Application of a permethrin immunosorbent assay method to residential soil and dust samples

A low-cost, high throughput bioanalytical screening method was developed for monitoring cis/trans-permethrin in dust and soil samples. The method consisted of a simple sample preparation procedure [sonication with dichloromethane followed by a solvent exchange into methanol:water (1:1)] with bioanalytical detection using a magnetic particle enzyme-linked immunosorbent assay (ELISA). Quantitative recoveries (83–126 %) of cis/trans-permethrin were obtained for spiked soil and dust samples. The percent difference of duplicate ELISA analyses was within ± 20 % for standards and ± 35 % for samples. Similar sample preparation procedures were used for the conventional gas chromatography/mass spectrometry (GC/MS) analysis except that additional cleanup steps were required. Recoveries of cis/trans-permethrin ranged from 81 to 108 % for spiked soil and dust samples by GC/MS. The ELISA-derived permethrin concentrations were highly correlated with the GC/MS-derived sum of cis/trans-permethrin concentrations with a correlation coefficient (r) of 0.986. The ELISA method provided a rapid qualitative screen for cis/trans-permethrin in soil and dust while providing a higher sample throughput with a lower cost as compared to the GC/MS method. The ELISA can be applied as a complementary, low-cost screening tool to prioritize and rank samples prior to instrumental analysis for exposure studies.     

Removal of Volatile Aliphatic Hydrocarbons in a Soil Bioreactor

Soil removal of propane, isobutane and n-butane from a waste air stream was evaluated in the laboratory and in a prototype soil bioreactor. Laboratory investigations indicated first-order kinetics and the potential to degrade light aliphatic hydrocarbons and trichlorethylene, a compound ordinarily resistant to aerobic biological treatment. The predicted behavior of the bioreactor, based on laboratory studies, agreed closely with the actual behavior of the Reid system. The prototype bioreactor reduced the hydrocarbon concentrations in the air by at least 90percent with a residence time of 15 minutes and a pressure drop of 85 cm of water. The bioreactor functioned well through a range of temperatures, 12°C to 24°C.     

The Effect of Fuel Composition on Atmospheric Aerosol Due to Auto Exhaust

Aerosols attributable to automobile exhaust can be classified as two types—primary aerosol (initially present in the exhaust) and secondary aerosol (generated photochemically from hydrocarbons and nitrogen oxides in the exhaust). In this study, investigation was made of possible effects of motor-fuel composition on the formation of these aerosols. Secondary aerosol, of principal interest in this work, was produced by irradiating auto exhaust in Battelle-Columbus’ 610 ft³ environmental chamber. A limited number of determinations of primary aerosol in diluted auto exhaust was made at the exit of a 36 ft dilution runnel. Determination of both primary and secondary aerosol was based on light-scattering measurements.

Exhaust was generated with seven full-boiling motor gasolines, both leaded and nonleaded, in a 1967 Chevrolet which was not equipped with exhaust-emission control devices. Changes in fuel composition produced a maximum factor of three difference in light scattering due to primary aerosol. Aerosol yields, for consecutive driving cycles on the same fuel, vary considerably; as a result, ranking the fuels on the basis of average primary aerosol yield was not very meaningful. In addition to fuel composition, the more important independent variables are initial SO₂ concentration, relative humidity and initial hydrocarbon concentration. Statistical analysis of the data indicates that the seven test fuels can be divided into two arbitrary groups with regard to secondary aerosol-forming potential. The fuels in the lower light-scattering group had aromatic contents of 15 and 21%, while those in the higher light-scattering group had aromatic contents of 25, 48, and 55%. Although the fuels can be grouped on the basis of a compositional factor, the grouping of fuels with aromatic content ranging from 25 to 55% indicates that this compositional factor cannot be equated simply with aromatic content. In an associated study of the aerosol-forming potential of individual hydrocarbons prominent in auto exhaust, it was observed that aromatics produce substantially more photochemical aerosol than olefins and paraffins. However, experiments with binar/hydrocarbon mixtures containing aromatjcs, as well as in these exhaust experiments, a strong dependence of aerosol yield on the aromatic components is is not observed. Thus, the data indicate that the dependence of secondary aerosol formation on fuel factors is a complex one and cannot be predicted solely on the basis of a sirigle hydrocarbon component reactivity scale.

