Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (k_obsd) and half‐lives (T_1/2) were 5.946 × 10^‐4 and 13.10 × 10^‐4 d^‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.     

Temperature enhanced effects of chlorine exposure on the health status of the sentinel organism Mytilus galloprovincialis

It now is widely recognised that the global temperature is rising, a phenomenon which could alter the effects of pollution on wildlife. In order to assess the role of temperature and exposure to chlorine due to cooling water discharges, a battery of metabolic, oxidative stress and histological parameters were evaluated in Mytilus galloprovincialis after 15 and 30 days at 15 °C and at two increased temperatures (+5 and +10 °C). Diverse gill pathologies such as haemolymphatic sinus dilatation, an increased number of mucocytes and granulocytes as well as a lower number of cilia were observed after 30 days exposure at higher temperatures. Protein, amino acid, triglyceride and fatty acid levels decreased when the temperature increased, as a consequence of higher energetic demand. Similarly, acetylcholinesterase, catalase and glutathione S-transferase activities showed an inhibition at higher temperatures, although gill lipid peroxidation levels remained unaffected. Our results suggest that increased temperatures induce deterioration in the health status of the mussels and in their defensive capacity against a polluted environment.     

Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue

The present investigation demonstrated pretreatment of lignocellulosic biomass rice straw using natural deep eutectic solvents (NADESs), and separation of high-quality lignin and holocellulose in a single step. Qualitative analysis of the NADES extract showed that the extracted lignin was of high purity (>90 %), and quantitative analysis showed that nearly 60?±?5 % (w/w) of total lignin was separated from the lignocellulosic biomass. Addition of 5.0 % (v/v) water during pretreatment significantly enhanced the total lignin extraction, and nearly 22?±?3 % more lignin was released from the residual biomass into the NADES extract. X-ray diffraction studies of the untreated and pretreated rice straw biomass showed that the crystallinity index ratio was marginally decreased from 46.4 to 44.3 %, indicating subtle structural alterations in the crystalline and amorphous regions of the cellulosic fractions. Thermogravimetric analysis of the pretreated biomass residue revealed a slightly higher T _dcp (295 °C) compared to the T _dcp (285 °C) of untreated biomass. Among the tested NADES reagents, lactic acid/choline chloride at molar ratio of 5:1 extracted maximum lignin of 68?±?4 mg g^?1 from the rice straw biomass, and subsequent enzymatic hydrolysis of the residual holocellulose enriched biomass showed maximum reducing sugars of 333?±?11 mg g^?1 with a saccharification efficiency of 36.0?±?3.2 % in 24 h at 10 % solids loading.     

Impact of crude oil exposure on nitrogen cycling in a previously impacted Juncus roemerianus salt marsh in the northern Gulf of Mexico

This study investigated potential nitrogen fixation, net nitrification, and denitrification responses to short-term crude oil exposure that simulated oil exposure in Juncus roemerianus salt marsh sediments previously impacted following the Deepwater Horizon accident. Temperature as well as crude oil amount and type affected the nitrogen cycling rates. Total nitrogen fixation rates increased 44 and 194 % at 30 °C in 4,000 mg kg^?1 tar ball and 10,000 mg kg^?1 moderately weathered crude oil treatments, respectively; however, there was no difference from the controls at 10 and 20 °C. Net nitrification rates showed production at 20 °C and consumption at 10 and 30 °C in all oil treatments and controls. Potential denitrification rates were higher than controls in the 10 and 30?ºC treatments but responded differently to the oil type and amount. The highest rates of potential denitrification (12.7?±?1.0 nmol N g^?1 wet h^?1) were observed in the highly weathered 4,000 mg kg^?1 oil treatment at 30 °C, suggesting increased rates of denitrification during the warmer summer months. These results indicate that the impacts on nitrogen cycling from a recurring oil spill could depend on the time of the year as well as the amount and type of oil contaminating the marsh. The study provides evidence for impact on nitrogen cycling in coastal marshes that are vulnerable to repeated hydrocarbon exposure.     

