Biodegradation of atrazine by Rhodococcus sp. BCH2 to N-isopropylammelide with subsequent assessment of toxicity of biodegraded metabolites

Atrazine is a persistent organic pollutant in the environment which affects not only terrestrial and aquatic biota but also human health. Since its removal from the environment is needed, atrazine biodegradation is achieved in the present study using the bacterium Rhodococcus sp. BCH2 isolated from soil, long-term treated with atrazine. The bacterium was capable of degrading about 75 % atrazine in liquid medium having pH 7 under aerobic and dark condition within 7 days. The degradation ability of the bacterium at various temperatures (20–60 °C), pH (range 3–11), carbon (glucose, fructose, sucrose, starch, lactose, and maltose), and nitrogen (ammonium molybdate, sodium nitrate, potassium nitrate, and urea) sources were studied for triumph optimum atrazine degradation. The results indicate that atrazine degradation at higher concentrations (100 ppm) was pH and temperature dependent. However, glucose and potassium nitrate were optimum carbon and nitrogen source, respectively. Atrazine biodegradation analysis was carried out by using high-performance thin-layer chromatography (HPTLC), Fourier transform infrared spectroscopy (FTIR), and liquid chromatography quadrupole time-of-flight (LC/Q-TOF-MS) techniques. LC/Q-TOF-MS analysis revealed formation of various intermediate metabolites including hydroxyatrazine, N-isopropylammelide, deisopropylhydroxyatrazine, deethylatrazine, deisopropylatrazine, and deisopropyldeethylatrazine which was helpful to propose biochemical degradation pathway of atrazine. Furthermore, the toxicological studies of atrazine and its biodegraded metabolites were executed on earthworm Eisenia foetida as a model organism with respect to enzymatic (SOD and Catalase) antioxidant defense mechanism and lipid peroxidation studies. These results suggest innocuous degradation of atrazine by Rhodococcus sp. BCH2 in nontoxic form. Therefore the Rhodococcus sp.BCH2 could prove a valuable source for the eco-friendly biodegradation of atrazine pesticide.     

The integrated biomarker response revisited: optimization to avoid misuse

The growing need to evaluate the quality of aquatic ecosystems led to the development of numerous monitoring tools. Among them, the development of biomarker-based procedures, that combine precocity and relevance, is recommended. However, multi-biomarker approaches are often hard to interpret, and produce results that are not easy to integrate in the environmental policies framework. Integrative index have been developed, and one of the most used is the integrated biomarker response (IBR). However, an analysis of available literature demonstrated that the IBR suffers from a frequent misuse and a bias in its calculation. Then, we propose here a new calculation method based on both a more simple formula and a permutation procedure. Together, these improvements should rightly avoid the misuse and bias that were recorded. Additionally, a case study illustrates how the new procedure enabled to perform a reliable classification of site along a pollution gradient based on biomarker responses used in the IBR calculations.     

Use of hairy roots extracts for 2,4-DCP removal and toxicity evaluation by Lactuca sativa test

2,4-Dichlorophenol (2,4-DCP) is widely distributed in wastewaters discharged from several industries, and it is considered as a priority pollutant due to its high toxicity. In this study, the use of different peroxidase extracts for 2,4-DCP removal from aqueous solutions was investigated. Tobacco hairy roots (HRs), wild-type (WT), and double-transgenic (DT) for tomato basic peroxidases (TPX1 and TPX2) were used to obtain different peroxidase extracts: total peroxidases (TPx), soluble peroxidases (SPx), and peroxidases ionically bound to the cell wall (IBPx). All extracts derived from DT HRs exhibited higher peroxidase activity than those obtained from WT HRs. TPx and IBPx DT extracts showed the highest catalytic efficiency values. The optimal conditions for 2,4-DCP oxidation were pH 6.5, H₂O₂ 0.5 mM, and 200 U mL^?1 of enzyme, for all extracts analyzed. Although both TPx extracts were able to oxidize different 2,4-DCP concentrations, the removal efficiency was higher for TPx DT. Polyethylene glycol addition slightly improved 2,4-DCP removal efficiency, and it showed some protective effect on TPx WT after 2,4-DCP oxidation. In addition, using Lactuca sativa test, a reduction of the toxicity of post removal solutions was observed, for both TPx extracts. The results demonstrate that TPx extracts from both tobacco HRs appear to be promising candidate for future applications in removing 2,4-DCP from wastewaters. This is particularly true considering that these peroxidase sources are associated with low costs and are readily available. However, TPx DT has increased peroxidase activity, catalytic efficiency, and higher removal efficiency than TPx WT, probably due to the expression of TPX1 and TPX2 isoenzymes.     

