Clearance of PCDD/Fs via the gastrointestinal tract in occupationally exposed persons.

A digestive tract mass balance was performed on six men with high body burdens of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Intake via food was measured by analyzing duplicate portions of the food consumed by the volunteers and excretion via feces was determined by quantitative collection and analysis of the feces. Blood samples were taken to determine the current body burden. The results showed that the quantity of non-metabolized chemical excreted in the feces clearly exceeded the uptake via food for all of the 2,3,7,8-substituted PCDDs and some of the PCDFs, indicating a significant clearance across the gastrointestinal tract. The concentrations of these PCDD/F congeners in blood and feces were highly correlated (r > 0.8), demonstrating that the fecal PCDD/F content was determined by the body burden. The half lives in the test persons due to fecal clearance of non-metabolized chemical were estimated from the excretion rate and the current body burden and ranged between 10 years (Cl8DD) and 33 years (2,3,4,7,8-Cl5DF). These were compared with the overall contaminant half-lives due to all clearance processes which were calculated from the body burden and the decrease in blood concentrations measured over several years. The fecal clearance of non-metabolized PCDD/F contributed on average between 37% (2,3,7,8-Cl4DD) and 90% (Cl8DD) to the total elimination. This indicates that the gastrointestinal pathway plays a decisive role in the clearance of most 2,3,7,8-subsituted PCDD/F congeners.     

Determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments.

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean-up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean-up for sediment extract was carried out on a 10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL. The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'-DDT and endosulfan sulphate, which was 0.01 mg/kg. The detection limit for organochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 microgram/kg and for organophosphate pesticides less than 10 micrograms/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Metabolism and body-burden of PCBs in lactating dairy cows.

This paper uses data from a detailed 4 month PCB mass balance study on lactating cows fed a naturally contaminated background diet to quantify the metabolism and body-burdens of a range of PCB congeners. Dietary intake fluxes and milk and faecal output fluxes reported previously are combined with subcutaneous fat and blood PCB concentrations and with data from tissue/organ samples from a slaughtered animal to estimate the degree of metabolism within the cow. A total body burden is derived, showing that fat deposits account for approximately 98% of total PCB present in the lactating cow. The daily intake through feed (ng day-1) accounted for between 0.9 and 1.5% of the total body burden for persistent congeners (e.g. PCB 153) and up to 43% for those congeners which are readily metabolised (e.g. PCB 52). Detailed balances for a range of tri- to octa-chlorinated PCBs are presented and clearly demonstrate that many congeners are metabolised effectively by lactating dairy cows (e.g. PCB 149) whilst others are efficiently transferred to human dairy food products. An approach to predicting the degree of metabolism for individual PCB congeners is presented which gives good agreement with observations.     

Polycyclic aromatic hydrocarbons in the ambient air of Greek towns in relation to other atmospheric pollutants

Polycyclic aromatic hydrocarbons (PAHs) were determined in the ambient air of six towns in N. Greece. This paper presents the variability of the particle-bound PAHs concentrations and the particle PAH content during the cold and the warm months. Correlations of total PAHs with other atmospheric pollutants were largely different among towns indicating that the relative contribution of emission sources is different in each location. In the warm months PAHs were significantly correlated with vehicular pollutants thus suggesting traffic as the major PAH emmitting source. The same was also deduced from the comparison of the ambient PAH profiles to the profiles of particular sources. The contribution of residential heating was significant in most towns during winter. Principal component analysis of the data did not result in a clear distinction between towns thus suggesting that all are influenced by similar source types. Finally, the risk associated with the inhallation of carcinogenic PAHs in each town was estimated and compared to the risk from more urbanized/industrialized sites in N. Greece.     

Distribution in Portugal of some pollutants in the lichen Parmelia sulcata

During the months of July and August 1993 a lichen (Parmelia sulcata Taylor) collection campaign was held in Portugal where samples were obtained from olive tree bark at 228 sites, following a grid of 10 x 10 km along the Atlantic coast and 50 x 50 km in the interior of the country. The samples were analysed by instrumental neutron activation analysis and proton induced X-ray emission techniques. Concentration data patterns for the pollutants As, Cr, Hg, Ni, Pb, S, Sb, Se, and V were obtained for the whole country surface by making use of an extinction rule of 1/r(3), preventing any cut-off distance from being artificially introduced. Some pollution sources were identified: (1) oil-powered plants on the Lisbon-Setúbal axis (V, Ni), (2) coal-power plants in Porto and Sines (S, Se), (3) traffic in the northern area and the Lisbon-Setúbal axis (Pb), (4) a chemical industry south of Porto (Hg, As), and (5) soil influence (Cr, Sb). Arsenic and chromium results largely exceed, in a few areas, the concentrations acceptable to plants, and in a few spots also Hg, Ni, and Pb data.     

