Effects of the organophosphate insecticide azinphos-methyl on the reproduction and cholinesterase activity of Biomphalaria glabrata

Azinphos-methyl is an organophosphate insecticide used for pest control on a number of food crops in many parts of the world. The snail Biomphalaria glabrata is a freshwater gastropod widely distributed in South America, Central America and Africa. The aim of the present work was to investigate whether azinphos-methyl causes alterations in the reproduction of B. glabrata. To this end, gastropod pigmented specimens were exposed to various concentrations of the insecticide (0.021, 0.5, 2.5, and 5 mg L⁻¹) for either 2 or 14 d. Along 14 d, several reproduction parameters and cholinesterase (ChE) activity were evaluated. In each group, the number of egg masses, the number of eggs per mass, the number of hatchings, the time to hatching, and the survival of the offspring after one month of treatment was evaluated. The results showed that, depending on the concentration and time of exposure, azinphos-methyl induced alterations in the reproduction of B. glabrata. These alterations were mainly represented by a decrease in the number of egg masses, and, in some cases, by a lower number or even the total absence of hatchings. Thus, the gastropods exposed to 2.5 and 5 mg L⁻¹ of azinphos-methyl for 14 d showed ChE inhibitions higher than 35% along time and completely lost their ability to reproduce. On the other hand, exposure to high acute concentrations or exposure to low concentrations for 14 d resulted in ChE inhibition equal to or lower than 35% between 7 and 14 d of treatment and similar alterations in reproduction. These were represented by a decrease in the number of egg masses. At low pestice levels, the number of egg masses and the number of offspring resulted to be more sensitive biomarkers than ChE inhibition. It is concluded that the insecticide azinphos-methyl can cause a decline in the reproductive performance of B. glabrata.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.     

Biodegradation of aromatic hydrocarbons by Haloarchaea and their use for the reduction of the chemical oxygen demand of hypersaline petroleum produced water

Ten halophilic Archaea (Haloarchaea) strains able to degrade aromatic compounds were isolated from five hypersaline locations; salt marshes in the Uyuni salt flats in Bolivia, crystallizer ponds in Chile and Cabo Rojo (Puerto Rico), and sabkhas (salt flats) in the Persian Gulf (Saudi Arabia) and the Dead Sea (Israel and Jordan). Phylogenetic identification of the isolates was determined by 16S rRNA gene sequence analysis. The isolated Haloarchaea strains were able to grow on a mixture of benzoic acid, p-hydroxybenzoic acid, and salicylic acid (1.5 mM each) and a mixture of the polycyclic aromatic hydrocarbons, naphthalene, anthracene, phenanthrene, pyrene and benzo[a]anthracene (0.3 mM each). Evaluation of the extent of degradation of the mixed aromatic hydrocarbons demonstrated that the isolates could degrade these compounds in hypersaline media containing 20% NaCl. The strains were shown to reduce the COD of hypersaline crude oil reservoir produced waters significantly beyond that achieved using standard hydrogen peroxide treatment alone.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

Effects of a glyphosate-based herbicide on mate location in a wolf spider that inhabits agroecosystems

Chemical communication is important to many arthropod species but the potential exists for anthropogenic chemicals to disrupt information flow. Although glyphosate-based herbicides are not acutely toxic to arthropods, little is known regarding their effects on natural chemical communication pathways. The wolf spider, Pardosamilvina, is abundant in agroecosystems where herbicides are regularly applied and uses air- and substrate-borne chemical signals extensively during mating. The aim of this study was to examine effects of a commercial formulation of a glyphosate-based herbicide on the ability of males to find females. In the field, virgin females, when hidden inside pitfall traps with herbicide, attracted fewer males than females with water. Likewise females in traps with a ring of herbicide surrounding the opening were less likely to attract males than those in traps surrounded by water. We explored the reaction of males to any airborne component of the herbicide in a laboratory two-choice olfactometer experiment. When no female pheromones were present, males were equally likely to select herbicide or water treated corridors and they all moved through the apparatus at similar speeds. When female pheromones were present, the males that selected control corridors moved more slowly than those that selected herbicide and, if we control for the initial decision time, more males selected the control corridors over the herbicide. These data suggest that glyphosate-based herbicides are “info-disruptors” that alter the ability of males to detect and/or react fully to female signals.     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

PCDD/F enviromental impact from municipal solid waste bio-drying plant

The present work indentifies some environmental and health impacts of a municipal solid waste bio-drying plant taking into account the PCDD/F release into the atmosphere, its concentration at ground level and its deposition. Four scenarios are presented for the process air treatment and management: biofilter or regenerative thermal oxidation treatment, at two different heights. A Gaussian dispersion model, AERMOD, was used in order to model the dispersion and deposition of the PCDD/F emissions into the atmosphere. Considerations on health risk, from different exposure pathways are presented using an original approach. The case of biofilter at ground level resulted the most critical, depending on the low dispersion of the pollutants. Suggestions on technical solutions for the optimization of the impact are presented.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.