Laboratory evaluation of an aldehyde scrubber system specifically for the detection of acrolein

We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.     

Chemical Constituents of Fugitive Dust

Wind erosion selectively winnows the fine, most chemically concentrated portions of surface soils and results in the inter-regional transport of fugitive dust containing plant nutrients, trace elements and other soil-borne contaminants. We sampled and analyzed surface soils, sediments in transport over eroding fields, and attic dust from a small area of the Southern High Plains of Texas to characterize the physical nature and chemical constituents of these materials and to investigate techniques that would allow relatively rapid, low cost techniques for estimating the chemical constituents of fugitive dust from an eroding field. From chemical analyses of actively eroding sediments, it would appear that Ca is the only chemical species that is enriched more than others during the process of fugitive dust production. We found surface soil sieved to produce a sub-sample with particle diameters in the range of 53–74 μm to be a reasonably good surrogate for fugitive dust very near the source field, that sieved sub-samples with particle diameters <10 μm have a crustal enrichment factor of approximately 6, and that this factor, multiplied by the chemical contents of source soils, may be a reasonable estimator of fugitive PM₁₀ chemistry from the soils of interest. We also found that dust from tractor air cleaners provided a good surrogate for dust entrained by tillage and harvesting operations if the chemical species resulting from engine wear and exhaust were removed from the data set or scaled back to the average of enrichment factors noted for chemical species with no known anthropogenic sources. Chemical analyses of dust samples collected from attics approximately 4 km from the nearest source fields indicated that anthropogenic sources of several environmentally important nutrient and trace element species are much larger contributors, by up to nearly two orders of magnitude, to atmospheric loading and subsequent deposition than fugitive dust from eroding soils.     

Immunological alterations in juvenile Pacific herring, Clupea pallasi, exposed to aqueous hydrocarbons derived from crude oil

The effects of acute and subchronic aqueous hydrocarbon exposures in the ppb range (0.2-127microg/L total PAH) on the immune system in Pacific herring (Clupea pallasi) were examined through specific immunocompetency assays and a host resistance model using Listonella anguillarum. Short-term hydrocarbon exposure at the highest concentration significantly enhanced respiratory burst activity (RBA) in macrophages and decreased plasma lysozyme concentrations, however, subchronic exposure (4-57d) reduced RBA. Fish in the high exposure group were also less susceptible to the pathogen L. anguillarum following acute hydrocarbon exposure; however, this group was the most susceptible following subchronic exposures. These results are explained by a measured transient physiological stress response and long-term effects on ionoregulation. This study illustrates that hydrocarbon-elicited effects are dynamic and that toxic outcomes with respect to the teleost immune system depend on chemical concentrations and composition, exposure durations and the specific pathogen challenge.     

Assessing energy, environmental, and economic tradeoffs in intermodal freight transportation

This paper presents an energy and environmental network analysis model to explore tradeoffs associated with freight transport. The geospatial model uses an intermodal network built by the authors to connect various modes (rail, road, water) via intermodal terminals. Routes along the network are characterized not only by temporal and distance attributes, but also by cost, energy, and emissions attributes (including emissions of carbon dioxide, particulate matter, sulfur oxides, volatile organic compounds, and oxides of nitrogen). Decision-makers can use the model to explore tradeoffs among alternative route selection across different modal combinations, and to identify optimal routes for objectives that feature energy and environmental parameters (e.g., minimize carbon dioxide emissions). The model is demonstrated with three case studies of freight transport along the U.S. eastern seaboard.     

Pathogen and indicator organism reduction through secondary effluent filtration: implications for reclaimed water production

The reduction of pathogens and indicator organisms through secondary effluent filtration was investigated at six full-scale treatment facilities, ranging in capacity from 0.04 to 1 m3/s (1 to 25 mgd). Grab samples were assayed for pathogens (cultivable enteric viruses, Giardia, and Cryptosporidium) and indicator organisms (coliforms, enterococci, Clostridium perfringens, and coliphages) quarterly under peak flow conditions from each facility over the course of 1 calendar year. Log10 removals resulting from filtration averaged 0.3 to 0.8 log10 for cultivable enteric viruses, 0.4 to 1.5 log10 for protozoan parasites, 0.01 to 3.7 log10 for indicator bacteria, and 0.3 to 1.1 log10 for coliphages. In addition to filter design (cloth, monomedium shallow- or deep-bed, or dual-media filters), differences in reduction of pathogens and indicators could be attributed to the combined effects of hydraulic loading rates, chemical addition practices, backwashing and postbackwashing operating strategies, and the effectiveness of upstream biological treatment and sedimentation.     

In vitro biotransformation of surfactants in fish. Part I: linear alkylbenzene sulfonate (C12-LAS) and alcohol ethoxylate (C13EO8)

