Formation of organic tracers for isoprene SOA under acidic conditions

The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC–MS methods. In addition to the known isoprene photooxidation products 2-methylglyceric acid, 2-methylthreitol, and 2-methylerythritol, three other peaks of note were detected: one of these was consistent with a silylated-derivative of sulfuric acid, while the remaining two were other oxidized organic compounds detected only when acidic aerosol was present. These two oxidation products were also detected in field samples, and their presence was found to be dependent on both the apparent degree of aerosol acidity as well as the availability of isoprene aerosol. The average concentrations of the sum of these two compounds in the ambient PM_2.5 samples ranged from below the GC–MS detection limit during periods when the isoprene emission rate or apparent acidity were low to approximately 200 ng m^?3 (calibrations being based on a surrogate compound) during periods of high isoprene emissions. These compounds presently unidentified have the potential to serve as organic tracers of isoprene SOA formed exclusively in the presence of acidic aerosol and may also be useful in assessments in determining the importance and impact of aerosol acidity on ambient SOA formation.     

Neurochemical and electrophysiological diagnosis of reversible neurotoxicity in earthworms exposed to sublethal concentrations of CL-20

Background, aim, and scope

Hexanitrohexaazaisowurtzitane (CL-20) is a relatively new energetic compound sharing some degree of structural similarity with hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a known neurotoxic compound. Previously, we demonstrated using a noninvasive electrophysiological technique that CL-20 was a more potent neurotoxicant than RDX to the earthworm Eisenia fetida. In the present study, we investigated the effect of CL-20 exposure and subsequent recovery on muscarinic acetylcholine receptors (mAChRs) to further define the mechanism of reversible neurotoxicity of CL-20 in E. fetida.

Materials and methods

We used a noninvasive electrophysiological technique to evaluate neurotoxicity in CL-20-treated worms, and then measured how such exposures altered levels of whole-body mAChR in the same animals.

Results and discussion

A good correlation exists between these two types of endpoints. Effect on mAChR levels was most prominent at day 6 of exposure. After 7 days of recovery, both conduction velocity and mAChR were significantly restored. Our results show that sublethal concentrations of CL-20 significantly reduced mAChR levels in a concentration- and duration-dependent manner, which was accompanied with significant decreases in the conduction velocity of the medial and lateral giant nerve fibers. After 7-day post exposure recovery, worms restored both neurochemical (mAChR) and neurophysiological (conduction velocity) endpoints that were reduced during 6-day exposures to CL-20 concentrations from 0.02 to 0.22 µg/cm².

Conclusions and perspectives

Our findings support the idea that CL-20 induced neurotoxic effects are reversible, and suggest that CL-20 neurotoxicity may be mediated through the cholinergic system. Future studies will investigate other neurotransmission systems such as GABA, glutamate, and monoamine. Ion channels in the nerve membrane should be examined to further define the precise mechanisms underlying CL-20 neurotoxicity.     

Contribution of primary and secondary sources to organic aerosol and PM2.5 at SEARCH network sites

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 microm or less in aerodynamic diameter (PM2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO4(2-)], nitrate [NO3-], ammonium [NH4+]), metals, and metal oxides and compared with the measured PM2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and beta-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12-42 microg m(-3). Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

A methodology for solid waste characterization based on diminishing marginal returns

A methodology is developed for estimating the number of waste sorts for characterizing solid wastes into categories based on diminishing minimum incremental information. Convergence in the square of the coefficient of variation with successive waste sorts is used to indicate cost-efficient termination of sampling at substantially reduced numbers of sorts in comparison with existing methodologies. These findings indicate that the numbers of waste sorts beyond that determined using the proposed methodology do not add substantial marginal gains in information and/or reduction in the confidence interval of the estimate. The methodology is demonstrated using waste composition analyses from the Greater Vancouver Regional District where 22 waste sorts are examined. The proposed methodology is simple, and the number of waste sorts can be estimated with a hand-held calculator and utilized in the field.     

Comparison of the industrial source complex and AERMOD dispersion models: case study for human health risk assessment

Air quality models are typically used to predict the fate and transport of air emissions from industrial sources to comply with federal and state regulatory requirements and environmental standards, as well as to determine pollution control requirements. For many years, the U.S. Environmental Protection Agency (EPA) widely used the Industrial Source Complex (ISC) model because of its broad applicability to multiple source types. Recently, EPA adopted a new rule that replaces ISC with AERMOD, a state-of-the-practice air dispersion model, in many air quality impact assessments. This study compared the two models as well as their enhanced versions that incorporate the Plume Rise Model Enhancements (PRIME) algorithm. PRIME takes into account the effects of building downwash on plume dispersion. The comparison used actual point, area, and volume sources located on two separate facilities in conjunction with site-specific terrain and meteorological data. The modeled maximum total period average ground-level air concentrations were used to calculate potential health effects for human receptors. The results show that the switch from ISC to AERMOD and the incorporation of the PRIME algorithm tend to generate lower concentration estimates at the point of maximum ground-level concentration. However, the magnitude of difference varies from insignificant to significant depending on the types of the sources and the site-specific conditions. The differences in human health effects, predicted using results from the two models, mirror the concentrations predicted by the models.     