Kinetics of imidazolium-based ionic liquids degradation in aqueous solution by Fenton oxidation

In the last few years, several works dealing with Fenton oxidation of ionic liquids (ILs) have proved the capability of this technology for their degradation, achieving complete ILs removal and non-toxic effluents. Nevertheless, very little is known about the kinetics of this process, crucial for its potential application. In this work, the effect of several operating conditions, including reaction temperature (50–90 °C), catalyst load (10–50 mg L^?1 Fe³⁺), initial IL concentration (100–2000 mg L^?1), and hydrogen peroxide dose (10–200% of the stoichiometric amount for the complete IL mineralization) on 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) oxidation has been investigated. Under the optimum operating conditions (T = 90 °C; [Fe³⁺]₀ = 50 mg L^?1; [H₂O₂]₀ = 100% of the stoichiometric amount), the complete removal of [C₄mim]Cl (1000 mg L^?1) was achieved at 1.5-min reaction time. From the experimental results, a potential kinetic model capable to describe the removal of imidazolium-based ILs by Fenton oxidation has been developed. By fitting the proposed model to the experimental data, the orders of the reaction with respect to IL initial concentration, Fe³⁺ amount and H₂O₂ dose were found to be close to 1, with an apparent activation energy of 43.3 kJ mol^?1. The model resulted in a reasonable fit within the wide range of operating conditions tested in this work.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Elevated water temperature reduces the acute toxicity of the widely used herbicide diuron to a green alga, Pseudokirchneriella subcapitata

In the actual environment, temperatures fluctuate drastically through season or global warming and are thought to affects risk of pollutants for aquatic biota; however, there is no report about the effect of water temperature on toxicity of widely used herbicide diuron to fresh water microalgae. The present research investigated inhibitory effect of diuron on growth and photosynthetic activity of a green alga Pseudokirchneriella subcapitata at five different temperatures (10, 15, 20, 25, and 30 °C) for 144 h of exposure. As a result, effective diuron concentrations at which a 50 % decrease in algal growth occurred was increased with increasing water temperature ranging from 9.2 to 20.1 μg L^–1 for 72 h and 9.4–28.5 μg L^–1 for 144 h. The photochemical efficiency of photosystem II (F _v/F _m ratio) was significantly reduced at all temperatures by diuron exposure at 32 μg L^–1 after 72 h. Inhibition rates was significantly increased with decreased water temperature (P?<?0.01). Intracellular H₂O₂ levels as an indicator of oxidative stress were also decreased with increasing temperature in both control and diuron treatment groups and were about 2.5 times higher in diuron treatment groups than that of controls (P?<?0.01). Our results suggest water temperatures may affect the toxicokinetics of diuron in freshwater and should therefore be considered in environmental risk assessment.     

Synergetic effects of Sr-doped CuBi<Subscript>2</Subscript>O<Subscript>4</Subscript> catalyst with enhanced photoactivity under UVA– light irradiation

Sr-doped CuBi₂O₄ micro-particles were successively synthesized via a solid-state technique and were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and UV–vis diffuse reflectance spectroscopy (UV–vis-DRS) techniques. Results show that Sr-doped CuBi₂O₄ was crystallized with a spinel-type structure and tetragonal crystal system, and the band gap energy was about 1.35 eV. The as-prepared Sr-doped CuBi₂O₄ treated at 573 °C for 12 h exhibited the highest efficiency, as a result of 97.22 % of CR degradation within 220 min, which is approximately 31 times greater than CR photodegradation when catalyzed by CuBi₂O₄ (3.13 %) and about 2.3 times superior than that catalyzed by the untreated Sr–doped CuBi₂O₄ sample (42.08 %). Pseudo-first-order kinetic model gave the best fit, with highest correlation coefficients (R ²?=?0.94–0.97). The Sr–doping and extending reaction time up to 12 h could be effective in producing Sr-doped CuBi₂O₄ materials that delay electron–hole recombination, thereby increasing the lifetime of the electron electron–hole separation and support the charge carrier transfer to the catalyst surface. On the basis of the calculated energy band positions, superoxide radical anions (O₂ ^?–) were the main oxidative species responsible for the photocatalytic degradation of CR dye solution.     

