Liquid chromatography study of pyrene degradation by two micromycetes in a freshwater sediment.

Pyrene biodegradation in a freshwater sediment without fungi supply, or inoculated with two sediment micromycetes, Mucor racemosus var. sphaerosporus and Phialophora alba was studied after 0, 5, 13, 28, 60 and 90 days. The influence of glucose addition was estimated, and a liquid chromatographic method for simultaneous quantitative determination of residual anthracene, fluoranthene and pyrene in the sediment was developed. Samples with PAHs were extracted in Soxhlet with ethyl acetate, and LC analysis was performed on a 5 microm Supelcosil column (150 x 4.6 mm I.D.) with gradient elution (2 ml min(-1)) of acetonitrile-water and UV detection at 254 nm. Recoveries of anthracene, fluoranthene and pyrene were 90.3%+/-1.1%, 93.2%+/-0.9% and 90.42%+/-1.9%, respectively, without interference. The native sediment microorganisms (with or without glucose added) have shown 35% pyrene degradation and sediment with glucose inoculated by the strains revealed 40%.     

PAH and soot emissions from burning components of medical waste: examination/surgical gloves and cotton pads

This is a laboratory investigation on the emissions from batch combustion of representative infectious ("red bag") medical waste components, such as medical examination latex gloves and sterile cotton pads. Plastics and cloth account for the majority of the red bag wastes by mass and, certainly, by volume. An electrically heated, horizontal muffle furnace was used for batch combustion of small quantities of shredded fuels (0.5-1.5 g) at a gas temperature of approximately 1000 degrees C. The residence time of the post-combustion gases in the furnace was approximately 1 s. At the exit of the furnace, the following emissions were measured: CO, CO2, NOx, particulates and polynuclear aromatic compounds (PACs). The first three gaseous emissions were measured with continuous gas analyzers. Soot and PAC emissions were simultaneously measured by passing the furnace effluent through a filter (to collect condensed-phase PACs) and a bed of XAD-4 adsorbent (to capture gaseous-phase PACs). Analysis involved soxhlet extraction, followed by gas chromatography-mass spectrometry (GC-MS). Results were contrasted with previously measured emissions from batch combustion of pulverized coal and tire-derived fuel (TDF) under similar conditions. Results showed that the particulate soot) and cumulative PAC emissions from batch combustion of latex gloves were more than an order of magnitude higher than those from cotton pads. The following values are indicative of the relative trends (but not necessarily absolute values) in emission yields: 26% of the mass of the latex was converted to soot, 11% of which was condensed PAC. Only 2% of the mass of cotton pads was converted to soot, and only 3% of the weight of that soot was condensed PAC. The PAC yields from latex were comparable to those from TDF. The PAC yields from cotton were higher than those from coal. A notable exception to this trend was that the three-ring gas-phase PAC yields from cotton were more significant than those from latex. Emission yields of CO and CO2 from batch combustion of cotton were, respectively, comparable and higher than those from latex, despite the fact that the carbon content of cotton was half that of latex. This is indicative of the more effective combustion of cotton. Nearly all of the mass of carbon of cotton gasified to CO and CO2 while only small fractions of the carbon in latex were converted to CO2 and CO (20% and 10%, respectively). Yields of NOx from batch combustions of latex and cotton accounted for 15% and 12%, respectively, of the mass of fuel nitrogen indicating that more fuel nitrogen was converted to NOx in the former case, possibly due to higher flame temperatures. No SO2 emissions were detected, indicating that during the fuel-rich combustion of latex, its sulfur content was converted to other compounds (such as H2S) or remained in the soot.     

Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

Removal of aqueous-phase polynuclear aromatic hydrocarbons using aspen wood fibers

Roadway runoff derived polynuclear aromatic hydrocarbons (PAHs) impact the quality of surface and ground water. Inexpensive aspen wood fibers have been investigated as a means to remove dissolved PAH under laboratory conditions. Our isotherm experiments demonstrated that the uptake of naphthalene, fluorene, anthracene, and pyrene required up to 12.5 days to reach equilibrium. Aspen wood-water sorption coefficients, Kww, were linearly correlated to octanol-water partition coefficients and the molecular weight of the studied PAH compounds. The correlation between Kww and molecular weight was the most significant. Column experiments were carried out to study the sorption and desorption of fluorene, anthracene, and pyrene under dynamic conditions. The results indicate linear sorption, but non-linear desorption behavior. The degree of desorption was inversely correlated to a compound's hydrophobicity. Flow interruption experiments showed that sorption and desorption was rate limited. A mass balance of the sorption and desorption tests indicated that sorptive uptake exceeded desorptive release over a given number of pore volumes. Further, absolute mass-removal efficiency increased with the molecular weight and hydrophobicity of the PAH compound. Batch and column studies demonstrated that aspen wood has the potential to become an effective remedial agent for PAH in stormwater runoff or other PAH contaminated waters.     

Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments

The following four methods were compared on the extraction efficiency of 16 EPA (US Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs): German method of the Verband Deutscher Landwirtschaftlicher Untersuchungs und Forschungsanstalten (VDLUFA), two methods of the International Organization for Standardization using shaking (ISO A) and Soxhlet extraction (ISO B) and an ultrasonic method. Recovery rates of 16 PAHs were determined in two soils. Extraction efficiency was evaluated in five soils and three sediments. Effect of drying soils and sediments on extraction efficiency was tested using the VDLUFA and the ultrasonic methods. Our study shows that the number of aromatic rings, rather than extraction procedures, significantly influenced recovery rates of individual PAHs. No significant differences in extraction efficiency of the four methods were observed for less polluted samples. For highly polluted soils, extraction efficiency decreased in the following order: VDLUFA method > ISO A > ultrasonic method > ISO B. Influence of soil moisture on extraction efficiency depended to some extent on both solvent used and content of PAHs in samples. A mixture of dichloromethane/acetone (5:1) is recommended for PAH extraction from moist samples when the ultrasonic method is used.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece)

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.     

The influence of gill and liver metabolism on the predicted bioconcentration of three pharmaceuticals in fish

The potential for xenobiotic compounds to bioconcentrate is typically expressed through the bioconcentration factor (BCF), which has gained increased regulatory significance over the past decade. Due to the expense of in vivo bioconcentration studies and the growing regulatory need to assess bioconcentration potential, BCF is often calculated via single-compartment models, using K(OW) as the primary input. Recent efforts to refine BCF models have focused on physiological factors, including the ability of the organism to eliminate the compound through metabolic transformation. This study looks at the ability of in vitro biotransformation assays using S9 fractions to provide an indication of metabolic potential. Given the importance of the fish gill and liver in metabolic transformation, the metabolic loss of ibuprofen, norethindrone and propranolol was measured using rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) gill and liver S9 fractions. Metabolic transformation rates (k(M)) were calculated and integrated into a refined BCF model. A significant difference was noted between BCF solely based on K(OW) and BCF including k(M). These studies indicate that the inclusion of k(M) in BCF models can bring predicted bioconcentration estimates closer to in vivo values.     

Effects of bis(tributyltin)oxide on antipredator behavior in threespine stickleback Gasterosteus aculeatus L.

Antipredator behavior was used as a parameter to detect effects caused by exposure to the organotin compound bis(tributyltin)oxide (TBTO). Three groups of threespine sticklebacks (Gasterosteus aculeatus L.) were exposed to 3, 9 and 27 ppb TBTO, respectively. A fourth control group was given the same treatment as the other three groups, but no TBTO. Antipredator behavior of the fish was evoked using a dummy heron (Ardea cinerea) bill. TBTO exposure caused significant changes in the spatial position of the fish in the aquarium (P(Loc)), their response to predator attack (P(Res)), recovery time (P(Rec)) and latency time (P(Lat)). Some of the effects were, however, reversible after the exposure was terminated. We suggest that behavior as an indicator of pollution may be used as an ecologically relevant integrative biomarker.     

Trace element speciation in poultry litter

Trace elements are added to poultry feed for disease prevention and enhanced feed efficiency. High concentrations are found in poultry litter (PL), which raises concerns regarding trace element loading of soils. Trace metal cation solubility from PL may be enhanced by complexation with dissolved organic carbon (DOC). Mineralization of organo-As compounds may result in more toxic species such as As(III) and As(V). Speciation of these elements in PL leachates should assist in predicting their fate in soil. Elemental concentrations of 40 PL samples from the southeastern USA were determined. Water-soluble extractions (WSE) were fractionated into hydrophobic, anionic, and cationic species with solid-phase extraction columns. Arsenic speciation of seven As species, including the main As poultry feed additives, roxarsone (ROX; 3-nitro-4-hydroxyphenylarsonic acid) and p-arsanilic acid (p-ASA; 4-aminophenylarsonic acid), was performed by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). Total As concentrations in the litter varied from 1 to 39 mg kg(-1), averaging 16 mg kg(-1). Mean total Cu, Ni, and Zn concentrations were 479, 11, and 373 mg kg(-1), respectively. Copper and Ni were relatively soluble (49 and 41% respectively) while only 6% of Zn was soluble. Arsenic was highly soluble with an average of 71% WSE. Roxarsone was the major As species in 50% of PL samples. However, the presence of As(V) as the major species in 50% of the PL samples indicates that mineralization of ROX had occurred. The high solubility of As from litter and its apparent ready mineralization to inorganic forms coupled with the large quantity of litter that is annually land-applied in the USA suggests a potential detrimental effect on soil and water quality in the long term.