Acute toxicity and ecotoxicological risk assessment of rice pesticides to Lithobates catesbeianus tadpoles

The objective of this study was to determine the acute toxicity of some pesticides used in irrigated rice farming to Lithobates catesbeianus tadpoles. The LC_50-96h for commercial formulations containing bentazon, penoxsulam, vegetable oil, permethrin and carbofuran, separately and their mixtures, were determined at the proportions commonly used in the field. The limits of risk concentrations of these products for the studied species were also established. The LC_50-96h for tadpoles was 4,530 mg L^?1 for bentazon; 7.52 mg L^?1 for penoxsulam + 145.66 mg L^?1 of vegetable oil; 81.57 mg L^?1 for vegetable oil; 0.10 mg L^?1 for permethrin; 29.90 mg L^?1 for carbofuran (active ingredients), and 38.79 times the dose used in the field for the mixture of these products. The environmental risk was determined only for permethrin, and care should be taken when using the vegetable oil.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Residues of carbosulfan and its metabolites carbofuran and 3-hydroxy carbofuran in rice field ecosystem in China

The fate of carbosulfan (seed treatment dry powder) was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of carbosulfan, carbofuran, and 3-hydroxyl carbofuran in brown rice, rice straw, paddy water, and soil. The target compounds were extracted using acetonitrile or dichloromethane, cleaned up on acidic alumina or florisil solid phase extraction (SPE) cartridge, and analyzed by gas chromatography. The average recoveries of carbosulfan, carbofuran and 3-hydroxy carbofuran in brown rice, rice straw, paddy water, and soil ranged from 72.71% to 105.07%, with relative standard deviations of 2.00–8.80%. The limits of quantitation (LOQs) of carbosulfan, carbofuran and 3-hydroxy carbofuran in the samples (brown rice, rice straw, paddy water and soil) were 0.011, 0.0091, 0.014, 0.010 mg kg^?1, 0.016, 0.019, 0.025, 0.013 mg kg^?1, and 0.031, 0.039, 0.035, 0.036 mg kg^?1, respectively. The trials results showed that the half-lives of carbosulfan, carbofuran and 3-hydroxy carbofuran in rice straw were 4.0, 2.6 days, 3.9, 6.0 days, and 5.8, 7.0 days in Zhejiang and Hunan, respectively. Carbosulfan, carbofuran and 3-hydroxy carbofuran were detected in soils. Carbosulfan and 3-hydroxy carbofuran were almost undetectable in paddy water. Carbofuran was detected in paddy water. The final residues of carbosulfan, carbofuran and 3-hydroxy carbofuran in brown rice were lower than 0.05 mg kg^?1, which were lower than 0.5 mg kg^?1 (MRL of carbosulfan) or 0.1 mg kg^?1 (MRL of carbofuran). Therefore, a dosage of 420 g active ingredient per 100 kg seed was recommended, which could be considered as safe to human beings and animals. These would contribute to provide the scientific basis of using this insecticide.     

Tea bag filter paper as a novel protective membrane for micro-solid phase extraction of butachlor in aqueous samples

An innovative, cost-effective, simple, and environmental friendly tea bag filter paper protected micro-solid phase extraction (μ-SPE) technique was developed for the first time with the aim to miniaturize and minimize the use of organic solvents for the extraction and determination of butachlor in aqueous samples. The μ-SPE device was produced by packing 3.0 mg of an easily synthesized new sorbent, hydroxyl-functionalized polypyrrole (OH-PPY), inside a small tea bag filter paper sachet (1.0 cm × 0.5 cm) that served as a protective envelope. Both the extraction and desorption procedures were facilitated by sonication. Due to the high porosity and the fast water absorption of the tea bag filter paper, the analyte could easily diffuse through and enhance the interaction with the sorbent. Under the optimized conditions for the GC-ECD and the μ-SPE, the limit of detection (S/N ≥ 3) was 2.0 μg L^?1 while the limit of quantitation (S/N ≥ 10) was 10.0 μg L^?1. The recoveries of the butachlor spiked at 0.050, 0.10, and 0.50 μg mL^?1 ranged from 77.9 ± 3.0 to 112.5 ± 2.9%. The proposed method was successfully applied for the determination of butachlor in water samples from paddy cultivation sites. The levels found were from non-detectable to 24.71 ± 0.37 μg L^?1.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Comparative analysis of trace contaminants in leachates before and after a pre-oxidation using a solar photo-Fenton reaction

