Identification of degradation products of thiram in water, soil and plants using LC-MS technique

In order to evaluate the deleterious effects of exposure to pesticides on a target population, a comprehensive study on their degradation in the various segments of ecosystem under varying environmental conditions is needed. In view of this, a study has been carried out on the metabolic pathways of thiram, a dithiocarbamate fungicide, in a variety of matrices namely water and soil under controlled conditions and plants in field conditions. The identification of degradation products was carried out in samples collected at various time points using LC-MS. The degradation products identified can be rationalized as originating by a variety of processes like hydrolysis, oxidation, N-dealkylation and cyclization. As a result of these processes the presence of some metabolites like dimethyl dithiocarbamate, bis(dimethyl carbamoyl) disulphide, bis(dimethyl dithiocarbamoyl) trisulphide and N-methyl-amino-dithiocarbamoyl sulphide was observed in all the cases. However, some different metabolites were observed with the change in the matrix or its characteristics such as cyclised products 2(N, N-dimethyl amino)thiazoline carboxylic acid and 2-thioxo-4-thiazolidine were observed only in plants. The investigations reflect that degradation initiates with hydrolysis, subsequently oxidation/dealkylation, followed by different types of reactions. The pathways seem to be complex and dependent on the matrices. Dimethyl dithiocarbamate and oxon metabolites, which are more toxic than parent compound, seem to persist for a longer time. Results indicate persistence vis-a-vis toxicity of pesticide and its metabolites and also provide a data bank of metabolites for forensic and epidemiological investigations.     

Determination of the emissions from an aircraft auxiliary power unit (APU) during the Alternative Aviation Fuel Experiment (AAFEX)

The emissions from a Garrett-AiResearch (now Honeywell) Model GTCP85-98CK auxiliary power unit (APU) were determined as part of the National Aeronautics and Space Administration's (NASA's) Alternative Aviation Fuel Experiment (AAFEX) using both JP-8 and a coal-derived Fischer Tropsch fuel (FT-2). Measurements were conducted by multiple research organizations for sulfur dioxide (SO2, total hydrocarbons (THC), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), speciated gas-phase emissions, particulate matter (PM) mass and number, black carbon, and speciated PM. In addition, particle size distribution (PSD), number-based geometric mean particle diameter (GMD), and smoke number were also determined from the data collected. The results of the research showed PM mass emission indices (EIs) in the range of 20 to 700 mg/kg fuel and PM number EIs ranging from 0.5 x 10(15) to 5 x 10(15) particles/kg fuel depending on engine load and fuel type. In addition, significant reductions in both the SO2 and PM EIs were observed for the use of the FT fuel. These reductions were on the order of approximately 90% for SO2 and particle mass EIs and approximately 60% for the particle number EI, with similar decreases observed for black carbon. Also, the size of the particles generated by JP-8 combustion are noticeably larger than those emitted by the APU burning the FT fuel with the geometric mean diameters ranging from 20 to 50 nm depending on engine load and fuel type. Finally, both particle-bound sulfate and organics were reduced during FT-2 combustion. The PM sulfate was reduced by nearly 100% due to lack of sulfur in the fuel, with the PM organics reduced by a factor of approximately 5 as compared with JP-8.     

Influence of soil type and extraction conditions on perchlorate analysis by ion chromatography

Perchlorate is a stable anion that has been introduced into the environment through activities related to its production and use as a solid rocket propellant. Perchlorate is thought to transport through soils without being adsorbed; thus, for determination of perchlorate in soil, samples are typically extracted with water prior to analysis. The completeness of extraction depends on perchlorate existing as a free ion within the soil matrix. In this study, perchlorate extraction efficiency was evaluated with five soil types under two different oxygen states. For each soil, 30% (w/w) slurries were prepared and equilibrated under either oxic or anoxic conditions prior to spiking with a stock solution of sodium perchlorate, and the slurries were then maintained for 1-week or 1-month. At the end of the exposure, slurries were centrifuged and separated into aqueous and soil phases. After phase separation, the soil was washed first with deionized water and then with 50mM NaOH, producing second and third aqueous phases, respectively. Perchlorate concentrations in the three aqueous phases were determined using ion chromatography. The results obtained from this study suggest that matrix interference and signal suppression due to high conductivity have greater effects upon observed perchlorate concentrations by ion chromatography than does perchlorate interaction with soil. Thus, a single water extraction is sufficient for quantitative determination of perchlorate in soil.     

