Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials

Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis- and trans-chlordane, heptachlor exo-epoxide, oxychlordane, U82, MC5, MC6, MC7, o,p^′-DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.     

Risk of motor vehicle accident death among 1.3 million veterans of the Iraq and Afghanistan wars

Objective: We conducted a cohort study of recent wartime veterans to determine the postservice mortality risk due to motor vehicle accidents (MVAs).

Methods: Veterans were identified from the Defense Manpower Data Center records. Deployment to te Iraq or Afghanistan war zone was determined from the Contingency Tracking System. Vital status of 317,581 deployed and 964,493 nondeployed veterans was followed from their discharge dates between 2001 to 2007 until earlier of date of death or December 31, 2009. Underlying causes of death were obtained from the National Death Index Plus.

Results: Based on 9,353 deaths (deployed, 1,650; nondeployed, 7,703), of which 779 were MVA deaths as drivers (166; 613), both cohorts had 25 to 24% lower mortality risk from all causes but had 44 to 45% higher risk of MVA deaths relative to the U.S. general population. The higher MVA mortality risk was not associated with deployment to the war zone. After controlling for age, sex, race, marital status, branch of service, and rank, the risk for deployed veterans was comparable to that of nondeployed veterans (hazard ratio = 0.91; 95% confidence interval, 0.77–1.09).

Conclusions: Veterans exhibit significantly higher risk of MVA deaths compared to the U.S. general population. However, deployment to the Iraq or Afghanistan war was not associated with the excess risk.     

Dual poroelastic response of a coal seam to CO2 injection

Although the influence of gas sorption-induced coal deformation on porosity and permeability has been widely recognized, prior studies are all under conditions of no change in overburden stress and effective stress-absent where effective stresses scale inversely with applied pore pressures. Here we extend formalism to couple the transport and sorption of a compressible fluid within a dual-porosity medium where the effects of deformation are rigorously accommodated. This relaxes the prior assumption that total stresses remain constant and allows exploration of the full range of mechanical boundary conditions from invariant stress to restrained displacement. Evolution laws for permeability and related porosity are defined at the micro-scale and applied to both matrix and an assumed orthogonal, regular and continuous fracture system. Permeability and porosity respond to changes in effective stress where sorption-induced strains may build total stresses and elevate effective stresses. Gas accumulation occurs in both free- and adsorbed-phases and due to effective grain and skeletal compressibilities. A finite element model is applied to quantify the net change in permeability, the gas flow, and the resultant deformation in a prototypical coal seam under in situ stresses. Results illustrate how the CO₂ injectivity is controlled both by the competition between the effective stress and the gas transport induced volume change within the matrix system and by the dynamic interaction between the matrix system and the fracture system. For typical parameters, initial injection-related increases in permeability due to reduced effective stresses may endure for days to years but are ultimately countered by long-term reductions in permeability which may decline by an order of magnitude. Models suggest the crucial role of stresses and the dynamic interaction between matrix and fractures in correctly conditioning the observed response.     

Effects of 17α-trenbolone and melengestrol acetate on Xenopus laevis growth, development, and survival

The synthetic growth-promoting hormones trenbolone and melengestrol acetate have been detected in the environment near beef cattle feedlots and are reportedly transported via wind-borne particulate matter. Therefore, movement of synthetic hormones from beef cattle feedlots to water bodies via particulate matter is possible. Our objective was to evaluate potential effects of 17α-trenbolone (17α-TB), melengestrol acetate (MGA), and combinations of both on growth, development, and survival of Xenopus laevis larvae. On post-hatch day 2 (stage 33/34), X. laevis larvae were exposed to three nominal concentrations of 17α-TB (10, 100, and 500 ng/L), MGA (1, 10, and 100 ng/L), a combination of both (1/10, 10/100, and 100/500 ng/L MGA/17α-TB), frog embryo teratogenesis assay-Xenopus medium, or a solvent control. Significant increases in all X. laevis growth metrics were observed among larvae in the 1 ng/L MGA?+?10 ng/L 17α-TB and 10 ng/L MGA?+?100 ng/L 17α-TB treatments. Stage of development was increased among larvae in the 1 ng/L MGA?+?10 ng/L 17α-TB treatment group and significantly decreased among those in the 500 ng/L 17α-TB treatment. Total body mass and snout–vent length of X. laevis larvae were significantly reduced in the 100 ng/L MGA and 100 ng/L MGA?+?500 ng/L 17α-TB treatment groups. Larvae exposed to 500 ng/L 17α-TB had decreased total body mass, snout–vent length, and total length. In general, growth measurements decreased with increasing concentration of MGA, 17α-TB, or a combination of both. Survival among all treatments was not significantly different from controls. Amphibians exposed to MGA and 17α-TB in the environment may experience alterations in growth and development.     

