Sulfur and oxygen isotope tracing in zero valent iron based In situ remediation system for metal contaminants

In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20 ± 1 °C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ³⁴S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ³⁴S and δ¹⁸O in biotic conditions and we also highlight a good relationship between δ³⁴S and sulfate reduction rate in biotic columns.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Impact of long‐term pesticide applications on some soil biological parameters

Abstract

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (São Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)‐activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron‐oxide reduction, and the microbial biomass was estimated by the substrate (glucose)‐indiced respiration. Increases in DHA‐activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron‐reduction. In the experimental field soil, the increases in DHA‐activity were followed only by decreases in iron‐reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

Phytoavailability and extractability of potassium,magnesium and manganese in calcareous soil amended with olive oil wastewater

Abstract

Land disposal of olive oil wastewater using it as a soil amendment requires a knowledge of the effects that its application may produce on the status of the mineral nutrients in the plant‐soil system. A pot experiment using calcareous soil was performed in a growth chamber to examine the effects of olive oil wastewater on the availability and postharvest soil extractability of K, Mg and Mn. The experiment included 6 treatments: two rates of olive oil wastewater, two mineral fertilizer treatments containing K (which supplied K in amounts equivalent to the K supplied by the olive oil wastewater treatments), a K‐free mineral fertilizer treatment, and a control. The pots were sown with ryegrass as the test plant, harvesting 3 times at intervals of one month. Olive oil wastewater has demonstrated a considerable capacity for supplying K that can be assimilated by the plant, tending in fact to surpass the mineral potassium fertilizer tested. The application of olive oil wastewater tends to reduce the concentration of Mg in the plant, similarly to the effect of adding mineral potassium fertilizer. An enhancement of Mn availability takes place in the soil amended with olive oil wastewater, which on occasion has produced Mn concentrations in plant that could be considered phytotoxic or at least excessive. After harvesting, we observed an increase in the amount of exchangeable K in soil with added industrial wastewater. However, these increases are lower than those in soil treated with mineral potassium fertilizer. The levels of exchangeable, carbonate‐bound, organic‐bound and residual Mg in soil were higher in treatments incorporating olive oil wastewater than in those with added mineral K, with the opposite tendency occurring in the amount of Fe‐Mn oxides‐bound Mg in soil. Treatments based on olive oil wastewater, especially in high doses, increased the amount of exchangeable and carbonate‐bound Mn in soil, in comparison with treatments adding mineral fertilizers with or without K. In contrast, the addition of industrial wastewater caused a drop in the amount of Fe‐Mn oxides‐bound and organic‐bound Mn in soil.     

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.     

Treatment of wastewater from red and tropical fruit wine production by zeolite anaerobic fluidized bed reactor

A study of the anaerobic treatment of wastewaters derived from red (RWWW) and tropical fruit wine (TFWWW) production was carried out in four laboratory-scale fluidized bed reactors with natural zeolite as bacterial support. These reactors operated at mesophilic temperature (35°C). Reactors R1 and R2 contained Chilean natural zeolite, while reactors R3 and R4 used Cuban natural zeolite as microorganism support. In addition, reactors R1 and R3 processed RWWW, while reactors R2 and R4 used TFWWW as substrate. The biomass concentration attached to zeolites in the four reactors studied was found to be in the range of 44–46 g volatile solids (VS)/L after 90 days of operation time. Both types of zeolites can be used indistinctly in the fluidized bed reactors achieving more than 80%–86% chemical oxygen demand (COD) removals for organic loading rates (OLR) of up to at least 20 g COD/L d. pH values remained within the optimal range for anaerobic microorganisms for OLR values of up to 20 and 22 g COD/L d for RWWW and TFWWW, respectively. Toxicity and inhibition levels were observed at an OLR of 20 g COD/L d in reactors R1 and R3 while processing RWWW, whereas the aforementioned inhibitory phenomena were not observed at an OLR of 24 g COD/L d in R2 and R4, treating TFWWW as a consequence of the lower phenolic compound content present in this substrate. The volatile fatty acid (VFA) levels were always lower in reactors processing TFWWW (R2 and R4) and these values (< 400 mg/L, as acetic acid) were lower than the suggested limits for digester failure. The specific methanogenic activity (SMA) was twice as high in reactors R2 and R4 than in R1 and R3 after 120 days of operation when all reactors operated at an OLR of 20 g COD/L d.     

