Photoinduced reduction of divalent mercury in ice by organic matter

Reduction of divalent mercury and subsequent emission to the atmosphere has been identified as loss process from surface snow, but its mechanism and importance are still unclear. The amount of mercury that stays in the snow pack until spring is of significance, because during snow melt it may be released to the aquatic environment and enter the food web. Better knowledge of its fate in snow might further assist the interpretation of ice core data as paleo-archive. Experiments were performed under well-controlled laboratory conditions in a coated wall flow tube at atmospheric pressure and irradiated with light between 300 nm and 420 nm. Our results show that the presence of benzophenone and of oxalic acid significantly enhances the release of mercury from the ice film during irradiation, whereas humic acid is less potent to promote the reduction. Further it was found that oxygen or chloride, and acidic conditions lowered the photolytically induced mercury release in the presence of benzophenone, while the release got larger with increasing temperatures.     

TiO₂-based nanoparticles released in water from commercialized sunscreens in a life-cycle perspective: structures and quantities

This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO₂-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO₂ concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO₂ residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO₂ initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO₂ residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO₂ potentially released into AQUATIC environment.     

Chlorpyrifos residues levels in fruits and vegetables after field treatment

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate) was applied with three different formulations on oranges, peaches, tomatoes, wine and table grapes, and its behaviour was evaluated after field treatment. The formulations applied were emulsifiable concentrates (EC), microencapsulates (ME), and wettable granules (WG). The residues were similar in all crops studied in the EC and WG experiments, except peaches with WG treatment, the residue amount was lower than EC values. Tomatoes which were grown in greenhouse showed similar residues in all treatments just after treatment. Wine and table grapes showed different decline curves in the EC experiments ascribable to the different growing technology. Instrumental limit of determination (LOD) and limit of quantification (LOQ) for all matrices were 0.01, and 0.03 mg kg?1, respectively. Repeated treatments showed that Chlorpyrifos can accumulate leading to residue levels at the preharvest interval (PHI) over the maximum residue level (MRL), especially on oranges and peaches. Among the formulates used ME showed the higher risk of residues over the MRL at harvest.     

Is the reproduction of Donax trunculus affected by their sites of origin contrasted by their level of contamination?

The reproductive cycle of bivalves is regulated by several natural environmental factors but exposure to chemical pollutants can also interfere and may result in advanced or delayed spawning season. To our knowledge, the gametogenic cycle of the suspension-feeder bivalve Donax trunculus has not yet been used as biomonitoring tool in ecotoxicological surveys. The aim of this study was to examine over a year physiological reproductive endpoints (sex-ratio, gametogenic and energy reserve cycles) and biological indices (condition index, allometry) in D. trunculus originating from two sites differing by their level of contamination. Specimens were collected bimonthly from November 2008 to October 2009 from a polluted site (Radès Méliane) and a comparatively reference site (Sidi Jehmi) in the Gulf of Tunis (Tunisia). Five stages were depicted by histological examination of gonads: undifferentiated, developing, mature, spawn and spent. Differences in the gametogenic cycle according to the site of origin of bivalves were observed. The spawning period began in March and was maximum in May in bivalves from both sites, but the percentage of spawning animals was higher in the polluted site vs the reference site. The spawning period was shorter in animals from the polluted site comparatively to the reference site. Energy reserves (glycogen, lipids) were higher in March and May comparatively to the other studied periods in bivalves from both sites. Lower energy reserves levels were usually observed in animals from the polluted site compared to the reference site. Seasonal variations of the condition index were associated to the reproductive and nutritive status of bivalves. Differences in allometry were depicted between bivalves from both studied sites. If we try to link allometry, energy reserves and reproduction, it can be hypothesized that for bivalves from the reference site, energy reserves are allocated to gametogenesis and length growth. For bivalves from the polluted site, energy reserves could be devoted to tolerance to chemical stress and to reproductive processes. Therefore, D. trunculus appears as a suitable sentinel species for the assessment of the ecotoxicological risk of contaminants such as endocrine disruptors.     

A soil sampling intercomparison exercise for the ALMERA network

Soil sampling and analysis for radionuclides after an accidental or routine release is a key factor for the dose calculation to members of the public, and for the establishment of possible countermeasures. The IAEA organized for selected laboratories of the ALMERA (Analytical Laboratories for the Measurement of Environmental Radioactivity) network a Soil Sampling Intercomparison Exercise (IAEA/SIE/01) with the objective of comparing soil sampling procedures used by different laboratories. The ALMERA network is a world-wide network of analytical laboratories located in IAEA member states capable of providing reliable and timely analysis of environmental samples in the event of an accidental or intentional release of radioactivity. Ten ALMERA laboratories were selected to participate in the sampling exercise. The soil sampling intercomparison exercise took place in November 2005 in an agricultural area qualified as a “reference site”, aimed at assessing the uncertainties associated with soil sampling in agricultural, semi-natural, urban and contaminated environments and suitable for performing sampling intercomparison. In this paper, the laboratories sampling performance were evaluated.     

