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.     

Controlling air pollution from passenger ferries: cost-effectiveness of seven technological options

Continued interest in improving air quality in the United States along with renewed interest in the expansion of urban passenger ferry service has created concern about air pollution from ferry vessels. This paper presents a methodology for estimating the air pollution emissions from passenger ferries and the costs of emissions control strategies. The methodology is used to estimate the emissions and costs of retrofitting or re-powering ferries with seven technological options (combinations of propulsion and emission control systems) onto three vessels currently in service in San Francisco Bay. The technologies include improved engine design, cleaner fuels (including natural gas), and exhaust gas cleanup devices. The three vessels span a range of ages and technologies, from a 25-year-old monohull to a modern, high-speed catamaran built only four years ago. By looking at a range of technologies, vessel designs, and service conditions, a sense of the broader implications of controlling emissions from passenger ferries across a range of vessels and service profiles is provided. Tier 2-certified engines are the most cost-effective choice, but all options are cost-effective relative to other emission control strategies already in place in the transportation system.     

Fertilizer Management in Watersheds of Two Ramsar Wetlands and Effects on Quality of Inflowing Water

Two field experiments were carried out in the watersheds of two Ramsar wetland areas, Lakes Koronia and Volvi (area A) and Lakes Mikri and Megali Prespa (area B), to study the effect of application of N fertilizer on wheat yields, the quality of runoff water, and the quality of stream water. The treatments were a combination of two methods of fertilizer application (total amount in fall, and 2/3 in fall + 1/3 in spring) at three rates (0, 100, and 200 kg N/ha) with four replications. Concentrations of NH₄ ⁺, NO₃ ⁻, NO₂ ⁻, P, and Cl⁻ and pH were determined in all water samples. Runoff water quality was not influenced by fertilizer application in either area. Chemical parameters for water did not differ along the selected watercourses in area B, while in area A they were higher in the samples taken near Lake Koronia than in the samples taken upstream, indicating that the watercourses are polluted downstream by nonagricultural sources. The differences in wheat yields between the 100 and 200 kg N/ha application rates were not high. These results call for better fertilizer management in order to achieve better yields and to diminish the possibility to have negative effects to the environment.     

Environmental radiological impact associated with non-uranium mining industries: a proposal for screening criteria

Niobium, phosphate, coal and gold mining facilities have been selected as case studies with the aim of identifying possible sources of radiological impact during and after cessation of industrial operations. The results have shown that acid drainage, as well as chemical processing of mineral ores, constitute relevant impact indicators for present-day and future scenarios. The possible use of solid wastes abandoned at the end of the operations represents a long-term radiological concern. Therefore, it is necessary that Brazilian legislation for environmental licensing be revised taking into account the potential environmental and radiological impacts caused by these industries and establishing remedial procedures for waste storage areas in the existing sites. The indicators developed and procedures carried out can be used in screening for decisions on the adoption of regulatory requirements for practices at such types of installations.     

Mechanistic studies of N-nitrosodimethylamine (NDMA) formation in chlorinated drinking water

Studies were conducted to investigate the hypothesis that N-nitrosodimethylamine (NDMA) is a potential disinfection by-product specifically produced during chlorination or chloramination. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed by the reaction of DMA with free chlorine in the presence of ammonia and also with monochloramine. We proposed a mechanism for NDMA formation in chlorinated or chloraminated water, which does not require nitrite as in N-nitrosation. The critical NDMA formation reactions consist of (i) the formation of monochloramine by combination of free chlorine with ammonia, (ii) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (iii) the oxidation of UDMH by monochloramine to NDMA, and (iv) the reversible chlorine transfer reaction between free chlorine/monochloramine and DMA which is parallel with (i) and (ii). A kinetic model was also developed to validate the proposed mechanism.     

