Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants.

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.

Spatial and temporal trends of POPs in Norwegian and UK background air: implications for global cycling.

Data are presented for PCBs and HCB measured by passive air samplers (SPMDs) along a latitudinal transect from the south of the UK to the north of Norway during 1998-2000. This work is part of an ongoing air sampling campaign in which data were previously gathered for 1994-1996. Comparisons of the masses of chemicals sequestered by the SPMDs during these different time intervals are used to investigate spatial and temporal trends. Results are discussed in the context of sources, long-range atmospheric transport, fractionation/cold condensation, and global clearance processes controlling ambient levels of POPs. Spatial trends show a decrease in absolute sequestered amounts of PCBs with increasing latitude i.e., with increasing distance from the source area. However, relative sequestered amounts of the homologue groups (expressed as a ratio to penta-PCB) show a clear latitudinal trend, with the relative contribution of the lighter congeners increasing with increasing latitude, providing evidence of latitudinal fractionation. Absolute amounts of HCB increase with latitude, suggesting this compound is undergoing cold condensation. Sequestered amounts of PCBs generally decreased between the two sampling periods by a factor 2-5 over 4 years, suggesting half-lives on the order of 1.7-4 years. The relative rates of decline (1998-2000 data as a percentage of the 1994-1996 data) were compared for different congeners and latitudes. No clear latitudinal trends were found, with all sites/congeners showing a similar marked decline over time to ca. 30% of the former value. We discuss the interpretation of these observations and conclude they imply that the underlying trends of current ambient levels of PCBs in European background air are still largely controlled by primary emissions, rather than recycling/secondary emissions from the major environmental repositories such as soils or water bodies.

Global distribution and budget of PCBs and HCB in background surface soils: implications for sources and environmental processes.

This paper presents data from a survey of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) concentrations in 191 global background surface (0-5 cm) soils. Differences of up to 4 orders of magnitude were found between sites for PCBs. The lowest and highest PCB concentrations (26 and 97,000 pg/g dw) were found in samples from Greenland and mainland Europe (France, Germany, Poland), respectively. Background soil PCB concentrations were strongly influenced by proximity to source region and soil organic matter (SOM) content Most (>80%) of the estimated soil PCB burden remains in the "global source region" of the Northern Hemisphere (NH) temperate latitudes (30-60 degrees N) or in the OM-rich soils just north of that %SOM correlated with PCB and HCB in the global data set, with the correlation coefficients being greater for HCB and the lighter PCBs than for heavier homologues. OM-rich soils in the NH consistently contained the highest burdens; such soils are a key global compartment for these compounds. Evidence for global fractionation of PCBs was found in the subset of soils from latitudes north of the global source region but was not discerned with the global data set The full data set was used to estimate the burden for individual congeners/homologues in surface background soils and a global soil total PCB burden of 21,000 t. The significance of the inventory is briefly discussed in relation to the latest estimates of global production and atmospheric emission.

Influence of environmental variables on the spatial distribution of PCBs in Norwegian and U.K. soils: implications for global cycling.

This paper reports the influence of environmental variables on soil concentrations of polychlorinated biphenyls (PCBs) and their global fractionation. Soils were sampled from remote woodland (coniferous and deciduous) and grassland locations on a latitudinal transect through the United Kingdom and Norway. Different processes control PCB concentrations and burdens in coniferous, deciduous, and grassland soil systems; these are discussed, with emphasis on the influence of canopy scavenging and soil organic matter (OM) content. In general, concentration differences between sites were 1-2 orders of magnitude for lighter PCBs and 2-3 orders of magnitude for heavier PCBs, when expressed on a pg g(-1) dry weight basis. These differences decreased by up to an order of magnitude when expressed as pg g(-1) OM. The dataset suggests that the more volatile PCBs are moving toward equilibrium with the OM burden of the soil compartment on a European regional scale, while the distribution of the "stickier", heavier homologues appears to still be primarily influenced by their preferential deposition closer to source areas. The relative concentration of the tri- and tetra-PCBs increases with latitude, while that of the hepta- and octa-PCBs decreases, consistent with the global fractionation theory. However, the regression slopes are quite shallow, with high scatter, implying that many environmental and soil-related factors (such as precipitation, organic carbon content and type, other soil properties, local sources, etc.) are also influencing the observed congener patterns. Temperature-driven fractionation, while clearly operating and detectable, needs to be considered in this broader context.