Tracing sources of atmospheric sulphur using epiphytic lichens

The overall objective of this work was to measure the spatial variation of sulphur isotopic composition of lichens across the island of Newfoundland in order to assess the degree to which the atmosphere is being affected by long-range transport of anthropogenic sulphur from eastern North America, and/or local pollution sources. A contour map (based on over 80 composite samples of the lichen Alectoria sarmentosa) illustrates the spatial distribution of sulphur isotopic composition of the Newfoundland atmosphere. It shows a gradient of delta(34)S of sulphur in lichen, decreasing from the coast to the interior of the island. It also shows local anomalies corresponding to the city of St. John's, the Come-By-Chance Oil Refinery, mining areas and fossil-fuel powered pulp and paper mills in central and western Newfoundland. The study strongly suggests that the isotopic composition of sulphur in the Newfoundland atmosphere is influenced more by the ocean (sea salt sulphate) and local anthropogenic activities in the province, than by long-range transport of continental North American sulphate.     

Temporal and spatial biomonitoring of heavy metals in Hong Kong coastal waters using Tetraclita squamosa

The barnacle Tetraclita squamosa (Crustacea: Cirripedia) was collected from 11 sites in the coastal waters of Hong Kong during three consecutive seasons, i.e. summer 1996, winter 1996-1997 and summer 1997. Barnacle soft tissues were analysed for cadmium, copper, manganese, iron and zinc using inductively coupled plasma atomic emission spectrophotometry. Analysis of covariance allowed inter-seasonal (temporal) and inter-site (spatial) comparisons of soft tissue metal concentrations to be made, from which bioavailabilities to T. squamosa have been inferred. Inter-seasonal variation was not greater than intra-seasonal and, therefore, seasonal variation in soft tissue metal concentrations can be considered relatively unimportant. Data were, however, characterised by high temporal variability. Spatial variation in metal bioavailabilities were consistent with earlier studies: cadmium soft tissue concentrations were elevated in barnacles collected from low salinity western waters, while copper and zinc concentrations were elevated in the urban-fringed central waters, in particular at one site, i.e. Aberdeen. In general, metal concentrations were much lower in barnacles collected from eastern water sites.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

Measurements of peroxyacyl nitrates (PANS) in Mexico City: implications for megacity air quality impacts on regional scales

Peroxyacyl nitrates (PANs) were measured using gas chromatography with electron capture detection (GC/ECD) in north central Mexico City during February–March of 1997. Peroxyacetyl nitrate (PAN) was observed to exceed 30 ppb during five days of the study, with peroxypropionyl nitrate (PPN) and peroxybutryl nitrate (PBN) reaching 6 and 1 ppb maximum, respectively. Levels of total PANs typically exceeded 10 ppb during the period of measurement and showed a very strong diurnal variation with PANs maximum during the early afternoon and falling to less than 0.1 ppb during the evening hours. These levels of PANs are the highest reported values in North America (and the world) for an urban center, since levels of approximately 30 ppb were reported during the late 1970s in the Los Angeles area (South Coast Air Basin, Tuazon et al., 1978). Hydrocarbon measurements indicate that the levels of olefins, specifically butenes are significant in Mexico City. A time series taken of source indicator hydrocarbons taken before and during a Mexican National Holiday with reduced automobile traffic clearly show that mobile sources of butenes are as important as liquefied petroleum gas. Observations of 10–40 ppb C methyl-t-butyl ether (MTBE) are consistent with MTBE/gasoline fuel usage as a source of isobutene and formaldehyde. Both these reactive species can lead to increased oxidant and PAN formation. The strong diurnal profiles of PANs are consistent with regional clearing of the Mexico City air basin on a daily basis. Estimates are given using a simple box model calculation for a number of key primary and secondary pollutant emissions from this megacity on an annual basis. These calculations indicate that megacities can be important sources of both primary and secondary pollutants, and that PANs produced in megacity environments are likely to contribute strongly to regional scale ozone and aerosol productions during long range transport.     

Ozone patterns for three metropolitan statistical areas in North Carolina, USA

As part of an effort by the state of North Carolina to develop a State Implementation Plan (SIP) for 1-h peak ozone control, a network of ozone stations was established to monitor surface ozone concentrations across the state. Between 19 and 23 ozone stations made continuous surface measurements between 1993 and 1995 surrounding three major metropolitan statistical areas (MSAs): Raleigh/Durham (RDU), Charlotte/Mecklenburg (CLT), and Greensboro/High Point/Winston-Salem (GSO). Statistical averages of the meteorological and ozone data were performed at each Metropolitan Statistical Area (MSA) to study trends and/or relationships on high ozone days (days in which one of the MSA sites measured an hourly ozone concentration90.0 ppbv). County emission maps of precursor gases, wind roses, total area averages of ozone, total downwind averages of ozone deviations, upwind averages of ozone, and a modified delta ozone analysis were all obtained and analyzed. The results of this study show a reduction in the delta ozone relative to an earlier study at RDU, but no average significant change at CLT (no comparison can be made for GSO). The statistical data analyses in this study are used to quantify the importance of local contributions and regional transport, to ozone air pollution in the MSAs.