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.     

Identification of perfluoroalkyl acid sources in Swiss surface waters with the help of the artificial sweetener acesulfame

Anthropogenic perfluorinated compounds (PFCs), especially the perfluoroalkyl acids (PFAAs) are ubiquitously found in surface waters around the globe. Emissions from households, industries and also atmospheric transport/deposition are discussed as the possible sources. In this study, these sources are evaluated using Switzerland as the study area. Forty-four surface water locations in different rivers and an Alpine lake were investigated for 14 PFAAs, four precursors and acesulfame, an artificial sweetener used as a population marker. Concentrations of individual PFAAs were generally low, between 0.02 and 10 ng/L. Correlation analysis showed that some PFAAs concentrations correlated well with population and less with catchment area, indicating that emissions from population, i.e., from consumer products, is the most important source to surface waters in Switzerland. The correlation with the population marker acesulfame confirmed this observation but highlighted also a few elevated PFAA levels, some of which could be attributed to industrial emissions.     

Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions

Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500 μM hydrogen peroxide solution or locally-collected melted snow were measured in a field campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500 μM hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0 °C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration.     

Arsenic strongly associates with ferrihydrite colloids formed in a soil effluent

Arsenic mobility may increase in liquid phase due to association with colloidal Fe oxides. We studied the association of As with Fe oxide colloids in the effluent from water-saturated soil columns run under anoxic conditions. Upon exfiltration, the solutions, which contained Fe²⁺, were re-aerated and ferrihydrite colloids precipitated. The entire amount of effluent As was associated with the ferrihydrite colloids, although PO₄³⁻, SiO₄⁴⁻, CO₃²⁻ and dissolved organic matter were present in the effluent during ferrihydrite colloid formation. Furthermore, no subsequent release of As from the ferrihydrite colloids was observed despite the presence of these (in)organic species known to compete with As for adsorption on Fe oxides. Arsenic was bound via inner-sphere complexation on the ferrihydrite surface. FTIR spectroscopy also revealed adsorption of PO₄³⁻ and polymerized silica. However, these species could not impede the quantitative association of As with colloidal ferrihydrite in the soil effluents.     

Field sampling of soil pore water to evaluate trace element mobility and associated environmental risk

Monitoring soil pollution is a key aspect in sustainable management of contaminated land but there is often debate over what should be monitored to assess ecological risk. Soil pore water, containing the most labile pollutant fraction in soils, can be easily collected in situ offering a routine way to monitor this risk. We present a compilation of data on concentration of trace elements (As, Cd, Cu, Pb, and Zn) in soil pore water collected in field conditions from a range of polluted and non-polluted soils in Spain and the UK during single and repeated monitoring, and propose a simple eco-toxicity test using this media. Sufficient pore water could be extracted for analysis both under semi-arid and temperate conditions, and eco-toxicity comparisons could be effectively made between polluted and non-polluted soils. We propose that in-situ pore water extraction could enhance the realism of risk assessment at some contaminated sites.     

Phytostabilization of semiarid soils residually contaminated with trace elements using by-products: sustainability and risks

We investigated the efficiency of various by-products (sugarbeet lime, biosolid compost and leonardite), based on single or repeated applications to field plots, on the establishment of a vegetation cover compatible with a stabilization strategy on a multi-element (As, Cd, Cu, Pb and Zn) contaminated soil 4-6 years after initial amendment applications. Results indicate that the need for re-treatment is amendment- and element-dependent; in some cases, a single application may reduce trace element concentrations in above-ground biomass and enhance the establishment of a healthy vegetation cover. Amendment performance as evaluated by % cover, biomass and number of colonizing taxa differs; however, changes in plant community composition are not necessarily amendment-specific. Although the translocation of trace elements to the plant biotic compartment is greater in re-vegetated areas, overall loss of trace elements due to soil erosion and plant uptake is usually smaller compared to that in bare soil.     

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs��a global perspective on the management of Lindane and its waste isomers

Purpose

Hexachlorocyclohexane (HCH) isomers (??-, ??- and ??- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries.

Results

In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tonnes of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tonnes, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs?? contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production.

Conclusion

It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilisation. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.     

