Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Salt marsh plants as key mediators on the level of cadmium impact on microbial denitrification

The fate of excess nitrogen in estuaries is determined by the microbial-driven nitrogen cycle, being denitrification a key process since it definitely removes fixed nitrogen as N₂. However, estuaries receive and retain metals, which may negatively affect this process efficiency. In this study, we evaluated the role of salt marsh plants in mediating cadmium (Cd) impact on microbial denitrification process. Juncus maritimus and Phragmites australis from an estuary were collected together with the sediment involving their roots, each placed in vessels and maintained in a greenhouse, exposed to natural light, with tides simulation. Similar non-vegetated sediment vessels were prepared. After 3 weeks of accommodation, nine vessels (three per plant species plus three non-vegetated) were doped with 20 mg/L Cd²⁺ saline solution, nine vessels were doped with 2 mg/L Cd²⁺ saline solution and nine vessels were left undoped. After 10 weeks, vessels were dissembled and denitrification potential was measured in sediment slurries. Results revealed that the addition of Cd did not cause an effect on the denitrification process in non-vegetated sediment but had a clear stimulation in colonized ones (39 % for P. australis and 36 % for J. maritimus). In addition, this increase on denitrification rates was followed by a decrease on N₂O emissions and on N₂O/N₂ ratios in both J. maritimus and P. australis sediments, increasing the efficiency of the N₂O step of denitrification pathway. Therefore, our results suggested that the presence of salt marsh plants functioned as key mediators on the degree of Cd impact on microbial denitrification.     

Natural Products: Repellency and Toxicity of Wild Tomato Leaf Extracts to the Two-Spotted Spider Mite,Tetranychus urticae Koch

The potential of using phytochemicals from leaves of wild tomato for controlling the two-spotted spider mite, Tetranychus urticae Koch, is explored in this study as a promising alternative to the use of synthetic pesticides. Wild tomato accessions of Lycopersicon hirsutum plants that are not consumed by humans were planted under greenhouse conditions for mass production of leaves. Crude extracts from leaves of three accessions of L. hirsutum, six accessions of L. hirsutum f. glabratum, and one accession each of L. pennellii and L. pimpinellifolium were prepared in chloroform, ethanol and hexane. Two spider mite bioassays, one a measure of antibiosis and the other a measure of repellency, were utilized to determine the acaricidal performance of the crude extracts. The bioassay for antibiosis was a 6-h no-choice test. The bioassay for repellency utilized a ring bioassay. Chloroform leaf extracts of L. hirsutum f. glabratum accessions (PI-251304, PI-134417, PI-134418, and PI-126449) exhibited greatest antibiotic activity on two-spotted spider mites; the hexane extracts exhibited greatest repellency. Extracts from PI-251304, PI-126449, PI-134417, and PI-134418 were especially lethal (chloroform) or repellent (hexane). We investigated differences in chemical composition of the crude leaf extracts that may explain the observed differences in mortality and repellency among the different accessions. Major chemical compounds (α -curcumene, α -zingiberene, trans-caryophyllene, 2-undecanone, and 2-tridecanone) known to have pesticidal efficacy were detected and quantified in the crude leaf extracts using a gas chromatograph (GC) equipped with a mass spectrometer (GC/MS). Lethality of extracts was mainly associated with the presence of high concentrations of 2-tridecanone; repellency of extracts was mainly associated with the presence of trans-caryophyllene. Leaf extracts of L. hirsutum f. glabratum accessions that contain significant quantities of 2-tridecanone and/or trans-caryophyllene could be useful for managing populations of spider mites, which could reduce reliance on synthetic pesticides.     

Growth Inhibition by Nitrocompounds of Selected Uric Acid-Utilizing Microorganisms Isolated from Poultry Manure

The overall objective of this study was to evaluate the potential ability of nitrocompounds to reduce ammonia volatilization by inhibiting uric acid–utilizing microorganisms. Experiment I was conducted to evaluate the effects of nitrocompounds on the growth of uric acid–utilizing microorganisms isolated from poultry manure during six-hour incubation. There were five treatments: (1) control, (2) 50 mM nitroethane, (3) 50 mM nitroethanol, (4) 50 mM nitropropanol, and (5) 50 mM nitropropionic acid. Optical density values of nitrocompounds were significantly lower than that of control at two, four, and six hours. Plate counts of uric acid–utilizing microorganisms after six-hour incubation exhibited that nitrocompounds greatly reduced the growth of these microorganisms except for the nitroethane (P < 0.05). The nitropropanol and nitropropionic acid treatments showed significantly higher inhibitory effects compared to the nitroethanol. Experiments II and III were conducted to evaluate inhibitory effects of nitrocompounds on growth of uric acid–utilizing microorganisms compared to non-nitrocompounds such as ethanol, propanol, and propionic acid. Experiments II and III consisted of seven treatments: (1) control, (2) nitroethanol, (3) nitropropanol, (4) nitropropionic acid, (5) ethanol, (6) propanol, and (7) propionic acid. The incubation times of Experiments II and III were 6 and 24 h, respectively. The nitrocompounds were significantly more successful in inhibiting growth of uric acid–utilizing microorganisms compared to those non-nitrocompounds. These results suggest that nitrocompounds exhibit potential to reduce ammonia volatilization in poultry manure by inhibiting growth of uric acid–utilizing microorganisms.     

