse event (AE) data from randomized placebo-controlled clinical trials (RPCCTs) of selected illnesses suggested that a substantial proportion of collected AEs are unrelated to the drug taken. This study analyzed the nonspecific AEs occurring with active-drug exposure in RPCCTs for a large range of medical conditions. METHODS: Randomized placebo-controlled clinical trials published in five prominent medical journals during 2006-2012 were searched. Only trials that evaluated orally or parenterally administered active drugs versus placebo in a head-to-head setting were selected. For AEs reported from ≥10 RPCCTs, Pearson's correlation coefficients (r) were calculated to determine the relationship between AE rates in placebo and active-drug recipients. Random-effects meta-analyses were used to compute proportions of nonspecific AEs, which were truncated at a maximum of 100%, in active-drug recipients. RESULTS: We included 231 trials addressing various medical domains or healthy participants. For the 88 analyzed AE variables, AE rates for placebo and active-drug recipients were in general strongly correlated (r > 0.50) or very strongly correlated (r > 0.80). The pooled proportions of nonspecific AEs for the active-drug recipients were 96.8% (95%CI: 95.5-98.1) for any AEs, 100% (97.9-100) for serious AEs, and 77.7% (72.7-83.2) for drug-related AEs. Results were similar for individual medical domains and healthy participants. The pooled proportion of nonspecificity of 82 system organ class and individual AE types ranged from 38% to 100%. CONCLUSION: The large proportion of nonspecific AEs reported in active-drug recipients of RPCCTs, including serious and drug-related AEs, highlights the limitations of clinical trial data to determine the tolerability of drugs. Copyright © 2017 John Wiley & Sons, Ltd.


Assuntos
Efeitos Colaterais e Reações Adversas Relacionados a Medicamentos/classificação , Placebos/efeitos adversos , Ensaios Clínicos Controlados Aleatórios como Assunto , Humanos
16.
Environ Sci Pollut Res Int ; 24(10): 9220-9228, 2017 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-28224335

RESUMO

Brownfield soils may contain high levels of organic pollutants particularly polycyclic aromatic hydrocarbons (PAHs). It is essential to predict their migration and fate and to evaluate the risk of transfer to sensitive targets, such as water resources, ecosystems and human health. In this study, soil samples have been taken from an experimental contaminated site of former steel activities located at Homecourt (Lorraine, France). These samples have been lixiviated in laboratory column in water-saturated condition at room temperature. The effluent has been collected by fraction and analysed by a standard method giving total concentration of each of 16 PAHs. The breakthrough curves of 16 PAHs significantly evolve in the same way according to the volume of effluent and tend to vanish to 12-15 pore volumes. If several PAHs remain at a concentration below the solubility, others clearly exceed this threshold. Material balance sheets show that only a very small fraction of PAHs is mobilised. These results are interpreted by postulating that PAHs are transported by the solution not only in the dissolved state but also by associations with particulate or dissolved organic matter.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Poluentes do Solo , Monitoramento Ambiental , França , Solo
17.
J Hazard Mater ; 329: 1-10, 2017 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-28119192

RESUMO

A bioslurry batch experiment was carried out over five months on three polycyclic aromatic compound (PAC) contaminated soils to study the PAC (PAH and polar-PAC) behavior during soil incubation and to evaluate the impact of PAC contamination on the abundance of microbial communities and functional PAH-degrading populations. Organic matter characteristics and reactivity, assessed through solvent extractable organic matter and PAC contents, and soil organic matter mineralization were monitored during 5 months. Total bacteria and fungi, and PAH-ring hydroxylating dioxygenase genes were quantified. Results showed that PAHs and polar-PACs were degraded with different degradation dynamics. Differences in degradation rates were observed among the three soils depending on PAH distribution and availability. Overall, low molecular weight compounds were preferentially degraded. Degradation selectivity between isomers and structurally similar compounds was observed which could be used to check the efficiency of bioremediation processes. Bacterial communities were dominant over fungi and were most likely responsible for PAC degradation. Abundance of PAH-degrading bacteria increased during incubations, but their proportion in the bacterial communities tended to decrease. The accumulation of some oxygenated-PACs during the bioslurry experiment underlines the necessity to monitor these compounds during application of remediation treatment on PAH contaminated soils.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Microbiologia do Solo , Poluentes do Solo/metabolismo , Biodegradação Ambiental , Resíduos Industriais , Análise Multivariada
18.
Anal Bioanal Chem ; 407(12): 3509-16, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25772555

RESUMO

Polycyclic aromatic hydrocarbons (PAHs) associated with two minerals (silica sand and bentonite) presenting opposite retention properties were analyzed with a thermodesorption (Td)-GC-MS coupling in order to validate this technique as a new and rapid way to evaluate the solid sorption properties. Two analysis modes were used, evolved gas analysis (EGA) and Td with cryo-trap. EGA allowed a real-time monitoring of the compounds desorbed during a temperature program and gave a first screening of the samples while Td gave more precise indications on compound abundances for selected temperature ranges. When associated with silica sand, PAHs were released at relatively low temperatures (<300 °C) close to corresponding boiling point, whereas for the PAH/bentonite mixture, PAHs were desorbed at much higher temperatures; they were also present in much lower abundance and were associated with mono-aromatic compounds. With bentonite, the PAH abundances decreased and the mono-aromatics increased with the increasing PAH molecular weight. These results indicated a clear PAH retention by the bentonite due to polymerization, followed by a thermal cracking at higher temperatures. The Td-GC-MS was proven to efficiently underline differences in retention properties of two minerals, and this study highlights the great potential of this technique to evaluate compound/matrix bond strength and interaction.


