Median lethal concentration of formaldehyde and its genotoxic potential in bullfrog tadpoles (Lithobates catesbeianus)

In order to avoid that contaminated frog farms animals escaping in the environment and become potential vector of emergent diseases, studies with disinfection protocol are strictly necessary. The formaldehyde is one of the compounds tested in fungal disinfection protocols and also used in aquaculture. This study aimed to determine the median lethal concentration (LC_50–96h) of formaldehyde in bullfrog tadpoles and to evaluate the possible genotoxic effects in acute exposition. Accordingly, the animals were exposed to formaldehyde in the concentrations of 6, 9, 12, 15, and 18 mg L^?1, and after 96 h blood samples were drawn for the micronucleus (MN) test. The LC_50–96h was 10.53 mg L^?1, and the MN frequency increased in proportion to the formaldehyde concentrations, with an estimated frequency in the negative control being 1.35 MN/individual. We concluded that formaldehyde is genotoxic to tadpoles of bullfrogs in the tested concentrations, and the choice of this chemical should be contemplated before its use in animals in captivity.     

Online microchannel preconcentrator for carbofuran detection

A simple and rapid online microchannel preconcentrator coupled with an amperometric detection for the analysis of carbofuran using polyethylene glycol coated onto magnetic particle (PEG-magnetic particles) sorbents was developed. This simple-to-prepare microchannel preconcentrator used an external magnet to retain the PEG-magnetic particle sorbents inside the microchannel. Under optimum conditions, the system provided two linear ranges, from 0.01 to 10.0 mg L^?1 and from 10.0 to 130.0 mg L^?1 with a limit of detection of 8.7 ± 0.1 μg L^?1. The microchannel preconcentrator provided very good stability; it can be used for up to 326 consecutive injections of 5.0 mg L^?1 carbofuran with a relative standard deviation of less than 3%. The developed system provided a good microchannel-to-microchannel and a good electrode-to-electrode reproducibility (n = 6, %RSD < 1). It also provided an excellent selectivity when it was tested with two other carbamate pesticides, carbaryl and methomyl, with a 43 and 256 times higher detection sensitivity for carbofuran, respectively. The developed system was successfully applied to detect carbofuran in surface water samples obtained near vegetable plantation areas. The concentrations of carbofuran in these samples were found to be in the range of non-detectable to 0.047 ± 0.001 mg L^?1. The developed system is easy to operate and easy to couple with other analytical instruments and it could be easily adapted for the analysis of other polar organic contaminants.     

Unexpected toxic interactions in the freshwater amphipod Gammarus pulex (L.) exposed to binary copper and nickel mixtures

To document the toxicity of copper and nickel in binary mixtures, freshwater amphipods Gammarus pulex were exposed to the metals given independently or as mixtures. Toxicity to Cu alone was relatively high: 96-h LC₁₀ and LC₅₀ were found at 91 and 196 μg L^?1, respectively. Toxicity to Ni alone was very low, with 96-h LC₁₀ and LC₅₀ of 44,900 and 79,200 μg L^?1, respectively. Mixture toxicities were calculated from single toxicity data using conventional models. Modeled toxicity was then compared with the measured toxicity of the binary mixture. Two kinds of mixtures were tested. Type I mixtures were designed as combinations of Cu and Ni given at the same effect concentrations, when taken independently, to identify possible interactions between copper and nickel. In type II mixtures, Cu concentrations varied from 0 to 600 μg L^?1 while the nickel concentration was kept constant at 500 μg L^?1 to mimic conditions of industrial wastewater discharges. Ni and Cu showed synergic effects in type I mixtures while type II mixtures revealed antagonistic effects. Low doses of Ni reduced Cu toxicity towards G. pulex. These results show that even for simple binary mixtures of contaminants with known chemistry and toxicity, unexpected interactions between the contaminants may occur. This reduces the reliability of conventional additivity models.     

Spatial and temporal variations of nitrous oxide flux between coastal marsh and the atmosphere in the Yellow River estuary of China