Developing regulatory activities (e.g., REACh, [DGEE. 2003. Directorates General Enterprise and Environment. The new EU chemicals legislation REACH. DG Enterprise, Brussels, Belgium. (http://www.europa.eu.int/comm/enterprise/reach/index_en.htm)]) will require bioaccumulation to be assessed for thousands of chemicals. Further, there is increasing pressure to reduce, refine or replace animal tests. Given this scenario, there is an urgent need to evaluate the feasibility of in vitro systems to supply data useful for bioaccumulation estimation. Subcellular and cellular hepatic systems were tested to determine the biotransformation of two surfactants: C12-2-LAS (2-phenyl dodecane p-sulfonate) and an alcohol ethoxylate C13EO8 (Octaethylene glycol monotridecyl ether). The subcellular systems tested were liver homogenates and microsomes from the common carp (Cyprinus carpio) and rainbow trout (Oncorhynchus mykiss). Cellular systems consisted of primary hepatocytes from the common carp (Cyprinus carpio) and PLHC-1 cells, hepatocarcinoma cells from the desert topminnow (Poeciliopsis lucida). All in vitro systems were exposed to radiolabeled test compounds and assayed for biotransformation using liquid scintillation and thin layer chromatographic methods. First-order kinetics were used to estimate rates of biotransformation. Bioconcentration of test materials in fish were predicted using an in vitro to in vivo metabolic rate extrapolation model linked to a mass-balance model commonly used to predict bioaccumulation in fish. Subcellular biotransformation rates for each of the surfactants were greatest with microsomes. Cellular loss rates exceeded subcellular rates, leading to lower predicted BCF values. Predicted BCFs corresponded closely to measured values in several fish species, verifying the utility of in vitro systems in refining Kow-only-based BCFs via the inclusion of biotransformation rates.     

Effects of HMX exposure upon metabolic rate of northern bobwhite quail (Colinus virginianus) in ovo

We evaluated the use of the gas exchange rate as an ecologically relevant indicator of chemical stress in avian embryos/eggs. Northern bobwhite quail (Colinus virginianus) were exposed to octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) via feed containing nominal concentrations of 0, 12.5, 50.0, and 125.0 mg kg(-1). Metabolic rates (oxygen consumption) of developing quail eggs were then measured via respirometry to examine potential effects of HMX exposure. Metabolic rates were examined on 5, 9, and 21 d of incubation. Next, concentrations of HMX in embryos/eggs were determined by liquid chromatography-mass spectrometry. Mean (+/-SE) concentrations of HMX in eggs were 21.0+/-5.9, 1113+/-79.0, 3864+/-154.0, and 7426+/-301.1 ng g(-1) in control, low, medium and high dose groups, respectively. There were significant differences in oxygen consumption among the three embryo ages, however differences among the ages were not consistent among dose groups (age x dose group interaction p<0.0001). Oxygen consumption rates did not vary as a function of HMX in embryos (p=0.18). No evidence was observed for alterations of in ovo metabolic rates associated with HMX exposure.     

Comparison of GC-MS and FTIR methods for quantifying naphthenic acids in water samples

The extraction of bitumen from the oil sands in Canada releases toxic naphthenic acids into the process-affected waters. The development of an ideal analytical method for quantifying naphthenic acids (general formula C(n)H(2n+Z)O(2)) has been impeded by the complexity of these mixtures and the challenges of differentiating naphthenic acids from other naturally-occurring organic acids. The oil sands industry standard FTIR method was compared with a newly-developed GC-MS method. Naphthenic acids concentrations were measured in extracts of surface and ground waters from locations within the vicinity of and away from the oil sands deposits and in extracts of process-affected waters. In all but one case, FTIR measurements of naphthenic acids concentrations were greater than those determined by GC-MS. The detection limit of the GC-MS method was 0.01 mg L(-1) compared to 1 mg L(-1) for the FTIR method. The results indicated that the GC-MS method is more selective for naphthenic acids, and that the FTIR method overestimates their concentrations.     

Extinction of a West African Red Colobus Monkey

Abstract: We provide the first documented case of the extinction in the twentieth century of a widely recognized primate taxon. During surveys in Ghana and Côte d'Ivoire in 1993–1999, we were unable to find any surviving populations of Miss Waldron's red colobus monkey (   Procolobus badius waldroni ), a primate taxon endemic to the forests of this part of West Africa. We conclude that this monkey, which at least one authority considers worthy of species status, is probably extinct. Hunting by humans appears to be the ultimate cause of the extinction. Until our surveys began, little attention had been paid to the plight of this red colobus monkey, despite its listing as endangered by the World Conservation Union. The extinction of other large animals in the Upper Guinea rainforest region is likely to follow soon unless more attention is paid to the full range of endangered forms and more resources are devoted to their rigorous protection.     

The Influence of Nutrients and Physical Habitat in Regulating Algal Biomass in Agricultural Streams

This study examined the relative influence of nutrients (nitrogen and phosphorus) and habitat on algal biomass in five agricultural regions of the United States. Sites were selected to capture a range of nutrient conditions, with 136 sites distributed over five study areas. Samples were collected in either 2003 or 2004, and analyzed for nutrients (nitrogen and phosphorous) and algal biomass (chlorophyll a). Chlorophyll a was measured in three types of samples, fine-grained benthic material (CHL_FG), coarse-grained stable substrate as in rock or wood (CHL_CG), and water column (CHL_S). Stream and riparian habitat were characterized at each site. TP ranged from 0.004–2.69 mg/l and TN from 0.15–21.5 mg/l, with TN concentrations highest in Nebraska and Indiana streams and TP highest in Nebraska. Benthic algal biomass ranged from 0.47–615 mg/m², with higher values generally associated with coarse-grained substrate. Seston chlorophyll ranged from 0.2–73.1 μg/l, with highest concentrations in Nebraska. Regression models were developed to predict algal biomass as a function of TP and/or TN. Seven models were statistically significant, six for TP and one for TN; r ² values ranged from 0.03 to 0.44. No significant regression models could be developed for the two study areas in the Midwest. Model performance increased when stream habitat variables were incorporated, with 12 significant models and an increase in the r ² values (0.16–0.54). Water temperature and percent riparian canopy cover were the most important physical variables in the models. While models that predict algal chlorophyll a as a function of nutrients can be useful, model strength is commonly low due to the overriding influence of stream habitat. Results from our study are presented in context of a nutrient-algal biomass conceptual model.