The two types of automobile aerosol did not have the same dependence on fuel, composition. The variation in total light scattering attributable to primary plus secondary aerosol was less than that due to either component alone. It therefore was concluded that the light scattering due to automobile exhaust emissions in these experiments was not significantly affected by changing fuel composition.     

Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

The race is not to the swift: long-term data reveal pervasive declines in California's low-elevation butterfly fauna

Understanding the ecology of extinction is one of the primary challenges facing ecologists in the 21st century. Much of our current understanding of extinction, particularly for invertebrates, comes from studies with large geographic coverage but less temporal resolution, such as comparisons between historical collection records and contemporary surveys for geographic regions or political entities. We present a complementary approach involving a data set that is geographically restricted but temporally intensive: we focus on three sites in the Central Valley of California, and utilize 35 years of biweekly (every two weeks) surveys at our most long-sampled site. Previous analyses of these data revealed declines in richness over recent decades. Here, we take a more detailed approach to investigate the mode of decline for this fauna. We ask if all species are in decline, or only a subset. We also investigate traits commonly found to be predictors of extinction risk in other studies, such as body size, diet breadth, habitat association, and geographic range. We find that population declines are ubiquitous: the majority of species at our three focal sites (but not at a nearby site at higher elevation) are characterized by reductions in the fraction of days that they are observed per year. These declines are not readily predicted by ecological traits, with the possible exception of ruderal/non-ruderal status. Ruderal species, in slightly less precipitous decline than non-ruderal taxa, are more dispersive and more likely to be associated with disturbed habitats and exotic hosts. We conclude that population declines and extirpation, particularly in regions severely and recently impacted by anthropogenic alteration, might not be as predictable as has been suggested by other studies on the ecology of extinction.     

Results of An Indoor Size Fractionated PM School Sampling Program in Libby, Montana

Libby, Montana is the only PM_2.5 nonattainment area in the western United States with the exceptions of parts of southern California. During January through March 2005, a particulate matter (PM) sampling program was conducted within Libby’s elementary and middle schools to establish baseline indoor PM concentrations before a wood stove change-out program is implemented over the next several years. As part of this program, indoor concentrations of PM mass, organic carbon (OC), and elemental carbon (EC) in five different size fractions (>2.5, 1.0–2.5, 0.5–1.0, 0.25–0.5, and <0.25 μm) were measured. Total measured PM mass concentrations were much higher inside the elementary school, with particle size fraction (>2.5, 0.5–1.0, 0.25–0.5, and <0.25 μm) concentrations between 2 and 5 times higher when compared to the middle school. The 1.0–2.5 μm fraction had the largest difference between the two sites, with elementary school concentrations nearly 10 times higher than the middle school values. The carbon component for the schools’ indoor PM was found to be predominantly composed of OC. Measured total OC and EC concentrations, as well as concentrations within individual size fractions, were an average of two to five times higher at the elementary school when compared to the middle school. For the ultrafine fraction (<0.25), EC concentrations were similar between each of the schools. Despite the differences in concentrations between the schools at the various fraction levels, the OC/EC ratio was determined to be similar.     

Inorganic nitrogen transformations in the treatment of landfill leachate with a high ammonium load: A case study

