Organic contaminants in mountains

The study of organic contaminants at high altitudes is motivated by the potential risk that they pose to humans living in, or depending on resources derived from, mountains and to terrestrial and aquatic ecosystems in alpine areas. Mountains are also ideal settings to study contaminant transport and behavior along gradients of climate and surface cover. Information on organic contaminants in mountains is compiled from the literature and synthesized, with a focus on atmospheric transport and deposition, contaminant dynamics in alpine lakes and aquatic organisms, and concentration differences with altitude. Diurnal mountain winds, in connection with enhanced deposition at higher elevations caused by low temperatures and high precipitation rates, conspire to make mid-latitude mountains become convergence zones for selected persistent organic chemicals. In particular, the more volatile constituents of contaminant mixtures seem to become enriched, relative to the less volatile constituents at higher altitudes. For selected contaminants, concentration inversions (i.e., concentrations that increase with elevation) have been observed. A notable difference between cold trapping in high latitudes and high altitudes is the likely importance of precipitation. High rates of snow deposition in mid- and high-latitude mountains may lead to a large contaminant release during snowmelt. Regions above the tree line often have little capacity to retain the released contaminants, suggesting the potential for a highly dynamic contaminant fate situation during the snow-free season with significant revolatilization and runoff. The chemical and environmental factors that control the orographic cold trapping of organic contaminants should be examined further by measuring and comparatively interpreting concentration gradients along several mountain slopes with widely different characteristics. Future efforts should further focus on the bioaccumulation and potential effects of contaminants in the upper trophic levels of alpine food chains, on measuring more water-soluble, persistent organic contaminants, and on studying how climate change may affect contaminant dynamics in mountain settings.     

Orographic cold-trapping of persistent organic pollutants by vegetation in mountains of western Canada

Conifer needles from mountain areas of Alberta and British Columbia, Canada, were collected from sites that ranged in altitude from 770 to 2200 masl and were analyzed for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) to determine if they are progressively concentrated in colder, more elevated mountain areas, where temperatures decrease as elevation increases. Concentrations of OCs in needles ranged from 43 to 2430 pg g(-1), 55-17500 pg g(-1), and 11-2930 pg g(-1) (dry weight), for total hexachlorocyclohexanes (HCHs), PCBs, and endosulfans, respectively. The more volatile OCs, with subcooled liquid vapor pressures (PL) > 0.1 Pa at 25 degrees C, increased at higher altitudes, whereas the less volatile OCs were either unrelated or inversely correlated with altitude. These spatial patterns were similar for species of spruce (Picea engelmannii and glauca) and pine (Pinus contorta and albicaulis). Back trajectories revealed that air masses arriving at these sites traveled over Asia and the Pacific Ocean before reaching the Rocky Mountains. Results from this study demonstrate that alpine ecosystems accumulate these chemicals to the same degree that is observed in polar environments that are known to receive contaminants by long-range transport.     

Atmospherically deposited PBDEs, pesticides, PCBs, and PAHs in western U.S. National Park fish: concentrations and consumption guidelines

Concentrations of polybrominated diphenyl ethers (PBDEs), pesticides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons were measured in 136 fish from 14 remote lakes in 8 western U.S. National Parks/Preserves between 2003 and 2005 and compared to human and wildlife contaminant health thresholds. A sensitive (median detection limit--18 pg/g wet weight), efficient (61% recovery at 8 ng/g), reproducible (4.1% relative standard deviation (RSD)), and accurate (7% deviation from standard reference material (SRM)) analytical method was developed and validated for these analyses. Concentrations of PCBs, hexachlorobenzene, hexachlorocyclohexanes, DDTs, and chlordanes in western U.S. fish were comparable to or lower than mountain fish recently collected from Europe, Canada, and Asia. Dieldrin and PBDE concentrations were higher than recent measurements in mountain fish and Pacific Ocean salmon. Concentrations of most contaminants in western U.S. fish were 1-6 orders of magnitude below calculated recreational fishing contaminant health thresholds. However, lake average contaminant concentrations in fish exceeded subsistence fishing cancer thresholds in 8 of 14 lakes and wildlife contaminant health thresholds for piscivorous birds in 1 of 14 lakes. These results indicate that atmospherically deposited organic contaminants can accumulate in high elevation fish, reaching concentrations relevant to human and wildlife health.     

