Distribution and relationships of As,Cd, Pb and Hg in freshwater fish from five French fishing areas

The concentrations of arsenic, cadmium, mercury and lead in 149 muscle samples of eight freshwater fish species (European eel, bream, common carp, European catfish, roach, perch, pike and pikeperch) from five different French fishing areas from contaminated and control sites were measured by inductively coupled plasma mass spectrometry after microwave digestion under pressure. No significant correlation was found between the condition factor (CF), based on the length–mass relationship, and As, Cd and Pb levels in all the samples analysed, but a positive correlation was detected between CF and Hg levels (P < 0.0001, R = 0.49). Positive correlations with body length were only found for Hg in roach (P < 0.05, R = 0.32) and Pb in bream (P < 0.05, R = 0.48) and correlations with both body weight and length were also found for Hg in pike (P < 0.05, R = 0.90 and 0.86) and Cd in European eel (P < 0.01, R = ?0.35 and ?0.37). The average content and the standard deviation in fish muscle samples was 0.007 ± 0.012, 0.102 ± 0.077, 0.142 ± 0.097 and 0.035 ± 0.053 mg kg^?1 of wet mass for Cd, As, Hg and Pb, respectively. Significant differences were established between groups of predatory fish and non-predatory fish for Hg and Pb, and between control and contaminated sites in the whole selection and also within feeding guilds, i.e. the values of Hg in the benthophagic fish were significantly different between these sites. Finally, these results were also compared for each species with previous French and European studies.     

pH-gradient real-time aeration control for nitritation community selection in a non-porous hollow fiber membrane biofilm reactor (MBfR) with dilute wastewater

Nitritation (ammonium to nitrite) as a pre-treatment of Anammox (anaerobic ammonium oxidation) is a key step for an energy-efficient nitrogen-removal alternative from dilute wastewaters, e.g. anaerobically-treated sewage, with which limited study has achieved sustainable nitritation at ambient temperature and short hydraulic retention times. To this end, pH-gradient real-time aeration control in an oxygen-based membrane biofilm reactor was observed at 20 °C in the sequencing batch mode. An optimum oxygen supply via diffusion for ammonium-oxidizing bacteria (AOB) was established, but nitrite-oxidizing bacteria (NOB) could be inhibited. The system achieved nitrite accumulation efficiencies varying from 88% to 94% with the aeration control. Mass balance and rate performance analyses indicate that this aeration control is able to supply an oxygen rate of 1.5 mol O₂ mol^?1 ammonium fed, the benchmark oxygenation rate based on stoichiometry for nitritation community selection. Microbial analyses confirmed AOB prevalence with NOB inhibition under this aeration control.     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.     

Solubilities of selected organic electronic materials in pressurized hot water and estimations of aqueous solubilities at 298.15 K

Increasing production and disposal of organic light-emitting diode (OLED) displays for smartphones and tablets may have impact on the environment depending on the aqueous solubility of the pertinent chemicals. Here, aqueous solubilities are presented for several compounds, mostly aromatic amines, used as hole transport materials in the OLED displays. Solute selection includes 1,4-bis(diphenylamino)benzene, tetra-N-phenylbenzidine, 4,4′-bis(N-carbazolyl)-1,1′-biphenyl, 1,3,5-tris(diphenylamino)benzene, and 9,10-bis(phenylethynyl)anthracene. The solubilities are those in pressurized hot water (PHW), i.e., measured at elevated temperature (up to 260 °C) and pressure. The semi-quantitative estimates of room-temperature solubilities of the solutes have been obtained from extrapolations of the solubilities in PHW. For the compounds studied, the estimated aqueous solubilities at room temperature do not exceed 2 × 10^?11 g of the solute per 1 kg of water. Aqueous solubilities of triphenylamine have also been measured and used to upgrade a recent group-contribution model of aqueous solubilities of organic nonelectrolytes with the parameters for the nitrogen atom in aromatic amines.     

Chiral signature of venlafaxine as a marker of biological attenuation processes

The chiral signature of the antidepressant venlafaxine was used in this study to gain insight into biological attenuation processes and to differentiate abiotic and biotic transformation processes in water. Laboratory scale experiments revealed that sorption and phototransformation processes were not enantioselective while venlafaxine was enantioselectively biotransformed into O-desmethylvenlafaxine. The enantiomeric fraction (EF) variations of venlafaxine appeared to be proportional to its microbial fractional conversion. Enantioselective biotransformation of venlafaxine was also investigated in a eutrophic French river. Venlafaxine was found to be racemic at the output of the main wastewater treatment plant discharging into the river, independently of the sampling date during the year. An analysis of EF variations might provide evidence of biodegradation along a 30 km river stretch.     

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.     

Screening Capsicum Accessions for Capsaicinoids Content

Ninety Capsicum accessions selected from the USDA Capsicum germplasm collection were screened for their capsaicinoids content using gas hromatography with nitrogen phosphorus detection (GC/NPD). Fresh fruits of Capsicum chinense, C. frutescens, C. baccatum, C. annuum, and C. pubescens were extracted with methanol and analyzed for capsaicin, dihydrocapsaicin, and nordihydrocapsaicin. Mass spectrometry of the fruit crude extracts indicated that the molecular ions at m/z 305, 307, and 293, which correspond to capsaicin, dihydrocapsaicin, and nordihydrocapsaicin, respectively, have a common benzyl cation fragment at m/z 137 that can be used for monitoring capsaicinoids in pepper fruit extracts. Capsaicin and dihydrocapsaicin were the dominant capsaicinoids detected. Capsaicin concentrations were typically greater than dihydrocapsaicin. Concentrations of total capsaicinoids varied from not detectable to 11.2 mg fruit^?1. Statistical analysis revealed that accession PI-441624 (C. chinense) had the highest capsaicin content (2.9 mg g^?1 fresh fruit) and accession PI-497984 (C. frutescens) had the highest dihydrocapsaicin content (2.3 mg g^?1 fresh fruit). Genebank accessions PI-439522 (C. frutescens) and PI-497984 contained the highest concentrations of total capsaicinoids.     

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.