To investigate the spatial and seasonal variations of nitrous oxide (N₂O) fluxes and understand the key controlling factors, we explored N₂O fluxes and environmental variables in high marsh (HM), middle marsh (MM), low marsh (LM), and mudflat (MF) in the Yellow River estuary throughout a year. Fluxes of N₂O differed significantly between sampling periods as well as between sampling positions. During all times of day and the seasons measured, N₂O fluxes ranged from ?0.0051 to 0.0805 mg N₂O m^?2 h^?1, and high N₂O emissions occurred during spring (0.0278 mg N₂O m^?2 h^?1) and winter (0.0139 mg N₂O m^?2 h^?1) while low fluxes were observed during summer (0.0065 mg N₂O m^?2 h^?1) and autumn (0.0060 mg N₂O m^?2 h^?1). The annual average N₂O flux from the intertidal zone was 0.0117 mg N₂O m^?2 h^?1, and the cumulative N₂O emission throughout a year was 113.03 mg N₂O m^?2, indicating that coastal marsh acted as N₂O source. Over all seasons, N₂O fluxes from the four marshes were significantly different (p?<?0.05), in the order of HM (0.0256?±?0.0040 mg N₂O m^?2 h^?1)?>?MF (0.0107?±?0.0027 mg N₂O m^?2 h^?1)?>?LM (0.0073?±?0.0020 mg N₂O m^?2 h^?1)?>?MM (0.0026?±?0.0011 mg N₂O m^?2 h^?1). Temporal variations of N₂O emissions were related to the vegetations (Suaeda salsa, Phragmites australis, and Tamarix chinensis) and the limited C and mineral N in soils during summer and autumn and the frequent freeze/thaw cycles in soils during spring and winter, while spatial variations were mainly affected by tidal fluctuation and plant composition at spatial scale. This study indicated the importance of seasonal N₂O contributions (particularly during non-growing season) to the estimation of local N₂O inventory, and highlighted both the large spatial variation of N₂O fluxes across the coastal marsh (CV?=?158.31 %) and the potential effect of exogenous nitrogen loading to the Yellow River estuary on N₂O emission should be considered before the annual or local N₂O inventory was evaluated accurately.     

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.     

Effectiveness evaluation of glyphosate oxidation employing the H2O2/UVC process: Toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles

The H₂O₂/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M_1, M₂, and M₃ following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H₂O₂. Subsamples of M₁, M₂, and M₃ were then used to create samples M_1,E, M_2,E and M_3,E in which the H₂O₂ had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M_1,E, which was collected early in the photodegradation process, caused 52% inhibition, while M_3,E, which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M₂, M₃, and in M_1,E, M_2,E and M_3,E. The lowest percentages of enzymatic inhibition were observed in samples without removal of H₂O₂: 13.96% (AChE) and 16% (BChE) for M₂, and 24.12% (AChE) and 13.83% (BChE) for M₃. These results show the efficiency of the H₂O₂/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M₂ (11 ± 1 mg a.e. L^?1 glyphosate and 11 ± 1 mg L^?1 H₂O₂) could be used as a final point for glyphosate treatment with the H₂O₂/UV process.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

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.     

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.     

Effects of previous sublethal pulse to ammonium nitrate on mortality and total length on Epidalea calamita larvae

Ammonium nitrate is one of the most widespread contaminants related with the viability of natural amphibian populations. In this study we have evaluated in terms of mortality and total length the effects that a previous sublethal pulse to ammonium nitrate generates in Epidalea calamita. Experiments were divided in two phases. In the first one, tadpoles were exposed to two different treatments, with and without a low ammonium nitrate concentration (22 mg NH₄NO₃ L⁻¹). The second phase consisted in static toxicity experiments from both origin treatments with five different nominal concentrations (0, 22, 45, 90 and 180 mg NH₄NO₃ L⁻¹). Results showed that tadpoles that had experienced a previous sublethal exposure showed a negative effect on survival (57% of reduction in the LC₅₀ value) and total length, throughout an increase in their sensitivity. These results could help us to understand the situation of amphibian populations inhabiting aquatic ecosystems exposed to discontinuous and variable pulses of pollutants.     

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.     

Combined toxic impacts of thiamethoxam and four pesticides on the rare minnow (Gobiocypris rarus)

To examine pesticide mixture toxicity to aqueous organisms, we assessed the single and combined toxicities of thiamethoxam and other four pesticides (chlorpyrifos, beta-cypermethrin, tetraconazole, and azoxystrobin) to the rare minnow (Gobiocypris rarus). Data from 96-h semi-static toxicity assays of various developmental phases (embryonic, larval, juvenile, and adult phases) showed that beta-cypermethrin, chlorpyrifos, and azoxystrobin had the highest toxicities to G. rarus, and their LC₅₀ values ranged from 0.0031 to 0.86 mg a.i. L^?1, from 0.016 to 6.38 mg a.i. L^?1, and from 0.39 to 1.08 mg a.i. L^?1, respectively. Tetraconazole displayed a comparatively high toxicity, and its LC₅₀ values ranged from 3.48 to 16.73 mg a.i. L^?1. By contrast, thiamethoxam exhibited the lowest toxic effect with LC₅₀ values ranging from 37.85 to 351.9 mg a.i. L^?1. Rare minnow larvae were more sensitive than embryos to all the pesticides tested. Our data showed that a pesticide mixture of thiamethoxam–tetraconazole elicited synergetic toxicity to G. rarus. Moreover, pesticide mixtures containing beta-cypermethrin in combination with chlorpyrifos or tetraconazole also had synergetic toxicities to fish. The majority of pesticides are presumed to have additive toxicity, while our data emphasized that the concurrent existence of some chemicals in the aqueous circumstance could cause synergetic toxic effect, leading to severe loss to the aqueous environments in comparison with their single toxicities. Thence, the synergetic impacts of chemical mixtures should be considered when assessing the ecological risk of chemicals.

     

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.     