Plant-soil distribution of potentially toxic elements in response to elevated atmospheric CO2

The distribution of contaminant elements within ecosystems is an environmental concern because of these elements' potential toxicity to animals and plants and their ability to hinder microbial ecosystem services. As with nutrients, contaminants are cycled within and through ecosystems. Elevated atmospheric CO2 generally increases plant productivity and alters nutrient element cycling, but whether CO2 causes similar effects on the cycling of contaminant elements is unknown. Here we show that 11 years of experimental CO2 enrichment in a sandy soil with low organic matter content causes plants to accumulate contaminants in plant biomass, with declines in the extractable contaminant element pools in surface soils. These results indicate that CO2 alters the distribution of contaminant elements in ecosystems, with plant element accumulation and declining soil availability both likely explained by the CO2 stimulation of plant biomass. Our results highlight the interdependence of element cycles and the importance of taking a broad view of the periodic table when the effects of global environmental change on ecosystem biogeochemistry are considered.     

PCBs and selected organochlorine compounds in Italian mountain air: the influence of altitude and forest ecosystem type

Passive air samplers (polyurethane foam disks) were deployed on an altitudinal transect in the rural Italian Alps to investigate the potential influence of forest cover on air concentrations. Samplers were exposed overtwo periods, each of several weeks, either in clearings or in forests. In the first period, there was high leaf coverage (high leaf area index, LAI); in the second, the LAI was low after the autumnal leaf fall. PCBs sequestered in the PUF generally declined with altitude, for example, in the clearings PCBs-28, 52, 90/101, 118, and 138, all showed statistically significant declines (p < 0.05). The mass of HCB sequestered increased with altitude, evidence of cold condensation. Ratios of the forest:clearing concentrations were calculated; this ratio expresses the filtering ability of forests to deplete air concentrations compared to the adjacent clearings. During the high LAI sampling period, these depletion factors ranged between 0.93 and 0.54 and were inversely correlated with temperature-corrected log K0A. This relationship was notobserved during the low LAI sampling period. The depletion factors were normalized using the LAI to give a density independent depletion factor (DIDF). The slopes of the correlations with K0A were comparable for broadleaf or coniferous forests at different altitudes, suggesting that leaf surfaces determine the exchanges with air. Broadleaf forests at 1000 and 1400 m showed similar behavior, while a conifer forest at 1800 m gave depletion factors which were higher by about a factor of 2. It is suggested that DIDF can be used in regional environmental fate models to estimate the contribution of forests to contaminant fate.     

Mass budgets, pathways, and equilibrium states of two hexachlorocyclohexanes in the Baltic Sea environment

The POPCYCLING-Baltic model, a non-steady-state multicompartmental mass balance model of long-term chemical fate in the Baltic Sea environment, is used to derive a quantitative understanding of the behavior of alpha- and gamma-hexachlorocyclohexane (HCH) from 1970 to 2000. The atmosphere is found to effectively distribute the HCHs within the Baltic Sea environment and beyond, resulting in relatively uniform concentrations in environmental compartments that do not directly receive emissions. This uniformity is the result of a large-scale redistribution of a relatively small fraction of the emitted HCHs from the agricultural systems in source areas to all other environmental compartments throughout the Baltic Sea region. The major fraction of the HCHs is degraded in the soils receiving the pesticide application. In areas where HCH-containing pesticides are used, HCHs evaporate from soils and water bodies and are advected away in the atmosphere. They are deposited to forests and water bodies when they reach remote regions. This redistribution is driven by the inclination of the HCHs to equalize their chemical potential within the environment, which is illustrated through the use of fugacity fractions. The model is believed to provide useful insight into the complex set of interactions that determine the overall fate of an environmental contaminant but which are inaccessible to measurements.     

