Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

Binary mixtures of azinphos-methyl oxon and chlorpyrifos oxon produce in vitro synergistic cholinesterase inhibition in Planorbarius corneus

In this study, the cholinesterase (ChE) and carboxylesterase (CES) activities present in whole organism homogenates from Planorbarius corneus and their in vitro sensitivity to organophosphorous (OP) pesticides were studied. Firstly, a characterization of ChE and CES activities using different substrates and selective inhibitors was performed. Secondly, the effects of azinphos-methyl oxon (AZM-oxon) and chlorpyrifos oxon (CPF-oxon), the active oxygen analogs of the OP insecticides AZM and CPF, on ChE and CES activities were evaluated. Finally, it was analyzed whether binary mixtures of the pesticide oxons cause additive, antagonistic or synergistic ChE inhibition in P. corneus homogenates. The results showed that the extracts of P. corneus preferentially hydrolyzed acetylthiocholine (AcSCh) over propionylthiocholine (PrSCh) and butyrylthiocholine (BuSCh). Besides, AcSCh hydrolyzing activity was inhibited by low concentrations of BW284c51, a selective inhibitor of AChE activity, and also by high concentrations of substrate. These facts suggest the presence of a typical AChE activity in this species. However, the different dose-response curves observed with BW284c51 when using PrSCh or BuSCh instead of AcSCh suggest the presence of at least another ChE activity. This would probably correspond to an atypical BuChE. Regarding CES activity, the highest specific activity was obtained when using 2-naphthyl acetate (2-NA), followed by 1-naphthyl acetate (1-NA); p-nitrophenyl acetate (p-NPA), and p-nitrophenyl butyrate (p-NPB). The comparison of the IC(50) values revealed that, regardless of the substrate used, CES activity was approximately one order of magnitude more sensitive to AZM-oxon than ChE activity. Although ChE activity was very sensitive to CPF-oxon, CES activity measured with 1-NA, 2-NA, and p-NPA was poorly inhibited by this pesticide. In contrast, CES activity measured with p-NPB was equally sensitive to CPF-oxon than ChE activity. Several specific binary combinations of AZM-oxon and CPF-oxon caused a synergistic effect on the ChE inhibition in P. corneus homogenates. The degree of synergism tended to increase as the ratio of AZM-oxon to CPF-oxon decreased. These results suggest that synergism is likely to occur in P. corneus snails exposed in vivo to binary mixtures of the OPs AZM and CPF.     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.     

An approach for restoration of the water quality with emphasis on the removal of organochlorine pesticides and eutrophic conditions in tropical rivers

This work deals with an approach for the water quality restoration with emphasis on the removal of organochlorine pesticides and eutrophic conditions in tropical rivers, causing influence on the management of the central-regional aqueduct, as a source of water supply for human consumption (4 million people) and industrial production in the states of Carabobo, Cojedes and Aragua, Venezuela, testing the phytoremediation techniques through Vetiveria zizanioides (VZ) species and coupled bioreactors, Sequencing Batch Reactor (SBR) followed by an Upflow Anaerobic Filter in Three Separate Stages (UAF-3SS). Five rivers are involved known as Chirgua, Paito Guacara, Ereigüe, and Tucutunemo, whose waters have been classified as hypereutrophic, and containing organochlorine pesticides (OCPs). As a sample, for Tucutunemo River, OCPs included to DDT (dichlorodiphenyltrichloroethane) and its isomers and DRINs (Aldrin, Endrin and Dieldrin) dissolved in water and sorbed on sediments, which were measured during the dry and rainy seasons in the period 2013 to 2016, in three monitoring stations distributed in a reach of 15 km. The results indicated that p.p′-DDT concentration dissolved in water was increased up to 10 times from rainy to dry seasons, indicating that a permanent use of it is being carried out by farmers in the agricultural activity development. Steady concentrations of the DTT isomers (e.g., p.p′-DDD and p.p′-DDE) and Aldrin isomers (e.g., Dieldrin) demonstrated that the anaerobic and aerobic biodegradation processes occurred along the river and between climatic seasons. At experimental scale, VZ hydroponic system developed over a period of 6 months for the removal of nutrients demonstrated moderately low to high removal efficiencies. With respect coupled bioreactors, each bioreactor has been experimentally tested, demonstrating satisfactory performance in Chemical Oxygen Demand (COD) removal from industrial wastewater containing recalcitrant and inhibitory substances (46%–98%), which was estimated in the influent ranging from 3500 to 5500 mg/L, evidencing that coupling of bioreactors might lead to a effluent COD complying with environmental regulations.     

Evaluation of the Impact of Acid Mine Drainage on the Chemistry and the Macrobenthos in the Carolina Stream (San Luis – Argentina)

The purpose of this study was to evaluate the impact of acid mine drainage on the chemistry and the macrobenthos of the Carolina stream (San Luis – Argentina). Samples were obtained in the years 1997–1998 at two sites: site C₁, located 200 m upstream of the drainage, and site C₂, located 800 m downstream. The system buffer capacity was evaluated in the non – contaminated site by means of the buffer index calculation. The physico – chemical changes observed as a consequence of the contribution of acid mine drainage (AMD) were: a decreasing of pH and an increase in the ionic concentration, especially sulfate and Fe coming from the oxidation produced by chemiolithotrophic bacteria. The values obtained indicated a low buffer capacity and a high intrinsic vulnerability of the system to resist the impact originated by the AMD, producing a remarkable decreasing of pH of the receiving stream. These changes caused modifications in the original benthic community that was replaced by organisms more tolerant to the acid stress. A reduction in the abundance and in the taxonomic richness of the benthic macroinvertebrates was observed when compared with the reference station. An increase in the proportion of Chironomidae and of Acari and a decrease in the proportion of the remaining taxa were observed. The most sensitive groups were Ephemeroptera, Trichoptera and Mollusca. The community was mostly affected by the following variables: pH, conductivity, sulfate and dissolved total Fe.     

