Simultaneous adsorption and degradation of γ-HCH by nZVI/Cu bimetallic nanoparticles with activated carbon support

Cu amended zero valent iron bimetallic nanoparticles were synthesized by doping Cu on the surface of iron. They were incorporated with granular activated carbon (AC) to prepare supported particles (AC-Fe⁰-Cu), which were used to remove γ-HCH. Cu on the surface of iron enhanced the dechlorination activity of Fe⁰. The dechlorination rate constant (k_obs) increased with the Cu loading on the surface of iron and the maximum was achieved with 6.073% Cu. AC as a support was effective for increasing the dispersion of the nanoparticles and avoiding the agglomeration of the metallic nanoparticles. The simultaneous adsorption of γ-HCH on AC accelerated the degradation rate of γ-HCH by the bimetals. After reaction for 165 min, around 99% of γ-HCH was removed by the solids of AC-Fe⁰-Cu. In addition, AC could adsorb the degradation products. The degradation of γ-HCH was mainly through dehydrochlorination and dichloroelmination based on the intermediate products detected by GC/MS.     

Co-composting of spent coffee ground with olive mill wastewater sludge and poultry manure and effect of Trametes versicolor inoculation on the compost maturity

The co-composting of spent coffee grounds, olive mill wastewater sludge and poultry manure was investigated on a semi-industrial scale. In order to reduce the toxicity of the phenolic fraction and to improve the degree of composting humification, composts were inoculated with the white-rot fungus Trametes versicolor in the early stages of the maturation phase.During composting, a range of physico-chemical parameters (temperature and both organic matter and C/N reduction), total organic carbon, total nitrogen, elemental composition, lignin degradation and spectroscopic characteristics of the humic acids (HAs) were determined; impacts of the composting process on germination index of Hordeum vulgare and Lactuca sativa were assessed. The coffee waste proved to be a highly compostable feedstock, resulting in mature final compost with a germination index of 120% in less than 5 months composting. In addition, inoculation with T. versicolor led to a greater degree of aromatization of HA than in the control pile. Moreover, in the inoculated mixture, lignin degradation was three times greater and HA increased by 30% (P < 0.05), compared to the control pile. In the T. versicolor inoculated mixture, the averages of C and N were significantly enhanced in the HA molecules (P < 0.05), by 26% and 22%, respectively. This improvement in the degree of humification was confirmed by the ratio of optical densities of HA solutions at 465 and 665 nm which was lower for HA from the treated mixture (4.5) than that from the control pile (5.4).     

Dynamic changes in functional gene copy numbers and microbial communities during degradation of pyrene in soils

This study investigates the dynamics of pyrene degradation rates, microbial communities, and functional gene copy numbers during the incubation of pyrene-spiked soils. Spiking pyrene to the soil was found to have negligible effects on the bacterial community present. Our results demonstrated that there was a significant difference in nidA gene copy numbers between sampling dates in QZ soil. Mycobacterium 16S rDNA clone libraries showed that more than 90% mycobacteria detected were closely related to fast-growing PAH-degrading Mycobacterium in pyrene-spiked soil, while other sequences related to slow-growing Mycobacterium were only detected in the control soil. It is suggested that nidA gene copy number and fast-growing PAH-degrading Mycobacterium could be used as indicators to predict pyrene contamination and its degradation activity in soils.     

Novel metabolic pathways of organochlorine pesticides dieldrin and aldrin by the white rot fungi of the genus Phlebia

White rot fungi can degrade a wide spectrum of recalcitrant organic pollutants, including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated biphenyls (PCBs). In this experiment, 20 white rot fungi, belonging to genus Phlebia, were investigated for their ability to degrade dieldrin. Based on the screening results, we further investigated Phlebia acanthocystis, Phlebia brevispora, and Phlebia aurea to determine their degradation capacity and metabolic products towards dieldrin and aldrin. The three fungi were able to remove over 50% of dieldrin in a low nitrogen medium, after 42 d of incubation. Three hydroxylated products were detected as metabolites of dieldrin, suggesting that in Phlebia strains, hydroxylation reactions might play an important role in the metabolism of dieldrin. In contrast to dieldrin, aldrin exhibited higher levels of degradation activity. Over 90% of aldrin was removed after 28 d of incubation, and several new metabolites of aldrin in microorganisms, including 9-hydroxyaldrin and two carboxylic acid products, were detected in fungal cultures. These results indicate that the methylene moiety of aldrin and dieldrin molecules might be prone to enzymatic attack by white rot fungi. In this study, we describe for the first time a new metabolic pathway of both compounds by fungi of genus Phlebia.     