Sanitary landfill leachates are a complex mixture of high-strength organic and inorganic persistent contaminants, which constitute a serious environmental problem. In this study, trace contaminants present in leachates were investigated by gas chromatography-mass spectrometry and gas chromatography-flame ionization detector before and after a pre-oxidation step using a solar photo-Fenton process. More than 40 organic compounds were detected and identified as benzene (0.09?±?0.07 mg?L^-1), trichlorophenol (TCP) (0.18?±?0.12 mg?L^-1), phthalate esters (Di-n-butyl phthalate (DBP), Butyl benzyl phthalate (BBP), Di(2-ethylhexyl) phthalate (DEHP)) (DBP: 0.47?±?0.01 mg?L^-1; BBP: 0.36?±?0.02 mg?L^-1; DEHP: 0.18?±?0.01 mg?L^-1), among others. Toluene, pentachlorophenol, dimethyl phthalate, diethyl phthalate, and Di-n-octyl phthalate were never detected in any of the samples. After the photo-Fenton treatment process, TCP decreased to levels below its detection limit, benzene concentration increased approximately three times, and DBP concentration decreased about 77 % comparatively to the raw leachate sample. The solar photo-Fenton process was considered to be very efficient for the treatment of sanitary landfill leachates, leading to the complete elimination of 24 of the detected micropollutants to levels below their respective detection limits and low to significant abatement of seven other organic compounds, thus resulting in an increase of the leachate biodegradability.     

Biodegradation of triazine herbicide metribuzin by the strain Bacillus sp. N1

By enrichment culturing of soil contaminated with metribuzin, a highly efficient metribuzin degrading bacterium, Bacillus sp. N1, was isolated. This strain grows using metribuzin at 5.0% (v/v) as the sole nitrogen source in a liquid medium. Optimal metribuzin degradation occurred at a temperature of 30ºC and at pH 7.0. With an initial concentration of 20 mg L^?1, the degradation rate was 73.5% in 120 h. If the initial concentrations were higher than 50 mg L^?1, the biodegradation rates decreased as the metribuzin concentrations increased. When the concentration was 100 mg L^?1, the degradation rate was only 45%. Degradation followed the pesticide degradation kinetic equation at initial concentrations between 5 mg L^?1 and 50 mg L^?1. When the metribuzin contaminated soil was mixed with strain N1 (with the concentration of metribuzin being 20 mg L^?1 and the inoculation rate of 10¹¹ g^?1 dry soil), the degradation rate of the metribuzin was 66.4% in 30 days, while the degradation rate of metribuzin was only 19.4% in the control soil without the strain N1. These results indicate that the strain N1 can significantly increase the degradation rate of metribuzin in contaminated soil.     

Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization,rate-constant determination and carbofuran degradation pathway analysis

Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO₂) catalyst was investigated. The effects of feed flow rate, TiO₂ concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO₂ concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO₂ concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R² ～ 0.964). The addition of 1 mL min^?1 hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ～50 mg L^?1, TiO₂ ～5 mg L^?1 and feed flow rate ～82.5 mL min^?1. Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO₂ catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Effect of the pesticide lindane on the biomass of the microalgae Nannochloris oculata

This study assesses the growth of the microalgae Nannochloris oculata in the presence of lindane and the ability of N. oculata to remove lindane from media. Algal biomass increased with 0.1 and 0.5 mg L^?1 of lindane, and lindane concentrations in the media decreased. N. oculata removed 73% and 68.2% of lindane in the 0.1 and 0.5 mg L^?1 media concentrations, respectively. Algal biomass decreased to the level of the control at lindane concentrations greater than 2.5 mg L^?1, probably due to toxicity. N. oculata removed lindane from the media at concentrations lower than 1.0 mg L^?1. Thus, N. oculata may be useful for lindane bioremediation in contaminated aquatic systems.     