Inhalation of vanadium modifies gap junctions in mouse seminiferous tubules

Vanadium (V) adhering to inhaled particles has been associated with male reproductive alterations. Intercellular junction proteins, such as connexin 43, constitute the blood-testes barrier. These proteins are crucial for the reconstitution of the barrier during spermatogenesis. Normally, connexins are located between cell membranes but in cells exposed to certain metals or which are transformed, their location is altered. The objective of this study was to examine the effect of the inhalation of vanadium pentoxide on the distribution of connexin 43 in seminiferous tubules of mice. Immunohistochemical localization of connexin 43 demonstrated the redistribution of the protein that increased with time of exposure while intensity of stain on the membranes decreased. In previous studies, reduction in the actin and γ-tubulin stain intensity upon V inhalation has been observed. All these alterations may explain the reprotoxic effect associated with vanadium.     

Effectiveness and potential ecological effects of offshore surface dispersant use during the Deepwater Horizon oil spill: a retrospective analysis of monitoring data

The Special Monitoring of Applied Response Technologies (SMART) program was used during the Deepwater Horizon oil spill as a strategy to monitor the effectiveness of sea surface dispersant use. Although SMART was implemented during aerial and vessel dispersant applications, this analysis centers on the effort of a special dispersant missions onboard the M/V International Peace, which evaluated the effectiveness of surface dispersant applications by vessel only. Water samples (n?=?120) were collected from background sites, and under naturally and chemically dispersed oil slicks, and were analyzed for polycyclic aromatic hydrocarbons (TPAHs), total petroleum hydrocarbons (TPH), and a chemical marker of Corexit® (dipropylene glycol n-butyl ether, DPnB). Water chemistry results were analyzed relative to SMART field assessments of dispersant effectiveness (“not effective,” “effective,” and “very effective”), based on in situ fluorometry. Chemistry data were also used to indirectly determine if the use of dispersants increased the risk of acute effects to water column biota, by comparison to toxicity benchmarks. TPAH and TPH concentrations in background, and naturally and chemically dispersed samples were extremely variable, and differences were not statistically detected across sample types. Ratios of TPAH and TPH between chemically and naturally dispersed samples provided a quantitative measure of dispersant effectiveness over natural oil dispersion alone, and were in reasonable agreement with SMART field assessments of dispersant effectiveness. Samples from “effective” and “very effective” dispersant applications had ratios of TPAH and TPH up to 35 and 64, respectively. In two samples from an “effective” dispersant application, TPHs and TPAHs exceeded acute benchmarks (0.81 mg/L and 8 μg/L, respectively), while none exceeded DPnB’s chronic value (1,000 μg/L). Although the primary goal of the SMART program is to provide near real-time effectiveness data to the response, and not to address concerns regarding acute biological effects, the analyses presented here demonstrate that SMART can generate information of value to a larger scientific audience. A series of recommendations for future SMART planning are also provided.     

Determination of three alkylphenol isomers in various water samples using a new HPLC method based on a duet stationary phase

The level of three alkylphenols (APs) 4-nonylphenol, 4-octylphenol and 4-tert-octylphenol was monitored in various water samples using a new developed and validated HPLC method. The HPLC method employed a column with a mixed-mode stationary phase (C18/SCX) using a mobile phase of water to methanol?=?15:85 (v/v) delivered at a flow rate of 1 mL/min at room temperature. Both diode array, DAD and fluorescence, FLD detectors were employed. The method is linear when APs concentration ranged from 0.025 to 0.5 μg/mL with a DAD detection at 279 nm and between 0.0008 and 0.1 μg/mL when the detection was made by FLD (excitation at 220 nm, emission at 315 nm). The limit of detection and limit of quantitation for alkylphenols were found to be 5 and 15 ng/mL, respectively (detection by DAD). The method was employed with good results for the determination of APs in the presence of polycyclic aromatic hydrocarbons in various water samples.     

Chloroperoxidase-mediated transformation of highly halogenated monoaromatic compounds

Peroxidase transformations of widely distributed pollutants, tetra- and penta-chlorinated phenols and anilines, were studied using different peroxidases. Chloroperoxidase from Caldariomyces fumago was able to transform tetra- and penta-chlorinated phenols and anilines, while horseradish peroxidase, lignin peroxidase from Phanerochaete chrysosporium and versatile peroxidase from Bjerkandera adusta were able only to transform the halogenated phenols. Chloroperoxidase showed a specific activity on pentachlorophenol two orders of magnitude higher than lignin peroxidase and horseradish peroxidase, and one order of magnitude higher than versatile peroxidase. The main product from peroxidase oxidation in all cases was a polymeric and insoluble material. The insolubilization of halogenated phenols and anilines permits their removal, reduces their bioavailability, and thus reduces their environmental impact. The other minor products from the enzymatic transformation of highly chlorinated compounds were determined by mass spectrometry. Tetrachloroquinone, dimers and trimers of halogenated compounds were also identified. Chloroperoxidase was able to halogenate tetrachloroaniline to form pentachloroaniline.