Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Variations in exposure to in-vehicle particle mass and number concentrations in different road environments

Road environments significantly affect in cabin concentration of particulate matter (PM). This study conducted measurements of in-vehicle and on-road concentrations of PM10, PM2.5, PM1, and particle number (PN) in size of 0.02–1 µm, under six ventilation settings in different urban road environments (tunnels, surface roads and elevated roads). Linear regression was then used to analyze the contributions of multiple predictor variables (including on-road concentrations, temperature, relative humidity, time of day, and ventilation settings) to measured variations. On-road measurements of PM2.5, PM1, and PN concentrations from the open surface roads were 5.5%, 3.7%, and 16% lower, respectively, than those measured in tunnels, but 7.6%, 7.1% and 24% higher, respectively, than those on elevated roads. The highest on-road PM10 concentration was observed on surface roads. The time series pattern of in-vehicle particle concentrations closely tracked the on-road concentrations outside of the car and exhibited a smoother profile. Irrespective of road environment, the average I/O ratio of particles was found to be the lowest when air conditioning was on with internal recirculation, the highest purification efficiency via ventilation was obtained by switching on external air recirculation and air conditioning. Statistical models showed that on-road concentration, temperature, and ventilation setting are common factors of significance that explained 58%-80%, 64%-97%, and 87%-98% of the variations in in-vehicle PM concentrations on surface roads, on elevated roads, and in tunnels, respectively.

Implications: Inside vehicles, both driver and passengers will be exposed to elevated particle concentrations. However, for in-vehicle particles, there has been no comprehensive comparative study of the three-dimensional traffic environment including tunnels surface roads and elevated roads. This study focuses on the analysis of the trends and main influencing factors of particle concentrations in different road environments. The results can provide suggestions for the driver's behavior, and provide data support for the environmental protection department to develop pollutant concentration limits within the vehicle.     

Seasonal dynamics of phytoplankton in response to environmental variables in contrasting coastal ecosystems

Environmental Science and Pollution Research - Seasonal distribution of phytoplankton community and size structure was assessed in three different tropical ecosystems of the western Bay of Bengal...     

Could curcumin ameliorate titanium dioxide nanoparticles effect on the heart? A histopathological,immunohistochemical, and genotoxic study

Environmental Science and Pollution Research - The evaluation of the toxicological effects of titanium dioxide nanoparticles (TiO2NPs) is increasingly important due to their growing occupational...     

Bromide affecting drinking water mutagenicity

The effect of bromide on the mutagenicity of artificially recharged groundwater and purified artificially recharged groundwater after chlorine, ozone, hydrogen peroxide, permanganate, and UV treatments alone and in various combinations was studied. The highest mutagenicity was observed after chlorination, while hydrogen peroxide-ozone-chlorine treatment produced the lowest value for both waters. Chlorinated waters, which were spiked with bromide, had up to 3.7 times more mutagenic activity than waters without bromide after every preoxidation method. 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to correspond as much as 76% of the overall mutagenicity in the waters not spiked with bromide. MX formation was found to be lower when the treated water contained bromide, implicating the formation of brominated MX analogues. Trihalomethane formation increased when the treated water contained bromide.     

Does the Harvard/U.S. Environmental Protection Agency Ambient Particle Concentrator change the toxic potential of particles?

Inhalation exposure to urban air particles is known to increase morbidity in humans and animals. Our group utilizes the Harvard/U.S. Environmental Protection Agency Ambient Particle Concentrator (HAPC) to generate concentrated aerosols of outdoor air particles for experimental exposures. We have reported increased pathologic responses to inhalation of concentrated urban air particles and identified silicon (as silicate) as an element associated with many of these responses. Using silicate-rich Mt. St. Helen's volcanic ash (MSHA), we exposed three groups of Sprague-Dawley rats by inhalation for 6 hr to filtered air, MSHA, or MSHA passed though the HAPC. Twenty-four hours following exposure, bronchoalveolar lavage was performed to assess total cell count, differential cell count, protein, lactate dehydrogenase, and n-beta-glucosaminidase levels. Peripheral blood was examined for packed cell volume, total protein, total white cells, and differential cell count. Morphologic studies localized particles in the lung and assessed pulmonary vasculature. No significant differences were observed among any of the groups in any parameter measured including morphometric analysis of pulmonary vasoconstriction. Scanning electron microscopy and X-ray analysis identified particles as silicates typical of MSHA throughout the lung. These findings suggest that particles passing through the HAPC have no change in their toxic potential in an exposure setting where particle deposition in the lung has occurred.     

