A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

Phytotoxicity to and uptake of RDX by rice

Phytoremediation is an emerging strategy to remediate soils contaminated with pollutants like explosives in which plants will uptake, degrade and/or accumulate pollutants. To implement this technology on a site contaminated with RDX, we chose rice, which is able to grow in lagoons, and we tested its ability to grow in soils with high levels of RDX and to decrease RDX concentrations in soil. Rice was grown for 40 days in soil contaminated with increasing [14C]RDX concentrations. Emergence and growth were not affected by RDX. Total chlorophyll content decreased with RDX concentrations of over 500 mg kg(-1). Amounts of chlorophyll were correlated with the appearance of necrosis in leaf extremities. After 40 days, rice translocated 89% of uptaken radioactivity to leaves with 90% in leaf extremities. Analyzes of leaf extracts showed that 95% of radioactivity was RDX in its parent form. Necrosis appears to be a phytotoxic symptom of RDX accumulation.     

Development of a test method against hot alkaline chemical splashes.

High temperature alkaline chemical liquids have caused injuries and hazardous situations in Finnish pulp manufacturing mills. There are no requirements and/or test method standards concerning protection against high temperature alkaline chemical splashes. This paper describes the test method development process to test and identify materials appropriate for hot liquid chemical hazard protection. In the first phase, the liquid was spilled through a stainless steel funnel and the protection performance was evaluated using a polyvinyl chloride (PVC) film under the test material. After several tentative improvements, a graphite crucible was used for heating and spilling the chemical, and a copper-coated K-type thermometer with 4 independent measuring areas was designed to measure the temperature under the material samples. The thermometer was designed to respond quickly so that peak temperatures could be measured. The main problem was to keep the spilled amount of chemical constant, which unfortunately resulted in significant variability in data.     

Occurrence of phenols in leachates from municipal solid waste landfill sites in Japan

The concentrations of 41 phenols in leachates from 38 municipal solid waste (MSW) landfill sites in Japan were measured. The main phenols detected in leachates were phenol, three cresols, 4-tert-butylphenol, 4-tertoctylphenol, 4-nonylphenol, bisphenol A, and some chlorophenols. The concentration levels of phenols were affected by the pH values of the leachates and the different types of landfill waste. The origins of phenol and p-cresol were considered to be incineration residues, and the major origin of 4-tert-butylphenol, bisphenol A, and 2,4,6-trichlorophenol was considered to be solidified fly ash. In contrast, the major origins of 4-tert-octylphenol and 4-nonylphenol were considered to be incombustibles. The discharge of leachates to the environment around MSW landfill sites without water treatment facilities can cause environmental pollution by phenols. In particular, the disposal of incineration residues including solidified fly ash and the codisposal of solidified fly ash and incombustibles might raise the possibility of environmental pollution. Moreover, the discharge of leachates at pH values of 9.8 or more could pollute the water environment with phenol. However, phenol, 4-nonylphenol, and bisphenol A can be removed to below the con centration levels that impact the environment around landfill sites by a series of conventional water treatment processes.     

A new tracer technique for monitoring groundwater fluxes: the Finite Volume Point Dilution Method

Quantification of pollutant mass fluxes is essential for assessing the impact of contaminated sites on their surrounding environment, particularly on adjacent surface water bodies. In this context, it is essential to quantify but also to be able to monitor the variations with time of Darcy fluxes in relation with changes in hydrogeological conditions and groundwater - surface water interactions. A new tracer technique is proposed that generalizes the single-well point dilution method to the case of finite volumes of tracer fluid and water flush. It is called the Finite Volume Point Dilution Method (FVPDM). It is based on an analytical solution derived from a mathematical model proposed recently to accurately model tracer injection into a well. Using a non-dimensional formulation of the analytical solution, a sensitivity analysis is performed on the concentration evolution in the injection well, according to tracer injection conditions and well-aquifer interactions. Based on this analysis, optimised field techniques and interpretation methods are proposed. The new tracer technique is easier to implement in the field than the classical point dilution method while it further allows monitoring temporal changes of the magnitude of estimated Darcy fluxes, which is not the case for the former technique. The new technique was applied to two experimental sites with contrasting objectives, geological and hydrogeological conditions, and field equipment facilities. In both cases, field tracer concentrations monitored in the injection wells were used to fit the calculated modelled concentrations by adjusting the apparent Darcy flux crossing the well screens. Modelling results are very satisfactory and indicate that the methodology is efficient and accurate, with a wide range of potential applications in different environments and experimental conditions, including the monitoring with time of changes in Darcy fluxes.     

