Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Removal of nickel (II) from aqueous solutions using marine macroalgae as the sorbing biomass

In the present study biosorption technique, the passive accumulation of metals by biomass, is used for the removal of nickel from aqueous medium. The brown algae, Sargassum sp., in its natural and acid treated forms are used as a low cost sorbent. The adsorption characteristics of nickel on Sargassum sp. are evaluated as a function of time, pH, adsorbent dosage and initial concentration of nickel. The equilibrium adsorption data are fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters are evaluated. Both the models represent the experimental data satisfactorily. The adsorption follows Lagergren first order kinetic model. The monolayer adsorption capacities of natural and acid treated forms of algae as obtained from Langmuir adsorption model are found to be 181 and 250mg g(-1) respectively.     

Synthesis of effects in four Arctic subregions

An assessment of impacts on Arctic terrestrial ecosystems has emphasized geographical variability in responses of species and ecosystems to environmental change. This variability is usually associated with north-south gradients in climate, biodiversity, vegetation zones, and ecosystem structure and function. It is clear, however, that significant east-west variability in environment, ecosystem structure and function, environmental history, and recent climate variability is also important. Some areas have cooled while others have become warmer. Also, east-west differences between geographical barriers of oceans, archipelagos and mountains have contributed significantly in the past to the ability of species and vegetation zones to relocate in response to climate changes, and they have created the isolation necessary for genetic differentiation of populations and biodiversity hot-spots to occur. These barriers will also affect the ability of species to relocate during projected future warming. To include this east-west variability and also to strike a balance between overgeneralization and overspecialization, the ACIA identified four major sub regions based on large-scale differences in weather and climate-shaping factors. Drawing on information, mostly model output that can be related to the four ACIA subregions, it is evident that geographical barriers to species re-location, particularly the distribution of landmasses and separation by seas, will affect the northwards shift in vegetation zones. The geographical constraints--or facilitation--of northward movement of vegetation zones will affect the future storage and release of carbon, and the exchange of energy and water between biosphere and atmosphere. In addition, differences in the ability of vegetation zones to re-locate will affect the biodiversity associated with each zone while the number of species threatened by climate change varies greatly between subregions with a significant hot-spot in Beringia. Overall, the subregional synthesis demonstrates the difficulty of generalizing projections of responses of ecosystem structure and function, species loss, and biospheric feedbacks to the climate system for the whole Arctic region and implies a need for a far greater understanding of the spatial variability in the responses of terrestrial arctic ecosystems to climate change.     

Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30 degrees F), "black" and "white" smokers, and a new-technology vehicle (tested at 72 degrees F). Diesel vehicles included current-technology vehicles (tested at 72 and 30 degrees F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.     

Cosolvent effect on the catalytic reductive dechlorination of PCE

Reductive dechlorination of chlorinated organic contaminants is an effective approach to treat this widespread group of environmentally hazardous substances. Metalloporphyrins can be used to catalyze reduction reactions by shuttling electrons from a reducing agent (electron donor) to chlorinated organic contaminants, thus rendering them to non-chlorinated acetylene, ethylene or ethane as major products. Iron, nickel and vanadium oxide tetraphenyl porphyrins (TPPs) were used as models of non-soluble metalloporphyrins that are common in subsurface environments, and hence may inflect on the ability to use natural ones. The effect of cosolvents on metalloporphyrins is demonstrated to switch the reduction of tetrachlorethylene (PCE) from no reaction to complete PCE transformation within 24 h and the production of final non-chlorinated compounds. Variations in product distributions for the different metalloporphyrins indicate that changes in the core metal can influence reaction rates and effective pathways. Furthermore, different cosolvents can generate varied product distributions, again suggesting that different pathways and/or rates are operative in the reduction reactions. Comparison of different cosolvent effects on PCE reduction using vitamin B12--a soluble natural metalloporphyrinogen--as the catalyst shows less pronounced differences between reactions in various cosolvent solutions versus only aqueous solution.     

Uncertainties and recommendations

An assessment of the impacts of changes in climate and UV-B radiation on Arctic terrestrial ecosystems, made within the Arctic Climate Impacts Assessment (ACIA), highlighted the profound implications of projected warming in particular for future ecosystem services, biodiversity and feedbacks to climate. However, although our current understanding of ecological processes and changes driven by climate and UV-B is strong in some geographical areas and in some disciplines, it is weak in others. Even though recently the strength of our predictions has increased dramatically with increased research effort in the Arctic and the introduction of new technologies, our current understanding is still constrained by various uncertainties. The assessment is based on a range of approaches that each have uncertainties, and on data sets that are often far from complete. Uncertainties arise from methodologies and conceptual frameworks, from unpredictable surprises, from lack of validation of models, and from the use of particular scenarios, rather than predictions, of future greenhouse gas emissions and climates. Recommendations to reduce the uncertainties are wide-ranging and relate to all disciplines within the assessment. However, a repeated theme is the critical importance of achieving an adequate spatial and long-term coverage of experiments, observations and monitoring of environmental changes and their impacts throughout the sparsely populated and remote region that is the Arctic.     

