Persistent organic pollutants are still present in surface marine sediments from the Seto Inland Sea, Japan.

Although persistent organic pollutants (POPs) are currently banned or strictly controlled under the Stockholm Convention on Persistent Organic Pollutants, POPs are still distributed worldwide due to their environmental persistence, atmospheric transport, and bioaccumulation. Herein we investigated the current concentrations of POPs in the sediments from Seto Inland Sea, Japan and sought to clarify the factors currently controlling the POPs concentration of the surface sediments from Seto Inland Sea. The concentrations of hexachlorocyclohexane isomers (HCHs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), and chlordane isomers (CHLs) in sediments from Seto Inland Sea were <0.002-1.20 ng g-1, 0.01-2.51 ng g-1, and 0.01-0.48 ng g-1, respectively. Resuspension increased the concentrations of HCHs, HCB, and DDTs in the surface sediment with the release of historically contaminated pollutants accumulated in a lower layer. We speculate that CHLs in air that were removed by atmospheric deposition affects the concentration of CHLs in surface sediments.

Variability and reliability of POP concentrations in multiple breast milk samples collected from the same mothers.

Risk assessment of infant using a realistic persistent organic pollutant (POP) exposure through breast milk is essential to devise future regulation of POPs. However, recent investigations have demonstrated that POP levels in breast milk collected from the same mother showed a wide range of variation daily and monthly. To estimate the appropriate sample size of breast milk from the same mother to obtain reliable POP concentrations, breast milk samples were collected from five mothers living in Japan from 2006 to 2012. Milk samples from each mother were collected 3 to 6 times a day through 3 to 7 days consecutively. Food samples as the duplicated method were collected from two mothers during the period of breast milk sample collection. Those were employed for POP (PCBs, DDTs, chlordanes, and HCB) analysis. PCB concentrations detected in breast milk samples showed a wide range of variation which was maximum 63 and 60% of relative standard deviation (RSD) in lipid and wet weight basis, respectively. The time course trend of those variations among the mothers did not show any typical pattern. A larger amount of PCB intake through food seemed to affect 10 h after those concentrations in breast milk in lipid weight basis. Intraclass correlation coefficient (ICC) analyses indicated that the appropriate sample size for good reproducibility of POP concentrations in breast milk required at least two samples for lipid and wet weight basis.

20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean.

The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals.

Multiwalled carbon nanotubes and c60 fullerenes differentially impact the accumulation of weathered pesticides in four agricultural plants.

The effect of multiwalled carbon nanotubes (MWCNT) or C60 fullerenes on the uptake of weathered chlordane or DDx (DDT + metabolites) by Cucurbita pepo (zucchini), Zea mays (corn), Solanum lycopersicum (tomato), and Glycine max (soybean) was investigated. The plants were grown in 50 g of soil with weathered chlordane (2150 ng/g) and DDx (118 ng/g) that was amended with 0, 500, 1000, or 5000 mg/kg MWCNT or C60. After 28 d, the root and shoot content of chlordane components and DDx was determined by GC-MS. Zucchini and tomato growth were unaffected by carbon nanomaterial coexposure, although C60 at 500 mg/kg reduced corn and soybean biomass by 36.5-45.0%. Total chlordane content ranged from 1490 (tomato) to 4780 (zucchini) ng; DDx amounts ranged from 77.8 (corn) to 395 ng (zucchini). MWCNT coexposure decreased chlordane and DDx accumulation 21-80% across all crops, depending on species and nanotube concentration. Conversely, C60 had species- and contaminant-specific effects on pesticide uptake, ranging from complete suppression of DDx uptake (corn/tomato) to 34.9% increases in chlordane accumulation (tomato/soybean). The data show that pesticide accumulation varies greatly with crop species and carbon nanomaterial type/concentration. These findings have implications for food safety and for the use of engineered nanomaterials in agriculture.

Distributions, possible sources and biological risk of DDTs, HCHs and chlordanes in sediments of Beibu Gulf and its tributary rivers, China.

