Reductive debromination of nonabrominated diphenyl ethers by sodium borohydride and identification of octabrominated diphenyl ether products

A method was developed to study reductive transformation of highly brominated diphenyl ethers (BDEs). The method development is a part of a broader project where it will be used to determine the susceptibility of environmental pollutants to reductive conditions, in an attempt to create a scheme for determination of chemical’s persistence. This paper focuses on identification of octabrominated diphenyl ether transformation products from reductive debromination of the three nonabrominated diphenyl congeners (nonaBDE), BDE-206, -207 and -208. Sodium borohydride was used to explore the reductive debromination of the nonaBDEs. The transformation products were collected at two time-points and identified products were quantified by GC-MS. The reduction of the nonaBDEs lead primarily to debrominated products, mainly octaBDEs. The three nonabrominated DEs gave isomer-related transformation product patterns. BDE-207 and BDE-208 showed a propensity for ortho-debromination in the initial reaction step, while no discrimination between initial debromination positions was seen for BDE-206. All three nonabrominated DEs displayed a preferred initial debromination on the fully brominated DE ring.     

Immunosuppression in the infaunal bivalve Scrobicularia plana environmentally exposed to mercury and association with its accumulation

This study aimed to test the hypothesis whether mercury (Hg) activates or suppresses inappropriately the immunity of the bivalve Scrobicularia plana inhabiting a Hg contaminated area (Laranjo basin, Ria de Aveiro, Portugal). Immunity endpoints, as well as lipid peroxidation (LPO) as a sign of damage, were evaluated in parallel with total Hg burden. Bivalves from both moderately (MO) and highly (HI) contaminated sites displayed higher haemolymph Hg load and reduced plasma agglutination. Increased haemocytes density and decreased phagocytosis were observed at HI, whereas increased oxidative burst activity (OBA) was observed at MO, pointing out that the immunotoxicity is a result of Hg direct contact involving no ROS intervention. OBA observed at MO was concomitantly associated to peroxidative damage as depicted by LPO increase in haemocytes and haemolymph plasma. Thus, S. plana can be suggested as a suitable bioindicator of metal pollution in coastal areas on the basis of Hg bioaccumulation and immunotoxicity responses.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

Reproduction and biochemical responses in Enchytraeus albidus (Oligochaeta) to zinc or cadmium exposures

To better understand chemical modes of action, emphasis has been given to stress responses at lower levels of biological organization. Cholinesterases and antioxidant defenses are among the most used biomarkers due to their crucial role in the neurocholinergic transmission and in cell homeostasis preventing DNA damage, enzymatic inactivation and lipid peroxidation. The main goal of this study was to investigate the effects of zinc and cadmium on survival and reproduction of E. albidus and to assess metals oxidative stress potential and neurotoxic effects at concentrations that affected reproduction. Both metals affected the enchytraeids’ survival and reproduction and induced significant changes in the antioxidant defenses as well as increased lipid peroxidation, indicating oxidative damage. This study demonstrates that determining effects at different levels of biological organization can give better information on the physiological responses of enchytraeids in metal contamination events and further unravel the mechanistic processes dealing with metal stress.     

Petroleum refinery stripped sour water treatment using the activated sludge process

A pilot study was performed over 91 days to determine if the activated sludge process could treat a segregated stripped sour water (SSW) stream from a petroleum refinery. The study was performed in two periods. The first period was terminated after 19 days, as a result of excessive sludge bulking. The elimination of sludge bulking during the 70-day second period is attributed to operational changes, which included aerating the influent to oxidize reduced sulfur, adjusting the influent pH, and adding micronutrients to satisfy biological requirements. The pilot plant provided a chemical oxygen demand (COD) removal of up to 93%. Nitrification was achieved, with effluent ammonia values < 1 mg-N/L. These results indicate that direct treatment of SSW with the activated sludge process is possible and has direct application to full-scale petroleum refinery wastewater plant upgrades.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Evaluation of groundwater contamination in a coastal area of south-eastern Sicily

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides…) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO?2?), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells.     

Detection of human-induced environmental disturbances in a show cave

Purpose  

We investigated the effects of human-induced disruption in a subterranean stable environment containing valuable Palaeolithic paintings and engravings (Ardales Cave, Southern Spain) using a double analytical approach.     

Temporal variations of atmospheric aerosol in four European urban areas

Purpose

The concentrations of PM₁₀ mass, PM_2.5 mass and particle number were continuously measured for 18 months in urban background locations across Europe to determine the spatial and temporal variability of particulate matter.

Methods

Daily PM₁₀ and PM_2.5 samples were continuously collected from October 2002 to April 2004 in background areas in Helsinki, Athens, Amsterdam and Birmingham. Particle mass was determined using analytical microbalances with precision of 1 ??g. Pre- and post-reflectance measurements were taken using smoke-stain reflectometers. One-minute measurements of particle number were obtained using condensation particle counters.

Results

The 18-month mean PM₁₀ and PM_2.5 mass concentrations ranged from 15.4 ??g/m³ in Helsinki to 56.7 ??g/m³ in Athens and from 9.0 ??g/m³ in Helsinki to 25.0 ??g/m³ in Athens, respectively. Particle number concentrations ranged from 10,091 part/cm³ in Helsinki to 24,180 part/cm³ in Athens with highest levels being measured in winter. Fine particles accounted for more than 60% of PM₁₀ with the exception of Athens where PM_2.5 comprised 43% of PM₁₀. Higher PM mass and number concentrations were measured in winter as compared to summer in all urban areas at a significance level p?Conclusions Significant quantitative and qualitative differences for particle mass across the four urban areas in Europe were observed. These were due to strong local and regional characteristics of particulate pollution sources which contribute to the heterogeneity of health responses. In addition, these findings also bear on the ability of different countries to comply with existing directives and the effectiveness of mitigation policies.