The inorganic nitrogen transformations occurring at a municipal waste leachate treatment facility were investigated. The treatment facility consisted of a collection well and an artificial wetland between two aeration ponds. The first aeration pond showed a decrease in ammonium (from 3480 (± 120) to 630(± 90) mg ⋅ L⁻¹), a reduction in inorganic nitrogen load (3480 to 1680 mg N ⋅ L⁻¹), and an accumulation of nitrite (< 1.3 mg-N ⋅ L⁻¹ in the collection well, to 1030 mg-N ⋅ L⁻¹). Incomplete ammonium oxidation was presumably the result of the low concentration of carbonate alkalinity (∼2 mg ⋅ L⁻¹), which may cause a limitation in the ammonium oxidation rate of nitrifiers. Low carbonate alkalinity levels may have been the result of stripping of CO₂ from the first aeration pond at the high aeration rates and low pH. Various chemodenitrification mechanisms are discussed as the reason for the reduction in the inorganic nitrogen load, including; the reduction of nitrite by iron (II) (producing various forms of gaseous nitrogen); and reactions involving nitrous acid. It is suggested that the accumulation of nitrite may be the result of inhibition of nitrite oxidizers by nitrous acid and low temperatures. Relative to the first aeration pond, the speciation and concentration of inorganic nitrogen was stable in the wetlands and 2nd aeration pond. The limited denitrification in the wetlands most probably occurred due to low concentrations of organic carbon, and short retention times.     

Mathematical Modeling of Column and Field Dense Nonaqueous Phase Liquid Tracer Tests

Mathematical models for the simulation of dense nonaqueous phase liquid tracer tests (DTTs) in laboratory columns and in the field are developed and examined. The DTT technique is a means of estimating the quantity of dense nonaqueous phase liquid (DNAPL) in a domain of interest in an aquifer. The two-dimensional field DTT model uses the Method of Principal Directions and an asymmetrical upwind algorithm for describing advective transport. Both models include diffusion transport of tracer into and from low-permeability porous structures such as clay lenses, as well as the mass transport kinetics of partitioning tracer to and from the DNAPL droplets. The dependence of the effluent tracer concentration curves on the parameters of the models is explored, and conclusions are drawn regarding the applicability of, and several possible problems with, the DTT technique. Model results indicate that the DTT performs well at locating distributed droplets of DNAPL, but is unlikely to be useful in the assessment of pooled DNAPL.     

Chlorinated Hydrocarbons in Livers of American Mink (Mustela vison) and River Otter (Lutra canadensis) from the Columbia and Fraser River Basins, 1990–1992

We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990–91 and 1991–92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 g/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978–79 and 1990–92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 g/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.     

Effects of restoration and reflooding on soil denitrification in a leveed Midwestern floodplain.

River floodplains have the potential to remove nitrate from water through denitrification, the anaerobic microbial conversion of nitrate to nitrogen gas. An important factor in this process is the interaction of river water with floodplain soil; however, many rivers have been disconnected from their historic floodplains by levees. To test the effect of reflooding a degraded floodplain on nitrate removal, we studied changes in soil denitrification rates on the Baraboo River floodplain in Wisconsin, USA, as it underwent restoration. Prior to this study, the site had been leveed, drained, and farmed for more than 50 years. In late fall 2002, the field drainage system was removed, and a gate structure was installed to allow controlled flooding of this site with river water. Soil moisture was extremely variable among zones and months and reflected local weather. Soil organic matter was stable over the study period with differences occurring along the elevation gradient. High soil nitrate concentrations occurred in dry, relatively organic-poor soil samples and, conversely, all samples with high moisture soils characterized by low nitrate. We measured denitrification in static cores and potential denitrification in bulk samples amended with carbon and nitrogen, one year before and two years following the manipulation. Denitrification rates showed high temporal and spatial variability. Static core rates of individual sites ranged widely (from 0.00 to 16.7 microg N2O-N x [kg soil](-1) x h(-1), mean +/- SD = 1.10 +/- 3.02), and denitrification enzyme activity (DEA) rates were similar with a slightly higher mean (from 0.00 to 15.0 microg N2O-N x [kg soil](-1) x h(-1), 1.41 +/- 1.98). Denitrification was not well-correlated with soil nitrate, organic matter content, or moisture levels, the three parameters typically thought to control denitrification. Static core denitrification rates were not significantly different across years, and DEA rates decreased slightly the second year after restoration. These results demonstrate that restored agricultural soil has the potential for denitrification, but that floodplain restoration did not immediately improve this potential. Future floodplain restorations should be designed to test alternative methods of increasing denitrification.