Noise Control Strategies for Occupational Safety and Better Working Environments

Hearing impairment in humans due to occupational noise exposure is one of the significant occupational diseases in many countries. The equipment to measure noise levels and daily noise exposure in existing noisy environments is readily available and can be used to assess the risk of hearing damage. This article examines the currently legislated hearing damage risk criterion and compares the two main noise level-time trade-off schemes being used. The engineering methods for controlling excessive noise levels and techniques to either bring them below the hearing damage risk threshold or to within an acceptable range for the workplace requirement are discussed, together with the expected improvements by such measures.     

Chemical and photochemical transformation of fenamiphos—an organophosphorus nematicide

Fenamiphos, an organophosphorus nematicide and its hydrolysis product 4‐methylthio‐m‐cresol under dye‐sensitized photo‐oxidative conditions yielded the corresponding sulfoxide analogs. Under UV‐photolytic conditions, fenamiphos in methanol solution gave mainly the cleavage products. To obtain standards of the oxidative degradation products/metabolites in larger quantities, fenamiphos and fenamiphos phenol was chemically transformed to the corresponding sulfoxide and sulfone. Their structures were confirmed by ‘HNMR and mass spectra.     

Reaction of chlorimuron‐ethyl with diazomethane

Methylation of chlorimuron‐ethyl with etheral solution of diazomethane gave ethyl‐2‐[[[[(4‐chloro‐6‐methoxy‐2‐pyrimidinyl) N‐methylamino] carbonyl] N‐methylamino] sulfonyl] benzoate (dimethyl derivative of chlorimuron‐ethyl) as the major product along with 4‐chloro‐6‐methoxy‐2‐N‐methylamino pyrimidine, 2‐aminomethyl sulfonyl benzoic acid, ethyl‐2‐[(N‐methylamino) sulfonyl] benzoate, ethyl‐2‐[N,N‐dimethylamino) sulfonyl] benzoate and o‐benzoic sulf‐N‐methylimide as the minor products.     

Light-induced transformation of tribenuron-methyl on glass, soil, and plant surface

Photolysis of tribenuron-methyl (methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5triazin-2-yl)methylamino]carbonyl]amino]sulfonyl]benzoate), a sulfonylurea herbicide, was studied as thin film on glass surface, soil surface, and plant surface. A number of photoproducts such as 4-methoxy-6-methyl-2-aminomethyl-1,3,5-triazine; methyl-2-(aminosulfonyl) benzoate; N-(2-carbomethoxyphenyl)-N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea; N-(2-carbomethoxyphenyl sulfonyl)-N-methyl urea; o-benzoic sulfimide and 4-methoxy-6-methyl-2-amino-1,3,5-triazine were identified by comparison of their GC-MS with the authentic standards. The rate of degradation in all the cases followed first-order kinetics with a statistically significant correlation coefficient. Rate of photodegradation was greater on glass surface than on soil surface.     

Effect of acute exposure of acephate on hemocyte abundance in a non-target victim Drosophila melanogaster

Organophosphate insecticide acephate was tested to investigate effects on hemocyte abundance in a non-target dipteran insect Drosophila melanogaster. For this purpose, third-instar larvae were fed on four graded concentrations (2, 4, 6, or 8 μg/ml) acephate for a period of 12 and 24 hr (acute treatment). Control groups were simultaneously maintained for comparison. Relative proportions of plasmatocytes in hemolymph smear were found to fall with increasing concentrations of the test chemical. Similar decreasing trend in population of lamellocytes was also noted after 12 and 24 hr chemical exposure. In contrast to plasmatocytes and lamellocytes, crystal cell number was found to rise with increasing pesticide concentration. Several factors like oxidative stress, apoptosis induction, and mitotic failure might be the cause of reduced plasmatocyte and lamellocyte count. The elevated number of crystal cells in hemolymph smears is directly indicative of high melanin synthesis that assists larvae to combat chemical stress, since melanin is well known for its potential to minimize physical, chemical, and pathogenic stress.     

Triethylamine induced photolysis of endosulphan

Photolysis of pure isomers of endosulphan in the presence of triethylamine gives products arising by the loss of a chlorine atom from the geminal bridge. The structures of these products have been established. The α‐isomer of endosulphan isomerised to ß‐isomer on a leaf surface.