Importance of heterocylic aromatic compounds in monitored natural attenuation for coal tar contaminated aquifers: A review

NSO heterocycles (HET) are typical constituents of coal tars. However, HET are not yet routinely monitored, although HET are relatively toxic coal tar constituents. The main objectives of the study is therefore to review previous studies and to analyse HET at coal tar polluted sites in order to assess the relevance of HET as part of monitored natural attenuation (MNA) or any other long-term monitoring programme. Hence, natural attenuation of typical HET (indole, quinoline, carbazole, acridine, methylquinolines, thiophene, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, methylbenzofurans, dimethylbenzofurans and xanthene) were studied at three different field sites in Germany. Compound-specific plume lengths were determined for all main contaminant groups (BTEX, PAH and HET). The results show that the observed plume lengths are site-specific and are above 250m, but less than 1000m. The latter, i.e. the upper limit, however mainly depends on the level of investigation, the considered compound, the lowest measured concentration and/or the achieved compound-specific detection limit and therefore cannot be unequivocally defined. All downstream contaminant plumes exhibited HET concentrations above typical PAH concentrations indicating that some HET are generally persistent towards biodegradation compared to other coal tar constituents, which results in comparatively increased field-derived half-lives of HET. Additionally, this study provides a review on physicochemical and toxicological parameters of HET. For three well investigated sites in Germany, the biodegradation of HET is quantified using the centre line method (CLM) for the evaluation of bulk attenuation rate constants. The results of the present and previous studies suggest that implementation of a comprehensive monitoring programme for heterocyclic aromatic compounds is relevant at sites, if MNA is considered in risk assessment and for remediation.     

Towards optimal sampling schedules for integral pumping tests

Ethanol use as a gasoline additive is increasing, as are the chances of groundwater contamination caused by gasoline releases involving ethanol. To evaluate the impact of ethanol on dissolved hydrocarbon plumes, a field test was performed in which three gasoline residual sources with different ethanol fractions (E0: no ethanol, E10: 10% ethanol and E95: 95% ethanol) were emplaced below the water table. Using the numerical model BIONAPL/3D, the mass discharge rates of benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene were simulated and results compared to those obtained from sampling transects of multilevel samplers. It was shown that ethanol dissolved rapidly and migrated downgradient as a short slug. Mass discharge of the hydrocarbons from the E0 and E10 sources suggested similar first-order hydrocarbon decay rates, indicating that ethanol from E10 had no impact on hydrocarbon degradation. In contrast, the estimated hydrocarbon decay rates were significantly lower when the source was E95. For the E0 and E10 cases, the aquifer did not have enough oxygen to support complete mineralization of the hydrocarbon compounds to the extent suggested by the field-based mass discharge. Introducing a heterogeneous distribution of hydraulic conductivity did little to overcome this discrepancy. A better match between the numerical model and the field data was obtained assuming partial degradation of the hydrocarbons to intermediate compounds. Besides depending on the ethanol concentration, the impact of ethanol on hydrocarbon degradation appears to be highly dependent on the availability of electron acceptors.     

Novel mesoporous microspheres of Al and Ni doped LMO spinels and their performance as cathodes in secondary lithium ion batteries

A facile, scalable, and solution-based technique is used to fabricate Al and Ni-doped (LiAl_0.1Mn_1.9O₄ and LiAl_0.1Ni_0.1Mn_1.8O₄) microspheres of lithium manganese oxide (LMO) spinels for use as reversible cathode materials for lithium ion batteries (LIBs). The spheres of the two samples exhibit different porosities. Cells with these LMO-based cathodes are then cycled between 4.5 V and 2 V to study their stabilities while simultaneously being subjected to the undesirable Jahn-Teller distortion that occurs around the ~3 V regime. The LiAl_0.1Mn_1.9O₄ (LAMO) and the LiAl_0.1Ni_0.1Mn_1.8O₄ (LANMO) cells exhibit comparable open circuit voltages (OCV) of 2.94 V and 2.97 V, respectively. During cell cycling, the LAMO cell exhibits a maximum specific capacity of 122.51 mAh g^?1 with a capacity fade of 65.35% after 75 cycles. The LiAl_0.1Ni_0.1Mn_1.8O₄ (LAMO) sample fares better and exhibits a maximum of 140.49 mAh g^?1 and a capacity drop of 52.59%. Detailed structural studies indicate that Ni doping and the greater degree of porosity of the LANMO sample to be a stabilizing factor. This is further confirmed by cyclic voltammetry (CV) and AC impedance spectra analysis.