Thirty-five surface sediment samples collected from Beibu Gulf and its tributary rivers, China were analyzed for DDTs, HCHs and chlordanes. Total concentrations of DDTs, HCHs and chlordanes in sediments ranged from 0.59 to 126 ng g(-)(1), ND to 2.65 ng g(-)(1) and 0.27 to 3.41 ng g(-)(1) based on dry weight (dw), respectively. Concentrations of DDTs were higher than those reported in the sediments from other regions of the world, while concentrations of HCHs and chlordanes were relatively low. High concentrations of DDTs were observed in the harbor region and aquaculture bases and high concentrations of HCHs were found in the Qin River Estuary. The ratios of (DDE+DDD)/DDTs reflected a mixed input of weathered and fresh DDTs. The predominant ß-HCH indicated that HCHs in the study area mainly originated from the historical usage of technical HCH. The residues of DDTs would pose adverse biological effects on the study area.

Risk posed by chlorinated organic compounds in Abu Qir Bay, East Alexandria, Egypt.

INTRODUCTION: In Egypt, the picture of threats to humans and the environment from the exposure to organic pollutants is still incomplete. Thus the objectives of this study were to assess the occurrence and distribution of polychlorinated biphenyls (PCBs), organochlorine pesticides, and chlorpyrifos in sediments and mussels of Abu Qir Bay and their risks for environment and human health. MATERIALS AND METHODS: Twenty-three different compounds organochlorines were determined in 20 surfacial sediment and 10 mussel samples by gas chromatography-electron capture detector. A Screening Level Ecological Risk Assessment (SLERA) and a Human Health Risk Assessment (HHRA) were performed with the data. RESULTS AND DISCUSSION: ΣDDT (DDT, DDE, DDD) (average concentration 27 µg/kg dw) dominated the detected organic pollutants in the sediments, followed by CHLs (chlordane, heptachlor, heptachloro epoxide), hexachlorocyclohexane, chlorpyrifos, endosulfane, dieldrine, Σ6 PCBs, aldrine, hexachlorobenzene, pentachlorobenzene, methoxychlor, and mirex. In general, concentrations of Σ6 PCBs in mussels were higher than their corresponding sediment concentrations reflecting their relatively high bioavailability and bioaccumulative potential. However, concentrations of the organochlorine pesticides in mussels were lower than their corresponding sediment samples. Nevertheless, the SLERA on the bay sediments revealed that adverse ecological effects to benthic species are expected to occur whereas the HHRA showed that adverse health effects are not expected to occur from the consumption of the mussels. CONCLUSIONS: With the help of a SLERA, it was possible to indicate which class of chlorinated organic compounds is of highest concern to assess and to improve the environmental quality of the bay. Monitoring of organochlorines and chlorpyrifos would be needed to control the future trend of pollution.

Accumulation dynamics of chlordanes and their enantiomers in cockerels (Gallus gallus) after oral exposure.

After a single oral exposure of technical chlordane, levels of cis-chlordane (CC), trans-chlordane (TC), heptachlor (HEP), heptachlorepoxide (HEPX), and oxychlordane (OXY) were determined in gastrointestinal residues, droppings, and various tissues of cockerels at times of 60, 120, 160, 200, 300, 500, 1000, and 2000 min. Over 98% of CC and TC were found to be bioaccessible; only 1.1% of CC and TC were directly excreted through droppings without further biotransformation. According to the single-compartment toxicokinetic modeling, CC and TC shared similar absorption rates in the whole body while TC showed a slightly more rapid elimination rate, with a half-life of 13.4 h for CC and 12.5 h for TC. The metabolites HEPX and OXY appeared quickly in tissues 60 min after exposure and were mainly accumulated in fat and liver tissues. Concentrations of CC, TC, and HEP in cockerel tissues roughly followed the order as fat > intestine > skin > liver> brain > muscle > blood. Levels of CC, TC, and HEP in various tissues showed significant correlation with the lipid contents of the tissues (p < 0.05) for samples beginning 500 min after exposure. A multicompartment toxicokinetic model was developed to characterize the accumulation dynamics of CC and TC in the various tissues. All tissues of cockerels enantioselectively accumulated (-)-CC and (+)-TC, and fat, skin, and liver tissues showed a relatively stronger capacity of enantioenrichment. The enantiomer fractions (EFs) of droppings remained nearly racemic at first but gradually decreased to less than 0.5 for CC and increased to more than 0.5 for TC, which could rule out enantioselective absorption and excretion of CC and TC in cockerels. The one-compartment toxicokinetic model was applied to the individual enantiomers of CC and TC. Different elimination rates but similar absorption rates were observed between the enantiomers for both CC and TC.

