Contaminant Exposure of Barn Swallows Nesting on Bayou D'Inde, Calcasieu Estuary, Louisiana, USA

Current and historical point source discharges, storm water runoff, and accidental spills have contaminated the water, sediment, and biota within the Calcasieu Estuary in southwestern Louisiana. In 2003, barn swallow (Hirundo rustica) eggs and nestlings were collected beneath two bridges that cross Bayou d′Inde, the most contaminated waterway within the Calcasieu Estuary. Samples were also collected from a bridge over Bayou Teche, a reference site in south central Louisiana. Polychlorinated biphenyl (PCB) concentrations in barn swallow eggs and nestlings were significantly higher at the downstream site on Bayou d′Inde (2.8 μ g/g PCBs in eggs and 1.5 μ g/g PCBs in nestlings) than at the other two sites (< 0.2 μ g/g PCBs in eggs and nestlings at both sites). Ethoxyresorufin-O-dealkylase activity in nestling livers was significantly higher at the downstream site on Bayou d′Inde (50 pmol/min/mg) compared to the other two locations (24 pmol/min/mg, each), probably because of exposure to PCBs. Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran concentrations in eggs and polycyclic aromatic hydrocarbons in nestlings were at background concentrations at all sites. Trace element concentrations in barn swallow eggs and nestling livers were at background levels and did not differ among the three sites. A biomarker of DNA damage did not differ among sites.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

Evaluation of short-term Ogawa passive, photolytic, and federal reference method sampling devices for nitrogen oxides in El Paso and Houston, Texas

Passive Sampling Devices (PSDs) have been successfully used by government and academic agencies to monitor common ambient air pollutants such as ozone and nitrogen dioxide (NO(2)). Most PSD studies have involved long-term (e.g. bi-weekly or monthly) sampling. But the Passive Ozone Network of Dallas (POND) studies of 1998 and 1999 showed that high quality 24-hour and 12-hour data using the Ogawa PSD could be collected for ambient ozone concentrations. This paper presents an evaluation of short-term passive sampling results for nitrogen oxides (NO(x)) in El Paso and Houston, Texas, using the Ogawa PSD. The Ogawa NO(x) PSDs were compared to both Federal Reference Method (FRM) monitors and a photolytic converter, with the photolytic converter designed to report closer concentrations to "true" NO(x) by more effectively limiting the interferences of other nitrogen species. Overall, good agreement was noted for all three monitor types in both cities, supporting the potential use of lower cost Ogawa PSDs for large multi-site episodic NO(x)/NO(2)/NO saturation screening studies. This evaluation was conducted during two separate six week periods of the cooler winter months so additional testing of the Ogawa PSDs during different seasons is recommended.     

Spatial factors of white-tailed deer herbivory assessment in the central Appalachian Mountains

Because moderate to over-abundant white-tailed deer (Odocoileus virginianus) herbivory impacts biodiversity and can alter community function, ecological benchmarks of herbivory impact are needed to assess deer impacts. We evaluated spatial patterns of deer herbivory and their relation to herbivory assessment by evaluating woody vegetation along 20 transects at each of 30 sites spread across a wide range of deer herd densities and vegetative condition throughout the biodiverse Appalachian Mountains of Virginia, USA. Surprisingly, herbivory patterns and the availability of woody forage generally were unchanged among physiographic regions and land use diversity classes. However, some relationships between browsing pattern and vegetation varied with scale. The total quantity of vegetation browsed on a given site and at the transect scale were related positively to the availability of forage, as the proportion of stems browsed decreased as stem density increased. However, this was only true when all stems were considered equally. When stem densities by species were weighted for deer preference, the proportion of stems browsed had no relationship or increased with stem density. Compared to the value from all transects sampled, on average, the mean of ≥?3 transects within a site was within 0.1 of the browsing ratio and stem densities were within 0.5 stems m^?2. Our results suggest that one transect per square kilometer with a minimum of three transects may be sufficient for most browsing intensity survey requirements to assess herbivory impacts in the Appalachian region of Virginia. Still, inclusion of spatial factors to help partition variation of deer herbivory potentially may allow for improved precision and accuracy in the design of field herbivory impact assessment methods and improve their application across various landscape contexts.     

Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation

Per‐ and polyfluoroalkyl substances (PFAS) are highly resistant to biotic and abiotic degradation and can withstand very high temperatures before breaking down. The storage of PFAS‐impacted water and sediments in a holding pond or stockpiled investigation or remedial action‐derived waste is occurring on an increasing number of sites. The most common PFAS water treatment options include granular‐activated carbon and resins and the most common soil treatment options have been primarily limited to excavation, offsite incineration, and, in some cases, soil stabilization. An increasing number of states across the United States are establishing part per trillion PFAS guidance levels for drinking water. Removing PFAS from soils removes PFAS source impacts to groundwater. In this study, volatilization of PFAS from soil treated using in situ thermal heating is evaluated as a treatment method to achieve a high degree of PFAS removal from soils. The evaluation of temperatures needed to achieve removal is described. To minimize vapor treatment required for PFAS thermal remediation, a scrubber was incorporated into the treatment train to transfer PFAS to the liquid phase in a concentrated, low‐volume solution. Vapor‐liquid equilibrium behavior and the extent of PFAS volatilization from impacted soil over a range of temperatures were evaluated. Results showed that heating soil to 350°C and 400°C reduces PFAS soil concentrations by 99.91% and 99.998%, respectively. It was also confirmed that sulfonate‐based PFAS generally required higher temperatures for volatilization to occur than carboxylate‐based PFAS.     

Love and work: career–family attitudes of new entrants into the labor force

This paper reports the development of the Career–Family Attitudes Measure (CFAM), a new 56-item instrument for measuring individuals' attitudes towards managing the career and family interface. The measure was administered to a large sample of high school students and factor analyzed to reveal six dimensions of career and family attitudes, which were then scaled. Females in the sample had significantly more positive attitudes towards Balance and Independence than did males, while males had significantly more positive attitudes towards Dominance and Spousal Support than did females. Antecedents such as parental employment history and educational aspirations were significantly related to several of the scales. Results indicated that career–family attitudes involve preferences for the integration of career and family rather than for trade-offs between them. Research to establish the validity and explore the many applications of the CFAM is needed. © 1998 John Wiley & Sons, Ltd.     

Ultra trace simultaneous determination of 50 polycyclic aromatic hydrocarbons in biota using pMRM GC-MS/MS

Abstract

A saponification extraction method with gas chromatography pseudo-MRM (pMRM) mass spectrometry detection was developed for the determination of 50 total polycyclic aromatic hydrocarbons (TPAH50, a combination of parent and alkylated homologues) in biota. The method was aimed at monitoring and identification of potential TPAH contaminants in bitumen impacted environments. Alkylated PAHs were determined by multi-level, quantitative calibration using parent PAHs. The developed and thoroughly validated method required only one injection for TPAH50 analysis which represents significant saving of time and expensive authentic alkylated standards. The current method was tested with certified reference mussel tissue NIST 1974c and performed well. In a comparison study, the method reached a limit of quantitation (LOQ) for the TPAH50 between 0.1 and 0.2?ng g^?1, while the QuEChERs enhanced matrix removal – lipid (EMR) kit produced by Agilent showed an LOQ of 5–10?ng g^?1. The current method relied on response factors (RF) for the quantitation of alkylated PAHs determined against parent PAHs. These RFs were shown to be stable and consistent over the course of 1 year, during which over 200 routine environmental biota monitoring samples were analyzed. The environmental biota monitoring samples analyzed include muscle, carcass and liver, with an average total PAH50 concentration of 13, 90 and 135?ng g^?1, respectively. Results show significant differences in the distributions of 1 ringed, 2 ringed, 3 ringed, 4 ringed, and 5+ ringed TPAHs between the types of biota samples.     