A two-generational reproductive toxicity study of zinc in rats

A two-generation reproductive toxicity study of zinc chloride (ZnCl₂) was conducted in rats. F_o male and female rats were administered 0.00 (control), 7.50 (low), 15.00 (mid) and 30.00 (high) mg/kg/day of ZnCl₂. Selected F₁ male and female rats were exposed to the same doses received by their parents (F_o). Exposure of F₀ parental rats to ZnCl₂ showed significant reduction in fertility, viability (days 0 and 4), and the body weight of F₁ pups from the high-dose group but caused no effects on litter size, weaning index, and sex ratio. Similarly, the continued exposure of F₁ parental rats to ZnCl₂ also reduced fertility, liter size, viability (day 0), and the body weight of F₂ pups within the high-dose group but caused no effects on weaning index and sex ratio. Exposure of ZnCl₂ to F₀ and F₁ parental males resulted in a significant reduction in their body weights, and the F₀ and F₁ parental females did not show any significant difference in their body weights compared to their control groups. However, the postpartum dam weights of both F₀ and F₁ female rats were significantly reduced compared to their controls. Exposure of ZnCl₂ to F_o and F₁ generation parental rats did not produce any significant change of their clinical signs as well as their clinical pathology parameters, except the alkaline phosphotase (ALK) level, which showed an upward trend in both sexes of both generations. Exposure of ZnCl₂ to F₀ rats resulted in a reduction of brain, liver, kidney, spleen and seminal vesicles weights of males and in the spleen and uterus of females. Similarly, exposure of F₁ rats to ZnCl₂ also resulted in reduction of brain, liver, kidney, adrenal, spleen, prostate and seminal vesicles weights of males and in spleen and uterus of females. ZnCl₂ exposure resulted in grossly observed gastro-intestianla (GI) tract, lymphoreticular/hematopoietic, and reproductive tract lesions in parental rats in both generations. Reduced body fat was also recorded in F₁ parental rats.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Effect of UV radiation and temperature on mineralization and volatilization of coumaphos in water

This study was undertaken to determine the dissipation and degradation of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] under different sunlight conditions and at different temperatures. The effect of the ultra violet (UV) component of solar radiation was also studied using quartz tubes in addition to other radiation in the visible range using glass tubes and the results were compared with those obtained under the dark light conditions. Water suspensions of coumaphos were incubated at three temperatures viz. 22°C, 37°C and 53°C in closed systems to study the effect of temperature. Volatilization, mineralization and degradation of coumaphos increased with an increase in temperature and exposure to solar radiation, particularly under the UV component of the solar radiation. Major loss of the pesticide occurred through volatilization. The optimum temperature for the degradation of coumaphos was found to be at 37°C. The data obtained from the mineralization and degradation studies indicated that 53°C crosses the biological range for suitable growth of microorganism. UV radiation exposure along with maintaining temperature at 37°C may prove useful in the dissipation and/or degradation of coumaphos prior to its disposal as waste from cattle dipping vats.     

Impact of redox conditions on metolachlor and metribuzin degradation in mississippi flood plain soils

Abstract

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd^‐1 and 25 ngd^‐1, respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd^‐1 and 32.5 ngd^‐1, respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd^‐1 and 12.0 ngd^‐1 for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd^‐1 and 5.35 ngd^‐1. Metribuzin degraded faster (12.0 ngd^‐1) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd^‐1).     

Use of cholinesterase activity in monitoring chlorpyrifos exposure of steer cattle after topical administration

The aim of this work was to study the pharmacokinetic behavior and the inhibitory effect of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities of chlorpyrifos (CPF) in steer cattle after pour-on administration. Determination of cholinesterase activity in plasma and erythrocyte was carried out according to Ellman kinetic method. CPF was analyzed by gas chromatography. AChE was the predominant form of cholinesterase analyzed, with low levels of BChE in plasma. Following the treatment with CPF, the maximum inhibitory effect on AChE or BChE were 50.88 ± 11.57 and 42.66 ± 12.01%, respectively. The chlorpyrifos plasma concentrations observed were low and they presented a high variability. Chlorpyrifos peak plasma concentration (10.42 ± 4.76 μ g/L) was reached at 8.42 ± 13.97 h. The pesticide was not detected in plasma after 48 h post treatment. The values of area under the curve (AUC) were 118.48 ± 87.46 μ g· h/L and mean resistance time (MRT) were 13.38 ± 10.41 h. The pour-on exposure to the organophosphate chlorpyrifos significantly reduced AChE and BChE activity in steer cattle and the recovery was not reached on 50 days post-treatment.