Biotransformation of the organochlorine pesticide trans-chlordane by wood-rot fungi.

There is very limited information on the biotransformation of organochlorine pesticide chlordane by microorganisms, and no systematic study on the metabolic products and pathways for chlordane transformation by wood-rot fungi has been conducted. In this study, trans-chlordane was metabolized with the wood-rot fungi species Phlebia lindtneri, Phlebia brevispora and Phlebia aurea, which are capable of degrading polychlorinated dibenzo-p-dioxin and heptachlor epoxide. At the end of 42 days of incubation, over 50% of trans-chlordane was degraded by the fungal treatments in pure cultures. These fungi transformed trans-chlordane to at least eleven metabolites including a large amount of hydroxylated products such as 3-hydroxychlordane, chlordene chlorohydrin, heptachlor diol, monohydroxychlordene and dihydroxychlordene. P. lindtneri particularly can metabolize oxychlordane, a recalcitrant epoxide product of chlordane, into a hydroxylated product through substitution of chlorine atom by hydroxyl group. The present results suggest that hydroxylation reactions play an important role in the metabolism of trans-chlordane by these Phlebia species. Additionally, transformation of trans-chlordane and production of hydroxylated metabolites were efficiently inhibited by the addition of cytochrome P450 inhibitors, piperonyl butoxide and 1-aminobenzotriazole, demonstrating that fungal cytochrome P450 enzymes are involved in some steps of trans-chlordane metabolism, particularly in the hydroxylation process.

Determination of some organochlorine pesticide residues in honeys from Konya, Turkey.

In this study, 24 organochlorine pesticide residues in 109 different honey samples collected from stores and open markets in Konya, Turkey were analyzed by gas chromatography-electron capture detection. Aldrin, cis-chlordane, trans-chlordane, oxy-chlordane, 2,4(')-DDE, and 4,4(')-DDE were found in all honey samples. The mean value was 0.0540 microg g(-1) for oxy-chlordane. In the 55 samples of 109, levels of organochlorine pesticide residues of oxy-chlordane were determined as higher than those of Turkish Alimentarius Codex maximum residual limits (MRLs). Other organochlorine pesticide residues also exceeded MRLs except for cis-heptachlor epoxide and alpha-hexachlorocyclohexane. Since all of the honey samples are found contaminated and most of these samples exceeded MRLs, a control of organochlorine pesticide residues in honey is necessary for consumer health.

Enantiomer fractions of chlordane components in sediment from U.S. Geological Survey sites in lakes and rivers.

Spatial, temporal, and sediment-type trends in enantiomer signatures were evaluated for cis- and trans-chlordane (CC, TC) in archived core, suspended, and surficial-sediment samples from six lake, reservoir, and river sites across the United States. The enantiomer fractions (EFs) measured in these samples are in good agreement with those reported for sediment, soil, and air samples in previous studies. The chlordane EFs were generally close to the racemic value of 0.5, with CC values ranging from 0.493 to 0.527 (usually >0.5) and TC values from 0.463 to 0.53 (usually <0.5). EF changes with core depth were detected for TC and CC in some cores, with the most non-racemic values near the top of the core. Surficial and suspended sediments generally have EF values similar to the top core layers but are often more non-racemic, indicating that enantioselective degradation is occurring before soils are eroded and deposited into bottom sediments. We hypothesize that rapid losses (desorption or degradation) from suspended sediments of the more bioavailable chlordane fraction during transport and initial deposition could explain the apparent shift to more racemic EF values in surficial and top core sediments. Near racemic CC and TC in the core profiles suggest minimal alteration of chlordane from biotic degradation, unless it is via non-enantioselective processes. EF values for the heptachlor degradate, heptachlor epoxide (HEPX), determined in surficial sediments from one location only were always non-racemic (EF approximately 0.66), were indicative of substantial biotic processing, and followed reported EF trends.

Concentrations and chiral signatures of POPs in soils and sediments: a comparative urban versus rural study in Canada and UK.