Field testing passive air samplers for current use pesticides in a tropical environment

Air was sampled for one year in the central valley of Costa Rica using an active high-volume sampler as well as passive samplers (PAS) based on polyurethane foam (PUF) disks and XAD-resin filled mesh cylinders. Extracts were analyzed for pesticides that are either banned or currently used in Costa Rican agriculture. Sampling rates for PUF-based passive air samplers, determined from the loss of depuration compounds spiked on the disks prior to deployment averaged 5.9 +/- 0.9 m3 x d(-1) and were higher during the windier dry season than during the rainy season. Sampling rates for the XAD-based passive sampler were determined from the slopes of linear relationships that were observed between the amount of pesticide sequestered in the resin and the length of deployment, which varied from 4 months to 1 year. Those sampling rates increased with decreasing molecular size of a pesticide, and their average of 2.1 +/- 1.5 m3 x d(-1) is higher than rates previously reported for temperate and polar sampling sites. Even though the trends of the sampling rate with molecular size and temperature are consistent with the hypothesis that molecular diffusion controls uptake in passive samplers, the trends are much more pronounced than a direct proportionality between sampling rate and molecular diffusivity would suggest. Air concentrations derived by the three sampling methods are within a factor of 2 of each other, suggesting that properly calibrated PAS can be effective tools for monitoring levels of pesticides in the tropical atmosphere. In particular, HiVol samplers, PUF-disk samplers, and XAD-based passive samplers are suitable for obtaining information on air concentration variability on the time scale of days, seasons and years, respectively. This study represents the first calibration study for the uptake of current use pesticides by passive air samplers.     

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.     

Chiral organochlorine pesticide signatures in global background soils

Chiral pesticides frequently undergo enantioselective degradation in soils. Prior studies to characterize chiral signatures have focused on treated agricultural soils, rather than background (untreated) soils, and tracking signatures in the atmosphere for source apportionment purposes. In this study, we investigated the chiral signatures in 65 background soils collected from different locations across the world. The soils were taken from different ecosystems (e.g., grasslands, forests), and the enantiomeric fractions (EFs) of chiral chlordanes, alpha-hexachlorocyclohexane (alpha-HCH), and o,p'-DDT were determined. Chlordanes in most of the soils showed the usual pattern of enantioselective degradation seen in agricultural soils, depletion of (+)-trans-chlordane (TC) and (-)-cis-chlordane (CC). However, some samples showed opposite enantiomer degradation patterns for TC, CC, and chlordane compound MC5. Correlations were tested between the deviation of EFs from racemic (DEVrac = absolute value of 0.500 - EF), the percent soil organic matter (% SOM), annual mean temperature, and the ratio of TC to the more stable compound trans-nonachlor (TN). Significant positive correlations were found between DEVrac and % SOM for TC and CC (p = 0.0022 and 0.0031), but not for the other OCPs. No significant correlations were found between DEVrac and annual mean temperature for any of the OCPs. DEVrac for TC was negatively correlated with the TC/TN ratio, but the regression was driven by two points with high ratios of TC/CC. Removing these two points resulted in a nonsignificant regression. The range of EFs for TC, CC, and alpha-HCH in soils was greater than in ambient air, providing evidence of in situ degradation after atmospheric deposition in some cases. Variable EFs in soil suggest that caution is needed when considering the enantiomer signatures in air as a marker of volatilization of weathered soil-derived organochlorines.     