Effects of the mosquito larvicide GB-1111 on bird eggs

Golden Bear Oil (GB-1111; legal trade name for GB-1313) is a petroleum distillate used in the United States and other countries as a mosquito larvicide. As part of an evaluation of the potential effects of GB-1111 on birds, fertile eggs of mallards (Anas platyrhynchos) and bobwhite (Colinus virginianus) were incubated in the laboratory, and treated on day 4 of incubation with external applications equivalent to either 0, 1/3, 1, 3 or 10 times the maximum rate (X) of 47 l/ha (5 gal/A) of field application of GB-1111. Hatching success was significantly reduced in mallards treated at 3 and 10 times the maximum field application, with a calculated approximate LD50 of 1.9 times the maximum field application. Most mortality occurred within a week of treatment. Hepatic P450-associated monooxygenase activity (ethoxyresorufin-O-dealkylase; EROD) was negatively related to dose. In the 3X group there was a significant increase in the concentration of hepatic reduced glutathione (GSH) but a decrease in protein-bound thiols (PBSH). Hatching success of bobwhite was marginally reduced at the highest level of treatment (10X). Other effects at this level in bobwhite included a significant increase in incidence of abnormal embryos or hatchlings, lower body and liver weights, and a two-fold increase in hepatic microsomal EROD activity in hatchlings. The recommended maximum rate of field application of GB-1111 is unlikely to impair the survival or development of bobwhite embryos but is potentially toxic to mallard embryos under conditions of larvicide drift or spray overlap.     

Cellular energy allocation in zebra mussels exposed along a pollution gradient: linking cellular effects to higher levels of biological organization

Organisms exposed to suboptimal environments incur a cost of dealing with stress in terms of metabolic resources. The total amount of energy available for maintenance, growth and reproduction, based on the biochemical analysis of the energy budget, may provide a sensitive measure of stress in an organism. While the concept is clear, linking cellular or biochemical responses to the individual and population or community level remains difficult. The aim of this study was to validate, under field conditions, using cellular energy budgets [i.e. changes in glycogen-, lipid- and protein-content and mitochondrial electron transport system (ETS)] as an ecologically relevant measurement of stress by comparing these responses to physiological and organismal endpoints. Therefore, a 28-day in situ bioassay with zebra mussels (Dreissena polymorpha) was performed in an effluent-dominated stream. Five locations were selected along the pollution gradient and compared with a nearby (reference) site. Cellular Energy Allocation (CEA) served as a biomarker of cellular energetics, while Scope for Growth (SFG) indicated effects on a physiological level and Tissue Condition Index and wet tissue weight/dry tissue weight ratio were used as endpoints of organismal effects. Results indicated that energy budgets at a cellular level of biological organization provided the fastest and most sensitive response and energy budgets are a relevant currency to extrapolate cellular effects to higher levels of biological organization within the exposed mussels.     

Polychlorinated biphenyls and chlorinated pesticides in mussels from the Egyptian Red Sea coast

The residues of 17 organochlorine pollutants were analyzed in bivalve Brachiodontes sp. collected from 11 different locations in April 2000 along the Egyptian Red Sea coast. The pollutants studied were 10 individual polychlorinated biphenyl (PCB) congeners, alpha,alpha,alpha-hexachlorocyclohexane (HCHs), cyclodienes (heptachlor, heptachlorepoxide, aldrin, dieldrin) and dichlorodiphenyltrichloroethanes (DDTs) (p,p'-DDE, p,p'-DDD and p,p'-DDT). The concentration of total DDTs ranged between 125 and 772 ng/g of wet weight whereas the concentration of the PCBs, HCHs and cyclodienes ranged from 6.7 to 66.4 ng/g; 16.2 to 183.4 ng/g and 8.8 to 221.6 ng/g of wet weight, respectively. The levels are low to moderate in relation to the published data from other coastal areas. The present results indicate low to moderate PCBs and pesticides contamination in the investigated mussels except DDTs.     

Non-aqueous phase liquid spreading during soil vapor extraction

Many non-aqueous phase liquids (NAPLs) are expected to spread at the air-water interface, particularly under non-equilibrium conditions. In the vadose zone, this spreading should increase the surface area for mass transfer and the efficiency of volatile NAPL recovery by soil vapor extraction (SVE). Observations of spreading on water wet surfaces led to a conceptual model of oil spreading vertically above a NAPL pool in the vadose zone. Analysis of this model predicts that spreading can enhance the SVE contaminant recovery compared to conditions where the liquid does not spread. Experiments were conducted with spreading volatile oils hexane and heptane in wet porous media and capillary tubes, where spreading was observed at the scale of centimeters. Within porous medium columns up to a meter in height containing stagnant gas, spreading was less than ten centimeters and did not contribute significantly to hexane volatilization. Water film thinning and oil film pinning may have prevented significant oil film spreading, and thus did not enhance SVE at the scale of a meter. The experiments performed indicate that volatile oil spreading at the field scale is unlikely to contribute significantly to the efficiency of SVE.