Hydrocarbon degradation, plant colonization and gene expression of alkane degradation genes by endophytic Enterobacter ludwigii strains

The genus Enterobacter comprises a range of beneficial plant-associated bacteria showing plant growth promotion. Enterobacter ludwigii belongs to the Enterobacter cloacae complex and has been reported to include human pathogens but also plant-associated strains with plant beneficial capacities. To assess the role of Enterobacter endophytes in hydrocarbon degradation, plant colonization, abundance and expression of CYP153 genes in different plant compartments, three plant species (Italian ryegrass, birdsfoot trefoil and alfalfa) were grown in sterile soil spiked with 1% diesel and inoculated with three endophytic E. ludwigii strains. Results showed that all strains were capable of hydrocarbon degradation and efficiently colonized the rhizosphere and plant interior. Two strains, ISI10-3 and BRI10-9, showed highest degradation rates of diesel fuel up to 68% and performed best in combination with Italian ryegrass and alfalfa. All strains expressed the CYP153 gene in all plant compartments, indicating an active role in degradation of diesel in association with plants.     

Fungal degradation of an acetolactate synthase (ALS) inhibitor pyrazosulfuron-ethyl in soil

Owing to reported phytotoxicity of some sulfonylurea class of herbicides in number of sensitive crops and higher persistence in soil, present study was conducted to isolate and identify pyrazosulfuron-ethyl degrading fungi from soil of rice field. Penicillium chrysogenum and Aspergillus niger, were isolated and identified from rhizospere soil of rice field, as potent pyrazosulfuron-ethyl degrading fungi. Degradation of pyrazosulfuron-ethyl by P. chrysogenum and A. niger, yielded transformation products/metabolites which were identified and characterized by LC/MS/MS. The rate of dissipation of pyrazosulfuron-ethyl was found higher in soil of rice field and soil inoculated with P. chrysogenum. This showed important route of degradation of pyrazosulfuron-ethyl by microbes apart from chemical degradation.     

Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Effects of bioturbation on the fate of oil in coastal sandy sediments--an in situ experiment

Effects of bioturbation by the common lugworm Arenicola marina on the fate of oil hydrocarbons (alkanes and PAHs) were studied in situ during a simulated oil spill in a shallow coastal area of Roskilde fjord, Denmark. The fate of selected oil compounds was monitored during 120 d using GC-MS and bioturbation activity (feces production and irrigation) was measured regularly during the experiment and used as input parameters in a mechanistic model describing the effects of A. marina on the transport and degradation of oil compounds in the sediment. The chemical analytical data and model results indicated that A. marina had profound and predictable effects on the distribution, degradation and preservation of oil and that the net effect depended on the initial distribution of oil. In sediment with an oil contaminated subsurface-layer A. marina buried the layer deeper in the sediment which clearly enhanced oil persistence. Conversely, A. marina stimulated both the physical removal and microbial degradation of oil compounds in uniformly oil contaminated sediments especially in deeper sediment layers (10-20 cm below the surface), whereas the fate of oil compounds deposited in surface layers (0-5 cm) mainly was affected by removal processes induced by wave actions and other bioturbating infauna such as Nereis diversicolor, Corophium volutator and Hydrobia spp. present in the experimental plots.     