Organochlorine pesticides in the soils and atmosphere of Costa Rica

A survey of the contamination of the physical environment of Costa Rica with banned organochlorine pesticides (OCPs) relied on sampling air and soil at 23 stations acrossthe country in 2004. Average annual air concentrations, determined with XAD-based passive samplers, and surface soil concentrations were generally low when compared to values reported for North and Central America, which is consistent with relatively low historical domestic use and little atmospheric inflow from neighboring countries. Statistical analysis and concentration maps reveal three types of spatial distribution: alpha-hexachlorocyclohexane and p,p'-DDD had a relatively uniform distribution across the country; other DDT-related species were greatly elevated over the national average at Manuel Antonio, a National Park on the Pacific coast; and dieldrin, lindane, and chlordane-related species had higher concentrations in Costa Rica's populated Central Valley. An altitudinal transect of stations in the Central Valley shows declining air-soil concentration ratios with elevation for lindane, likely driven by atmospheric inversions and soil organic carbon content. Enantiomeric composition of chiral OCPs in air and soil was close to racemic, with slight depletion of (-)-alpha-HCH, (-)-cis-chlordane, and (+)-trans-chlordane. Estimated air-soil fugacity fractions are highly uncertain but indicate equilibrium conditions for most OCPs, net volatilization of lindane at some sites, and net deposition for p,p'-DDE. The study demonstrates an approach for quickly evaluating the spatial distribution of OCPs in an understudied area, identifying regionally important contaminants and areas of elevated concentrations.     

Seabird guano is an efficient conveyer of persistent organic pollutants (POPs) to Arctic lake ecosystems

Migratory seabirds have been linked to localized "hotspots" of contamination in remote Arctic lakes. One of these lakes is Lake Ellasj?en on Bj?rn?ya in the Barents Sea. Here we provide quantitative evidence demonstrating that even relatively small populations of certain seabird species can lead to major impacts for ecosystems. In the present example, seabird guano accounts for approximately 14% of the contaminant inventory of the Lake Ellasj?en catchment area, approximately 80% of the contaminant inventory of the lake itself, and is approximately thirty times more efficient as a contaminant transport pathway compared to atmospheric long-range transport. We have further shown that this biological transport mechanism is an important contaminant exposure route for ecosystems, responsible for POPs levels in freshwater fish that are an order of magnitude higher than those in Arctic top predators. Given the worldwide presence of seabird colonies in coastal marine areas where resources are also harvested by humans, this biological transport pathway may be a greater source of dietary contamination than is currently recognized with consequent risks for human health.     

Role of soil health in maintaining environmental sustainability of surface coal mining

Mountaintop coal mining (MCM) in the Southern Appalachian forest region greatly impacts both soil and aquatic ecosystems. Policy and practice currently in place emphasize water quality and soil stability but do not consider upland soil health. Here we report soil organic carbon (SOC) measurements and other soil quality indicators for reclaimed soils in the Southern Appalachian forest region to quantify the health of the soil ecosystem. The SOC sequestration rate of the MCM soils was 1.3 MgC ha(-1) yr(-1) and stocks ranged from 1.3 ± 0.9 to 20.9 ± 5.9 Mg ha(-1) and contained only 11% of the SOC of surrounding forest soils. Comparable reclaimed mining soils reported in the literature that are supportive of soil ecosystem health had SOC stocks 2.5-5 times greater than the MCM soils and sequestration rates were also 1.6-3 times greater. The high compaction associated with reclamation in this region greatly reduces both the vegetative rooting depth and infiltration of the soil and increases surface runoff, thus bypassing the ability of soil to naturally filter groundwater. In the context of environmental sustainability of MCM, it is proposed that the entire watershed ecosystem be assessed and that a revision of current policy be conducted to reflect the health of both water and soil.     

Time trends of Arctic contamination in relation to emission history and chemical persistence and partitioning properties