Toward a Practical Method for Setting Screening-Level, Ecological Risk-Based Water Temperature Criteria and Monitoring Compliance

We integrated basic concepts from fisheries science and toxicological risk assessment to form a potential method for setting screening-level, risk-based, site-specific water quality objectives for temperature. In summary, the proposed approach: (a) uses temperature impacts upon specific growth as a measure of chronic (cumulative) temperature effects; (b) explicitly incorporates the consequences of both magnitude and cumulative duration of exposures; (c) adjusts the result for local watershed conditions, reducing the likelihood that naturally warm systems are identified as thermally polluted while helping to ensure that naturally cool systems are closely monitored for ecologically harmful changes in thermal regime; and (d) expresses the net result both graphically and as a risk quotient, RQ, closely analogous to that used in toxicological risk assessments. The latter yields a site-specific, risk-based water quality objective and may serve as a straightforward decision rule for environmental managers. The method was applied to historical data from a small British Columbia stream subject to increasing urban development pressures. We also illustrate how the technique might be used to explore potential climatic change impacts, using coupled general circulation model predictions in conjunction with empirical downscaling. Overall, the method and results are presented as an introduction and illustration of concept, intended as a step toward the development of a logistically feasible risk-based approach to establishing screening-level, site-specific water temperature objectives, and monitoring compliance, in the context of large-scale, many-site, environmental monitoring networks. With further work, the technique offers potential to fill the gap between the temperature threshold-based targets typically specified in regulatory guidelines, which may be hydroecologically unrealistic, and detailed biophysical modelling, which typically is logistically infeasible in a day-to-day environmental monitoring and management context.     

A GIS tool to estimate West Nile virus risk based on a degree-day model

West Nile virus (Flaviviridae: Flavivirus) is a serious infectious disease that recently spread across the North America continent. A spatial analysis tool was developed on the ArcMap 9.x platform to estimate potential West Nile virus activity using a spatially explicit degree-day model. The model identifies when the virus Extrinsic Incubation Period (EIP) is completed within the vector longevity during mid-summer months. The EIP is treated as a threshold indicator of the potential for virus emergence and activity. Comparing the number of West Nile virus cases in Wyoming reported from 2003 to 2005 with model results, actual cases and predicted events of West Nile virus activity match relatively well. The model represents a useful method for estimating potential West Nile virus activity in a large spatial scale.     

Measurement Error in Recreation Demand Models: The Joint Estimation of Participation, Site Choice, and Site Characteristics

In the demand for recreational fishing sites, an important explanatory variable differentiating sites is the unobserved expected catch rate. Since the observed catch rate is subject to sampling variability, using the average of a site's observed catch rates causes the parameter estimator on catch to be biased downward. We develop and demonstrate a solution to this errors-in-variables problem when there are repeated measurements on the catch rate. Consistent and efficient estimates of both the demand parameters and the expected catch rates are obtained by simultaneously estimating them by maximum likelihood. An empirical example demonstrates the importance of simultaneous estimation.     

Sediment quality triad assessment of an industrialized estuary of the northeastern USA

The lower Passaic River in northern New Jersey (USA) has been heavily industrialized since the mid-nineteenth century and its shoreline and aquatic habitats degraded or destroyed. Similar to other urban systems, Passaic River sediments, both surface and buried, historically have contained elevated levels of numerous contaminants that may pose risks to ecological receptors and humans. Sediments from 15 stations in the lower Passaic River and 3 reference stations in the Mullica River in southern New Jersey were sampled in 1999 and characterized for chemical contamination, toxicity, and impairment of the benthic community. The objective of this study was to determine the incidence, degree, and nature of degraded surficial sediments in the area to support subsequent plans for restoration of the system. Results demonstrated that Passaic River sediments had concentrations of many organic and inorganic contaminants at levels significantly greater than the reference area and effect-based guidelines. Sediments were toxic to marine amphipods at 11 stations and the benthic assemblages were impaired relative to the reference area at all stations. The weight-of-evidence of this sediment quality triad (SQT) assessment indicates that impacts from multiple contaminants are occurring throughout the lower Passaic River and, that these impacts must be evaluated further and addressed as part of ongoing restoration initiatives for the river.