Pathways for the oxidation of sarin in urban atmospheres

The nerve agent sarin has recently been deployed by terrorists in a major city. The molecule is volatile and made its way to many victims by passing as vapor through a highly reactive medium. Here we estimate rates and pathways for the removal of gas phase sarin from a generalized urban atmosphere. Only information from the open scientific literature is used. By structure reactivity comparisons with the organophosphorus pesticides, hydroxyl radical hydrogen abstraction may occur in as little as one hour. Decomposition of side chains after hydroxyl attack leads to organic oxygenates which preserve the phosphonofluoridate and so toxicity. The aqueous aerosol surface is contacted in minutes and offers access to a range of dissolved nucleophiles. Substitution displaces the fluoride leaving group, giving safe phosphoric acid analogs. Because of uncertainties in the electron distribution and in aqueous decay mechanisms, the time constants must be viewed as lower limits.     

Trihalomethane formation in ozonated and chlorinated surface water

The relatively recent discovery of disinfection by-products has driven the main regulatory organisms to set maximum contaminant levels for certain substances in drinking water. Trihalomethanes can be deemed as the most important group of by-products in chlorinated surface waters. The present work has focused on trihalomethane formation in a full-scale water treatment plant. We studied the effect of several factors, including ozonation, on trihalomethane levels in chlorinated treated water. The treatment scheme also includes an ozonation step. Electronic Publication     

Flame retardants and legacy contaminants in polar bears from Alaska, Canada, East Greenland and Svalbard, 2005-2008

Flame retardants and legacy contaminants were analyzed in adipose tissue from 11 circumpolar polar bear (Ursus maritimus) subpopulations in 2005-2008 spanning Alaska east to Svalbard. Although 37 polybrominated diphenyl ethers (PBDEs), total-(α)-hexabromocyclododecane (HBCD), 2 polybrominated biphenyls (PBBs), pentabromotoluene, pentabromoethylbenzene, hexabromobenzene, 1,2-bis(2,4,6-tribromophenoxy(ethane) and decabromodiphenyl ethane were screened, only 4 PBDEs, total-(α-)HBCD and BB153 were consistently found. Geometric mean ΣPBDE (4.6-78.4 ng/g lipid weight (lw)) and BB153 (2.5-81.1 ng/g lw) levels were highest in East Greenland (43.2 and 39.2 ng/g lipid weight (lw), respectively), Svalbard (44.4 and 20.9 ng/g lw) and western (38.6 and 30.1 ng/g lw) and southern Hudson Bay (78.4 and 81.1 ng/g lw). Total-(α)-HBCD levels (<0.3-41.1 ng/g lw) were lower than ΣPBDE levels in all subpopulations except in Svalbard, consistent with greater European HBCD use versus North American pentaBDE product use. ΣPCB levels were high relative to flame retardants as well as other legacy contaminants and increased from west to east (1797-10,537 ng/g lw). ΣCHL levels were highest among legacy organochlorine pesticides and relatively spatially uniform (765-3477 ng/g lw). ΣDDT levels were relatively low and spatially variable (31.5-206 ng/g lw). However, elevated proportions of p,p'-DDT to ΣDDT in Alaska and Beaufort Sea relative to other subpopulations suggested fresh inputs from vector control use in Asia and/or Africa. Comparing earlier circumpolar polar bear studies, ΣPBDE, total-(α)-HBCD, p,p'-DDE and ΣCHL levels consistently declined, whereas levels of other legacy contaminants did not. International regulations have clearly been effective in reducing levels of several legacy contaminants in polar bears relative to historical levels. However, slow or stalling declines of certain historic pollutants like PCBs and a complex mixture of "new" chemicals continue to be of concern to polar bear health and that of their arctic marine ecosystems.     

Erratum to: Estimating urban water demand under conditions of rapid growth: the case of Shanghai

Regional Environmental Change - Many of the world’s major cities are expected to face significant water shortages in coming decades, largely due to increased demand arising from economic and...     

Sequestration of priority pollutant PAHs from sediment pore water employing semipermeable membrane devices

Semipermeable membrane devices (SPMDs) were employed to sample sediment pore water in static exposure studies under controlled laboratory conditions using (control pond and formulated) sediments fortified with 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs). The sediment fortification level of 750 ng/g was selected on the basis of what might be detected in a sediment sample from a contaminated area. The sampling interval consisted of 0, 4, 7, 14, and 28 days for each study. The analytical methodologies, as well as the extraction and sample cleanup procedures used in the isolation, characterization, and quantitation of 15 PPPAHs at different fortification levels in SPMDs, water, and sediment were reported previously (Williamson, M.S. Thesis, University of Missouri-Columbia, USA; Williamson et al., Chemosphere (This issue--PII: S0045-6535(02)00394-6)) and used for this project. Average (mean) extraction recoveries for each PPPAH congener in each matrix are reported and discussed. No procedural blank extracts (controls) were found to contain any PPPAH residues above the method quantitation limit, therefore, no matrix interferences were detected. The focus of this publication is to demonstrate the ability to sequester environmental contaminants, specifically PPPAHs, from sediment pore water using SPMDs and two different types of fortified sediment.     

On the tragedy of the commons: When predation and livestock loss may improve the economic lot of herders

This paper studies the practice of semi-domestic reindeer (Rangifer t. tarandus) herding in Finnmark county in northern Norway. In this area, the Saami reindeer herders compete for space and grazing areas and keep large herds, while at the same time, the reindeer population is heavily exposed to carnivore predation by the lynx (Lynx lynx), the wolverine (Gulo gulo), and the golden eagle (Aquila chrysaetos). It is demonstrated that predation actually may improve the economic lot of livestock holders in this unmanaged local common setting. There are ecological as well as economic reasons as to why this happens. The ecological reason is that predation compensates for natural mortality; that is, increased predation reduces natural mortality, indicating that the net loss due to predation actually may be quite small. When predation reduces livestock density, the feeding conditions of the animals will improve, resulting in increased livestock weight and higher per animal slaughter value. At the same time, a smaller stock reduces the operating costs of the herders.     

Determining floodplain sedimentation rates using Cs in a low fallout environment dominated by channel- and cultivation-derived sediment inputs, central Queensland, Australia

Fallout ¹³⁷Cs has been widely used to determine floodplain sedimentation rates in temperate environments, particularly in the northern hemisphere. Its application in low fallout, tropical environments in the southern hemisphere has been limited. In this study we assess the utility of ¹³⁷Cs for determining rates of floodplain sedimentation in a dry-tropical catchment in central Queensland, Australia. Floodplain and reference site cores were analysed in two centimetre increments, depth profiles were produced and total ¹³⁷Cs inventories calculated from the detailed profile data. Information on the rates of ¹³⁷Cs migration through local soils was obtained from the reference site soil cores. This data was used in an advection–diffusion model to account of ¹³⁷Cs mobility in floodplain sediment cores. This allowed sedimentation rates to be determined without the first year of detection for ¹³⁷Cs being known and without having to assume that ¹³⁷Cs remains immobile following deposition. Caesium-137 depth profiles in this environment are demonstrated to be an effective way of determining floodplain sedimentation rates. The total ¹³⁷Cs inventory approach was found to be less successful, with only one of the three sites analysed being in unequivocal agreement with the depth profile results. The input of sediment from catchment sources that have little, or no, ¹³⁷Cs attached results in true depositional sites having total inventories that are not significantly different from those of undisturbed reference sites.