A stochastic Lagrangian micromixing model for the dispersion of reactive scalars in turbulent flows: role of concentration fluctuations and improvements to the conserved scalar theory under non-homogeneous conditions

Several reaction schemes, based on the conserved scalar theory, are implemented within a stochastic Lagrangian micromixing model to simulate the dispersion of reactive scalars in turbulent flows. In particular, the formulation of the reaction-dominated limit (RDL) reaction scheme is here extended to improve the model performance under non-homogeneous conditions (NHRDL scheme). The validation of the stochastic model is obtained by comparison with the available measurements of reactive pollutant concentrations in a grid-generated turbulent flow. This test case describes the dispersion of two atmospheric reactant species (NO and O₃) and their reaction product (NO₂) in an unbounded turbulent flow. Model inter-comparisons are also assessed, by considering the results of state-of-the-art models for pollutant dispersion. The present validation shows that RDL reaction scheme provides a systematic overestimation (relative error of ca. 85% around the centreline) in computing the local reactant consumption/production rate, whereas the NHRDL scheme drastically reduces this gap (relative error lower than 5% around the centreline). In terms of NO₂ production (or reactant consumption), neglecting concentration fluctuations determines overestimations of the product mean of around 100% and a NO₂ local production of one order of magnitude higher than the reference simulation. In terms of standard deviations, the concentration fluctuations of both the passive and reactive scalars are generally of the same order of magnitude or up to 1 or 2 orders of magnitudes higher than the corresponding ensemble mean values, except for the background reactant close to the plume edges. The study highlights the importance of modelling pollutant reactions depending on the instantaneous instead of the mean concentrations of the reactants, thus quantifying the role of the turbulent fluctuations of concentration, in terms of scalar statistics (mean, standard deviation, intensity of fluctuations, skewness and kurtosis of concentration, segregation coefficient, simulated reaction rate). This stochastic particle method represents an efficient numerical technique to solve the convection–diffusion equation for reactive scalars and involves several application fields: micro-scale air quality (urban and street-canyon scales), accidental releases, impact of odours, water quality and fluid flow industrial processes (e.g. combustion).     

Local Arctic air pollution: Sources and impacts

Local emissions of Arctic air pollutants and their impacts on climate, ecosystems and health are poorly understood. Future increases due to Arctic warming or economic drivers may put additional pressures on the fragile Arctic environment already affected by mid-latitude air pollution. Aircraft data were collected, for the first time, downwind of shipping and petroleum extraction facilities in the European Arctic. Data analysis reveals discrepancies compared to commonly used emission inventories, highlighting missing emissions (e.g. drilling rigs) and the intermittent nature of certain emissions (e.g. flaring, shipping). Present-day shipping/petroleum extraction emissions already appear to be impacting pollutant (ozone, aerosols) levels along the Norwegian coast and are estimated to cool and warm the Arctic climate, respectively. Future increases in shipping may lead to short-term (long-term) warming (cooling) due to reduced sulphur (CO₂) emissions, and be detrimental to regional air quality (ozone). Further quantification of local Arctic emission impacts is needed.     

Methane biofiltration in the presence of ethanol vapor under steady and transient state conditions: an experimental study

Methane (CH₄) removal in the presence of ethanol vapors was performed by a stone-based bed and a hybrid packing biofilter in parallel. In the absence of ethanol, a methane removal efficiency of 55 ± 1% was obtained for both biofilters under similar CH₄ inlet load (IL) of 13 ± 0.5 g_CH4 m^?3 h^?1 and an empty bed residence time (EBRT) of 6 min. The results proved the key role of the bottom section in both biofilters for simultaneous removal of CH₄ and ethanol. Ethanol vapor was completely eliminated in the bottom sections for an ethanol IL variation between 1 and 11 g_ethanol m^?3 h^?1. Ethanol absorption and accumulation in the biofilm phase as well as ethanol conversion to CO₂ contributed to ethanol removal efficiency of 100%. In the presence of ethanol vapor, CO₂ productions in the bottom section increased almost fourfold in both biofilters. The ethanol concentration in the leachate of the biofilter exceeding 2200 g_ethanol m^?3 _leachate in both biofilters demonstrated the excess accumulation of ethanol in the biofilm phase. The biofilters responded quickly to an ethanol shock load followed by a starvation with 20% decrease of their performance. The return to normal operations in both biofilters after the transient conditions took less than 5 days. Unlike the hybrid packing biofilter, excess pressure drop (up to 1.9 cmH₂O m^?1) was an important concern for the stone bed biofilter. The biomass accumulation in the bottom section of the stone bed biofilter contributed to 80% of the total pressure drop. However, the 14-day starvation reduced the pressure drop to 0.25 cmH₂O m^?1.     

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.     

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.