Surface soils and sediments were collected in Toronto, Canada to investigate the concentrations and enantiomeric signatures of urban versus rural locations. Samples were analyzed for polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs). In soils, the sum of 10 PCB congeners (Sigma PCB 28, 52, 95, 101, 118, 136, 138, 149, 153, 180) and 15 PAHs (Sigma PAHs) ranged from 0.76-58 to 58-3200 ng g(-1), respectively. The most abundant OCs detected were DDTs, followed by chlordanes and endosulfans. Sigma PAHs exhibited an urban-rural gradient of up to 60 times but a gradient was not observed for Sigma PCBs and OCs which may reflect local sources of these chemicals. In sediments, Sigma PCBs and Sigma PAHs ranged from 0.03-23 ng g(-1) to 42-3300 ng g(-1), respectively. Sigma PCBs, Sigma PAHs, chlordanes and DDTs exhibited weak urban-rural gradients. Chiral signatures of PCB 95, 136, 149, trans-chlordane (TC), cis-chlordane (CC) and o,p-DDT were characterized to study the enantiomeric degradation in urban versus rural areas and its relation to contaminant levels. Supplementary to these data, we also report on the chiral signatures of PCBs in UK lake sediments from a variety of urban and rural locations. The extent of enantiomeric degradation was expressed as the enantiomeric excess (EE%) which is defined as 100x(E1-E2)/(E1+E2), where E1 is always the most abundant enantiomer and E2 is the least abundant enantiomer. The EE% of PCB 149 in the UK sediments was negatively correlated (p<0.05) with Sigma PAHs suggesting either more recent emissions of this PCB congener in the more contaminated urban locations and hence a more racemic signature or less enantiomeric degradation of the congener in more contaminated urban soils. However, no significant correlation was observed between EE% of any of the chiral chemicals and contaminant levels in the Toronto soils.

Biodegradability and toxicity assessment of trans-chlordane photochemical treatment.

The removal of trans-chlordane (C(10)H(6)Cl(8)) from aqueous solutions was studied using UV, UV/H(2)O(2), UV/H(2)O(2)/Fe(2+), UV/TiO(2), or UV/TiO(2)/H(2)O(2) treatment using either UV/Vis blue lamps or UVC lamps (254 nm). H(2)O(2), FeSO(4) and TiO(2) were added at 1700, 456, and 2500 mgL(-1), respectively. trans-Chlordane was not significantly removed in non-irradiated controls and in samples irradiated with UV/Vis. It was also not removed in the absence of surfactant Triton X-114 added at 250 mgL(-1). In the presence of the surfactant, trans-chlordane concentration was reduced by 95-100% after 48 h of UVC and UVC/H(2)O(2) treatments and 70-80% after UVC/H(2)O(2)/Fe(2+), UVC/TiO(2) and UVC/H(2)O(2)/TiO(2) treatments. Based on these results, UVC, UVC/H(2)O(2) and UVC/TiO(2) treatments were further investigated. UVC treatment supported the highest pollutant removal (100% in 48 h), dechlorination efficiency (81% in 48 h), and detoxification to Lepidium sativum seed germination and activated sludge respiration although irradiated samples remained toxic to Chlorella vulgaris. Biodegradation of the UVC irradiated samples removed the source of algae toxicity but this could not be clearly attributed to the removal of trans-chlordane photoproducts because the surfactant interfered with the chemical and biological assays. Evidence was found that trans-chlordane was photodegraded through photolysis causing its successive dechlorination. trans-Chlordane removal was well described by a first order kinetic model at a rate of 0.21±0.01h(-1) at the 95% confidence interval.

Measurement and modeling of diel variability of polybrominated diphenyl ethers and chlordanes in air.