Influence of long-term consumption of bitter apricot seeds on risk factors for cardiovascular diseases

The present study was designed to reveal whether long-term consumption of bitter apricot seeds causes changes in lipid profile and other risk factors for cardiovascular diseases. The study group consisted of 12 healthy adult volunteers (5 females and 7 males). The average age of women was 41.60 ± 11.28 years and the average age of men was 36.71 ± 13.70 years. Volunteers consumed 60 mg kg^?1 of body weight of bitter apricot seeds divided into 8–12 doses daily for 12 weeks. Volunteers were recruited from the general population of Slovak Republic. After 12 weeks, mean body weight of the participants increased from 77.34 to 78.22 kg (P > 0.05). The average total cholesterol levels decreased from 4.86 mmol L^?1 at the beginning of the study to 4.44 mmol L^?1 at the end of the study (P < 0.05). We did not observe any significant increase in high-density cholesterol (from 1.55 to 1.60 mmol L^?1). The average low-density cholesterol levels decreased from 2.93 mmol L^?1 at the beginning of the study to 2.31 mmol L^?1 at the end of the study (P < 0.001). Concentration of triglycerides increased significantly over the 12-week intervention period from 0.84 to 1.17 mmol L^?1. After the intervention, the high-sensitivity C-reactive protein level decreased from 1.92 to 1.23 mg L^?1, but results were non-significant (P > 0.05). Creatine kinase serum levels increased from 2.31 to 2.77 mg L^?1 (P > 0.05) over the 12-week intervention period. The results suggest that regular intake of bitter apricot seeds may be considered potentially useful for prevention of cardiovascular diseases.     

Toxicity of mancozeb,chlorothalonil, captan,fluopyram, boscalid,and difenoconazole to Didymella applanata isolates from Serbia

Field isolates of Didymella applanata, the causal agent of spur blight of raspberry, were evaluated in vitro for their sensitivity to mancozeb, chlorothalonil, captan, fluopyram, boscalid and difenoconazole. A total of 10 isolates, collected during 2013 at five localities in the major raspberry growing region in Serbia, and characterized as copper hydroxide, dithianon, and tebuconazole (sensitive), pyraclostrobin (sensitive or highly resistant) and fluazinam (sensitive or moderately resistant), were used in this study. The EC₅₀ values for the isolates ranged from 1.33 to 2.88 mg L^?1 for mancozeb, from 3.18 to 6.65 mg L^?1 for chlorothalonil, from 15.75 to 24.69 mg L^?1 for captan and from 1.80 to 8.20 mg L^?1 for fluopyram. The narrowest range of EC₅₀ values was recorded for difenoconazole (0.23–0.49 mg L^?1), whereas the widest range was obtained for boscalid (4.49–49.25 mg L^?1). The calculated resistance factors showed that all D. applanata isolates were sensitive to mancozeb, chlorothalonil, captan, and difenoconazole. Four isolates were moderately resistant to boscalid, while three of them were also moderately resistant to fluopyram. This finding of moderately resistant isolates to these SDHI fungicides indicates a possible cross-resistance which should be clarified in further investigations.     

