Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Effect of variations in the redox potential of Gleysol on barium mobility and absorption in rice plants

Two assays were designed to obtain information about the influence of redox potential variations on barium mobility and bioavailability in soil. One assay was undertaken in leaching columns, and the other was conducted in pots cultivated with rice (Oryza sativa) using soil samples collected from the surface of Gleysol in both assays. Three doses of barium (100,300 mg kg⁻¹ and 3000 mg kg⁻¹-soil dry weight) and two redox potential values (oxidizing and reducing) were evaluated. During the incubation period, the redox potential (Eh) was monitored in columns and pots until values of −250 mV were reached. After the incubation period, geochemical partitioning was conducted on the barium using the European Communities Bureau of Reference (BCR) method. Rainfall of 200 mm d⁻¹ was simulated in the columns and in the planting of rice seedlings in the pots. The results of the geochemical partitioning demonstrated that the condition of reduction favors increased barium concentrations in the more labile chemical forms and decreased levels in the chemical forms related to oxides. The highest barium concentrations in leached extracts (3.36 mg L⁻¹) were observed at the highest dose and condition of reduction at approximately five times above the drinking water standard. The high concentrations of barium in the soil did not affect plant dry matter production. The highest levels and accumulation of barium in roots, leaves, and grains of rice were found at the highest dose and condition of reduction. These results demonstrate that reduction leads to solubilization of barium sulfate, thereby favoring greater mobility and bioavailability of this element.     

Hg concentrations and related risk assessment in coral reef crustaceans, molluscs and fish from New Caledonia

There is a dramatic lack of data on Hg levels in marine organisms from tropical areas, and in particular from New Caledonia. For the first time, this study reports the total Hg concentrations in the tissues of several marine taxa from the New Caledonian lagoon. Seafood from both wild and farmed populations was considered. Hg concentrations varied over three orders of magnitudes according to factors including species, age (size/weight), trophic level, lifestyle and geographical origin. Taking into account the edible tissues, estimations of the amount of flesh that should be consumed by a 60-kg person to reach the Hg Provisional Tolerable Weekly Intake (PTWI) reveal acceptable risk for Human health in general. However, a risk was clearly identified in one site of the lagoon (i.e. Grande Rade) where high Hg concentrations were measured. These concentrations were higher than values reported in the current literature.     

Elimination of endocrine disrupting chemicals nonylphenol and bisphenol A and personal care product ingredient triclosan using enzyme preparation from the white rot fungus Coriolopsis polyzona

The biocatalytic elimination of the endocrine disrupting chemicals (EDC) nonylphenol (NP) and bisphenol A (BPA) and the personal care product ingredient triclosan (TCS) by the enzyme preparation from the white rot fungus Coriolopsis polyzona was investigated. Analysis of variance methodology showed that the pH and the temperature are statistically significant factors in the removal of NP, BPA and TCS. The elimination of NP and TCS was best at a temperature of 50 degrees C and the disappearance of BPA at 40 degrees C, whereas the most suitable pH for all three micropollutants was 5. After a 4-h treatment of the three target compounds at concentrations of 5 mg l(-1) all of the NP and BPA were eliminated. In the case of TCS, 65% was removed after either a 4 or an 8-h treatment. The utilisation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) in the laccase/mediator system significantly increased the efficiency of the enzymatic treatment. The elimination of NP and BPA was directly associated with the disappearance of the estrogenic activity. Mass spectrometry analysis showed that the enzymatic treatment produced high molecular weight metabolites through a radical polymerization mechanism of NP, BPA and TCS. These oligomers were produced through the formation of C-C or C-O bonds. The polymerization of NP produced dimers, trimers, tetramers and pentamers which had molecular weights of 438, 656, 874 and 1092 amu respectively. The polymerization of BPA produced dimers, trimers and tetramers which had molecular weights of 454, 680 and 906 amu. Finally, the polymerization of TCS produced dimers, trimers and tetramers which had molecular weights of 574, 859 and 1146 amu.     

