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.     

PM10 emission factors for non-exhaust particles generated by road traffic in an urban street canyon and along a freeway in Switzerland

Recent studies have shown clear contributions of non-exhaust emissions to the traffic related PM10 load of the ambient air. These emissions consist of particles produced by abrasion from brakes, road wear, tire wear, as well as vehicle induced resuspension of deposited road dust. The main scope of the presented work was to identify and quantify the non-exhaust fraction of traffic related PM10 for two roadside locations in Switzerland with different traffic regimes. The two investigated locations, an urban street canyon with heavily congested traffic and an interurban freeway, are considered as being typical for Central Europe. Mass-relevant contributions from abrasion particles and resuspended road dust mainly originated from particles in the size range 1–10 μm. The results showed a major influence of vehicle induced resuspension of road dust. In the street canyon, the traffic related PM10 emissions (LDV: 24 ± 8 mg km^?1 vehicle^?1, HDV: 498 ± 86 mg km^?1 vehicle^?1) were assigned to 21% brake wear, 38% resuspended road dust and 41% exhaust emissions. Along the freeway (LDV: 50 ± 13 mg km^?1 vehicle^?1, HDV: 288 ± 72 mg km^?1 vehicle^?1), respective contributions were 3% brake wear, 56% resuspended road dust and 41% exhaust emissions. There was no indication for relevant contributions from tire wear and abrasion from undamaged pavements.     

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.     

A Special Purpose Plant Environmental Chamber for Air Pollution Studies

The controlled atmosphere aspects of the environmental chambers at the University of Utah are described. Control of wind velocity, CO₂, concentration, temperature, relative humidity, and pollutant concentration are discussed. Requirements of our research program dictating the chamber design include: (1) ability to expose plants to air pollutants under the same environmental conditions at different times; (2) ability to simulate field environmental conditions within acceptable limits; (3) ability to study the effects of temperature, light, relative humidity, and wind velocity on response of plants to air pollutants; (4) ability to measure growth suppression, respiration, and transpiration; and (5) ability to measure the pollutant uptake rate of the plants.     

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.     

Random forest models to estimate bankfull and low flow channel widths and depths across the conterminous United States

Channel dimensions (width and depth) at varying flows influence a host of instream ecological processes, as well as habitat and biotic features; they are a major consideration in stream habitat restoration and instream flow assessments. Models of widths and depths are often used to assess climate change vulnerability, develop endangered species recovery plans, and model water quality. However, development and application of such models require specific skillsets and resources. To facilitate acquisition of such estimates, we created a dataset of modeled channel dimensions for perennial stream segments across the conterminous United States. We used random forest models to predict wetted width, thalweg depth, bankfull width, and bankfull depth from several thousand field measurements of the National Rivers and Streams Assessment. Observed channel widths varied from <5 to >2000 m and depths varied from <2 to >125 m. Metrics of watershed area, runoff, slope, land use, and more were used as model predictors. The models had high pseudo R² values (0.70–0.91) and median absolute errors within ±6% to ±21% of the interquartile range of measured values across 10 stream orders. Predicted channel dimensions can be joined to 1.1 million stream segments of the 1:100 K resolution National Hydrography Dataset Plus (version 2.1). These predictions, combined with a rapidly growing body of nationally available data, will further enhance our ability to study and protect aquatic resources.