Understanding the patterns and mechanisms of urban water ecosystem degradation: phytoplankton community structure and water quality in the Qinhuai River, Nanjing City, China

The temporal and spatial distribution characteristics of environmental parameters and the phytoplankton community were investigated in October 2010 and January 2011 in the Qinhuai River, Nanjing, China. Results showed that the water quality in the study area was generally poor, and the main parameters exceeding standards (level V) were nitrogen and phosphorus. The observed average concentrations of the total nitrogen (TN) were 4.90 mg?L^?1 in autumn and 9.29 mg?L^?1 in winter, and those of the total phosphorus (TP) were 0.24 mg?L^?1 in autumn and 0.88 mg?L^?1 in winter, respectively. Thirty-seven species, 30 genera, and four phyla of phytoplankton were detected in the river. Cyanophyta and Bacillariophyta were the dominant phyla in autumn, with average abundance and biomass of 221.5?×?10⁴?cells?L^?1 and 4.41 mg?L^?1, respectively. The dominant population in winter was Bacillariophyta, and the average abundance and biomass were 153.4?×?10⁴?cells?L^?1 and 6.58 mg?L^?1, respectively. The results of canonical correspondence analysis (CCA) between environmental parameters and phytoplankton communities showed that Chlorophyta could tolerate the higher concentrations of the permanganate index, nitrogen, and phosphorus in eutrophic water; Bacillariophyta could adapt well to changing water environments; and the TN/TP ratio had obvious impacts on the distributions of Cyanophyta, Euglenophyta, and some species of Chlorophyta. CCA analyses for autumn and winter data revealed that the main environmental parameters influencing phytoplankton distribution were water temperature, conductivity, and total nitrogen, and the secondary factors were dissolved oxygen, NH₄ ⁺–N, NO₃–N, TN, COD_Mn, TN/TP ratio, and oxidation-reduction potential.     

Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01–2 mg L^?1, with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg^?1, with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg^?1.     

Preliminary toxicological assessment of phthalate esters from drinking water consumed in Portugal

This paper reports, for the first time, the concentrations of selected phthalates in drinking water consumed in Portugal. The use of bottled water in Portugal has increased in recent years. The main material for bottles is polyethylene terephthalate (PET). Its plasticizer components can contaminate water by leaching, and several scientific studies have evidenced potential health risks of phthalates to humans of all ages. With water being one of the most essential elements to human health and because it is consumed by ingestion, the evaluation of drinking water quality, with respect to phthalate contents, is important. This study tested seven commercial brands of bottled water consumed in Portugal, six PET and one glass (the most consumed) bottled water. Furthermore, tap water from Lisbon and three small neighbor cities was analyzed. Phthalates (di-n-butyl phthalate ester (DnBP), bis(2-ethylhexyl) phthalate ester (DEHP), and di-i-butyl phthalate ester (DIBP)) in water samples were quantified (PET and glass) by means of direct immersion solid-phase microextraction and ionic liquid gas chromatography associated with flame ionization detection or mass spectrometry due to their high boiling points and water solubility. The method utilized in this study showed a linear range for target phthalates between 0.02 and 6.5 μg L^?1, good precision and low limits of detection that were between 0.01 and 0.06 μg L^?1, and quantitation between 0.04 and 0.19 μg L^?1. Only three phthalates were detected in Portuguese drinking waters: dibutyl (DnBP), diisobutyl (DIBP), and di(ethylhexyl) phthalate (DEHP). Concentrations ranged between 0.06 and 6.5 μg L^?1 for DnBP, between 0.02 and 0.16 μg L^?1 for DEHP, and between 0.1 and 1.89 μg L^?1 for DIBP. The concentration of DEHP was found to be up to five times higher in PET than in glass bottled water. Surprisingly, all the three phthalates were detected in glass bottled water with the amount of DnBP being higher (6.5 μg L^?1) than in PET bottled water. These concentrations do not represent direct risk to human health. Regarding potable tap water, only DIBP and DEHP were detected. Two of the cities showed concentration of all three phthalates in their water below the limits of detection of the method. All the samples showed phthalate concentrations below 6 μg L^?1, the maximum admissible concentration in water established by the US Environmental Protection Agency. The concentrations measured in Portuguese bottled waters do not represent any risk for adult's health.     