Exposure to mixtures of organohalogen contaminants and associative interactions with thyroid hormones in East Greenland polar bears (Ursus maritimus)

We investigated the multivariate relationships between adipose tissue residue levels of 48 individual organohalogen contaminants (OHCs) and circulating thyroid hormone (TH) levels in polar bears (Ursus maritimus) from East Greenland (1999-2001, n=62), using projection to latent structure (PLS) regression for four groupings of polar bears; subadults (SubA), adult females with cubs (AdF_N), adult females without cubs (AdF_S) and adult males (AdM). In the resulting significant PLS models for SubA, AdF_N and AdF_S, some OHCs were especially important in explaining variations in circulating TH levels: polybrominated diphenylether (PBDE)-99, PBDE-100, PBDE-153, polychlorinated biphenyl (PCB)-52, PCB-118, cis-nonachlor, trans-nonachlor, trichlorobenzene (TCB) and pentachlorobenzene (QCB), and both negative and positive relationships with THs were found. In addition, the models revealed that DDTs had a positive influence on total 3,5,3'-triiodothyronine (TT3) in AdF_S, and that a group of 17 higher chlorinated ortho-PCBs had a positive influence on total 3,5,3',5'-tetraiodothyronine (thyroxine, TT4) in AdF_N. TH levels in AdM seemed less influenced by OHCs because of non-significant PLS models. TH levels were also influenced by biological factors such as age, sex, body size, lipid content of adipose tissue and sampling date. When controlling for biological variables, the major relationships from the PLS models for SubA, AdF_N and AdF_S were found significant in partial correlations. The most important OHCs that influenced TH levels in the significant PLS models may potentially act through similar mechanisms on the hypothalamic-pituitary-thyroid (HPT) axis, suggesting that both combined effects by dose and response addition and perhaps synergistic potentiation may be a possibility in these polar bears. Statistical associations are not evidence per se of biological cause-effect relationships. Still, the results of the present study indicate that OHCs may affect circulating TH levels in East Greenland polar bears, adding to the "weight of evidence" suggesting that OHCs might interfere with thyroid homeostasis in polar bears.     

Modelling small groundwater systems: experiences from the Braunton Burrows and Ainsdale coastal dune systems,UK

Coastal dunes are delicate systems that are under threat from a variety of human and natural influences. Groundwater modelling can provide a better understanding of how these systems operate and can be a useful tool towards the effective management of a coastal dune system, e.g. by identifying strategically important locations for flora and fauna and guiding the planning of management operations through predicting impacts from climatic change, sea level rise and land use management. Most dune systems are small, typically of the size 10–100 km², compared with inland groundwater systems. Applying conventional groundwater modelling approaches to these small systems presents a number of challenges due to the local scale of the system and the fact that the system boundaries (sea, drains, ponds etc.) are close to the main body of the aquifer. In this paper, two case studies will be presented using different modelling approaches to understand the groundwater balance in two dune systems in the UK. The studies demonstrate that, although conventional hydraulic models can describe the general system behaviour, a fuller understanding of the recharge mechanisms and system boundaries is needed to represent adequately system dynamics of small groundwater systems.     

Development of engine activity cycles for the prime movers of unconventional natural gas well development

With the advent of unconventional natural gas resources, new research focuses on the efficiency and emissions of the prime movers powering these fleets. These prime movers also play important roles in emissions inventories for this sector. Industry seeks to reduce operating costs by decreasing the required fuel demands of these high horsepower engines but conducting in-field or full-scale research on new technologies is cost prohibitive. As such, this research completed extensive in-use data collection efforts for the engines powering over-the-road trucks, drilling engines, and hydraulic stimulation pump engines. These engine activity data were processed in order to make representative test cycles using a Markov Chain, Monte Carlo (MCMC) simulation method. Such cycles can be applied under controlled environments on scaled engines for future research. In addition to MCMC, genetic algorithms were used to improve the overall performance values for the test cycles and smoothing was applied to ensure regression criteria were met during implementation on a test engine and dynamometer. The variations in cycle and in-use statistics are presented along with comparisons to conventional test cycles used for emissions compliance.

Implications: Development of representative, engine dynamometer test cycles, from in-use activity data, is crucial in understanding fuel efficiency and emissions for engine operating modes that are different from cycles mandated by the Code of Federal Regulations. Representative cycles were created for the prime movers of unconventional well development—over-the-road (OTR) trucks and drilling and hydraulic fracturing engines. The representative cycles are implemented on scaled engines to reduce fuel consumption during research and development of new technologies in controlled laboratory environments.     

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L_3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L_3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L_3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu₂S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.     

The academic medical centre and nongovernmental organisation partnership following a natural disaster

The global response to the 12 January 2010 earthquake in Haiti revealed the ability to mobilise medical teams quickly and effectively when academic medical centres partner non-governmental organisations (NGO) that already have a presence in a zone of devastation. Most established NGOs based in a certain region are accustomed to managing the medical conditions that are common to that area and will need additional and specialised support to treat the flux of myriad injured persons. Furthermore, an NGO with an established presence in a region prior to a disaster appears better positioned to provide sustained recovery and rehabilitation relief. Academic medical centres can supply these essential specialised resources for a prolonged time. This relationship between NGOs and academic medical centres should be further developed prior to another disaster response. This model has great potential with regard to the rapid preparation and worldwide deployment of skilled medical and surgical teams when needed following a disaster, as well as to the subsequent critical recovery phase.