Estimation of sampling uncertainty for determination of pesticide residues in plant commodities

In order to provide residue data for refining the estimated sampling uncertainty, a coordinated research program was initiated for performing field studies on residues in individual items of leafy vegetables, small and large crops. The trials were carried out in 13 countries with 3 small fruits, 5 large crops, 2 medium/large crops and 3 leafy vegetables. The 25 pesticide active ingredients applied represented the dicarboximide (3), organophosphorus (8), synthetic pyrethroids (5), phthalimides (2), organochlorine (1) and other types of pesticides (6). In addition, 11 supervised field trials were performed in grapes and lettuce by the pesticide manufacturers, and their results were provided for evaluation. The studies represented actual agriculture practice around the world, and provide reliable data for estimation of sampling uncertainty. Based on the 12346 residue data, the best estimate for the relative sampling uncertainty for composite samples, assuming sample size of 10 for small crops and leafy vegetables and 5 for large crops, with 95% confidence limits in brackets are: small commodities: 0.25 (0.20–0.29); Brassica leafy vegetables: 0.20 (0.16–0.24); large commodities: 0.33 (0.29–0.38).     

Alterations in the rabbit lymphoid tissue after bendiocarb administration

Various pesticides have immuno-suppressive effects, and thus the organisms become responsive to viral, bacterial and parasitic diseases and neoplasm. The aim of the study was to observe the structure of the small intestine (height of enterocytes and crypts), mucosal lymphoid tissue (Payer's patches, lymphocytes in lamina propria) and a lymph node after administration of bendiocarb (2,2-dimethyl-1,3-benzodioxol-4-yl-methylcarbamate) on days 3, 10, 20, 30 and 60 of the experiment. The height of the observed enterocytes showed an increasing tendency. On days 20, 30 and 60 we also observed an increase in diameter of crypts located in intestinal epithelium. The number of cells in lamina propria mucosae was significantly reduced on days 20 and 30 after administration of bendiocarb. Observations of the lymph node showed that on days 10 and 20 there was a significant increase in relative volume of medulla at the expense of the relative volume of the cortex and a decrease in the number of lymphocytes. However, we recorded an increase in diameter of lymphocytes. The intracellular parasite Toxoplasma gondii (T. gondii) belongs to the most common pathogenic parasites in the world and it can cause serious health complications in pregnant and immunodeficient individuals. DNA isolation, standard polymerase chain reaction (PCR) and visualization in a 2.5 % agarose gel, the presence of DNA T. gondii was detected in no examined rabbit brain samples. Using real time PCR T. gondii DNA was detected and quantified in the three rabbit brain samples (10 %).     

Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

Micronucleus frequency in sheep lymphocytes after in vitro exposure to fungicide tolylfluanid

The fungicide tolylfluanid (N - dichlorofluoromethylthio-N′, N - dimethyl - N - p - tolylsulfamide), was investigated by cytokinesis-block micronucleus assay. Tolylfluanid at the lowest concentration (1 × 10^{? 6}mol L^{? 1})did not influence significantly the frequency of micronuclei in sheep lymphocyte cultures in comparison with control (32.33 ± 3.51/1000 binucleated cells versus 30.33 ± 2.82/1000 binucleated cells in dimethylsulfoxide (DMSO) control, P = 0.44). Higher tolylfluanid concentrations (1 × 10^{? 4} and, 1 × 10^{? 5} mol L^{? 1}) resulted in a significant dose-dependent increase in the number of micronuclei in comparison with control (74.00 ± 13.00/1000 binucleated cells and 52.67 ± 10.12/1000 binucleated cells versus 30.33 ± 2. 82/1000 binucleated cells in DMSO control, P = 0.005 and 0.02, respectively, ANOVA followed by Tukey test P < 0.05). Many of the treated cells also possessed multiple micronuclei. Tolylfluanid did not affect the nuclear division index at all treatment concentrations. Our in vitro results thus demonstrate that tolylfluanid had a significant genotoxic effect at only the highest concentration tested.