Assessment of Organochlorine Pesticide Residues in Water,Sediment, and Fish of the Songhua River,China

This study examined residual concentrations and associated ecological risks of the organochlorine pesticides (OCPs) hexa- chlorocyclohexane (HCH) and dichloro-diphenyl-trichloroethane (DDT) in water, sediment, and fish of the Songhua River in Zhaoyuan County, China. In June 2012, 10 water, 10 sediment, and 20 fish samples were collected. Residual concentrations of ΣHCH and ΣDDT ranged from 10.0–35.59 ng L^?1 (mean 28.03 ± 11.66 ng L^?1) and 5.12–39.66 ng L^?1 (mean 32.36 ± 11.58 ng L^?1) for water. Residual concentrations of ΣHCH and ΣDDT ranged from 0.52–3.00 ng g^?1 (mean 2.04 ± 0.73 ng g^?1) and 0.34–3.41 ng g^?1 (mean 2.38 ± 0.92 ng g^?1) for sediment. The ratios of α-HCH/γ-HCH were close to 1 at the majority of sampling points, indicating considerable new pollution from the use of lindane. The ratios of p,p′-DDE + p,p′-DDD/ΣDDT were less than 0.5, indicating recent inputs from DDT impurities in dicofol. All HCH and DDT isomers except for p,p′-DDD were detected in fish tissue samples, but the associated ecological risks were estimated to be below levels of concern. The study revealed a historical usage of OCPs in the Zhaoyuan section of the Songhua River and new OCP from the use of lindane and dicofol.     

Acute and chronic ecotoxicity of carbaryl with a battery of aquatic bioassays

The ecotoxic effects of carbaryl (carbamate insecticide) were investigated with a battery of four aquatic bioassays. The nominal effective concentrations immobilizing 50% of Daphnia magna (EC50) after 24 and 48 h were 12.76 and 7.47 µg L^?1, respectively. After 21 days of exposure of D. magna, LOECs (lowest observed effect concentrations) for cumulative molts and the number of neonates per surviving adult were observed at carbaryl concentration of 0.4 µg L^?1. An increase of embryo deformities (curved or unextended shell spines) was observed at 1.8 and 3.7 µg L^?1, revealing that carbaryl could act as an endocrine disruptor in D. magna. Other bioassays of the tested battery were less sensitive: the IC50-72h and IC10-72h of the algae Pseudokirchneriella subcapitata were 5.96 and 2.87 mg L^?1, respectively. The LC50-6d of the ostracod Heterocypris incongruens was 4.84 mg L^?1. A growth inhibition of H. incongruens was registered after carbaryl exposure and the IC20-6d was 1.29 mg L^?1. Our results suggest that the daphnid test sensitivity was better than other used tests. Moreover, carbaryl has harmful and toxic effects on tested species because it acts at low concentrations on diverse life history traits of species and induce embryo deformities in crustaceans.     

Insights into real cotton-textile dyeing wastewater treatment using solar advanced oxidation processes

Different advanced oxidation processes (AOPs) were applied to the treatment of a real cotton-textile dyeing wastewater as a pre-oxidation step to enhance the biodegradability of the recalcitrant compounds, which can be further oxidized using a biological process. Tests were conducted on a lab-scale prototype using artificial solar radiation and at pilot scale with compound parabolic collectors using natural solar radiation. The cotton-textile dyeing wastewater presents a lilac color, with a maximum absorbance peak at 641 nm, alkaline pH (pH?=?8.2), moderate organic content (DOC?=?152 mg C L^?1, COD?=?684 mg O₂ L^?1) and low-moderate biodegradability (40 % after 28 days in Zahn–Wellens test). All the tested processes contributed to an effective decolorization and mineralization, but the most efficient process was the solar-photo-Fenton with an optimum catalyst concentration of 60 mg Fe²⁺ L^?1, leading to 98.5 % decolorization and 85.5 % mineralization after less than 0.1 and 5.8 kJ_UV L^?1, respectively. In order to achieve a final wastewater with a COD below 250 mg O₂ L^?1 (discharge limit into water bodies imposed by the Portuguese Legislation-Portaria no. 423/97 of 25 June 1997), considering the combination of a solar-photo-Fenton reaction with a biological process, the phototreatment energy required is 0.5 kJ_UV L^?1, consuming 7.5 mM hydrogen peroxide, resulting in 58.4 % of mineralization $ \left({t}_{30\mathrm{W}}=3.2\ \min; \overline{T}=30.7\ {}^{\circ}\mathrm{C};\overline{\mathrm{pH}}=2.80;{\overline{\mathrm{UV}}}_{G,n}={13\ \mathrm{W}\ \mathrm{m}}^{-2}\right). $      