Evaluation of UV/TiO(2) and UV/ZnO photocatalytic systems coupled to a biological process for the treatment of bleaching pulp mill effluent

This paper presents an exploratory study of pulp mill bleaching effluent treatment by a biological-photocatalytic coupled system. A fungus, Trametes pubescens, immobilized on polyurethane foam was used to inoculate the biological pre-treatment system. The pretreated effluent was then exposed to a photocatalytic treatment in which two catalysts (TiO₂ and ZnO) and two supports (aluminum foil and Luffa cylindrica) were tested. Catalyst characterization was carried out by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Information about crystalline structure, chemical composition, morphology, homogeneity and distribution on the support surface area was obtained. The overall biological-photocatalytic coupled system achieved degradation of 96% of initial total organic carbon (TOC), 97% of 2-chlorophenol (2-CP), 90% of 2,4-dichlorophenol (2,4-CP) and 99% of 2,4,6-trichlorophenol (2,4,6-TCP). This approach of synergistic coupling of T. pubescens and a semiconductor photocatalyst appears to be a viable alternative for the treatment of these non-biodegradable effluents.     

Evaluation of the antifungal effects of bio-oil prepared with lignocellulosic biomass using fast pyrolysis technology

This study was performed to investigate the utility of bio-oil, produced via a fast pyrolysis process, as an antifungal agent against wood-rot fungi. Bio-oil solutions (25-100 wt.%) were prepared by diluting the bio-oil with EtOH. Wood block samples (yellow poplar and pitch pine) were treated with diluted bio-oil solutions and then subjected to a leaching process under hot water (70 °C) for 72 h. After the wood block samples were thoroughly dried, they were subjected to a soil block test using Tyromyces palustris and Trametes versicolor. The antifungal effect of the 75% and 100% bio-oil solutions was the highest for both wood blocks. Scanning electron microscopy analysis indicated that some chemical components in the bio-oil solution could agglomerate together to form clusters in the inner part of the wood during the drying process, which could act as a wood preservative against fungal growth. According to GC/MS analysis, the components of the agglomerate were mainly phenolic compounds derived from lignin polymers.     

Bioaugmentation of a 4-chloronitrobenzene contaminated soil with Pseudomonas putida ZWL73

The strain Pseudomonas putida ZWL73, which metabolizes 4-chloronitrobenzene (4CNB) by a partial-reductive pathway, was inoculated into lab-scale 4CNB-contaminated soil for bioaugmentation purposes in this study. The degradation of 4CNB was clearly stimulated, as indicated with the gradual accumulation of ammonium and chloride. Simultaneously, the diversity and quantity of cultivable heterotrophic bacteria decreased due to 4CNB contamination, while the quantity of 4CNB-resistant bacteria increased. During the bioaugmentation, denaturing gradient gel electrophoresis analysis showed the changes of diversity in dominant populations of intrinsic soil microbiota. The results showed that Alphaproteobacteria and Betaproteobacteria were not distinctly affected, but Actinobacteria were apparently stimulated. In addition, an interesting dynamic within Acidobacteria was observed, as well as an influence on ammonia-oxidizing bacteria population. These combined findings demonstrate that the removal of 4CNB in soils by inoculating strain ZWL73 is feasible, and that specific populations in soils rapidly changed in response to 4CNB contamination and subsequent bioaugmentation.     

Acute toxicity, biochemical and gene expression responses of the earthworm Eisenia fetida exposed to polycyclic musks

Phytoremediation is a novel and promising approach for the treatment of pollutants. This study did explore the potential of Aster amellus Linn. to decolorize a sulfonated azo dye Remazol Red (RR), a mixture of dyes and a textile effluent. Induction in the activities of lignin peroxidase, tyrosinase, veratryl alcohol oxidase and riboflavin reductase was observed during RR decolorization, suggesting their involvement in the metabolism of RR. UV-Visible absorption spectrum, HPLC and FTIR analysis confirmed the degradation of RR. Four metabolites after the degradation of the dye were identified as 2-[(3-diazenylphenyl) sulfonyl] ethanesulfonate, 4-amino-5-hydroxynaphthalene-2,7-disulfonate, naphthalene-2-sulfonate and 3-(1,3,5-triazin-2-ylamino)benzenesulfonate by using GC/MS. Textile effluent and mixture of dyes showed 47% and 62% decrease respectively in American Dye Manufacturers Institute value. BOD of textile effluent and mixture of dyes were reduced by 75% and 48% respectively, COD of industrial effluent and mixture of dyes was reduced by 60% and 75% and TOC was reduced by 54% and 69% respectively after the treatment by A. amellus for 60 h; this indicated that the plant can be used for cleaning textile effluents. Toxicity study revealed the phytotransformation of RR into non-toxic products.     

