Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane

Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by ¹H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.     

A vehicle emissions system using a car simulator and a geographical information system: Part 1--System description and testing

A methodology for estimating vehicular emissions comprising a car simulator, a basic traffic model, and a geographical information system is capable of estimating vehicle emissions with high time and space resolution. Because of the extent of the work conducted, this article comprises two sections: In Part 1 of this work, we describe the system and its components and use examples for testing it. In Part 2 we will study in more detail the emissions of the sample fleet using the system and will make comparisons with another emission model. The experimental data for the car simulator is obtained using on-board measuring equipment and laboratory Fourier transform IR (FTIR) measurements with a dynamometer following typical driving cycles. The car simulator uses this data to generate emission factors every second. These emission factors, together with information on car activity and velocity profiles of highways and residential and arterial roads in Mexico City in conjunction with a basic traffic model, provide emissions per second of a sample fleet. A geographical information system is used to localize these road emissions.     

Large emissions of sesquiterpenes and methyl chavicol quantified from branch enclosure measurements

Multiple field studies have suggested chemistry within a forest canopy is poorly understood due to inadequate detection and quantification of reactive biogenic emissions, such as terpenes. To measure emission rates of terpenes at Blodgett Forest, a coniferous forest in the Sierra Nevada mountains of California, we placed enclosures over branches of the dominant species at the site – Ponderosa pine, manzanita, and ceanothus – in the summer of 2005. Zero air, with ambient CO₂ concentrations, flowed through the chamber system and volatile organic compound (VOC) emission measurements were made by proton transfer reaction mass spectrometry (PTR-MS), solid phase microextraction (SPME) on fibers followed by direct injection into a gas chromatograph with an ion trap mass spectrometer (GC-ITMS), and by in situ GC with a flame ionization detector (GC-FID). We show that previously undetected sesquiterpenes and methyl chavicol significantly contribute to the total reactive biogenic emission profile from this field site.     

Serum concentrations of selected organochlorine pesticides in a Lebanese population and their associations to sociodemographic,anthropometric and dietary factors: ENASB study

Organochlorine pesticides (OCPs) were banned by the Stockholm Convention many years ago; however, they are still detected in the environment due to their high persistence, their current illegal use, and their import from countries where they have not been banned. We evaluated the serum concentrations of selected OCPs (hexachlorobenzene (HCB), β-hexachlorocyclohexanes (β-HCH), p,p′-dichlorodiphenyltrichloroethane (DDT) and its metabolite p,p′-dichlorodiphenyldichloroethylene (DDE) in a sample of Lebanese adults using gas chromatography coupled to an ion trap mass spectrometer detector. The mean concentrations of HCB, β-HCH, DDT, and DDE were 7.1, 8.6, 2.1, and 18.9 ng/g of lipids, respectively, and the major contributor among the four OCPs was DDE. The OCP levels in the present study were in general lower than the values observed in several countries worldwide and their concentrations at the 95th percentile were lower than the biomonitoring equivalents (BEs) excluding any appreciable health risk. We observed an inverse association between HCB concentrations and body mass index (BMI) as well as HCB, β-HCH, and DDE levels, and smoking habits. Milk consumption however was positively associated with an increased serum level of β-HCH. This study, which was the first to investigate OCP serum levels in a Lebanese population, provides a baseline to which future measurements can be compared.     

In vitro cytotoxicity assessment of a West Virginia chemical spill mixture involving 4-methylcyclohexanemethanol and propylene glycol phenyl ether

Thousands of gallons of industrial chemicals, crude 4-methylcyclohexanemethanol (MCHM) and propylene glycol phenyl ether (PPh), leaked from industrial tanks into the Elk River in Charleston, West Virginia, USA, on January 9, 2014. A considerable number of people were reported to exhibit symptoms of chemical exposure and an estimated 300,000 residents were advised not to use or drink tap water. At the time of the spill, the existing toxicological data of the chemicals were limited for a full evaluation of the health risks, resulting in concern among those in the impacted regions. In this preliminary study, we assessed cell viability and plasma membrane degradation following a 24-h exposure to varying concentrations (0–1000 μM) of the two compounds, alone and in combination. Evaluation of different cell lines, HEK-293 (kidney), HepG2 (liver), H9c2 (heart), and GT1-7 (brain), provided insight regarding altered cellular responses in varying organ systems. Single exposure to MCHM or PPh did not affect cell viability, except at doses much higher than the estimated exposure levels. Certain co-exposures significantly reduced metabolic activity and increased plasma membrane degradation in GT1-7, HepG2, and H9c2 cells. These findings highlight the importance of examining co-exposures to fully understand the potential toxic effects.     

Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe

Purpose  

Nanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed.     

Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Relative kinetic studies have been performed on the reactions of Cl atoms with a series of methyl alkyl esters in a 405-liter borosilicate glass chamber at (298 ± 3) K and one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. Rate coefficients (in units of cm³ molecule^?1 s^?1) were determined for the following compounds: methyl acetate (2.48 ± 0.58) × 10^?12; methyl propanoate (1.68 ± 0.36) × 10^?11; methyl butanoate (4.77 ± 0.87) × 10^?11; methyl pentanoate (7.84 ± 1.15) × 10^?11; methyl hexanoate (1.09 ± 0.31) × 10^?10; methyl heptanoate (1.56 ± 0.37) × 10^?10; methyl cyclohexane carboxylate (3.32 ± 0.76) × 10^?10; methyl-2-methyl butanoate (9.41 ± 1.39) × 10^?11.In addition rate coefficients (in units of 10^?11 cm³ molecule^?1 s^?1) have been obtained for the reactions of OH radicals with the following compounds: methyl butanoate (3.55 ± 0.71), methyl pentanoate (5.41 ± 1.08), and methyl-2-methyl butanoate (4.08 ± 0.82).Using the kinetic rate data tropospheric lifetimes for the methyl alkyl esters with respect to their reactions with OH, and Cl have been estimated for typical ambient air concentrations of these oxidants.     

Cross-sensitivities of electrochemical detectors used to monitor worker exposures to airborne contaminants: false positive responses in the absence of target analytes

Ideally, the response of electrochemical detectors is proportional to the concentration of targeted airborne chemicals and is not be affected by concomitantly present substances. Manufacturers provide a limited list of cross-sensitivities but end-users have anecdotally reported unexpected interferences by other substances. Electrochemical detectors designed to measure airborne levels of CO, H(2)S, NO, NO(2), or SO(2), were challenged with potentially interfering substances in the absence of target analytes. Cross-sensitivities undocumented by the manufacturers were observed and were found to vary between different models of instruments for the same challenge chemical.