Improve Compliance with Limited Resources by a Three-Group Inspection Regime

Frequent monitoring and relatively high fines are usually necessary to bring about improvements in environmental quality, but more challenging for many countries with limited human, material, and financial resources is to put them into practice. This paper developed a three-group model of a state-dependent enforcement in a repeated game to improve the policy implementation under limited inspection capacities. A certain number of firms are grouped (group 1, group 2, group 3) for different supervision intensity (e.g., the order of inspection probability corresponding to each group is p ₁?<?p ₂?<?p ₃) based on their environmental performance. The optimal policy parameters, such as inspection probability of each group and the probability that a firm found in compliance is moved to a better reputation group, were obtained as the basis for regulator’s policy making. Numerical simulations indicated that the three-group inspection regime can significantly increase compliance rate as compared with static enforcement with the same monitoring probability. Among the number of firms in each group under steady state conditions, group 2 had the most, group 1 was the second, and group 3 had the smallest. Analysis and prediction of a three-group reputation example provided a good experiment for the model. The results give a practical reference for the policy makers with inspection capacity constraints to achieve higher compliance rate.     

Modeling of Cr contamination in the agricultural lands of three villages near the leather industry in Kasur,Pakistan, using statistical and GIS techniques

Kasur is one of the hubs of leather industry in the Punjab, Pakistan, where chrome tanning method of leather processing is extensively being used. Chromium (Cr) accumulation levels in the irrigation water, soil, and seasonal vegetables were studied in three villages located in the vicinity of wastewater treatment plant and solid waste dumping site operated by the Kasur Tanneries Waste Management Agency (KTWMA). The data was interpreted using analysis of variance (ANOVA), clustering analysis (CA), and principal component analysis (PCA). Interpolated surface maps for Cr were generated using the actual data obtained for the 30 sampling sites in each of the three villages for irrigation water, soil, and seasonal vegetables. The level of contamination in the three villages was directly proportional to their distance from KTWMA wastewater treatment plant and the direction of water runoff. The highest level of Cr contamination in soil (mg kg^?1) was observed at Faqeeria Wala (37.67), intermediate at Dollay Wala (30.33), and the least in Maan (25.16). A gradational variation in Cr accumulation was observed in the three villages from contaminated wastewater having the least contamination level (2.02–4.40 mg L^?1), to soil (25.16–37.67 mg kg^?1), and ultimately in the seasonal vegetable crops (156.67–248.33 mg kg^?1) cultivated in the region, having the highest level of Cr contamination above the permissible limit. The model used not only predicted the current situation of Cr contamination in the three villages but also indicated the trend of magnification of Cr contamination from irrigation water to soil and to the base of the food chain. Among the multiple causes of Cr contamination of vegetables, soil irrigation with contaminated groundwater was observed to be the dominant one.     

A moving target—incorporating knowledge of the spatial ecology of fish into the assessment and management of freshwater fish populations

Freshwater fish move vertically and horizontally through the aquatic landscape for a variety of reasons, such as to find and exploit patchy resources or to locate essential habitats (e.g., for spawning). Inherent challenges exist with the assessment of fish populations because they are moving targets. We submit that quantifying and describing the spatial ecology of fish and their habitat is an important component of freshwater fishery assessment and management. With a growing number of tools available for studying the spatial ecology of fishes (e.g., telemetry, population genetics, hydroacoustics, otolith microchemistry, stable isotope analysis), new knowledge can now be generated and incorporated into biological assessment and fishery management. For example, knowing when, where, and how to deploy assessment gears is essential to inform, refine, or calibrate assessment protocols. Such information is also useful for quantifying or avoiding bycatch of imperiled species. Knowledge of habitat connectivity and usage can identify critically important migration corridors and habitats and can be used to improve our understanding of variables that influence spatial structuring of fish populations. Similarly, demographic processes are partly driven by the behavior of fish and mediated by environmental drivers. Information on these processes is critical to the development and application of realistic population dynamics models. Collectively, biological assessment, when informed by knowledge of spatial ecology, can provide managers with the ability to understand how and when fish and their habitats may be exposed to different threats. Naturally, this knowledge helps to better evaluate or develop strategies to protect the long-term viability of fishery production. Failure to understand the spatial ecology of fishes and to incorporate spatiotemporal data can bias population assessments and forecasts and potentially lead to ineffective or counterproductive management actions.