Assuntos
Bentonita/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/química , Dióxido de Silício/química , Bentonita/análise , Minerais/análise , Minerais/química , Peso Molecular , Dióxido de Silício/análise , Temperatura
19.
J Hazard Mater ; 286: 55-63, 2015 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-25557939

RESUMO

Three chemical oxidation treatments (KMnO4, H2O2 and Fenton-like) were applied on three PAH-contaminated soils presenting different properties to determine the potential use of these treatments to evaluate the available PAH fraction. In order to increase the available fraction, a pre-heating (100 °C under N2 for one week) was also applied on the samples prior oxidant addition. PAH and extractable organic matter contents were determined before and after treatment applications. KMnO4 was efficient to degrade PAHs in all the soil samples and the pre-heating slightly improved its efficiency. H2O2 and Fenton-like treatments presented low efficiency to degrade PAH in the soil presenting poor PAH availability, however, the PAH degradation rates were improved with the pre-heating. Consequently H2O2-based treatments (including Fenton-like) are highly sensitive to contaminant availability and seem to be valid methods to estimate the available PAH fraction in contaminated soils.


Assuntos
Temperatura Alta , Hidrocarbonetos Policíclicos Aromáticos/química , Poluentes do Solo/química , Biodegradação Ambiental , Carbono/química , Radioisótopos de Carbono/química , Poluição Ambiental , Óxido Ferroso-Férrico/química , Peróxido de Hidrogênio/química , Ferro/química , Nitrogênio/química , Compostos Orgânicos/química , Oxirredução , Oxigênio/química , Permanganato de Potássio/química , Solo/química
20.
Environ Sci Pollut Res Int ; 22(18): 13724-38, 2015 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-25616383

RESUMO

The high organic pollutant concentration of aged polycyclic aromatic hydrocarbon (PAH)-contaminated wasteland soils is highly recalcitrant to biodegradation due to its very low bioavailability. In such soils, the microbial community is well adapted to the pollution, but the microbial activity is limited by nutrient availability. Management strategies could be applied to modify the soil microbial functioning as well as the PAH contamination through various amendment types. The impact of amendment with clay minerals (montmorillonite), wood sawdust and organic matter plant roots on microbial community structure was investigated on two aged PAH-contaminated soils both in laboratory and 1-year on-site pot experiments. Total PAH content (sum of 16 PAHs of the US-EPA list) and polar polycyclic aromatic compounds (pPAC) were monitored as well as the available PAH fraction using the Tenax method. The bacterial and fungal community structures were monitored using fingerprinting thermal gradient gel electrophoresis (TTGE) method. The abundance of bacteria (16S rRNA genes), fungi (18S rRNA genes) and PAH degraders (PAH-ring hydroxylating dioxygenase and catechol dioxygenase genes) was followed through qPCR assays. Although the treatments did not modify the total and available PAH content, the microbial community density, structure and the PAH degradation potential changed when fresh organic matter was provided as sawdust and under rhizosphere influence, while the clay mineral only increased the percentage of catechol-1,2-dioxygenase genes. The abundance of bacteria and fungi and the percentage of fungi relative to bacteria were enhanced in soil samples supplemented with wood sawdust and in the plant rhizospheric soils. Two distinct fungal populations developed in the two soils supplemented with sawdust, i.e. fungi related to Chaetomium and Neurospora genera and Brachyconidiellopsis and Pseudallescheria genera, in H and NM soils respectively. Wood sawdust amendment favoured the development of PAH-degrading bacteria holding Gram-negative PAH-ring hydroxylating dioxygenase, catechol-1,2-dioxygenase and catechol-2,3-dioxygenase genes. Regarding the total community structure, bacteria closely related to Thiobacillus (ß-Proteobacteria) and Steroidobacter (γ-Proteobacteria) genera were favoured by wood sawdust amendment. In both soils, plant rhizospheres induced the development of fungi belonging to Ascomycota and related to Alternaria and Fusarium genera. Bacteria closely related to Luteolibacter (Verrucomicrobia) and Microbacterium (Actinobacteria) were favoured in alfalfa and ryegrass rhizosphere.


Assuntos
Silicatos de Alumínio/farmacologia , Bactérias/efeitos dos fármacos , Fungos/efeitos dos fármacos , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Microbiologia do Solo , Poluentes do Solo/metabolismo , Madeira/química , Bactérias/genética , Bactérias/isolamento & purificação , Bactérias/metabolismo , Biodegradação Ambiental/efeitos dos fármacos , Argila , Fungos/genética , Fungos/isolamento & purificação , Fungos/metabolismo , Raízes de Plantas/efeitos dos fármacos , Raízes de Plantas/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/isolamento & purificação , RNA Ribossômico 16S/genética , Rizosfera , Poluentes do Solo/isolamento & purificação
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