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.     

Assessing national sustainable development strategies: Strengthening the links to operational policy

At the Earth Summit in Rio de Janeiro in 1992, it was agreed that all countries should develop a national sustainable develop‐ment strategy (NSDS) as a key component of implementing the goals of Agenda 21. Progress has been limited. Few countries have established a formal strategy, and many of the strategies that exist have been only partially implemented. This article proposes an approach that addresses the need to improve existing strategic planning mechanisms. The approach is based on a periodic assessment of existing systems, to evaluate the extent to which they incorporate NSDS principles, and identify areas to be strengthened. The article describes an assessment methodology, presents examples of its use, and discusses ways in which current approaches to NSDS may be complemented by continual review and improvement of existing planning processes.     

The use and abuse of scientific studies

In response to Evelyn Pluhar'sWho Can Be Morally Obligated to Be a Vegetarian? in this journal issue, the author has read all of Pluhar's citations for the accuracy of her claims and had these read by an independent nutritionist. Detailed analysis of Pluhar's argument shows that she attempts to make her case by consistent misappropriation of the findings and conclusions of the studies she cites. Pluhar makes sweeping generalizations from scanty data, ignores causal explanations given by scientists, equates hypothesis with fact, draws false cause conclusions from studies, and in one case claims a conclusion opposite of what the scientist published. Such poor reasoning cannot be the basis of an argument for moral vegetarianism. A broader search of the literature and attention to reviews and textbooks in nutrition shows that each of Pluhar's claims is suspect or incorrect. Pluhar has not undermined my central claims: even if animals have certain rights and well-planned vegetarian diets are safe in complex industrialized societies, these diets cannot be so regarded if the presuppositions of high levels of wealth, education, and medical care do not exist; and, women, children, the aged and some ill persons are at greater risk on restrictive vegan diets. Thus, any duty of moral vegetarianism is not categorical but provisional in nature.     

ADAPTATION TO ARIDITY: WATER DEVELOPMENT IN SOUTH AFRICA1

ABSTRACT The Republic of South Africa, legatee of a three-century history of recurring drought, is firmly committed to a program of the optimum use of its water for the national benefit. Its water law encourages centralized planning in that water is held to be the property of the state and is assignable without requiring acquiescence by the basin or province of origin. Interbasin diversions from the Tugela River to the Vaal River Basin, from the Orange River to the Fish and Sundays River Basins, and from several basins to Cape Town are under construction as are facilities for water importation from Lesotho and Angola. For satisfaction of demands beyond the year 2000 the nation may depend increasingly on a shift of its power production and water-using industry from the coal fields of the central plateau to nuclear power development with associated desalination along its coasts. Alternatively, and preferably, it may cooperate in a co-prosperity bloc in Southern Africa aiding the economies of its neighbors by development for mutual advantage of the water and power resources of the Okavango and other northern rivers.     

Interrelationship of macropores and subsurface drainage for conservative tracer and pesticide transport

Macropore flow results in the rapid movement of pesticides to subsurface drains, which may be caused in part by a small portion of macropores directly connected to drains. However, current models fail to account for this direct connection. This research investigated the interrelationship between macropore flow and subsurface drainage on conservative solute and pesticide transport using the Root Zone Water Quality Model (RZWQM). Potassium bromide tracer and isoxaflutole, the active ingredient in BALANCE herbicide [(5-cyclopropyl-4-isoxazolyl) [2(methylsulfonyl)-4-(trifluoromethyl)phenyl] methanone], with average half-life of 1.7 d were applied to a 30.4-ha Indiana corn (Zea mays L.) field. Water flow and chemical concentrations emanating from the drains were measured from two samplers. Model predictions of drain flow after minimal calibration reasonably matched observations (slope = 1.03, intercept = 0.01, and R(2) = 0.75). Without direct hydraulic connection of macropores to drains, RZWQM under predicted bromide and isoxaflutole concentration during the first measured peak after application (e.g., observed isoxaflutole concentration was between 1.2 and 1.4 mug L(-1), RZWQM concentration was 0.1 mug L(-1)). This research modified RZWQM to include an express fraction relating the percentage of macropores in direct hydraulic connection to drains. The modified model captured the first measured peak in bromide and isoxaflutole concentrations using an express fraction of 2% (e.g., simulated isoxaflutole concentration increased to 1.7 mug L(-1)). The RZWQM modified to include a macropore express fraction more accurately simulates chemical movement through macropores to subsurface drains. An express fraction is required to match peak concentrations in subsurface drains shortly after chemical applications.     