Links among nitrification, nitrifier communities, and edaphic properties in contrasting soils receiving dairy slurry

Soil biotic and abiotic factors strongly influence nitrogen (N) availability and increases in nitrification rates associated with the application of manure. In this study, we examine the effects of edaphic properties and a dairy (Bos taurus) slurry amendment on N availability, nitrification rates and nitrifier communities. Soils of variable texture and clay mineralogy were collected from six USDA-ARS research sites and incubated for 28 d with and without dairy slurry applied at a rate of ~300 kg N ha(-1). Periodically, subsamples were removed for analyses of 2 M KCl extractable N and nitrification potential, as well as gene copy numbers of ammonia-oxidizing bacteria (AOB) and archaea (AOA). Spearman coefficients for nitrification potentials and AOB copy number were positively correlated with total soil C, total soil N, cation exchange capacity, and clay mineralogy in treatments with and without slurry application. Our data show that the quantity and type of clay minerals present in a soil affect nitrifier populations, nitrification rates, and the release of inorganic N. Nitrogen mineralization, nitrification potentials, and edaphic properties were positively correlated with AOB gene copy numbers. On average, AOA gene copy numbers were an order of magnitude lower than those of AOB across the six soils and did not increase with slurry application. Our research suggests that the two nitrifier communities overlap but have different optimum environmental conditions for growth and activity that are partly determined by the interaction of manure-derived ammonium with soil properties.     

Evaluation of a denitrification wall to reduce surface water nitrogen loads

Denitrification walls have significantly reduced nitrogen concentrations in groundwater for at least 15 yr. This has spurred interest in developing methods to efficiently increase capture volume to reduce N loads in larger watersheds. The objective of this study was to maximize treatment volume by locating a wall where a large groundwatershed was funneled toward seepage slope headwaters. Nitrogen concentration and load were measured before and after wall installation in paired treatment and control streams. Beginning 2 d after installation, nitrogen concentration in the treatment stream declined from 6.7 ± 1.2 to 3.9 ± 0.78 mg L and total N loading rate declined by 65% (391 kg yr) with no corresponding decline in the control watershed. This wall, which only comprised 10 to 11% of the edge of field area that contributed to the treatment watershed, treated approximately 60% of the stream discharge, which confirmed the targeted approach. The total load reduction measured in the stream 155 m downstream from the wall (340 kg yr) was higher than that found in another study that measured load reductions in groundwater wells immediately around the wall (228 kg yr). This indicated the possibility of an extended impact on denitrification from carbon exported beyond the wall. This extended impact was inauspiciously confirmed when oxygen levels at the stream headwaters temporarily declined for 50 d. This research indicates that targeting walls adjacent to streams can effectively reduce N loading in receiving waters, although with a potentially short-term impact on water quality.     

Characterization of fine primary biogenic organic aerosol in an urban area in the northeastern United States

Scanning electron microscopy coupled to energy-dispersive x-ray spectroscopy (SEM/EDX) was used to quantify individual bioparticles in PM_2.5 samples collected during the Pittsburgh Air Quality Study. Microscopy-based estimates of primary biogenic organic aerosol (PBOA) mass were compared to carbohydrate mass associated with PM_2.5. Carbohydrates show substantial seasonal variations, with higher concentrations in the spring and the fall. During the summer, carbohydrates were about 30% of the estimated PBOA concentrations, but in the winter carbohydrate concentrations often greatly exceeded the PBOA mass estimate. Spores and insect detritus were the most abundant PBOA types in the summer samples, while winter samples were comprised predominantly of a mixture of microorganisms, insect and vegetative detritus. During the summer PBOA contributed on average 6.9 ± 5.4% by mass of the PM_2.5 versus 3.3 ± 1.4% of the PM_2.5 mass during the winter.