Solubilization of municipal sewage waste activated sludge by novel lytic bacterial strains

Extracellular polymeric substances (EPS) are an extracellular matrix found in sludge which plays a crucial role in flocculation by interacting with the organic solids. Therefore, to enhance pretreatment of sludge, EPS have to be removed. In this study, EPS were removed with a chemical extractant, NaOH, to enhance the bacterial pretreatment. A lysozyme secreting bacterial consortium was isolated from the waste activated sludge (WAS). The result of density gradient gel electrophoresis (DGGE) analysis revealed that the isolated consortium consists of two strains. The two novel strains isolated were named as Jerish03 (NCBI accession number KC597266) and Jerish 04 (NCBI accession number KC597267) and they belong to the genus Bacillus. Pretreatment with these novel strains enhances the efficiency of the aerobic digestion of sludge. Sludge treated with the lysozyme secreting bacterial consortium produced 29 % and 28.5 % increase in suspended solids (SS) reduction and chemical oxygen demand (COD) removal compared to the raw activated sludge (without pretreatment) during aerobic digestion. It is specified that these two novel strains had a high potential to enhance WAS degradation efficiency in aerobic digestion.     

Bages-Sigean and Canet-St Nazaire lagoons (France): physico-chemical characteristics and contaminant concentrations (Cu,Cd, PCBs and PBDEs) as environmental quality of water and sediment

Environmental characteristics in water and sediments of two contrasted coastal Mediterranean lagoons, Bages-Sigean and Canet-St Nazaire, were measured over a three season survey. The urban pollution (treatment plant discharges) is very important in Canet-St Nazaire lagoon reflecting untreated sewages, while in Bages-Sigean, the northern part appears more impacted due to larger anthropogenic inputs. Dissolved Cd concentrations are on the whole similar in both lagoons, whereas Cu concentrations are by far higher in lagoon Canet-St Nazaire. Cu concentrations appear to be highly dependent on dissolved organic carbon whereas salinity seems to control Cd variations. Concerning the sediments, the confined northern part of lagoon Bages-Sigean shows organic carbon and total nitrogen enrichment whereas lipid concentrations are much higher in the Canet-St Nazaire lagoon. Cu complexation seems to be strongly related to organic matter as evidenced by the two significant positive relationships, on one hand between Cu and organic carbon, and on the other hand, between Cu and lipids. On the contrary, Cd concentrations appear to be mainly controlled by carbonates. PCBs and PBDEs were detected only in sediments and show relatively low concentrations compared to similar lagoon environments. Regarding the sediment quality guidelines, Cd, Cu and PCBs in both lagoons did not exceed any Probable Effect Concentration (PEC).     

Increased bioavailability of metals in two contrasting agricultural soils treated with waste wood-derived biochar and ash

Recycled waste wood is being increasingly used for energy production; however, organic and metal contaminants in by-products produced from the combustion/pyrolysis residue may pose a significant environmental risk if they are disposed of to land. Here we conducted a study to evaluate if highly polluted biochar (from pyrolysis) and ash (from incineration) derived from Cu-based preservative-treated wood led to different metal (e.g., Cu, As, Ni, Cd, Pb, and Zn) bioavailability and accumulation in sunflower (Helianthus annuus L.). In a pot experiment, biochar at a common rate of 2 % w/w, corresponding to ～50 t ha^?1, and an equivalent pre-combustion dose of wood ash (0.2 % w/w) were added to a Eutric Cambisol (pH 6.02) and a Haplic Podzol (pH 4.95), respectively. Both amendments initially raised soil pH, although this effect was relatively short-term, with pH returning close to the unamended control within about 7 weeks. The addition of both amendments resulted in an exceedance of soil Cu statutory limit, together with a significant increase of Cu and plant nutrient (e.g., K) bioavailability. The metal-sorbing capacity of the biochar, and the temporary increase in soil pH caused by adding the ash and biochar were insufficient to offset the amount of free metal released into solution. Sunflower plants were negatively affected by the addition of metal-treated wood-derived biochar and led to elevated concentration of metals in plant tissue, and reduced above- and below-ground biomass, while sunflower did not grow at all in the Haplic Podzol. Biochar and ash derived from wood treated with Cu-based preservatives can lead to extremely high Cu concentrations in soil and negatively affect plant growth. Identifying sources of contaminated wood in waste stream feedstocks is crucial before large-scale application of biochar or wood ash to soil is considered.     