Copper bioaccumulation,photosystem II functioning,and oxidative stress in the seagrass <Emphasis Type="Italic">Cymodocea nodosa</Emphasis> exposed to copper oxide nanoparticles

Photosynthetic activity, oxidative stress, and Cu bioaccumulation in the seagrass Cymodocea nodosa were assessed 4, 12, 24, 48, and 72 h after exposure to two copper oxide nanoparticle (CuO NP) concentrations (5 and 10 mg L^?1). CuO NPs were characterized by scanning electron microscopy (SEM) and dynamic light scattering measurements (DLS). Chlorophyll fluorescence analysis was applied to detect photosystem II (PSII) functionality, while the Cu accumulation kinetics into the leaf blades was fitted to the Michaelis-Menten equation. The uptake kinetics was rapid during the first 4 h of exposure and reached an equilibrium state after 10 h exposure to 10 mg L^?1 and after 27 h to 5 mg L^?1 CuO NPs. As a result, 4-h treatment with 5 mg L^?1 CuO NPs, decreased the quantum yield of PS II photochemistry (Φ _PSΙΙ ) with a parallel increase in the regulated non-photochemical energy loss in PSII (Φ _NPQ ). However, the photoprotective dissipation of excess absorbed light energy as heat, through the process of non-photochemical quenching (NPQ), did not maintain the same fraction of open reaction centers (q _p ) as in control plants. This reduced number of open reaction centers resulted in a significant increase of H₂O₂ production in the leaf veins serving possibly as an antioxidant defense signal. Twenty-four-hour treatment had no significant effect on Φ _PSΙΙ and q _p compared to controls. However, 24 h exposure to 5 mg L^?1 CuO NPs increased the quantum yield of non-regulated energy loss in PSII (Φ _NO ), and thus the formation of singlet oxygen (¹O₂) via the triplet state of chlorophyll, possible because the uptake kinetics had not yet reached the equilibrium state as did 10 mg L^?1. Longer-duration treatment (48 and 72 h) had less effect on the allocation of absorbed light energy at PSII and the fraction of open reaction centers, compared to 4-h treatment, suggesting the function of a stress defense mechanism. The response of C. nodosa leaves to CuO NPs fits the “Threshold for Tolerance Model” with a threshold time (more than 4 h) required for induction of a stress defense mechanism, through H₂O₂ production.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Influence of short-time imidacloprid and acetamiprid application on soil microbial metabolic activity and enzymatic activity

The influence of two neonicotinoids, i.e., imidacloprid (IMI) and acetamiprid (ACE), on soil microbial activities was investigated in a short period of time using a combination of the microcalorimetric approach and enzyme tests. Thermodynamic parameters such as Q _T (J g^?1 soil), ?H _met (kJ mol^?1), J _Q/S (J g^?1 h^?1), k (h^?1), and soil enzymatic activities, dehydrogenase, phosphomonoesterase, arginine deaminase, and urease, were used to evaluate whole metabolic activity changes and acute toxicity following IMI and ACE treatment. Various profiles of thermogenic curves reflect different soil microbial activities. The microbial growth rate constant k, total heat evolution Q _T (expect for IMI), and inhibitory ratio I show linear relationship with the doses of IMI and ACE. Q _T for IMI increases at 0.0–20 μg g^?1 and then decreases at 20–80 μg g^?1, possibly attributing to the presence of tolerant microorganisms. The 50 % inhibitory ratios (IC₅₀) of IMI and ACE are 95.7 and 77.2 μg g^?1, respectively. ACE displays slightly higher toxicity than IMI. Plots of k and Q _T against microbial biomass-C indicate that the k and Q _T are growth yield-dependent. IMI and ACE show 29.6; 40.4 and 23.0; and 23.3, 21.7, and 30.5 % inhibition of dehydrogenase, phosphomonoesterase, and urease activity, respectively. By contrast, the arginine deaminase activity is enhanced by 15.2 and 13.2 % with IMI and ACE, respectively. The parametric indices selected give a quantitative dose-response relationship of both insecticides and indicate that ACE is more toxic than IMI due to their difference in molecular structures.     