How long does ittake for organic contaminant concentrations to decline in the Arctic after regulatory measures have succeeded in reducing emissions globally? This question is explored by using a zonally averaged global distribution model to estimate the lag-time between the period when emissions begin to decrease and when a decline in a chemical's Arctic Contamination Potential is observed. A long lag is problematic, as contaminant concentrations can continue to increase well after a potential hazard is recognized. Using three different emission scenarios, the chemical property combinations that are most likely to experience a lag on the order of decades were identifed among 96 hypothetical chemicals with different partitioning and reactivity properties. The first such property combination comprises the persistent "swimmers" that reach the Arctic by slow long-range oceanic transport. They require a half-life (t(1/2)) in water of more than 10 years for a significant lag to occur. The second group of compounds experiencing a long lag includes semivolatile chemicals that are in dynamic exchange between atmosphere and ocean. These "multihoppers", with air-water partition coefficients, K(AW) of approximately 0.01, need to be highly persistent in air (t(1/2) >3 years) and surface media (t(1/2) >10 years). Their lag depends both on the oceans' large storage capacity and relatively low stickiness, i.e., a high likelihood of return to the atmosphere. Notably, no lag is predicted for less water soluble multihoppers (K(AW) >1), which are more likely to distribute into soils and foliage, because the terrestrial environment is "stickier" than the oceans, greatly reducing the number of hops these chemical will experience. The oceans thus play a crucial role in facilitating delayed Arctic contamination, either by transporting dissolved contaminants slowly to higher latitudes, or by providing a relatively nonsticky temporary storage reservoir which is in constant exchange with the atmosphere. Precaution advises a swift regulatory response to increasing concentrations in remote marine organisms of substances that have property combinations that are predicted to result in a significant delay between emission reductions and concentration declines.     

Threshold increases in soil lead and mercury from tropospheric deposition across an elevational gradient

Atmospheric deposition is the primary mechanism by which remote ecosystems are contaminated, but few data sets show how fluxes change and control soil metal burdens at the landform scale. We present mercury (Hg), lead ((210)Pb and total Pb), and cosmogenic beryllium-7 ((7)Be) measurements in organic (O) soil horizons at high-resolution elevation intervals of ～60 m from 540 to 1160 m on Camels Hump in northern Vermont, USA. Across this gradient, average O horizon Hg ranges from 0.99 mg m(-2) in the low elevation deciduous forest zone to 7.6 mg m(-2) in the higher elevation coniferous forest at 1030 m. We measure two pronounced threshold increases in soil metal burdens above 801 and 934 m, corresponding to the two most common altitudes of cloud base, which coincide with changes in vegetation species. Lead-210, a unique tracer of tropospheric deposition, also increased from 3200 Bq m(-2) to 11?500 Bq m(-2) in O horizons, exhibiting threshold responses at the same elevations as Hg and total Pb. Concentrations of (210)Pb and Hg in foliage double from 760 to 900 m elevation, indicating enhanced deposition across the transition from deciduous to coniferous forest. In contrast, (7)Be is constant across the entire elevational gradient because of its upper atmospheric source. This indicates that the effects of orographic precipitation have a smaller control on soil contaminant burdens than the coupled cloudwater deposition-vegetation scavenging effect in the presence of upwind sources. By measuring soil contaminants and unique tracers of atmospheric deposition, we show that tropospheric fluxes of Hg and Pb are higher by a factor of 2 in high-elevation coniferous forests than in adjacent lowlands. Total O horizon Hg and Pb burdens increase by over 4-fold with elevation because of the compounding effects of enhanced deposition and longer metal residence times at higher elevations (>50 years).     

Influence of Asian and Western United states agricultural areas and fires on the atmospheric transport of pesticides in the Western United States

Historic and current use pesticides (HUPs and CUPs), with respect to use in the United States and Canada, were identified in trans-Pacific and regional air masses at Mt. Bachelor Observatory (MBO), a remote high elevation mountain in Oregon's Cascade Range located in the United States, during the sampling period of April 2004 to May 2006 (n = 69), including NASA's INTEX-B campaign (spring 2006). Elevated hexachlorobenzene (HCB) and alpha-hexachlorocyclohexane (alpha-HCH) concentrations were measured during trans-Pacific atmospheric transport events at MBO, suggesting that Asia is an important source region for these HUPs. Regional atmospheric transport events at MBO resulted in elevated dacthal, endosulfan, metribuzin, triallate, trifluralin, and chlorpyrifos concentrations, with episodic increases in concentration during some spring application periods, suggesting that the Western U.S. is a significant source region for these CUPs. Endosulfan I, gamma-HCH, and dacthal concentrations were significantly positively correlated (p-value < 0.05) with increased air mass time in Western U.S. agricultural areas. Elevated gamma-HCH concentrations were measured at MBO during both trans-Pacific and regional atmospheric transport events, including regional fire events. In addition to gamma-HCH, elevated sigmachlordane, alpha-HCH, HCB, and trifluralin concentrations were associated with fires in Western North America due to revolatilization of these pesticides from soils and vegetation. Trans-chlordane/cis-chlordane and alpha-HCH/gamma-HCH ratios were calculated and may be used to distinguish between free tropospheric and regional and/or Asian air masses.     

