Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.     

Heavy metal concentrations in Squilla mantis (L.) (Crustacea,Stomatopoda) from the gulf of cadiz evaluation of the impact of the Aznalcollar mining spill

After the Aznalcóllar mining spill (25th April 1998), considerable social concern arose amongst the inhabitants of the SW Iberian Peninsula concerning the consumption of local seafood. Squilla mantis was collected in four regions of the Gulf of Cádiz with a dual objective: to analyze the heavy metal levels for human consumption and as part of biomonitoring program. Heavy metal concentrations (Fe, Mn, Zn, Cu, Cd and Pb) were analyzed in soft tissues and cuticle. The highest values were found in the soft tissues for zinc, copper and cadmium and in the cuticle for iron, manganese and lead. The mean copper concentration in the soft tissue, corresponding to the edible part, was 27.1 microg x g(-1) wet weight. Approximately 80% of stations showed values higher than 20 microg x g(-1) wet weight of copper, the Spanish legal limit for the concentration of this metal in the crustacean for human consumption. For Zn and Cu no significant differences were found between regions, probably related with the capacity for regulation of S. mantis. The highest values found for copper in the Gulf of Cádiz compared to other areas is likely to be related with contamination from terrestrial mining activities (copper and pyrites) in the region, dating back to the times of Tartessians and Romans, rather than the effects of mining spill which was shown not to create any significant increases in heavy metal concentrations of organisms of the Guadalquivir River or the adjacent coastal area.     

Renewable Resources and Enzymatic Processes to Create Functional Polymers: Adapting Materials and Reactions from Food Processing

We are exploiting materials and concepts from food science to create functionalized, environmentally friendly derivatives of the biopolymer chitosan, a byproduct of seafood processing. Functional groups are grafted onto chitosan using tyrosinase, the enzyme responsible for food browning. The functionalizing groups studied include low-molecular-weight phenols derived from natural sources and high-molecular-weight proteins. The approach of using low-molecular-weight phenols to functionalize chitosan is illustrated with arbutin, a natural phenol found in pears. Results demonstrate that tyrosinase initiates reactions that lead to the conversion of arbutin–chitosan solutions into gels. These gels can be rapidly broken by treatment with the chitosan-hydrolyzing enzyme chitosanase, demonstrating that the chitosan derivatives remain biodegradable. We briefly review other studies in which low-molecular-weight natural phenols are enzymatically grafted onto chitosan to confer functional properties. The creation of co-polymers is illustrated by results in which tyrosinase is used to couple gelatin onto chitosan. Gelatin is a proteinaceous byproduct of meat production. The tyrosinase-generated gelatin–chitosan conjugates have been observed to offer interesting rheological and thermal properties. These results demonstrate the potential for using renewable resources and enzymatic processing to create environmentally friendly polymers with useful functional properties.     

Chemical Changes in Sediment Pore-Waters of an Acidic Mining Lake After Addition of Organic Substrate and Lime for Stimulating Lake Remediation

In the past five years, enclosures have beeninstalled in an acidic mining lake in Lusatia to investigate insitu remediation processes. They were treated with straw, withstraw and Carbokalk, or with Carbokalk alone, where Carbokalkis a by-product of the sugar industry (solid precipitate ofnon-sugars after lime clarification of extracted sugar beetjuice). Sediment samples were taken as cores to get informationabout the behaviour of organic and inorganic components insediment pore-water with depth. Vertical distributions of pH,soluble reactive phosphate, nitrate, ammonium, silica,aluminium, iron, manganese, calcium, magnesium, sodium,potassium, sulphate, and DOC were measured. The resultingprofiles, each consisting of 15 data points at differentdepths, were compared by cluster analysis. The similarities ofsediment cores from different treated enclosures relating toprofiles of chemical components were discussed. Increasedconcentrations of potassium and sulphate were found in pore-water after substrate treatment. The data imply dissolution ofpotassium iron sulphate hydroxide minerals (jarosite) after anincrease of pH caused by dissolution of lime and by sulphatereducing processes which were stimulated by organic substrateaddition.     

