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.     

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.     

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.     

PLANNING FOR THE REHABILITATION OF GRAVEL PITS1

ABSTRACT: By field investigations and planning, it is profitable to rehabilitate gravel pits as recreational lakes in urban areas. Some of the important aspects to be considered are topography, soil, surface water and groundwater. A case study is presented and some general guidelines in the rehabilitation process are given. This kind of a use for derelict land is important at the present time as there is a growing demand for recreational lakes in urban areas.     

WATER RIGHTS,EMINENT DOMAIN,AND THE PUBLIC TRUST1

ABSTRACT: Faced with the necessity of meeting growing municipal water requirements in areas where available supplies are completely allocated, numerous cities throughout the West are turning to their eminent domain powers to affect a reallocation of water from less preferred uses to municipal uses, thus bringing about a sharp conflict with agricultural interests. As a basis for discussing these eminent domain powers, this paper begins with a brief review of the development of property rights. The existence of both private and public (social) rights in the “bundle of rights” is noted. In recent years the Public Trust Doctrine has been used to limit private rights in property, and to protect and strengthen social rights. A case study which focuses on a conflict between individual and social interests in water rights is discussed. This case involves the City of Thorton, Colorado which initiated municipal condemnation proceedings to acquire the water rights and structures of two nearby irrigation companies. The case represents an attempt to incorporate the spirit of the Public Trust Doctrine into legislation which sets forth procedures for resolution of similar water rights conflicts that will inevitably become more numerous throughout the West in the future.     

Investigation of real-life operating patterns of wood-burning appliances using stack temperature data

ABSTRACT

A study was undertaken to identify patterns of consumer use of outdoor wood boilers or outdoor wood furnaces (technically referred to as outdoor wood-fired hydronic heaters (OWHHs)) and indoor wood stoves (IWSs) to inform the development of performance testing protocols that reflect real-life operating conditions. These devices are manually fed, and their usage protocols are a function of a number of variables, including user habits, household characteristics, and environmental factors. In this study, researchers logged the stack wall temperatures of 4 OWHH and 20 IWS units in the states of New York and Washington over two heating seasons. Stack wall temperature is an indicator of changes in combustion modes. Two algorithms were developed to identify usage modes and cold and warm start refueling events from the stack wall temperature time series. A linear correlation analysis was conducted to evaluate the effect of heat demand on usage patterns. The results and methods presented here will inform the cataloging of typical operational patterns of OWHHs and IWSs as a step in the development of performance testing procedures that represent actual in-home usage patterns.

Implications: Current US regulatory programs for residential wood heating use a certification program to assess emissions and efficiency performance. Testing under this program uses a test that burns 100% of a single, standardized wood fuel charge to assess performance at different steady-state load conditions. This study assessed in-field operational patterns to determine if the current certification approach accurately characterized typical homeowner use patterns. The data from this study can be used to inform revisions to testing methods to increase certification test comparability between lab and field performance.     

Ecosystem responses to climate change at a Low Arctic and a High Arctic long-term research site

Long-term measurements of ecological effects of warming are often not statistically significant because of annual variability or signal noise. These are reduced in indicators that filter or reduce the noise around the signal and allow effects of climate warming to emerge. In this way, certain indicators act as medium pass filters integrating the signal over years-to-decades. In the Alaskan Arctic, the 25-year record of warming of air temperature revealed no significant trend, yet environmental and ecological changes prove that warming is affecting the ecosystem. The useful indicators are deep permafrost temperatures, vegetation and shrub biomass, satellite measures of canopy reflectance (NDVI), and chemical measures of soil weathering. In contrast, the 18-year record in the Greenland Arctic revealed an extremely high summer air-warming of 1.3 °C/decade; the cover of some plant species increased while the cover of others decreased. Useful indicators of change are NDVI and the active layer thickness.     

Exploring the association between working memory and driving performance in Parkinson's disease

Objective: The aim of this study was to explore whether varying levels of operational and tactical driving task demand differentially affect drivers with Parkinson's disease (PD) and control drivers in their sign recall.

Methods: Study participants aged between 50 and 70 years included a group of drivers with PD (n = 10) and a group of age- and sex-matched control drivers (n = 10). Their performance in a sign recall task was measured using a driving simulator.

Results: Drivers in the control group performed better than drivers with PD in a sign recall task, but this trend was not statistically significant (P =.43). In addition, regardless of group membership, subjects' performance differed according to varying levels of task demand. Performance in the sign recall task was more likely to drop with increasing task demand (P =.03). This difference was significant when the variation in task demand was associated with a cognitive task; that is, when drivers were required to apply the instructions from working memory.

Conclusions: Although the conclusions drawn from this study are tentative, the evidence presented here is encouraging with regard to the use of a driving simulator to examine isolated cognitive functions underlying driving performance in PD. With an understanding of its limitations, such driving simulation in combination with functional assessment batteries measuring physical, visual, and cognitive abilities could comprise one component of a multitiered system to evaluate medical fitness to drive.