Risk assessment of inhalation exposure to polycyclic aromatic hydrocarbons in school children

Polycyclic aromatic hydrocarbons (PAHs) associated with the inhalable fraction of particulate matter were determined for 1 year (2009–2010) at a school site located in proximity of industrial and heavy traffic roads in Delhi, India. PM₁₀ (aerodynamic diameter ≤10 μm) levels were ～11.6 times the World Health Organization standard. Vehicular (59.5 %) and coal combustion (40.5 %) sources accounted for the high levels of PAHs (range 38.1–217.3 ng m^?3) with four- and five-ring PAHs having ～80 % contribution. Total PAHs were dominated by carcinogenic species (～75 %) and B[a]P equivalent concentrations indicated highest exposure risks during winter. Extremely high daily inhalation exposure of PAHs was observed during winter (439.43 ng day^?1) followed by monsoon (232.59 ng day^?1) and summer (171.08 ng day^?1). Daily inhalation exposure of PAHs to school children during a day exhibited the trend school hours?>?commuting to school?>?resting period in all the seasons. Vehicular source contributions to daily PAH levels were significantly correlated (r?=?0.94, p?<?0.001) with the daily inhalation exposure level of school children. A conservative estimate of ～11 excess cancer cases in children during childhood due to inhalation exposure of PAHs has been made for Delhi.     

Medium optimization for the production of anti-cyanobacterial substances by Streptomyces sp. HJC-D1 using response surface methodology

Bioremediation using isolated anti-cyanobacterial microorganism has been widely applied in harmful algal blooms (HABs) control. In order to improve the secretion of activated anti-cyanobacterial substances, and lower the cost, a sequential optimization of the culture medium based on statistical design was employed for enhancing the anti-cyanobacterial substances production and chlorophyll a (Chl a) removal by Streptomyces sp. HJC-D1 in the paper. Sucrose and KNO₃ were selected as the most suitable carbon and nitrogen sources based on the one-at-a-time strategy method, and sucrose, KNO₃ and initial pH were found as major factors that affected the anti-cyanobacterial ability of the isolated stain via the Plackett–Burman design. Based on the response surface and canonical analysis, the optimum condition of culture medium was obtained at 22.73 g l^-1 of sucrose, 0.96 g l^-1 of KNO₃, and initial pH 8.82, and the Chl a removal efficiency by strain HJC-D1 increased from 63?±?2 % to 78?±?2 % on the optimum conditions.     

Approximation and spatial regionalization of rainfall erosivity based on sparse data in a mountainous catchment of the Yangtze River in Central China