Soil distribution of fipronil and its metabolites originating from a seed-coated formulation

Seed-coating with the insecticide fipronil has been intensively used in sunflower cultivation to control soil pests such as wireworms. A research project was undertaken to determine the soil distribution of fipronil and of its main phenylpyrazole metabolites. Under agronomic conditions, the quantity of fipronil in the seed-coat (437 microg/seed) decreased continuously during the cultivation period (3.9 microg day(-1) during the first two months; 0.3 microg day(-1) during the next four months). At the end of the cultivation period, 42% of all phenylpyrazole compounds remained in the seed-coat. Fipro nil was poorly mobile in soil, and at the end of the cultivation period it was mostly concentrated in the soil layer close to the seed (3240 microg kg(-1) soil). Starting from the seed-coating, a fipronil concentration gradient was measured in the soil, up to a distance of 11 cm from the seed. Degradation in the soil occurred at a moderate rate, probably due to the fact that water solubilization of the solid active ingredient present in the seed coating was rate limiting. Indeed, after 6 months of cultivation, only 51% of the fipronil seed-coating was found in the soil, about 7% having been absorbed by the sunflower plant, and 42% remaining in the seed coat. The predominant metabolites produced in the soil were sulfone-fipronil, sulfide-fipronil and amide-fipronil, which were produced at average rates of 5 microg kg(-1) soil day(-1), 3 microg kg(-1) soil day(-1), and 0.4 microg kg(-1) soil day(-1), respectively. In contrast, the photoproduct, desulfinyl-fipronil, was barely detected. All phenylpyrazole compounds were poorly mobile, except for the amide derivative, which is devoid of insecticidal activity in marked contrast to the other metabolites. Furthermore, detectable soil contamination was limited to a zone of about 11 cm around the seed.     

In situ stabilization of trace metals in a copper-contaminated soil using P-spiked Linz-Donawitz slag

Purpose  

A former wood exploitation revealing high Cu and As concentration of the soils served as a case study for assisted phytoextraction.     

Simultaneous immobilization of metals and arsenic in acidic polluted soils near a copper smelter in central Chile

Introduction  

Acidic and metal(oid)-rich topsoils resulted after 34 years of continuous operations of a copper smelter in the Puchuncaví valley, central Chile. Currently, large-scale remediation actions for simultaneous in situ immobilization of metals and As are needed to reduce environmental risks of polluted soils. Aided phytostabilization is a cost-effective alternative, but adequate local available soil amendments have to be identified and management options have to be defined.     

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU_FCV,43). Samples were assigned to risk categories according to ESBTU_FCV,43 values: no-risk (≤1), low (>1-≤2), low-medium (>2-≤3), medium (>3-≤5) and high-risk (>5). Sixty seven percent of samples had ESBTU_FCV,43 > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War.     

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales

This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O₃ in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.     

Characterisation of particulate exposure during fireworks displays

Little is known about the level and content of exposure to fine particles (PM_2.5) among persons who attend fireworks displays and those who live nearby. An evaluation of the levels of PM_2.5 and their elemental content was carried out during the nine launches of the 2007 Montréal International Fireworks Competition. For each event, a prediction of the location of the firework plume was obtained from the Canadian Meteorological Centre (CMC) of the Meteorological Service of Canada. PM_2.5 was measured continuously with a photometer (Sidepak?, TSI) within the predicted plume location (“predicted sites”), and integrated samples were collected using portable personal samplers. An additional sampler was located on a nearby roof (“fixed site”). The elemental composition of the collected PM_2.5 samples from the “predicted sites” was determined using both a non-destructive energy dispersive ED-XRF method and an ICP-MS method with a near-total microwave-assisted acid digestion. The elemental composition of the “fixed site” samples was determined by the ICP-MS with the near-total digestion method. The highest PM_2.5 levels reached nearly 10 000 μg m^?3, roughly 1000 times background levels. Elements such as K, Cl, Al, Mg and Ti were markedly higher in plume-exposed filters. This study shows that 1) persons in the plume and in close proximity to the launch site may be exposed to extremely high levels of PM_2.5 for the duration of the display and, 2) that the plume contains specific elements for which little is known of their acute cardio-respiratory toxicity.