Nutrient and enzymatic changes of hydrolysed tannery solid waste treated with epigeic earthworm Eudrilus eugeniae and phytotoxicity assessment on selected commercial crops

Animal fleshing (ANFL) is the predominant proteinaceous solid waste generated during processing of leather and it is confronting disposal problems. The aim of this study was to assess the potential of epigeic earthworm Eudrilus eugeniae to utilize and transform the fermented ANFL in the solid state (SSF) and submerged state (SmF) into a value added product along a low residence period (25 days). A total of six treatment units containing different waste mixture compositions were established. Fifty healthy and non-clitellated earthworms were introduced in three different treatment containers: control, SSF, and SmF (+worm). Another set of treatment mixtures (control, SSF, SmF) was established without earthworms (?worm) to compare the results. The products were characterized for physico-chemical, enzymatic analysis and seedling growth parameters to compare the differences in the process with and without earthworms. The changes observed in the analytical parameters were in the following order: SSF > SmF > control mixtures (p?<?0.05). The vermicompost showed a significant reduction in heavy metals, total organic carbon and an increase in total Kjeldhal nitrogen as compared to the product untreated by earthworms. The maximum enzymatic activities were observed after 21 days of vermicomposting. The relative seed germination of vermicompost extracts were in the order of tomato (Lycopersicon esculentum) > green gram (Vigna radiata) > cucumber (Cucumis sativus) > bottle gourd (Lagenaria siceraria (Mol.) Standl.) and showed no phytotoxicity effects. The results indicated that the combination of both ANFL hydrolysis through fermentation and vermicomposting is a good alternative to the management of this kind of waste.     

Green synthesis of silver nanoparticles by microorganism using organic pollutant: its antimicrobial and catalytic application

A novel approach for the green synthesis of silver nanoparticles (AgNPs) from aqueous solution of AgNO₃ using culture supernatant of phenol degraded broth is reported in this work. The synthesis was observed within 10 h, and AgNPs showed characteristic surface plasmon resonance around 410 nm. Spherical nanoparticles of size less than 30 nm were observed in transmission electron microscopy. X-ray diffraction pattern corresponding to 111, 200, 220, and 311 revealed the crystalline nature of the as-formed nanoparticles. It was found that the colloidal solution of AgNP suspensions exhibited excellent stability over a wide range of ionic strength, pH, and temperature. The effect of pH and ionic strength indicated that stabilization is due to electrostatic repulsion arising from the negative charge of the conjugate proteins. The AgNPs showed highly potent antimicrobial activity against Gram-positive, Gram-negative, and fungal microorganisms. The as-prepared AgNPs showed excellent catalytic activity in reduction of 4-nitrophenol to 4-aminophenol by NaBH₄. By manufacturing magnetic alginate beads, the reusability of the AgNPs for the catalytic reaction has been demonstrated.     

Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

Marine organisms as heavy metal bioindicators in the Persian Gulf and the Gulf of Oman

In the present study, cadmium and lead concentrations were compared in barnacles, ghost shrimps, polychaetes, bivalves, and sediment from ten different locations along the intertidal zone of the Persian Gulf and the Gulf of Oman. The results revealed significant differences in the heavy metal concentrations between the organisms with barnacles showing, by far, the highest metal concentrations. The bioaccumulation factor of Cd in different animals follows this pattern with barnacles?>?bivalves?>?polychaetes?>?ghost shrimps, while the pattern for Pb was barnacles?>?polychaetes?>?bivalves?>?ghost shrimps. In most of the stations, sediments showed the lowest lead and cadmium concentrations. Therefore, it is concluded that barnacles with Pb concentrations between 0.17 and 2,016.1 μg/g and Cd concentrations ranging from 0.4 to 147.1 μg/g are the best organisms to be employed in monitoring programs designed to assess pollution with bioavailable metals in the Persian Gulf and the Gulf of Oman.