In densely populated countries like China, clean water is one of the most challenging issues of prospective politics and environmental planning. Water pollution and eutrophication by excessive input of nitrogen and phosphorous from nonpoint sources is mostly linked to soil erosion from agricultural land. In order to prevent such water pollution by diffuse matter fluxes, knowledge about the extent of soil loss and the spatial distribution of hot spots of soil erosion is essential. In remote areas such as the mountainous regions of the upper and middle reaches of the Yangtze River, rainfall data are scarce. Since rainfall erosivity is one of the key factors in soil erosion modeling, e.g., expressed as R factor in the Revised Universal Soil Loss Equation model, a methodology is needed to spatially determine rainfall erosivity. Our study aims at the approximation and spatial regionalization of rainfall erosivity from sparse data in the large (3,200 km²) and strongly mountainous catchment of the Xiangxi River, a first order tributary to the Yangtze River close to the Three Gorges Dam. As data on rainfall were only obtainable in daily records for one climate station in the central part of the catchment and five stations in its surrounding area, we approximated rainfall erosivity as R factors using regression analysis combined with elevation bands derived from a digital elevation model. The mean annual R factor (R _a) amounts for approximately 5,222 MJ?mm?ha^?1?h^?1?a^?1. With increasing altitudes, R _a rises up to maximum 7,547 MJ?mm ha^?1?h^?1 a^?1 at an altitude of 3,078 m a.s.l. At the outlet of the Xiangxi catchment erosivity is at minimum with approximate R _a?=?1,986 MJ?mm?ha^?1?h^?1?a^?1. The comparison of our results with R factors from high-resolution measurements at comparable study sites close to the Xiangxi catchment shows good consistance and allows us to calculate grid-based R _a as input for a spatially high-resolution and area-specific assessment of soil erosion risk.     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.     

Physiological characteristics of <Emphasis Type="Italic">Plantago major</Emphasis> under SO<Subscript>2</Subscript> exposure as affected by foliar iron spray

Sulfur dioxide (SO₂) is considered as a main air pollutant in industrialized areas that can damage vegetation. In the present study, we investigated how exposure to SO₂ and foliar application of iron (Fe) would affect certain physiological characteristics of Plantago major. The plant seedlings exposed or unexposed to SO₂ (3900 μg m^?3) were non-supplemented or supplemented with Fe (3 g L^?1) as foliar spray. Plants were exposed to SO₂ for 6 weeks in 100 × 70 × 70 cm chambers. Fumigation of plants with SO₂ was performed for 3 h daily for 3 days per week (alternate day). Lower leaf Fe concentration in the plants exposed to SO₂ at no added Fe treatment was accompanied with incidence of chlorosis symptoms and reduced chlorophyll concentration. No visible chlorotic symptoms were observed on the SO₂-exposed plants supplied with Fe that accumulated higher Fe in their leaves. Both at with and without added Fe treatments, catalase (CAT) and peroxidase (POD) activity was higher in the plants fumigated with SO₂ in comparison with those non-fumigated with SO₂. Foliar application of Fe was also effective in increasing activity of antioxidant enzymes CAT and POD. Exposure to SO₂ led to reduced cellulose but enhanced lignin content of plant leaf cell wall. The results obtained showed that foliar application of Fe was effective in reducing the effects of exposure to SO₂ on cell wall composition. In contrast to SO₂, application of Fe increased cellulose while decreased lignin content of the leaf cell wall. This might be due to reduced oxidative stress induced by SO₂ in plants supplied with Fe compared with those unsupplied with Fe.     

Studies on the removal of nickel from aqueous solutions using modified riverbed sand

This paper highlights the utility of riverbed sand (RS) for the treatment of Ni(II) from aqueous solutions. For enhancement of removal efficiency, RS was modified by simple methods. Raw and modified sands were characterized by scanning electron microscope (SEM), Energy Dispersive Spectroscopy (EDS), and Fourier Transform Infrared Spectroscopy (FTIR) to investigate the effect of modifying the surface of RS. For optimization of various important process parameters, batch mode experiments were conducted by choosing specific parameters such as pH (4.0–8.0), adsorbent dose (1.0–2.0 g), and metal ion concentrations (5–15 mg/L). Removal efficiency decreased from 68.76 to 54.09 % by increasing the concentration of Ni(II) in solution from 5 to 15 mg/L. Removal was found to be highly dependent on pH of aqueous solutions and maximum removal was achieved at pH 8.0. The process of removal follows first-order kinetics, and the value of rate constant was found to be 0.048 min^?1 at 5 mg/L and 25 °C. Value of intraparticle diffusion rate constant (k _id) was found to be 0.021 mg/g min^1/2 at 25 °C. Removal of Ni(II) decreased by increasing temperature which confirms exothermic nature of this system. For equilibrium studies, adsorption data was analyzed by Freundlich and Langmuir models. Thermodynamic studies for the present process were performed by determining the values of ΔG°, ΔH°, and ΔS°. Negative value of ?H° further confirms the exothermic nature of the removal process. The results of the present investigation indicate that modified riverbed sand (MRS) has high potential for the removal of Ni(II) from aqueous solutions, and resultant data can serve as baseline data for designing treatment plants at industrial scale.     