Characteristic levels of heavy metals in sediments and dredged sediments of a municipal creek in the Niger delta, Nigeria

Characteristic levels of metal ions in post dredged sediment and dredged sediments materials of a municipal creek in the Niger Delta show that significant concentrations of heavy metals are found to be accumulated more on the surface (0–15cm depth) of the dredged material as compared to the sub surface (15–30cm) and post dredged sediments. The distribution patterns were in the following order Fe > Mn > Zn > Cu > Pb > Ni > Cd and Fe > Mn > Zn > Pb > Cu > Ni > Cd for the post dredged sediment and dredged sediment materials respectively. The levels of the various metals were far below the EPA screening levels for open water disposal, consequently total levels of heavy metal found in these sediments pose no problem by open-water or upland disposal     

SUBALPINE,COLD CLIMATE,STORMWATER TREATMENT WITH A CONSTRUCTED SURFACE FLOW WETLAND1

The Tahoe City Wetland Treatment System (TCWTS) was constructed in 1997 to treat stormwater runoff from 23 ha of commercial, highway, and residential land use in the Lake Tahoe Basin. This subalpine, constructed, surface flow wetland treatment system consists of two cells in series, with a design water surface area of about 0.6 ha. Water quality monitoring from October 2002 through September 2003 was conducted with autosamplers at the inflow and outflow sites during 24 sampling events, with a median duration of 53 hours, representing 42 percent of total inflow to this wetland during the year. Monitoring data indicate an improvement of 49 percent or greater in effluent concentrations of dissolved phosphorus, nitrate, orthophosphorus, and total suspended solids. On average, event mean concentrations of total phosphorus were reduced from a median 279 μg/l at the inflow to 94 μg/l at the outflow. Event mean concentrations of total nitrogen were reduced from a median 1,599 μg/l at the inflow to 810 μg/l at the outflow. Net nutrient retention for the sampling period was estimated at 3 g phosphorus (P)/m²/y and 13 g nitrogen (N)/m²/y. Almost 4,000 kg of suspended sediment was captured by this wetland system during the year.     

COMPARISON OF PROCESS‐BASED AND ARTIFICIAL NEURAL NETWORK APPROACHES FOR STREAMFLOW MODELING IN AN AGRICULTURAL WATERSHED1

ABSTRACT: The performance of the Soil and Water Assessment Tool (SWAT) and artificial neural network (ANN) models in simulating hydrologic response was assessed in an agricultural watershed in southeastern Pennsylvania. All of the performance evaluation measures including Nash‐Sutcliffe coefficient of efficiency (E) and coefficient of determination (R²) suggest that the ANN monthly predictions were closer to the observed flows than the monthly predictions from the SWAT model. More specifically, monthly streamflow E and R² were 0.54 and 0.57, respectively, for the SWAT model calibration period, and 0.71 and 0.75, respectively, for the ANN model training period. For the validation period, these values were ?0.17 and 0.34 for the SWAT and 0.43 and 0.45 for the ANN model. SWAT model performance was affected by snowmelt events during winter months and by the model's inability to adequately simulate base flows. Even though this and other studies using ANN models suggest that these models provide a viable alternative approach for hydrologic and water quality modeling, ANN models in their current form are not spatially distributed watershed modeling systems. However, considering the promising performance of the simple ANN model, this study suggests that the ANN approach warrants further development to explicitly address the spatial distribution of hydrologic/water quality processes within watersheds.     

COST EFFECTIVE ARSENIC REDUCTIONS IN PRIVATE WELL WATER IN MAINE1

ABSTRACT: This study was undertaken to investigate the cost effectiveness of selected arsenic avoidance methods. Annual costs of reverse osmosis (RO), activated alumina (AA), bottled water, and rented and purchased water coolers for various household sizes in Maine were compared. Relative ranking of systems shows that RO ($411 annually) is the most cost effective, followed by AA ($518) and one‐gallon jugs of water ($321 to $1,285), respectively, for households larger than one person. One‐gallon jugs ($321) followed by 2.5‐gallon jugs ($358) of water were found to be the most cost effective for households of one person or for households with arsenic III concentrations of 0.02 to 0.06 mg/L and arsenic V concentrations of 0.08 to 1.0 mg/L. Point‐of‐entry systems and water coolers were not found to be cost effective under any of the study's conditions. The research reported here will help states make more definitive treatment recommendations to households regarding the cost effectiveness of alternative treatment systems to reduce arsenic concentrations below 0.01 mg/L. While arsenic removal technologies are improving, which enhances removal rates and reduces costs, the major insights from this analysis appear to be reinforced by technological improvements.