The effect of five forage species on transport and transformation of atrazine and isoxaflutole (balance) in lysimeter leachate

A field lysimeter study with bare ground and five different ground covers was established to evaluate the effect of forage grasses on the fate and transport of two herbicides in leachate. The herbicides were atrazine (ATR; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and isoxaflutole [IXF; 5-cyclopropyl-4-(2-methylsulfonyl-4-trifluormethyl-benzoyl)isoxazole], which has the commercial name Balance (Aventis Crop Science, Strasbourg, France). The ground covers included orchardgrass (Dactylis glomerata L.), smooth bromegrass (Bromus inermis Leyss.), tall fescue (Festuca arundinacea Schreb.), timothy (Phleum pratense L.), and switchgrass (Panicum virgatum L.). The results suggested that the total IXF (parent + metabolites) showed higher mobility than ATR and its metabolites. Differences in the timing of transport reflected the rapid degradation of IXF to the more soluble, stable, and biologically active diketonitrile (DKN) metabolite in the system. Although grass treatments did not promote the hydrolysis of DKN, they significantly reduced its transport in the leachate through enhanced evapotranspiration. Grass treatments significantly enhanced ATR degradation in the leachates and soils, especially through N dealkylation, but they did not reduce total ATR transported in the leachate. Leachate from the orchardgrass lysimeters contained the highest proportion of ATR metabolites (64.2%). Timothy and smooth bromegrass treatments also displayed a significant increase in ATR metabolites in leachate. Grass-treated lysimeters showed higher microbial biomass carbon than bare ground. For ATR treatments, the proportion of metabolites in the leachate strongly correlated with the elevated soil microbial biomass carbon in forage treatments. In contrast, DKN degradation was poorly correlated with soil microbial biomass carbon, suggesting that DKN degradation is an abiotic process.     

Relating net nitrogen input in the Mississippi River basin to nitrate flux in the lower Mississippi River: a comparison of approaches

A quantitative understanding of the relationship between terrestrial N inputs and riverine N flux can help guide conservation, policy, and adaptive management efforts aimed at preserving or restoring water quality. The objective of this study was to compare recently published approaches for relating terrestrial N inputs to the Mississippi River basin (MRB) with measured nitrate flux in the lower Mississippi River. Nitrogen inputs to and outputs from the MRB (1951 to 1996) were estimated from state-level annual agricultural production statistics and NOy (inorganic oxides of N) deposition estimates for 20 states that comprise 90% of the MRB. A model with water yield and gross N inputs accounted for 85% of the variation in observed annual nitrate flux in the lower Mississippi River, from 1960 to 1998, but tended to underestimate high nitrate flux and overestimate low nitrate flux. A model that used water yield and net anthropogenic nitrogen inputs (NANI) accounted for 95% of the variation in riverine N flux. The NANI approach accounted for N harvested in crops and assumed that crop harvest in excess of the nutritional needs of the humans and livestock in the basin would be exported from the basin. The U.S. White House Committee on Natural Resources and Environment (CENR) developed a more comprehensive N budget that included estimates of ammonia volatilization, denitrification, and exchanges with soil organic matter. The residual N in the CENR budget was weakly and negatively correlated with observed riverine nitrate flux. The CENR estimates of soil N mineralization and immobilization suggested that there were large (2000 kg N ha-1) net losses of soil organic N between 1951 and 1996. When the CENR N budget was modified by assuming that soil organic N levels have been relatively constant after 1950, and ammonia volatilization losses are redeposited within the basin, the trend of residual N closely matched temporal variation in NANI and was positively correlated with riverine nitrate flux in the lower Mississippi River. Based on results from applying these three modeling approaches, we conclude that although the NANI approach does not address several processes that influence the N cycle, it appears to focus on the terms that can be estimated with reasonable certainty and that are correlated with riverine N flux.     

Production of radioactive particles for use in environmental studies

This paper presents an aerosol generation technique developed to produce dry aerosol particles of various sizes from aqueous solutions of salt. The technique was tested with sodium chloride, lithium carbonate and uranyl acetate at various aqueous concentrations which produced particles in the size range of 0.13-1.37 microm Mass Median Diameter (MMD). The generated aerosols were acceptably monodisperse with a geometric standard deviation of 1.4-2. Both MMD and Mass Median Aerodynamic Diameter (MMAD) increased significantly (p<0.001) with increased concentration of the salt in solution. The technique can also be used to generate aerosols of different chemical species. The results obtained indicate that the system is convenient for use with various aerosol-forming materials, with a stable particle size distribution being maintained for a long period of steady operation. The technique was successfully applied in wind tunnel studies to simulate the release of submicron radioactive particles and their interception by crops, grass and tree canopies. The relevance and application of the technique in other areas of environmental assessment studies is discussed.