Evaluation of the capacity of the cyanobacterium Microcystis novacekii to remove atrazine from a culture medium

The bioaccumulation of atrazine and its toxicity were evaluated for the cyanobacterium Microcystis novacekii. Cyanobacterial cultures were grown in WC culture medium with atrazine at 50, 250 and 500 μg L^?1. After 96 hours of exposure, 27.2% of the atrazine had been removed from the culture supernatant. Spontaneous degradation was found to be insignificant (< 9% at 500 μg L^?1), indicating a high efficiency for the bioaccumulation of atrazine by M. novacekii. There were no atrazine metabolites detected in the culture medium at any of the doses studied. The acute toxicity (EC₅₀) of atrazine to the cyanobacterium was 4.2 mg L^?1 at 96 hours demonstrating the potential for M. novacekii to tolerate high concentrations of this herbicide in fresh water environments. The ability of M. novacekii to remove atrazine combined with its tolerance of the pesticide toxicity showed in this study makes it a potential biological resource for the restoration of contaminated surface waters. These findings support continued studies of the role of M. novacekii in the bioremediation of fresh water environments polluted by atrazine.     

Distinctive effects of nano-sized permethrin in the environment

Pesticides are an essential tool in integrated pest management. Nanopermethrin was prepared by solvent evaporation from an oil-in-water volatile microemulsion. The efficacy of the formulated nanopermethrin was tested against Aedes aegypti and the results compared to those of regular, microparticular permethrin. The 24 h LC₅₀ for nanopermethrin and permethrin was found to be 0.0063 and 0.0199 mg/L, respectively. The formulated nanopermethrin was tested for toxicity against non-target organisms. Nanopermethrin did not show antibacterial activity against Escherichia coli (ATCC 13534 and 25922) or against Bacillus subtilis. Phytotoxicity studies of nanopermethrin to the seeds of Lycopersicum esculentum, Cucumis sativus, and Zea mays showed no restraint in root length and germination percentage. In the Allium cepa test, regular microparticular permethrin treatment of 0.13 mg/L showed a mitotic index (MI) of 46.8 % and chromosomal aberration of 0.6 %, which was statistically significant (p?<?0.05) compared to control. No significant differences were observed in 0.13 mg/L nanopermethrin exposure as compared to control (MI of 52.0 and 55.03 % and chromosomal aberration of 0.2 and 0 %, respectively). It was concluded that formulated nanopermethrin can be used as a safe and effectual alternative to commercially available permethrin formulation in agricultural practices.     

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.     

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.     

Effect of ibuprofen exposure on blood,gill, liver,and brain on common carp (Cyprinus carpio) using oxidative stress biomarkers

Although trace concentrations of ibuprofen (IBP) have been detected in diverse water bodies, there is currently insufficient information on the potentially deleterious effects of this xenobiotic. The present study aimed to determine whether IBP induces oxidative stress in brain, liver, gill, and blood of the common carp Cyprinus carpio. To this end, the median lethal concentration at 96 h (96-h LC₅₀) was determined and the lowest observed adverse effect level was established. Carp were exposed to the latter concentration (17.6 mg L^?1) for 12, 24, 48, 72, and 96 h, and the following biomarkers were evaluated: lipid peroxidation (LPX) and activity of the antioxidant enzymes superoxide dismutase, catalase, and glutathione peroxidase. Results indicated that LPX and antioxidant enzymes’ activity increased significantly (p?<?0.05) with respect to the control group in liver, gill, and blood, while no significant differences occurred in brain. In conclusion, IBP induced oxidative stress on C. carpio, the liver being the organ most affected by this damage.     

Environmental effects of anticholinesterasic therapeutic drugs on a crustacean species,Daphnia magna

The presence of pharmaceutical drugs in the environment is an important field of toxicology, since such residues can cause deleterious effects on exposed biota. This study assessed the ecotoxicological acute and chronic effects of two anticholinesterasic drugs, neostigmine and pyridostigmine in Daphnia magna. Our study calculated 48 h-EC₅₀ values for the immobilization assay of 167.7 μg L^?1 for neostigmine and 91.3 μg L^?1 for pyridostigmine. In terms of feeding behavior, we calculated a 5 h-EC₅₀ for filtration rates of 7.1 and 0.2 μg L^?1 for neostigmine and pyridostigmine, respectively; for the ingestion rates, the calculated EC₅₀ values were, respectively, 7.5 and 0.2 μg L^?1 for neostigmine and pyridostigmine. In the reproduction assay, the most affected parameter was the somatic growth rate (LOECs of 21.0 and 2.9 μg L^?1 for neostigmine and pyridostigmine, respectively), followed by the fecundity (LOECs of 41.9 and 11.4 μg L^?1 for neostigmine and pyridostigmine, respectively). We also determined a 48 h-IC₅₀ for cholinesterase activity of 1.7 and 4.5 μg L^?1 for neostigmine and pyridostigmine, respectively. These results demonstrated that both compounds are potentially toxic for D. magna at concentrations in the order of the μg L^?1.     

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). $