Short-term variability of concentrations of polybrominated diphenyl ethers (PBDEs) and chlordanes in air at a semirural site in England over a 5 day period is reported. Four-hour air samples were collected during a period dominated by a high pressure system that produced stable diel (24-h) patterns of meteorological conditions such as temperature and atmospheric boundary layer height. PBDE and chlordane concentrations showed clear diel variability with concentrations in the afternoon and evening being 1.9 - 2.7 times higher than in the early morning. The measurements are interpreted using a multimedia mass balance model parametrized with forcing functions representing local temperature, atmospheric boundary layer height, wind speed and hydroxyl radical concentrations. Model results indicate that reversible, temperature-controlled air-surface exchange is the primary driver of the diel concentration pattern observed for chlordanes and PBDE 28. For higher brominated PBDE congeners (47, 99 and 100), the effect of variable atmospheric mixing height in combination with irreversible deposition on aerosol particles is dominant and explains the diel patterns almost entirely. Higher concentrations of chlordanes and PBDEs in air observed at the end of the study period could be related to likely source areas using back trajectory analysis. This is the first study to clearly document diel variability in concentrations of PBDEs in air over a period of several days. Our model analysis indicates that high daytime and low nighttime concentrations of semivolatile organic chemicals can arise from different underlying driving processes, and are not necessarily evidence of reversible air-surface exchange on a 24-h time scale.

Photodegradation fates of cis-chlordane, trans-chlordane, and heptachlor in ethanol.

cis-Chlordane, trans-chlordane, and heptachlor were photodegraded in ethanol, and their degradation fates and degradation products were determined by a computational chemical method. The most degradable material was heptachlor (first-order reaction constant k=0.13 min(-1)). Chlorine balances changed during UV irradiation, and the chlorine atoms in chlordane and heptachlor were eventually mineralized. cis-Chlordane, trans-chlordane and heptachlor each generated two di-dechlorinated products. Reactivities at various positions in these compounds were predicted on the basis of bond dissociation energies calculated by nonempirical molecular orbital calculation (Gaussian 98W).

The occurrence of organochlorines in marine avian top predators along a latitudinal gradient.

The aim of this study was to determine the role of cold condensation and fractionation on the occurrence of organochlorine contaminants (OCs) in avian marine top predators along a latitudinal gradient. We measured 24 polychlorinated biphenyl (PCB) congeners and six pesticide OCs in blood of great black-backed gulls (Larus marinus) from the Norwegian Coast (58 degrees N-70 degrees N) and glaucous gulls (Larus hyperboreus) from Bjornoya in the Norwegian Arctic (74 degrees N). Glaucous gulls had up to 3 times higher sigmaOC concentrations compared to the great black-backed gulls, and a OC pattern dominated largely by persistent and low volatile compounds such as highly chlorinated PCBs and metabolites such as oxychlordane. This was not consistent with cold condensation and fractionation theory, but probably related to diet and elevated biomagnification. Among great black-backed gulls, however, there were indications of both cold condensation and fractionation. Higher and lower chlorinated PCBs had highest absolute concentrations in the south and in the north, respectively, except for one location at an intermediate latitude, where concentrations of most OCs exceeded all other locations. In terms of proportional contribution to sigmaOC (pattern), relatively volatile OCs such as HCB, oxychlordane and tri- to penta- PCB congeners were more important at northern latitudes, while hexa- to nona-PCBs made up a larger proportion of sigmaOC in the south. The results thus showed that differences in global distribution of compounds with different physicochemical properties could be detected in avian top predators such as large gulls, even if biomagnification and biotransformation influence both the absolute concentrations and the patterns of OCs.

Chlordanes in the indoor and outdoor air of three U.S. cities.

Indoor and outdoor concentrations of six chlordane components (trans-chlordane, cis-chlordane, trans-nonachlor, cis-nonachlor, oxychlordane, and MC5) were measured at 157 residences, all of which were inhabited by nonsmoking individuals, in three urban areas during June 1999-May 2000. The analyses were conducted on a subset of 48 h integrated samples collected in Los Angeles County, CA, Houston, TX, and Elizabeth, NJ within the Relationship of Indoor, Outdoor, and Personal Air (RIOPA) study. Both particle-bound (PM2.5; quartz fiber filter) and vapor-phase (PUF sorbant) chlordane concentrations were separately measured by GC/EI MS after solvent extraction. The outdoor (gas + particle) total chlordane (trans-chlordane + cis-chlordane + trans-nonachlor + cis-nonachlor) concentrations ranged from 0.036 to 4.27 ng m(-3) in Los Angeles County, from 0.008 to 11.00 ng m(-3) in Elizabeth, and from 0.062 to 1.77 ng m(-3) in Houston. The corresponding indoor total chlordane concentrations ranged from 0.037 to 112.0 ng m(-3) in Los Angeles County, from 0.260 to 31.80 ng m(-3) in Elizabeth, and from 0.410 to 38.90 ng m(-3) in Houston study homes. Geometric mean concentrations were higher in indoor air than outdoor air (1.98 vs 0.58 ng m(-3) in CA; 1.30 vs 0.17 ng m(-3) in NJ; 4.18 vs 0.28 ng m(-3) in TX), which suggests there are significant indoor sources of chlordane species in a subset of homes in each of the three cities. Calculated source strengths relate to home age, with the highest apparent indoor source strengths occurring in unattached single-family homes built during the period from 1945 to 1959. Principle indoor sources of chlordanes likely include volatilization from residues of indoor application of chlordanes and infiltration from subsurface and foundation application of chlordane-containing termiticides during home construction.

