In situ transformations of fine lead oxide particles in different soils

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of (14)C-labeled sulfadiazine ((14)C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A(p) horizon of loamy sand, orthic luvisol; A(p) horizon of silt loam, cambisol) amended with fresh and aged (6 months) (14)C-manure [40 g kg(-1) of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with (14)C-SDZ. Mineralization of (14)C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable (14)C (ethanol-water, 9:1, v/v) decreased with time to 4-13% after 218 days of incubation with fresh and aged (14)C-manure and both soils. Non-extractable residues were the main route of the fate of the (14)C-SDZ residues (above 90% of total recovered (14)C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the (14)C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl(2) solution) also decreased with increasing incubation period (5-7% after 218 days). Due to thin-layer chromatography (TLC), 500 microg of (14)C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh (14)C-manure, and about 50 microg kg(-1) after 218 days. Bioavailable (14)C-SDZ portions present in the CaCl(2) extracts were about 350 microg kg(-1) with amendment. Higher concentrations were initially detected with aged (14)C-manure (ethanol-water extracts: 1,920 microg kg(-1); CaCl(2) extracts: 1,020 microg kg(-1)), probably due to release of (14)C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the (14)C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble (14)C-SDZ residues contained in (14)C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Particulate matter sources on an hourly timescale in a rural community during the winter

Particulate matter (PM) sources at four different monitoring sites in Alexandra, New Zealand, were investigated on an hourly timescale. Three of the sites were located on a horizontal transect, upwind, central, and downwind of the general katabatic flow pathway. The fourth monitoring site was located at the central site, but at a height of 26 m, using a knuckleboom, when wind conditions permitted. Average hourly PM₁₀ (PM with an aerodynamic diameter <10 μm) concentrations in Alexandra showed slightly different diurnal profiles depending on the sampling site location. Each location did, however, feature a large evening peak and smaller morning peak in PM₁₀ concentrations. The central site in Alexandra experienced the highest PM₁₀ concentrations as a result of PM transport along a number of katabatic flow pathways. A significant difference in PM₁₀ concentrations between the central and elevated sites indicated that a shallow inversion layer formed below the elevated site, limiting the vertical dispersion of pollutants. Four PM₁₀ sources were identified at each of the sites: biomass combustion, vehicles, crustal matter, and marine aerosol. Biomass combustion was identified as the most significant source of PM₁₀, contributing up to 91% of the measured PM₁₀. Plots of the average hourly source contributions to each site revealed that biomass combustion was responsible for both the evening and morning peaks in PM₁₀ concentrations observed at each of the sites, suggesting that Alexandra residents were relighting their fires when they rose in the morning. The identification of PM sources on an hourly timescale can have significant implications for air quality management.

Implications: Monitoring the sources of PM₁₀ on an hourly timescale at multiple sites within an airshed provides extremely useful information for air quality management. Sources responsible for observed peaks in measured diurnal PM₁₀ concentration profiles can be easily identified and targeted for reduction. Also, hourly PM₁₀ sampling can provide crucial information on the role meteorology plays in the development of elevated PM₁₀ concentrations.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

Impact of fungicides on active oxygen species and antioxidant enzymes in spring barley (Hordeum vulgare L.) exposed to ozone.

Two modern fungicides, a strobilurin, azoxystrobin (AZO), and a triazole, epoxiconazole (EPO), applied as foliar spray on spring barley (Hordeum vulgare L. cv. Scarlett) 3 days prior to fumigation with injurious doses of ozone (150-250 ppb; 5 days; 7 h/day) induced a 50-60% protection against ozone injury on leaves. Fungicide treatments of barley plants at growth stage (GS) 32 significantly increased the total leaf soluble protein content. Additionally, activities of the antioxidative enzymes superoxide dismutase (SOD), catalase (CAT), ascorbate-peroxidase (APX) and glutathione reductase (GR) were increased by both fungicides at maximal rates of 16, 75, 51 and 144%, respectively. Guiacol-peroxidase (POX) activity was elevated by 50-110% only in AZO treated plants, while this effect was lacking after treatments with EPO. This coincided with elevated levels of hydrogen peroxide (H2O2) only in EPO and not in AZO treated plants. The enhancement of the plant antioxidative system by the two fungicides significantly and considerably reduced the level of superoxide (O2*-) in leaves. Fumigation of barley plants for 4 days with non-injurious ozone doses (120-150 ppb, 7 h/day) markedly and immediately stimulated O2*- accumulation in leaves, while H2O2 was increased only after the third day of fumigation. Therefore, O2*- itself or as precursor of even more toxic oxyradicals appears to be more indicative for ozone-induced leaf damage than H2O2. Ozone also induced significant increases in the activity of antioxidant enzymes (SOD, POX and CAT) after 2 days of fumigation in fungicide untreated plants, while after 4 days of fumigation these enzymes declined to a level lower than in unfumigated plants, due to the oxidative degradation of leaf proteins. This is the first report demonstrating the marked enhancement of plant antioxidative enzymes and the enhanced scavenging of potentially harmful O2*- by fungicides as a mechanism of protecting plants against noxious oxidative stress from the environment. The antioxidant effect of modern fungicides widely used in intense cereal production in many countries represents an important factor when evaluating potential air pollution effects in agriculture.     

Well-designed environmental regulation and firm performance: Swedish evidence on the Porter hypothesis and the effect of regulatory time strategies

Using recent data on a cross-section of Swedish chemical and pulp and paper firms, this paper provides novel empirical insights into the Porter hypothesis. Well-designed environmental regulation can stimulate firms’ innovative capabilities, while at the same time generating innovation offsets that may both offset net compliance costs and yield a competitive edge over those firms that are not affected by such regulations. In doing so, we also test the alleged effectiveness of regulatory time strategies in stimulating innovation activities of regulated firms. We find evidence for the effectiveness of such well-designed regulations: announced rather than existing regulation induces innovation and some innovation offsets. Our results imply that empirical tests of the Porter hypothesis that do not account for its dynamic nature, and that do not measure well-designed regulations, might provide misleading conclusions as to its validity.     

Removal of inorganic colour pigments from acrylonitrile butadiene styrene by dissolution-based recycling

Reinserting thermoplastic industrial scrap materials back into the production process must be feasible and cost-effective. Unfortunately, many thermoplastic materials contain colour pigments that cause undesired colour effects and, therefore, have to be removed before recycling. The purpose of this study was to reduce the inorganic colour pigments titanium dioxide, chromium(III) oxide and iron(III) oxide from acrylonitrile butadiene styrene. Based on experiences with dissolution-based polymer recycling, the two methods for removing these colour pigments studied in this project were filtration and centrifugation. Multiple laboratory-scale experiments were performed with two solvent formulations, acetone and CreaSolv^? SB. Using the filtration method, both solvent formulations achieved reduction rates of 80% for titanium and iron and 90% for chromium. While similar reduction rates were obtained with high-speed laboratory-type centrifuges for acetone solutions, the results for CreaSolv^? SB solutions were considerably lower under the same experimental conditions. Increasing the temperature or centrifugation speed, however, will also increase the reduction rates. Thereby, CreaSolv^? SB solutions become suitable for industrial-scale processes. This is important because industrial processes based on CreaSolv^? SB solutions are significantly safer than acetone-based processes.