Hydroxylated polychlorobornanes--synthesis and characterization of new potential toxaphene metabolites

For decades, toxaphene had been used as a major chloropesticide. Degradation of the multicomponent mixture in the environment was mainly reported to be due to anaerobic dechlorination and hydrodechlorination. Little was known about oxidative transformation processes and the potential hydroxylated metabolites were not available as standard compounds. For this reason we synthesized hydroxylated polychlorobornanes by the UV-induced photochlorination of 2-endo-bornyl acetate with sulfuryl chloride followed by hydrolysis of the acetate moiety. The released polychlorinated 2-endo-hydroxybornanes were slightly higher chlorinated the longer the reaction was maintained. After 8 h, the main products were pentachlorinated hydroxybornanes followed by hexa- and heptachlorinated homologues. Traces of octachlorinated hydroxybornanes were also observed. The GC/ECNI-MS spectra of the products were characterized by the molecular ions and the [M-Cl]⁻ fragment ions. The molecular ions of the polychlorinated hydroxybornanes are isobaric with those of polychlorinated biphenyls. E.g. hexachlorohydroxybornanes (C₁₀H₁₂Cl₆O) and hexachlorobiphenyls (C₁₂H₄Cl₆) show the molecular ion at m/z 358. Based on fractionation experiments on silica with the synthesis products it might be possible that OH-CTTs if present in samples will elute into a more polar fraction usually discarded or not collected. Both problems might explain why these compounds have not been more frequently described in the scientific literature.     

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.     

Characterizing and locating air pollution sources in a complex industrial district using optical remote sensing technology and multivariate statistical modeling

Emissions of volatile organic compounds (VOCs) are most frequent environmental nuisance complaints in urban areas, especially where industrial districts are nearby. Unfortunately, identifying the responsible emission sources of VOCs is essentially a difficult task. In this study, we proposed a dynamic approach to gradually confine the location of potential VOC emission sources in an industrial complex, by combining multi-path open-path Fourier transform infrared spectrometry (OP-FTIR) measurement and the statistical method of principal component analysis (PCA). Close-cell FTIR was further used to verify the VOC emission source by measuring emitted VOCs from selected exhaust stacks at factories in the confined areas. Multiple open-path monitoring lines were deployed during a 3-month monitoring campaign in a complex industrial district. The emission patterns were identified and locations of emissions were confined by the wind data collected simultaneously. N,N-Dimethyl formamide (DMF), 2-butanone, toluene, and ethyl acetate with mean concentrations of 80.0?±?1.8, 34.5?±?0.8, 103.7?±?2.8, and 26.6?±?0.7 ppbv, respectively, were identified as the major VOC mixture at all times of the day around the receptor site. As the toxic air pollutant, the concentrations of DMF in air samples were found exceeding the ambient standard despite the path-average effect of OP-FTIR upon concentration levels. The PCA data identified three major emission sources, including PU coating, chemical packaging, and lithographic printing industries. Applying instrumental measurement and statistical modeling, this study has established a systematic approach for locating emission sources. Statistical modeling (PCA) plays an important role in reducing dimensionality of a large measured dataset and identifying underlying emission sources. Instrumental measurement, however, helps verify the outcomes of the statistical modeling. The field study has demonstrated the feasibility of using multi-path OP-FTIR measurement. The wind data incorporating with the statistical modeling (PCA) may successfully identify the major emission source in a complex industrial district.     

Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (k_ua) and no SPMD air partitioning coefficient (K_sa) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining k_ua and K_sa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The k_uas were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07 m³ g^?1 d^?1. In cases where uptake was approaching equilibrium, K_sas were approximated. K_sa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean k_ua values (n = 3) of anthracene and p,p′-DDE at 0.96 and 1.57 m³ g^?1 d^?1 with relative standard deviations of 8.4% and 8.6% respectively.     

Non-polar halogenated natural products bioaccumulated in marine samples. I. 2,3,3',4,4',5,5'-Heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

This presentation adds new spectroscopic and analytical data on the natural product Q1 that was recently identified by synthesis as 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole. Solid state magic angle spinning 13C NMR data of Q1 is presented as an option for structural proof. Furthermore, the UV spectrum of neat Q1 (absorption maximum at 223 nm) was recorded and, with NMR spectroscopic data, confirmed a twisted bipyrrole ring system. A quantitative standard of Q1 was prepared which allowed to correct previous concentration estimates relative to the electron capture detector response factor of trans-nonachlor. As a result, the actual Q1 response was only 0.65+/-15% of the response factor of trans-nonachlor. Therefore, actual Q1 levels are about 50% higher than the previous estimates. With this result the highest (corrected) Q1 concentration determined to date in the blubber of marine mammals from Australia is 14 mg/kg lipid. Analysis of Q1 and trans-nonachlor in specimens from the German North Sea coast suggests that harbor seals are more able to metabolize Q1 than harbor porpoises. Finally, we calculated that 79 congeners of Q1 (i.e. lower chlorinated 1(')-methyl-1,2(')-bipyrroles) are theoretically possible and present their structures.     

