Comparison of an assay for Dehalococcoides DNA and a microcosm study in predicting reductive dechlorination of chlorinated ethenes in the field

The study aims to compare the detection of 16S rRNA gene of Dehalococcoides species and the microcosm study for biotransformation in predicting reductive dechlorination of chlorinated ethenes in ground water at hazardous waste sites. A total of 72 ground water samples were collected from 12 PCE or TCE contaminated sites in the United States. The samples were analyzed and used to construct microcosms in the laboratory. The results showed that the presence of Dehalococcoides DNA was well associated with dechlorination to ethene in the field. Nearly half of the wells where Dehalococcoides DNA was detected had ethene as a dechlorination end product. In comparison, for ground water samples of 16 wells where ethene was detected, ethene was produced in 11 of the corresponding microcosms. For most microcosms, during two years of incubation, dechlorination was less extensive than that observed in the field.     

The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

Rapid measurement of emissions from military aircraft turbine engines by downstream extractive sampling of aircraft on the ground: Results for C-130 and F-15 aircraft

Aircraft emissions affect air quality on scales from local to global. More than 20% of the jet fuel used in the U.S. is consumed by military aircraft, and emissions from this source are facing increasingly stringent environmental regulations, so improved methods for quickly and accurately determining emissions from existing and new engines are needed. This paper reports results of a study to advance the methods used for detailed characterization of military aircraft emissions, and provides emission factors for two aircraft: the F-15 fighter and the C-130 cargo plane. The measurements involved outdoor ground-level sampling downstream behind operational military aircraft. This permits rapid change-out of the aircraft so that engines can be tested quickly on operational aircraft. Measurements were made at throttle settings from idle to afterburner using a simple extractive probe in the dilute exhaust. Emission factors determined using this approach agree very well with those from the traditional method of extractive sampling at the exhaust exit. Emission factors are reported for CO₂, CO, NO, NO_x, and more than 60 hazardous and/or reactive organic gases. Particle size, mass and composition also were measured and are being reported separately. Comparison of the emissions of nine hazardous air pollutants from these two engines with emissions from nine other aircraft engines is discussed.     

Aerosol formation yields from the reaction of catechol with ozone

The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm^?3. Analysis of the data clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation can be expressed by a one-product gas–particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.     

An analysis of assessment outcomes from eight years' operation of the Australian border weed risk assessment system

The majority of Australian weeds are exotic plant species that were intentionally introduced for a variety of horticultural and agricultural purposes. A border weed risk assessment system (WRA) was implemented in 1997 in order to reduce the high economic costs and massive environmental damage associated with introducing serious weeds. We review the behaviour of this system with regard to eight years of data collected from the assessment of species proposed for importation or held within genetic resource centres in Australia. From a taxonomic perspective, species from the Chenopodiaceae and Poaceae were most likely to be rejected and those from the Arecaceae and Flacourtiaceae were most likely to be accepted. Dendrogram analysis and classification and regression tree (TREE) models were also used to analyse the data. The latter revealed that a small subset of the 35 variables assessed was highly associated with the outcome of the original assessment. The TREE model examining all of the data contained just five variables: unintentional human dispersal, congeneric weed, weed elsewhere, tolerates or benefits from mutilation, cultivation or fire, and reproduction by vegetative propagation. It gave the same outcome as the full WRA model for 71% of species. Weed elsewhere was not the first splitting variable in this model, indicating that the WRA has a capacity for capturing species that have no history of weediness. A reduced TREE model (in which human-mediated variables had been removed) contained four variables: broad climate suitability, reproduction in less or than equal to 1year, self-fertilisation, and tolerates and benefits from mutilation, cultivation or fire. It yielded the same outcome as the full WRA model for 65% of species. Data inconsistencies and the relative importance of questions are discussed, with some recommendations made for improving the use of the system.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Mercury bioaccumulation and risk to three waterbird foraging guilds is influenced by foraging ecology and breeding stage

We evaluated mercury (Hg) in five waterbird species representing three foraging guilds in San Francisco Bay, CA. Fish-eating birds (Forster's and Caspian terns) had the highest Hg concentrations in thier tissues, but concentrations in an invertebrate-foraging shorebird (black-necked stilt) were also elevated. Foraging habitat was important for Hg exposure as illustrated by within-guild differences, where species more associated with marshes and salt ponds had higher concentrations than those more associated with open-bay and tidal mudflats. Importantly, Hg concentrations increased with time spent in the estuary. Surf scoter concentrations tripled over six months, whereas Forster's terns showed an up to 5-fold increase between estuary arrival and breeding. Breeding waterbirds were at elevated risk of Hg-induced reproductive impairment, particularly Forster's terns, in which 48% of breeding birds were at high risk due to their Hg levels. Our results highlight the importance of habitat and exposure timing, in addition to trophic position, on waterbird Hg bioaccumulation and risk.     

Limitations of an optimum sustainable population or potential biological removal approach for conserving marine mammals: Pacific walrus case study

Decision rules are the agreed-upon points at which specific management interventions are initiated. For marine mammal management under the U.S. Marine Mammal Protection Act (MMPA), decision rules are usually based on either a numeric population or biological-removal approach. However, for walrus and other ice-associated pinnipeds, the inability to reliably assess population numbers or biological removals highlights a significant gap in the MMPA, particularly when the Arctic environment is rapidly changing. We describe the MMPA's ecosystem-based management goals, and why managers have bypassed these goals in favor of an approach that depends upon numerical population assessment. We then revisit the statute's primary goals in light of current knowledge about the Pacific walrus ecosystem and new developments in environmental governance. We argue that to monitor and respond to changes in the walrus ecosystem, decision rules should be based on scientific criteria that depend less on the currently-impractical goal of accurately enumerating population size and trends, or removals from that population. Rather, managers should base decisions on ecological needs and observed ecological changes. To implement this approach would require an amendment to the MMPA that supports filling the gap in management with achievable decision rules. Alternatively, walrus and other ice-associated pinnipeds will remain largely unmanaged during a period of profound environmental change.