Polychlorinated naphthalenes in U.K. soils: time trends, markers of source, and equilibrium status.

Polychlorinated naphthalenes (PCNs) have been analyzed in archived soil from the U.K. to investigate historical trends. Samples were obtained from the Broadbalk experiment plots (1944-1986) and Luddington experiment station (1968-1990). Luddington samples also include a set of soils that received a one-time sludge treatment in 1968, and duplicate samples of this archived sludge were also analyzed. Peak residues of sumPCN (sum of all PCN congeners quantified) were approximately 9000 pg g(-1) dry weight in 1956, declining to approximately 300 pg g(-1) in contemporary soils. The one-time sludge application resulted in elevated soil residues that were 1.5-6 times higher than the control plot over the time series. This increase is consistent with the known application rate and the amount of sumPCN in the applied sludge (approximately 250,000 pg g(-1) dry wt). Half-lives forthe Luddington control soil and the sludge-amended soil for the period 1972-1990 were 5.3 and 9.9 years, respectively. Investigation of time trends revealed differences between homologue groups with the higher molecular weight congeners peaking earlier in the time series (pre-1950) and the lower molecular weight congeners peaking later, ca. 1970. Time trends of individual congeners were investigated in terms of their relative mass percent contribution to the sum of their homologue group. Significant (p < 0.05) increasing trends were observed for several congeners associated with combustion sources (CN-29, -51, -52/60, -54, and -66/67) suggesting that combustion related sources are more important now than they were in the past. However, no decreasing trend was observed for congeners that were thought to be susceptible to degradation by photolysis suggesting that this may not be a key elimination pathway of PCNs in the environment. A simple calculation of the fugacity status of PCNs in air and soil showed that the tri-CNs are exhibiting net outgassing, while the penta-CNs are still being deposited to soil. Interestingly, the penta-CNs associated with combustion show the largest gradient for air-to-soil transfer, supporting the notion that combustion sources are important contributors to contemporary air burdens of these congeners.

Organochlorine pesticide residues in archived UK soil.

Archived background soils ("Broadbalk', 1944-1986) and sludge-amended soils ("Luddington", 1968-1990), collected from long-term agricultural experiments in the UK, were analyzed for a range of organochlorine (OC) pesticides to establish trends over time. Concentrations typically ranged from 0.1 to 10 ng/g of soil (dry weight), with gamma-hexachlorocyclohexane (gamma-HCH), dieldrin, and p,p'-DDE consistently having the highest concentrations. The trends in the Broadbalk background soils are largely consistent with usage patterns, with peak concentrations occurring in the 1960s for DDTs and between the 1960s and the 1980s for the other OCs. In the Luddington control and sludge-amended soils, several of the OCs show a significant decline in concentrations from the late 1960s to 1990, with half-lives ranging from approximately 7 years (alpha-HCH) to approximately 25 years (dieldrin). The sludge-amended plot received 125 tonnes of sludge per ha in 1968, which was mixed in to a depth of 15 cm. It appears that the sludge treatment had little effect on concentrations in the soil, with no significant difference between control soil and sludge-amended soil for most compounds, except for HCB, p,p'-DDE, and dieldrin. Enantiomeric fractions (EFs) of some chiral pesticides (alpha-HCH, cis- and trans-chlordane, and o,p'-DDT) were determined in the Luddington soils. Results reveal that enantioselective degradation of OC pesticides is occurring in these soils for trans-chlordane (TC) and cis-chlordane (CC). However, the depletion over time is not statistically significant, and there is no statistically significant difference between EFs in the control soil and sludge-amended soil. This indicates that enantioselective microbial degradation was not consistent over time and that the addition of sludge to soil did not significantly alter the enantiomeric preference of the microbial community.