Determination of benzotriazoles in dishwasher tabs from Germany and estimation of the discharge into German waters

A method was developed for the determination of benzotriazoles (BTs) in dishwasher tabs. BTs consist of 1H-benzotriazole and/or tolyltriazole, i.e., a technical mixture of the two isomers 4-methylbenzotriazole and 5-methylbenzotriazole (5-MBT). The method consisted of weighing of an aliquot of the tab, addition of the internal standard 5-MBT, precipitation of the soaps with CaCl₂ and KOH, derivatization of the filtrate with acetic acid anhydride in a two-phase system, and analysis of the organic toluene layer by gas chromatography with mass spectrometry in the selected ion monitoring mode. Eleven of 12 different dishwasher tabs from the German market were tested positive with BTs ranging from 2 to 66 mg/tab. Dishwashing experiments were performed to show that at least 99 % of the BT amount used in the dishwasher did not remain on the dishes but was released into the wastewater treatment system. The annual release of BTs into the water system was estimated to be ~80 tons. Since 70 % or less of the BTs can be degraded in wastewater treatment plants, at least 24 tons are annually released into rivers in Germany.     

Determination of diazepam in aquatic samples by capillary liquid chromatography-electrospray tandem mass spectrometry

In recent years growing attention has been paid toward the discharge, presence and potential adverse effects of pharmaceuticals in the environment. Using different existing analytical methods several studies have already identified a variety of drugs in waste-, surface- and drinking water. The monitoring of surface waters for drugs is of great importance because drugs are designed to be biological very active substances. A capillary LC/ES-MS-MS method has been developed that enables the sensitive and specific detection of diazepam in water samples up to 0.1 ng/ml (LOD). It requires neither multiple extraction steps, nor the use of large volumes of organic solvent. Applying this assay we have detected diazepam in 'in/effluent samples' collected in Belgium and demonstrated the applicability for water analysis without off-line pre-concentration of the analyte.     

Responses to projected changes in climate and UV-B at the species level

Environmental manipulation experiments showed that species respond individualistically to each environmental-change variable. The greatest responses of plants were generally to nutrient, particularly nitrogen, addition. Summer warming experiments showed that woody plant responses were dominant and that mosses and lichens became less abundant. Responses to warming were controlled by moisture availability and snow cover. Many invertebrates increased population growth in response to summer warming, as long as desiccation was not induced. CO2 and UV-B enrichment experiments showed that plant and animal responses were small. However, some microorganisms and species of fungi were sensitive to increased UV-B and some intensive mutagenic actions could, perhaps, lead to unexpected epidemic outbreaks. Tundra soil heating, CO2 enrichment and amendment with mineral nutrients generally accelerated microbial activity. Algae are likely to dominate cyanobacteria in milder climates. Expected increases in winter freeze-thaw cycles leading to ice-crust formation are likely to severely reduce winter survival rate and disrupt the population dynamics of many terrestrial animals. A deeper snow cover is likely to restrict access to winter pastures by reindeer/caribou and their ability to flee from predators while any earlier onset of the snow-free period is likely to stimulate increased plant growth. Initial species responses to climate change might occur at the sub-species level: an Arctic plant or animal species with high genetic/racial diversity has proved an ability to adapt to different environmental conditions in the past and is likely to do so also in the future. Indigenous knowledge, air photographs, satellite images and monitoring show that changes in the distributions of some species are already occurring: Arctic vegetation is becoming more shrubby and more productive, there have been recent changes in the ranges of caribou, and "new" species of insects and birds previously associated with areas south of the treeline have been recorded. In contrast, almost all Arctic breeding bird species are declining and models predict further quite dramatic reductions of the populations of tundra birds due to warming. Species-climate response surface models predict potential future ranges of current Arctic species that are often markedly reduced and displaced northwards in response to warming. In contrast, invertebrates and microorganisms are very likely to quickly expand their ranges northwards into the Arctic.