Efficient removal of pollutants from olive washing wastewater in bubble-column bioreactor by Trametes versicolor

The white-rot fungi Panus tigrinus, Funalia trogii and Trametes versicolor have been tested in shake flasks for the reduction of olive washing wastewater (OWW) pollutants and production of oxidases on OWW-based media. P. tigrinus was rejected for its scarce performance. F. trogii showed best production of laccase (27 000 U g⁻¹), while T. versicolor appeared a good pollutant degrader reducing colour, COD and phenols by 60, 72 and 87%, respectively. Only T. versicolor grew well in bubble-column bioreactor: its OWW depollution, in continuous process, led to colour, COD and phenols reduction by 65%, 73% and 89%, respectively. Optimal dilution rate was 0.225 d⁻¹ (0.225 m³ of effluent treated daily per m³ of bioreactor). Thus, a small bioreactor (10 m³) could treat daily the amount of OWW produced by a standard olive washing machine (2 m³ d⁻¹). For these reasons, this process could be proposed as a simple, efficient and low-cost OWW treatment.     

Identification of various laccases induced by anthracene and contribution to its degradation in a Mediterranean coastal pine litter

Mediterranean coastal ecosystems are known to be highly subject to natural and anthropic environmental stress. In this study, we examine the effects of anthracene as a common pollutant on the total microbial communities from a Pinus halepensis litter of a typical Mediterranean coastal site (Les Calanques, Marseille). The main objective was to identify the microbial factors leading the resilience of this ecosystem. Two questions were addressed: (i) how lignin-degrading enzymes (Laccase, Lignin-peroxidase and Mn-peroxidase) are affected by the presence of this molecule, (ii) whether the indigenous consortia are involved in its degradation in mesocosms under favorable incubation conditions (25 °C, 60% WHC) and after different time intervals (1 and 3 month(s)). We found a strong increase in laccase production in the presence of anthracene after 3 months, together with anthracene degradation (28% ± 5). Moreover 9,10-anthraquinone is detected as the product of anthracene oxidation after 3 months. However neither lignin-peroxidase activity nor Mn-peroxidase activity is detected. Laccase proteins directly extracted from litter were sequenced via Nano-LC-MS/MS and reveal twelve different peptide sequences induced by the presence of anthracene in the mesocoms. Our study confirms the major detoxification role of this enzymatic system and highlights the high degradation potential of fungal species inhabiting P. halepensis litter, a factor in the resilience of Mediterranean ecosystems.     

Behavior of decabromodiphenyl ether (BDE-209) in soil: effects of rhizosphere and mycorrhizal colonization of ryegrass roots

A rhizobox experiment was conducted to investigate degradation of decabromodiphenyl ether (BDE-209) in the rhizosphere of ryegrass and the influence of root colonization with an arbuscular mycorrhizal (AM) fungus. BDE-209 dissipation in soil varied with its proximity to the roots and was enhanced by AM inoculation. A negative correlation (P < 0.001, R² = 0.66) was found between the residual BDE-209 concentration in soil and soil microbial biomass estimated as the total phospholipid fatty acids, suggesting a contribution of microbial degradation to BDE-209 dissipation. Twelve and twenty-four lower brominated PBDEs were detected in soil and plant samples, respectively, with a higher proportion of di- through hepta-BDE congeners in the plant tissues than in the soils, indicating the occurrence of BDE-209 debromination in the soil-plant system. AM inoculation increased the levels of lower brominated PBDEs in ryegrass. These results provide important information about the behavior of BDE-209 in the soil-plant system.     