Volatilization of weathered chiral and achiral chlordane residues from soil.

To mitigate the impact on the environment of persistent organic pollutants (POPs), we must understand thoroughly their environmental fate. Residues of many of these pollutants are still present in soil years after their legitimate uses were banned. In this report, the volatilization of one such persistent pollutant, chlordane, from a field where it was applied approximately 40 years ago, is examined in detail overthe course of several years. Ambient air samples were collected at three heights above the treated soil throughout the investigation. Air samples were also collected at several background sites in Connecticut for comparison. Analysis of these samples shows that chlordane volatilization from soil continues to occur long after initial application, at rates dependent on both temperature and cultivation of the soil. Comparison of relative concentrations and enantiomeric profiles for components of technical chlordane in atmospheric samples from a variety of sources suggests a regional, urban input of chlordane to the ambient air over Connecticut, possibly related to the widespread termiticidal use of chlordane in home foundation soils.

Tracking chlordane compositional and chiral profiles in soil and vegetation.

The cycling of chlordane and other persistent organic pollutants through the environment must be comprehensively elucidated to assess adequately the human health risks posed from such contaminants. In this study the compositional and chiral profiles of weathered chlordane residues in the soil and vegetative compartments were investigated in order to provide details of the fate and transport of this persistent pesticide. Zucchini was planted in a greenhouse in three bays containing chlordane-contaminated soil. At harvest the vegetation and soil were extracted and analyzed for chlordane content using chiral gas chromatography/ion trap mass spectrometry. Both achiral and chiral chlordane components were quantified. The chlordane concentration in the rhizosphere (soil attached to roots) was significantly less than that in the bulk soil. However, the enantiomeric ratio of the chiral components and overall component ratios had changed little in the rhizosphere relative to the bulk soil. Significant levels of chlordane were detected in the vegetation, the amount varying in different plant tissues from a maximum in roots to a minimum in fruit. In addition to the chlordane concentration gradient in plant tissues, significant shifts in compositional profile, as indicated by the component ratios, and in chiral profile, as indicated by the enantiomeric ratio, of the contaminant were observed in the plant tissues. The data indicate that abiotic processes dominate the transport of the chlordane components through the soil to the plant. This is the first report of the effect of rapid biotic processes within the plant compartment on chlordane compositional and chiral profiles.

Chlordane enantiomers and temporal trends of chlordane isomers in arctic air.

A 14-year data set (1984-1998) for chlordane compounds in arctic airwas examined to discern temporal trends. trans-Chlordane (TC), cis-chlordane (CC), and trans-nonachlor (TN) declined significantly (p < 0.001-0.02), with apparent times for 50% reduction of 4.9-9.7 y. The isomer fraction of TC = (TC/(TC + CC) also declined significantly (p < 0.001 -0.014) over the same time period. The enantiomeric composition of TC and CC was determined in air samples collected at arctic stations in Canada (1993-1996), Russia (1994), and Finland (1998), and a temperate station on the Swedish west coast (1998). Enantiomer fractions, EF = (+)/[(+) + (-)], were significantly different from measured EFs of racemic standards (0.498-0.501) at all stations for TC (p < 0.001) and two stations for CC (p < 0.001 to <0.05). These observations suggest changing source composition of chlordane in arctic air, with a greater proportion of weathered residues in recent years, possibly derived from soils. Identification of nonracemic (mean EFs = 0.662-0.703) heptachlor exo-epoxide (HEPX) at the four air stations further exemplifies contributions of soil emissions to long-range transport of chlordane-related compounds.