Performance of Exhaust Control Devices on 1966 Model Passenger Cars

Road tests have been carried out in five different cities with a fleet of 300 passenger cars consisting of three different makes, half of which are equipped with the 1966 exhaust control devices required by the state of California. The performance of these devices during the first series of tests has been evaluated. All three makes of device-equipped cars produced significantly lower emissions of hydrocarbons and carbon monoxide than did similar cars tested in 1962 and 1963. There were no consistent differences among the three makes of cars with respect to carbon monoxide and hydrocarbon emissions.     

DFT M06-2X investigation of alkaline hydrolysis of nitroaromatic compounds

The nitroaromatic compounds 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT) and 2,4-dinitroanisole (DNAN) are potential environmental contaminants and their transformations under a variety of environmental conditions are consequently of great interest. One possible method to safely degrade these nitrocompounds is alkaline hydrolysis. A mechanism of the initial stages of this reaction was investigated computationally. Simulations of UV-VIS and NMR spectra for this mechanism were also produced. The results obtained were compared to available experimental data on the alkaline hydrolysis of TNT and suggest that the formation of Meisenheimer complexes and an anion of TNT are potential first-step intermediates in the reaction path. As the reaction proceeds, computational results indicate that polynegative complexes dominate the degradation pathway, followed by cycles of carbon chain opening and breaking. A second possible pathway was identified that leads to polymeric products through Janovsky complex formation. Results from this study indicate that the order of increasing resistance to alkaline hydrolysis is TNT, DNT and DNAN.     

Dissipation, half-lives, and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre(-1). Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T(1/2) = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T(1/2) = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

Evaluation of the dependence of aqueous solubility of nitro compounds on temperature and salinity: a COSMO-RS simulation

The solubility in pure and saline water at various temperatures was calculated for selected nitro compounds (nitrobenzene, 1,3,5-trinitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene, 2,3-dinitrotoluene, 3,4-dinitrotoluene, 2,4,6-trinitrotoluene) using the Conductor-like Screening model for Real Solvents (COSMO-RS). The results obtained were compared with experimental values. The COSMO-RS predictions have shown high accuracy in reproducing the trends of aqueous solubilities for both temperature and salinity. The proposed methodology was then applied to predict the aqueous solubilities of 19 nitro compounds in the temperature range of 5-50 °C in saline solutions. The salting-out parameters of the Setschenow equation were also calculated. The predicted salting-out parameters were overestimated when compared to the measured values, but these parameters can still be used for qualitative estimation of the trends.     

CO2 transportation for carbon capture and storage: Sublimation of carbon dioxide from a dry ice bank

Climate change is being caused by greenhouse gases such as carbon dioxide (CO₂). Carbon capture and storage (CCS) is of interest to the scientific community as one way of achieving significant global reductions of atmospheric CO₂ emissions in the medium term. CO₂ would be captured from large stationary sources such as power plants and transported via pipelines under high pressure conditions to underground storage. If a downward leakage from a surface transportation system module occurs, the CO₂ would undergo a large temperature reduction and form a bank of “dry ice” on the ground surface; the sublimation of the gas from this bank represents an area source term for subsequent atmospheric dispersion, with an emission rate dependent on the energy balance at the bank surface. Gaseous CO₂ is denser than air and tends to remain close to the surface; it is an asphyxiant, a cerebral vasodilator and at high concentrations causes rapid circulatory insufficiency leading to coma and death. Hence a subliming bank of dry ice represents safety hazard. A model is presented for evaluating the energy balance and sublimation rate at the surface of a solid frozen CO₂ bank under different environmental conditions. The results suggest that subliming gas behaves as a proper dense gas (i.e. it remains close to the ground surface) only for low ambient wind speeds.     

Zonal management of arsenic contaminated ground water in Northwestern Bangladesh

This paper used ordinary kriging to spatially map arsenic contamination in shallow aquifers of Northwestern Bangladesh (total area  35,000 km²). The Northwestern region was selected because it represents a relatively safer source of large-scale and affordable water supply for the rest of Bangladesh currently faced with extensive arsenic contamination in drinking water (such as the Southern regions). Hence, the work appropriately explored sustainability issues by building upon a previously published study (Hossain et al., 2007; Water Resources Management, vol. 21: 1245–1261) where a more general nation-wide assessment afforded by kriging was identified. The arsenic database for reference comprised the nation-wide survey (of 3534 drinking wells) completed in 1999 by the British Geological Survey (BGS) in collaboration with the Department of Public Health Engineering (DPHE) of Bangladesh. Randomly sampled networks of zones from this reference database were used to develop an empirical variogram and develop maps of zonal arsenic concentration for the Northwestern region. The remaining non-sampled zones from the reference database were used to assess the accuracy of the kriged maps. Two additional criteria were explored: (1) the ability of geostatistical interpolators such as kriging to extrapolate information on spatial structure of arsenic contamination beyond small-scale exploratory domains; (2) the impact of a priori knowledge of anisotropic variability on the effectiveness of geostatistically based management. On the average, the kriging method was found to have a 90% probability of successful prediction of safe zones according to the WHO safe limit of 10 ppb while for the Bangladesh safe limit of 50 ppb, the safe zone prediction probability was 97%. Compared to the previous study by Hossain et al. (2007) over the rest of the contaminated country side, the probability of successful detection of safe zones in the Northwest is observed to be about 25% higher. An a priori knowledge of anisotropy was found to have inconclusive impact on the effectiveness of kriging. It was, however, hypothesized that a preferential sampling strategy that honored anisotropy could be necessary to reach a more definitive conclusion in regards to this issue.