Assessment of the potential for soil acidification in North India using the critical load approach and locally derived data for acidic and basic inputs

Major ions (Cl-, NO3(-), SO4(2-), Ca2+, Mg2+, Na+, K+ and NH4(+)) were analysed in wet and dry deposition samples collected for 2 years using a polyethylene bottle and funnel collector at Agra in India. The deposition of ionic components (Ca2+ and Mg2+) derived from natural sources i.e. soil were higher than those of anthropogenic origin. In rainwater samples, non-sea-salt fraction was found to be 60-90%. In both wet and dry deposition Ca2+ was found to be the dominant ion which may be due to its large particle diameter. Results suggest that most of the acidity, which occurs due to NO3(-), SO4(2-) and Cl- is neutralized by alkaline constituents, which originate from airborne local soil and dust transported from the Thar desert. Acid neutralizing capacity of soil has also been quantified and found to be 33 x 10(3) neqg(-1). Using deposition data, the critical load for acidity of soil with respect to Ashoka and Eucalyptus was evaluated. The present level of deposition of S and N was found to be much lower than critical loads calculated for S and N. Critical load of exceedance in terms of deposition acidity was also calculated and found to be negative. This indicates that with respect to these species, the ecosystem is protected at the current level of deposition.     

Predicting logP of pesticides using different software

We compared experimental and calculated logP values using a data set of 235 pesticides and experimental values from four different sources: The Pesticide Manual, Hansch Manual, ANPA and KowWin databases. LogP were calculated with four softwares: HyperChem, Pallas, KowWin and TOPKAT. Crossed comparison of the experimental and calculated values proved useful, especially for pesticides. These are harder to study than simpler organic compounds. Structurally they are complex, heterogeneous and similar to drugs from a chemical point of view. They offer an interesting way to verify the goodness of the different methods. Other studies compared several logP predictors using a single set of experimental values taken as a reference. Here we discuss the utility of the different logP predictors, with reference to experimental data found in different databases. This offers three advantages: (1) it avoids bias due to the assumption that one single data set is correct; (2) a given predictor can be developed on the same data set used for evaluation; (3) it takes account of experimental variability and can compare it with the predictor's variability. In our study Pallas and KowWin gave the best results for prediction, followed by TOPKAT.     

Development of a microscale emission factor model for particulate matter for predicting real-time motor vehicle emissions

The U.S. Environmental Protection Agency's National Exposure Research Laboratory is pursuing a project to improve the methodology for modeling human exposure to motor vehicle emissions. The overall project goal is to develop improved methods for modeling the source through the air pathway to human exposure in significant exposure microenvironments. Current particulate matter (PM) emission models, particle emission factor model (used in the United States, except California) and motor vehicle emission factor model (used in California only), are suitable only for county-scale modeling and emission inventories. There is a need to develop a site-specific real-time emission factor model for PM emissions to support human exposure studies near roadways. A microscale emission factor model for predicting site-specific real-time motor vehicle PM (MicroFacPM) emissions for total suspended PM, PM less than 10 microm aerodynamic diameter, and PM less than 2.5 microm aerodynamic diameter has been developed. The algorithm used to calculate emission factors in MicroFacPM is disaggregated, and emission factors are calculated from a real-time fleet, rather than from a fleet-wide average estimated by a vehicle-miles-traveled weighting of the emission factors for different vehicle classes. MicroFacPM requires input information necessary to characterize the site-specific real-time fleet being modeled. Other variables required include average vehicle speed, time and day of the year, ambient temperature, and relative humidity.     

Trimethylbenzoic acids as metabolite signatures in the biogeochemical evolution of an aquifer contaminated with jet fuel hydrocarbons

Evolution of trimethylbenzoic acids in the KC-135 aquifer at the former Wurtsmith Air Force Base (WAFB), Oscoda, MI was examined to determine the functionality of trimethylbenzoic acids as key metabolite signatures in the biogeochemical evolution of an aquifer contaminated with JP-4 fuel hydrocarbons. Changes in the composition of trimethylbenzoic acids and the distribution and concentration profiles exhibited by 2,4,6- and 2,3,5-trimethylbenzoic acids temporally and between multilevel wells reflect processes indicative of an actively evolving contaminant plume. The concentration levels of trimethylbenzoic acids were 3-10 orders higher than their tetramethylbenzene precursors, a condition attributed to slow metabolite turnover under sulfidogenic conditions. The observed degradation of tetramethylbenzenes into trimethylbenzoic acids obviates the use of these alkylbenzenes as non-labile tracers for other degradable aromatic hydrocarbons, but provides rare field evidence on the range of high molecular weight alkylbenzenes and isomeric assemblages amenable to anaerobic degradation in situ. The coupling of actual tetramethylbenzene loss with trimethylbenzoic acid production and the general decline in the concentrations of these compounds demonstrate the role of microbially mediated processes in the natural attenuation of hydrocarbons and may be a key indicator in the overall rate of hydrocarbon degradation and the biogeochemical evolution of the KC-135 aquifer.