Suitability of different salt marsh plants for petroleum hydrocarbons remediation

The suitability of the salt-marsh species Halimione portulacoides, Scirpus maritimus, Juncus maritimus and an association of the last two for remediation of petroleum hydrocarbons (PHC) in soil was investigated. An outdoor laboratory experiment (microcosm-scale) was carried out using contaminated soil collected in a refinery, as a complement of another study carried out in the refinery environment (mesocosm-scale). Soil samples with old contamination (mainly crude oil) and with a mixture of the old and recent (turbine oil) contamination were tested. Studies in both micro- and mesocosm-scale provided results coherent in substance. The presence of S. maritimus caused removal of old contamination which was refractory to natural attenuation (after 7 months of exposure, efficiency was 13% when only old contamination was present and 40% when the soil also contained recent contamination). H. portulacoides (only included in the microcosm-scale study) revealed also potentiality for PHC remediation, although with less efficiency than S. maritimus. Degradation of recent contamination was also faster in the presence of plants (after 7 months: 100% in the presence of S. maritimus vs. 63% in its absence). As these species are common in salt marsh areas in Atlantic coast of Europe, it is probable they will be also useful for recovering coast sediments. In contrast, J. maritimus and association did not reveal capability to remove PHC from soil, the presence of J. maritimus inhibiting the capability of S. maritimus.     

Bioremediation of tributyltin contaminated sediment: degradation enhancement and improvement of bioavailability to promote treatment processes

Bioremediation of tributyltin (TBT) contaminated sediment was studied and degradation enhancement and improvement of bioavailability were also investigated. In TBT spiked sediment, the half-life of TBT in the control sample, representing natural attenuation, was 578 d indicating its persistence. In the stimulated sample (pH 7.5, aeration and incubated at 28 °C), the half-life was significantly reduced to 11 d. Further stimulation by nutrient addition (succinate, glycerol and l-arginine) or inoculation with Enterobacter cloacae (∼10⁷ viable cells g⁻¹ of sediment) resulted in half-life reduction to 9 and 10 d, respectively. In non-spiked sediment, the indigenous microorganisms were able to degrade aged TBT, but the extended period of contamination decreased the degradation efficiency. To improve bioavailability, addition of surfactant, adjustment of salinity and sonication were studied. The highest percentage solubilisation of TBT in water was obtained by adjusting salinity to 20 psu, which increased the solubility of TBT from 13% to 33%. Half-lives after bioavailability was improved were 5, 4 and 4 d for stimulation, stimulation w/nutrient addition and stimulation w/inoculation, respectively. However, natural attenuation in the control sample was not enhanced. The results show that providing suitable conditions is important in enhancing TBT biodegradation, and bioavailability improvement additionally increased the rate and degraded amount of TBT. Unfortunately, nutrient addition and inoculation of the degrader did not enhance the degradation appreciably.     

Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

A rapid bioassay for detecting saxitoxins using a Daphnia acute toxicity test

Bioassays using Daphnia pulex and Moina micrura were designed to detect cyanobacterial neurotoxins in raw water samples. Phytoplankton and cyanotoxins from seston were analyzed during 15 months in a eutrophic reservoir. Effective time to immobilize 50% of the exposed individuals (ET₅₀) was adopted as the endpoint. Paralysis of swimming movements was observed between ∼0.5-3 h of exposure to lake water containing toxic cyanobacteria, followed by an almost complete recovery of the swimming activity within 24 h after being placed in control water. The same effects were observed in bioassays with a saxitoxin-producer strain of Cylindrospermopsis raciborskii isolated from the reservoir. Regression analysis showed significant relationships between ET₅₀vs. cell density, biomass and saxitoxins content, suggesting that the paralysis of Daphnia in lake water samples was caused by saxitoxins found in C. raciborskii. Daphnia bioassay was found to be a sensitive method for detecting fast-acting neurotoxins in natural samples, with important advantages over mouse bioassays.