Biodegradation of imidacloprid in liquid media by an isolated wastewater fungus Aspergillus terreus YESM3

In the present study, a new fungal strain capable of imidacloprid degradation was isolated from agricultural wastewater drain. The fungal strain of YESM3 was identified as Aspergillus terreus based on ITS1-5.8S rDNA-ITS2 gene sequence by PCR amplification of a 500 bp sequence. Screening of A. terreus YESM3 to the insecticide imidacloprid tolerance was achieved by growing fungus in Czapek Dox agar for 6 days at 28°C. High values (1.13 and 0.94 cm cm^?1) of tolerance index (TI) were recorded at 25 and 50 mg L^?1 of imidacloprid, respectively in the presence and absence of sucrose. However, at 400 mg L^?1 the fungus did not grow. Effects of the imidacloprid concentration, pH, and inoculum size on the biodegradation percentage were tested using Box–Behnken statistical design and the biodegradation was monitored by HPLC analysis at different time intervals. Box–Behnken results indicated that optimal conditions for biodegradation were at pH 4 and two fungal discs (10 mm diameter) in the presence of 61.2 mg L^?1 of imidacloprid. A. terreus YESM3 strain was capable of degrading 85% of imidacloprid 25 mg L^?1 in Czapek Dox broth medium at pH 4 and 28°C for 6 days under static conditions. In addition, after 20 days of inoculation, biodegradation recorded 96.23% of 25 mg L^?1 imidacloprid. Degradation kinetics showed that the imidacloprid followed the first order kinetics with half-life (t₅₀) of 1.532 day. Intermediate product identified as 6-chloronicotinic acid (6CNA) as one of the major metabolites during degradation of imidacloprid by using HPLC. Thus, A. terreus YESM3 showed a potential to reduce pollution by pesticides and toxicity in the effected environment. However, further studies should be conducted to understand the biodegradation mechanism of this pesticide in liquid media.     

Psychotropic drugs in mixture alter swimming behaviour of Japanese medaka (<Emphasis Type="Italic">Oryzias latipes</Emphasis>) larvae above environmental concentrations

Psychiatric pharmaceuticals, such as anxiolytics, sedatives, hypnotics and antidepressors, are among the most prescribed active substances in the world. The occurrence of these compounds in the environment, as well as the adverse effects they can have on non-target organisms, justifies the growing concern about these emerging environmental pollutants. This study aims to analyse the effects of six psychotropic drugs, valproate, cyamemazine, citalopram, sertraline, fluoxetine and oxazepam, on the survival and locomotion of Japanese medaka Oryzias latipes larvae. Newly hatched Japanese medaka were exposed to individual compounds for 72 h, at concentrations ranging from 10 μg L^?1 to 10 mg L^?1. Lethal concentrations 50 % (LC₅₀) were estimated at 840, 841 and 9,136 μg L^?1 for fluoxetine, sertraline and citalopram, respectively, while other compounds did not induce any significant increase in mortality. Analysis of the swimming behaviour of larvae, including total distance moved, mobility and location, provided an estimated lowest observed effect concentration (LOEC) of 10 μg L^?1 for citalopram and oxazepam, 12.2 μg L^?1 for cyamemazine, 100 μg L^?1 for fluoxetine, 1,000 μg L^?1 for sertraline and >10,000 μg L^?1 for valproate. Realistic environmental mixture of the six psychotropic compounds induced disruption of larval locomotor behaviour at concentrations about 10- to 100-fold greater than environmental concentrations.