Sorbent-assisted liquid-liquid extraction (Chem-Elut) of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in the lipid fraction of human blood plasma

This work compares two lipid extraction methods for determining 24 polychlorinated biphenyls (PCBs), seven dibenzo-p-dioxins (PCDDs) and ten dibenzofurans (PCDFs) in human blood plasma. The first method was based on conventional liquid-liquid partitioning with chloroform-methanol and the other made use of a sorbent (Chem-Elut) to facilitate the partitioning of lipids into a mixture of hexane and 2-propanol. A multi-layer-silica column including acid- and base-impregnated silica gel was used to reduce the amounts of lipid present in the samples before a basic alumina clean-up step and activated carbon fractionation of planar analytes (PCDD/Fs and non-ortho-PCBs) and non-planar analytes (including ortho-chlorinated PCBs). Gas chromatography coupled to high resolution mass spectrometry was used to identify and quantify the analytes in the two fractions. The wet weight based concentrations obtained by the two methods were in agreement but both methods suffer from large organic solvent consumption. The toxic equivalencies derived for PCBs and PCDD/Fs using the two methods were also in agreement. However, the chloroform-methanol method gave slightly higher lipid recoveries, although with greater variation, than the sorbent-assisted method. Nevertheless, despite giving lower lipid recoveries, the sorbent-assisted method has advantages in ease of use and applicability to whole blood samples. The formation of emulsions was avoided with the Chem-Elut method, which probably explains the lower variability in the lipid determinations.     

Evaluating multimedia/multipathway model intake fraction estimates using POP emission and monitoring data

This paper presents a structured evaluation of a novel multimedia chemical fate and multi-pathway human exposure model for Western Europe, IMPACT 2002, using data for PCDD/F congeners. PCDD/F congeners provide an illustration of the potential use of POPs (Persistent Organic Pollutant) data for the evaluation of such models. Based on available emission estimates, model predictions with and without spatial resolution are evaluated at three different stages against monitored data: at environmental contamination levels, food exposure concentration, and in terms of human intake fractions (iF): the fraction of an emission that is taken in by the population. The iF is approximately 3.5.10(-3) for emissions of dioxin in Western Europe. This iF compares well to the traditional non-spatial multi-media/-pathway model predictions of 3.9.10(-3) for the same region and to 2.10(-3) for the USA. Approximately 95% of the intake from Western European emissions occurs within the same region, 5% being transferred out of the region in terms of food contaminants and atmospheric advective transport.     

Monitoring of persistent organic pollutants (POPs): examples from Lake Vättern, Sweden

Lake V?ttern in southern Sweden is a large oligotrophic lake with high surface to catchment area ratio (ca. 0.4) and a water residence time of 60 years. The lake combines sensitivity to atmospheric POP-pollution with general susceptibility for effects of POPs and slow concentration decline. Time series, from the 1960s until 1996, of PCBs and DDT in fish and data on TCDD in sediment of L. V?ttern are presented and compared to other large lakes. The long time dataset of POPs in Arctic char (Salvelinus salvelinus) shows a significant annual decline of about 5% for PCBs and 13% for DDT. These rates are in agreement with other studies. Nutrients as well as biological effects and factors affecting the fate of POPs in oligotrophic lakes with long residence times are discussed. We propose that oligotrophic clear lakes are important ecosystems for monitoring POPs in biota.     

Soviet and post-Soviet environmental management: lessons from a case study on lead pollution

Through a case study on lead pollution in the former Soviet Union, the linkage of policy, environmental science, and environmental management is explored, and compared with the US experience. Soviet bans on leaded gasoline and lead-based paint appear to have been effective. Regional governments, in cooperation with the petroleum industry, are taking the initiative in phasing out leaded gasoline, to some extent in defiance of federal policy. Problems with management of lead-acid batteries have been worsened by the collapse of the political system. Lack of reliable environmental data impedes reliable environmental assessment. The types of environmental measurements reflect an emphasis on multipollutant environmental contamination, rather than on human exposure to single pollutants.     

Effect of boiler operation and RDF feedstock on emissions of dioxins and furans from an RDF fired sp reader-stoker system in Albany, NY

The data on dioxin and furan emissions revealed, based on individual analysis for 2,3,7,8-TCDD, TCDD, 2,3,7,8-TCDF and TCDF for the six test periods and the operation of the two RDF-fired boilers, that there is no apparent consistent relationship between the dioxin and furan emissions and the individual or combined (averaged) boiler steam flow, total flue gas flow, sidewall furnace temperature, furnace temperature at 2-second residence time, or total furnace residence time at this plant. Only RDF feeder balance begins to show a correlation. However, there was a difference between RDF-natural gas firing and RDF-only firing; the RDF-only firing had lower PCDD and PCDF emissions while consistently operating at lower excess air.