A comparative study of risk perception in small and large communities where chemical industries are present

Opinion polls were conducted to assess the level of risk perceived by the citizens in communities of different sizes where chemical industries were present. The aim of the study was to relate the risk perceived to variables such as the nature of risks, the specific information received regarding the industrial activity and the economic impact of this activity in the community.     

WATER QUALITY MODELING OF ALTERNATIVE AGRICULTURAL SCENARIOS IN THE U.S. CORN BELT1

ABSTRACT: Simulated water quality resulting from three alternative future land‐use scenarios for two agricultural watersheds in central Iowa was compared to water quality under current and historic land use/land cover to explore both the potential water quality impact of perpetuating current trends and potential benefits of major changes in agricultural practices in the U.S. Corn Belt. The Soil Water Assessment Tool (SWAT) was applied to evaluate the effect of management practices on surface water discharge and annual loads of sediment and nitrate in these watersheds. The agricultural practices comprising Scenario 1, which assumes perpetuation of current trends (conversion to conservation tillage, increase in farm size and land in production, use of currently‐employed Best Management Practices (BMPs)) result in simulated increased export of nitrate and decreased export of sediment relative to the present. However, simulations indicate that the substantial changes in agricultural practices envisioned in Scenarios 2 and 3 (conversion to conservation tillage, strip intercropping, rotational grazing, conservation set‐asides and greatly extended use of best management practices (BMPs) such as riparian buffers, engineered wetlands, grassed waterways, filter strips and field borders) could potentially reduce current loadings of sediment by 37 to 67 percent and nutrients by 54 to 75 percent. Results from the study indicate that major improvements in water quality in these agricultural watersheds could be achieved if such environmentally‐targeted agricultural practices were employed. Traditional approaches to water quality improvement through application of traditional BMPs will result in little or no change in nutrient export and minor decreases in sediment export from Corn Belt watersheds.     

MAKING SMARTER ENVIRONMENTAL MANAGEMENT DECISIONS1

ABSTRACT: This paper outlines a sound, practical approach for making more informed decisions about environmental policy choices. It emphasizes the importance of using a structured decision process to specify and organize values, use these values to create alternatives, and assess tradeoffs to help achieve a desired balance across key objectives. Although these decision making steps are based on common sense, they are often neglected or poorly carried out as part of the complex evaluations of natural resource options. We discuss several reasons for this frequent neglect of decision making principles and provide examples from recent water use planning projects to demonstrate some of the benefits of using a structured, decision focused approach: new and better solutions, increased and more productive participation by stakeholders, and greater defensibility and acceptance of the resource management evaluation process and its conclusions.     

OPTIMIZING WELL PLACEMENT IN A COASTAL AQUIFER: OUTER CAPE COD,MASSACHUSETTS1

ABSTRACT: An inverse‐simulation approach is used to determine optimal strategies for developing public water‐supply systems in a shallow, coastal aquifer on the outermost arm of the Cape Cod peninsula in Massachusetts. Typically a forward simulation (or “trial and error”) approach is used to find best pumping strategies, but the chances of finding success with this tact diminish as the number of potential options grows large. Well locations and pumping rates are optimized with respect to: (1) providing sufficient water to areas of water‐quality impairment, (2) minimizing impacts to nearby surface waters, (3) preventing saltwater contamination due to overpumping, and (4) minimizing financial cost of well development. Potential well sites and water‐supply scenarios are separated into “politically‐based” and “resource‐based” categories to gain insight into the degree that pre‐existing political boundaries hinder best management practices. The approach provides a promising tool in transboundary water‐resources settings because it allows stakeholders to find solutions that best meet everyone's goals, as opposed to pursuing options that will create conflict, or are less than optimal.     

Evaluating regulatory issues and emission control equipment for air toxics applications

This article describes regulatory issues and emission control equipment for air toxics applications. A brief history of air quality legislation is provided, illustrating the difficulty government has had in implementing air quality statutes; this has contributed to the complexity of air quality regulations. Evaluation methodologies are described for three different emission control technologies: thermal oxidation, catalytic oxidation, and adsorption. Brief case histories are provided that describe the pitfalls and benefits associated with each technology. The benefits of integrating health risk assessment into an air quality program are also discussed.