Pesticides in western Canadian mountain air and soil

The distribution of organochlorine pesticides (OCP; in past and current use) in the mountains of western Canada was determined by sampling air, soil, and lichen along three elevational transects in 2003-2004. Two transects west of the Continental Divide were located in Mount Revelstoke and Yoho National Park, while the Observation Peak transect in Banff National Park is east of the divide. XAD-based passive air samplers, yielding annually averaged air concentrations, were deployed, and soils were collected at all 22 sampling sites, whereas lichen were only sampled in Revelstoke. Back trajectory analysis showed limited air mass transport from the Prairies to the east, but a high frequency of air arriving from the southwest, which includes agricultural regions in British Columbia and Washington State. Endosulfan, dieldrin, and a-hexachlorocyclohexane were the most prevalent OCPs in air and soil; hexachlorobenzene was only abundant in air; chlorothalonil, dacthal, and pentachloronitrobenzene were also consistently present. OCP air concentrations were similar across the three transects, suggesting efficient atmospheric mixing on a local and regional scale. Soil concentrations and soil/air concentration ratios of many OCPs were significantly higher west of the Continental Divide. The soil and lichen concentrations of most OCPs increased with altitude in Revelstoke, and displayed maxima at intermediate elevations at Yoho and Observation Peak. These distribution patterns can be understood as being determined by the balance between atmospheric deposition to, and retention within, the soils. Higher deposition, due to more precipitation falling at lower temperatures, likely occurs west of the divide and at higher elevations. Higher retention, due to higher soil organic matter content, is believed to occur in soils below the tree line. Highest pesticide concentrations are thus found intemperate mountain soils that are rich in organic matter and receive large amounts of cold precipitation.     

An assessment of air-soil exchange of polychlorinated biphenyls and organochlorine pesticides across central and southern Europe

Estimating the net flux direction of polychlorinated biphenyls and organochlorine pesticides is importantfor understanding the role of soil as a sink or source of these chemicals to the atmosphere. In this study, the soil-air equilibrium status was investigated forvarious soil categories in Central and Southern Europe using an extensive database of coupled soil and time-integrated air samples. Samples were collected from 47 sites over a period of 5 months to assess both site-specific as well as seasonal variations in fugacity fractions, calculated as a potential measure of soil-air exchange. Sampling sites were carefully selected to represent a variety of background, rural, urban, and industrial areas. Special attention was given to sites in the former Yugoslavia, a country affected by recent conflicts, where soils were found to be highly contaminated with polychlorinated biphenyls (PCBs). Industrial soils from the Czech Republic, heavily polluted as a result of previous pesticide production, were also included in the survey. Soil was found to be a sink for highly chlorinated PCBs and for dichlorodiphenyltrichloroethane (DDT); for dichlorodiphenyldichloroethylene (DDE), the status was closer to equilibrium, with a tendency for net deposition during winter and net volatilization during summer. For lower-molecular-weight PCB congeners, as well as for alpha-HCH, soil tends to be a source of pollution to the air, especially, but not exclusively, during summer. Fugacity fractions were found to decrease during the colder seasons, especially for the more volatile compounds, although in both the war-damaged areas and the heavily contaminated industrial sites, seasonal variability was very low, with fugacity fractions close to 1, indicating strong net soil-to-air transfer for all seasons. The original assumption that residents of the Western Balkans are still exposed to higher levels of PCBs due to the recent wars was confirmed. In general, the soil-air transfer of PCBs and organochlorine pesticides was found to be site-specific and dependent on the physicochemical properties of the contaminant in question, the soil properties, the historical contamination record and a site's vicinity to sources, and the local meteorological conditions.     