Neurotoxicological evaluation of microcystin-LR exposure at environmental relevant concentrations on nematode Caenorhabditis elegans

Previous studies have not examined the adverse effects of microcystin-LR (MC-LR) at environmental relevant concentrations on the development and functions of nervous system. The neurotoxic effects of MC-LR exposure on neurotransmitter systems were investigated in Caenorhabditis elegans. After exposing L1 larvae to 0.1, 1, 10, and 100 μg?l^?1 of MC-LR for 8 and 24 h, the adverse effects on GABAergic, cholinergic, serotonergic, dopaminergic, and glutamatergic neurons were examined. The expression levels of genes required for development and functions of GABAergic neurons were further investigated. Body bend frequency and head thrash frequency decreased significantly after MC-LR exposure for 8 h at concentrations more than 1 μg?l^?1 and after MC-LR exposure for 24 h at concentrations more than 0.1 μg?l^?1. Loss of GABAergic neurons increased significantly in a dose-dependent manner after MC-LR exposure at concentrations more than 0.1 μg?l^?1. In contrast, no obvious neuronal losses or morphologic changes were observed in cholinergic, serotonergic, dopaminergic, and glutamatergic neurons in MC-LR-exposed nematodes. Quantitative real-time PCR assay further showed that expression levels of unc-30, unc-46, unc-47, and exp-1 genes required for development and function of GABAergic neurons decreased significantly in nematodes exposed to MC-LR at concentrations more than 0.1 or 1 μg?l^?1. MC-LR at environmental relevant concentrations caused neurobehavioral defects, which may be largely due to the neuronal loss and the alterations of expression level of genes required for GABAergic neurotransmitter system in C. elegans.     

Toxic effects of hexaflumuron on the development of Coccinella septempunctata

Studying the toxic risk of pesticide exposure to ladybird beetles is important from an agronomical and ecological perspective since larval and adult ladybirds are dominant predators of herbivorous pest insects (e.g., aphids) in various crops in China. This article mainly deals with the long-term effects of a single application of the insect growth regulator hexaflumuron on Coccinella septempunctata. A 72-h and a 33-day toxicity test with hexaflumuron (single application) were performed, starting with the second instar larvae of C. septempunctata. Exposure doses in the long-term experiment were based on the estimated 72-h acute LR₅₀ (application rate causing 50 % mortality) value of 304 g active ingredient (a.i.) ha^?1 for second instar larvae of C. septempunctata. The long-term test used five hexaflumuron doses as treatment levels (1/50, 1/100, 1/200, 1/400, and 1/800 of the 72-h acute LR₅₀), as well as a solvent control and blank control treatment. The measurement endpoints used to calculate no observed effect application rates (NOERs) included development time, hatching, pupation, adult emergence, survival, and number of eggs produced. Analyzing the experimental data with one-way analysis of variance showed that the single hexaflumuron application had significant effects on C. septempunctata endpoints in the 33-day test, including effects on development duration (NOER 1.52 g a.i. ha^?1), hatching (NOER 3.04 g a.i. ha^?1), pupation (NOER 3.04 g a.i. ha^?1), and survival (NOER 1.52 g a.i. ha^?1). These NOERs are lower than the reported maximum field application rate of hexaflumuron (135 g a.i. ha^?1) in cotton cultivation, suggesting potential risks to beneficial arthropods.