The dioxin and furan emissions from this testing are comparable to the low end of the range of these emissions measured by the U.S. EPA at resource recovery plants in the past 4 years. This may be due in part to the calculated average furnace retention of 4 to 5 seconds during Tests #4–6, with average furnace temperatures at 2-second residence time from 1650°F to 1750°F. However, there was no correlation between dioxin and furan emissions in the stack and individual boiler operation, as judged by the average concentrations of O₂, CO, CO₂, 1-CO/CO₂), NO_x, HCl, SO₂, or TSP, and furnace upset conditions versus normal operation as judged by instantaneous steam flow, sidewall furnace temperature, O₂, CO, NO_x, or SO₂.     

Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs)

Two novel gas-tight snow samplers (snow-can and snow-tube) are presented and the performance of the snow-can in a field trial was assessed. The methodology for the sampling, extraction and analysis of persistent organic pollutants (POPs) are detailed. These samplers allow the various components of a snow sample to be analysed separately; these included the meltwater (MW), particulate matter (GFF) and vapour in the headspace (HS). Snow samples collected on the Punta Indren glacier in the Italian Alps revealed the occurrence of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OC). Replicate samples of the same snow type were undertaken as a test of sampling precision. Relative standard deviations (RSDs) for SigmaPCBs and SigmaPAHs were approximately 30% and approximately 35% respectively. The lowest precision was found for the particle-laden snow, notably for the heavier PCB homologues. For the chlorinated compounds, the pesticides lindane and endosulfan-I had the highest levels in snow, with mean concentrations of 402 and 103 pgl(-1) (snow meltwater) respectively. The vapour present in the headspace (HS) comprised a minor component of a collected sample for all compounds, but HS concentrations for three lighter PAHs gave good agreement with those calculated based on their dimensionless Henry's law constants. This suggests that volatilisation during melting of aged snow-can be reasonably predicted with knowledge of the temperature-dependent Henry's law constant.     

Recruitment of pelagic fish in an unstable climate: studies in Sweden's four largest lakes

Pelagic fish population biology was studied in the large Swedish lakes V?nern, V?ttern, M?laren and Hj?lmaren. It is crucial for fish fry in temperate regions to hatch early in the growth season to survive, and achieve large size before winter, and it is suggested that the key factors are to match the spring development of phyto- and zooplankton, but to avoid predation. This is more easily accomplished by the studied spring spawners smelt (Osmerus eperlanus) and pike-perch (Stizostedion lucioperca) than autumn spawners, such as vendace (Coregonus albula). It is shown that hatching of vendace fry shortly after ice-break-up is beneficial for year-class strength. In oligotrophic large lakes with few predatory species a rapid increase in water temperature after ice-break is also promoting recruitment, whereas this is not the case in eutrophic lakes where predation pressure from other species may become too high. The results indicate that autumn spawners will have difficulties in adapting to global warming and it is also suggested that the life history can explain the large variations observed in year-class strength between years.     

Effects of spent lubricating oil on the growth of Capsicum annum L. and Lycopersicon esculentum Miller

Susceptibility of the hot pepper (Capsicum annum L.) and the tomato (Lycopersicon esculentum Miller) to spent lubricating oil was investigated in soils supplemented with concentrations of oil ranging from 1-5% w/w. Treatment of soil with 4 and 5% spent oil consistently inhibited germination of both crops. Eighty-four days after sowing, the mean height and leaf area of C. annum in soil treated with 3% spent oil gave the lowest values. These were 3.14 +/- 0.6 cm and 0.24 +/- 0.01 cm(2) compared with respective values of 19.2 +/- 0.2 cm and 2.9 +/- 0.3 cm(2) for control plants. Premature death was observed in the case of L. esculentum plants treated with all tested strengths of spent lubricating oil.     

Acceleration of 13C-labelled photosynthate partitioning from leaves to panicles in rice plants exposed to chronic ozone at the reproductive stage

To investigate the effects of low (0.05 micromol/mol) and relatively low (0.10 micromol/mol) concentrations of ozone on photoassimilate partitioning, rice plants grown in a water culture were fed with (13)C-labelled carbon dioxide at the reproductive stage in an assimilation chamber with constant concentration of (12)CO(2) and (13)CO(2). Rice plants were exposed to ozone 4 weeks before and 3 weeks after (13)CO(2) feeding. The dry weight of whole plants decreased with increasing ozone concentration, whereas net photosynthetic rate (apparent CO(2) uptake per unit leaf area) was unaffected, compared with the control, at the time of (13)CO(2) feeding. Dry matter distribution into leaf sheaths and culms was reduced more than that into leaf blades by ozone exposure. Although panicle dry weight per plant was reduced by ozone, the percentage of panicle dry weight to the whole plant tended to increase considerably. Exposure to ozone accelerated translocation of (13)C from source leaves to other plant parts. Partitioning of (13)C to panicles and roots was higher under ozone treatment than in the control. Respiratory losses of fixed (13)C from plants tended to decrease under treatment with ozone. The increase in photoassimilate partitioning in panicles can be considered to be an acclimation response of rice plants to complete reproductive stage under the restricted biomass production caused by ozone.