XAS evidence of As(V) association with iron oxyhydroxides in a contaminated soil at a former arsenical pesticide processing plant

The molecular-level speciation of arsenic has been determined in a soil profile in the Massif Central near Auzon, France that was impacted by As-based pesticides by combining conventional techniques (XRD, selective chemical extractions) with X-ray absorption spectroscopy (XAS). The arsenic concentration is very high at the top (>7000 mg kg(-1)) and decreases rapidly downward to a few hundreds of milligrams per kilogram. A thin layer of schultenite (PbHAsO4), a lead arsenate commonly used as an insecticide until the middle of the 20th century, was found at 10 cm depth. Despite the occurrence of this As-bearing mineral, oxalate extraction indicated that more than 65% of the arsenic was released upon dissolution of amorphous iron oxides, suggesting a major association of arsenic with these phases within the soil profile. Since oxalate extraction cannot unambiguously distinguish among the various chemical forms of arsenic, these results were confirmed by a direct in situ determination of arsenic speciation using XAS analysis. XANES data indicate that arsenic occurs mainly as As(V) along the soil profile except for the topsoil sample where a minor amount (7%) of As(III) was detected. EXAFS spectra of soil samples were fit by linear combinations of model compounds spectra and by a shell-by-shell method. These procedures clearly confirmed that As(V) is mainly (at least 80 wt %) associated with amorphous Fe(III) oxides as coprecipitates within the soil profile. If any, the proportion of schultenite, which was evidenced by XRD in a separate thin white layer, does not account for more than 10 wt % of arsenic in soil samples. This study emphasizes the importance of iron oxides in restricting arsenic dispersal within soils following dissolution of primary As-bearing solids manufactured for use as pesticides and released into the soils.     

Carbon isotope signature of polycyclic aromatic hydrocarbons (PAHs): evidence for different sources in tropical and temperate environments?

In tropical soils, naphthalene and, partly also, perylene occur at elevated concentrations while pyrolytic higher molecular weight PAHs are almost absent. We hypothesize that there are recent biological PAH sources in the tropical environment related with woody plants and termites. We used the C isotope signature of individual PAHs in temperate and tropical soils and in tropical wood and termite nests to distinguish different PAH sources. The mean delta13C values of the benzo[b+j+k]fluoranthenes and of benzo[a+e]pyrenes in temperate soils ranged between -24.6/1000 and -25.3/1000, being similar to values reported in the literature for PAHs with pyrolitic origin. The mean delta13C values of perylene decreased in the order temperate soils (-27.0/1000) > termite nests (-31.4/1000) > tropical soil (-32.4/1000), while those of naphthalene (-24.6/1000 to -26.2/1000) were similar among the tropical and temperate soils, tropical wood, and termite nests. Our results support the assumption that perylene in the tropical environment is recently biologically produced, as indicated by the depletion in 13C. The C isotope composition of naphthalene, however, cannot be used to distinguish different sources.     

Emission of chiral organochlorine pesticides from agricultural soils in the cornbelt region of the U.S

Several organochlorine pesticides are chiral molecules manufactured as racemic mixtures. Past research has shown that selective degradation of pesticide enantiomers by microorganisms occurs resulting in nonracemic signatures in soils. In this work, volatilization of chiral pesticides from soil was investigated to determine if enantioselective breakdown in soils could be used as a source signature to track releases of chiral pesticides to the atmosphere. Air samples were taken directly above agricultural soils at several sites, and enantiomeric signatures were found to be nonracemic following patterns found in the soil. A follow up study at one site showed that for most compounds concentration decreased with increasing height above the soil, while enantiomer fractions for chiral pesticides were similar to that found in the soil, signifying the soil as a source to the air. The enantiomer fractions of ambient air samples from rural nonagricultural areas in the region were also found to be nonracemic.