Characterization of substances released from crumb rubber material used on artificial turf fields.

Crumb rubber material (CRM) used as infill on artificial turf fields can be the source of a variety of substances released to the environment and to living organisms in the vicinity of the CRM. To assess potential risks of major volatilized and leached substances derived from CRM, methods were developed to identify organic compounds and elements, either in the vapor phase and/or the leachate from CRM. A qualitative method based on solid phase micro-extraction (SPME) coupled with gas chromatography/mass spectrometry (GC-MS) was developed to identify the major volatile and semi-volatile organic compounds out-gassing from CRM samples under defined laboratory conditions. Direct vapor phase injection into the GC-MS was applied for the quantitative analysis. Ten organic compounds were identified in the vapor phase by the SPME method. Volatile benzothiazole (BT) was detected at the highest level in all commercial CRM samples, in the range 8.2-69 ng g(-1) CRM. Other volatile PAHs and antioxidants were quantified in the vapor phase as well. A decrease of volatile compounds was noted in the headspace over CRM samples from 2-years-old fields when compared with the virgin CRM used at installation. An outdoor experiment under natural weathering conditions showed a significant reduction of out-gassing organic compounds from the CRM in the first 14 d; thereafter, values remained consistent up to 70 d of observation. Zinc was the most abundant element in the acidified leachate (220-13000 microg g(-1)), while leachable BT was detected at relatively low amounts.

Modeling the difference among Cucurbita in uptake and translocation of p,p'-dichlorophenyl-1,1-dichloroethylene.

Uptake of organic chemicals into plants depends on the properties of the contaminant and the physiology of the plant. A mass balance model based on fugacity was developed to quantify the uptake and transport in plants of a very hydrophobic chemical, p,p'-dichlorophenyl-1,1-dichloroethylene (DDE). The model included processes for sorption or influx of chemical with water from hydroponic solution to root and sorption or exchange of chemical between the shoot and air. Movement among compartments of the plant was governed by the transfer of water in xylem and phloem. The movement of water was entirely determined by transpiration, growth rate, and weight distribution among tissues. This model was used to predict the kinetics of uptake and movement of DDE from hydroponic solution by seedlings of two species of Cucurbitacea, cucumber and zucchini. These predictions were compared to the results of experiments in a companion paper. These experiments showed that the translocation of DDE in zucchini was much greater than in cucumber. The model correctly predicted the negligible uptake into the shoot of cucumber. The model predicted the greater uptake of DDE by zucchini only if the apparent partitioning of DDE in the xylem was 25-fold higher than that expected in pure water. Predictions using similar parameters were made for uptake and distribution of DDE for plants grown into fruit production in field soil contaminated with DDE. To match the observed concentration of DDE in fruit, the model coefficient for partitioning of DDE into water in phloem had to be increased to 200 times that in pure water.

Uptake and translocation of p,p'-dichlorodiphenyldichloroethylene supplied in hydroponics solution to Cucurbita.

Field studies show shoots of zucchini (Cucurbita pepo L.) accumulate various hydrophobic contaminants from soil, although many other plants do not, including cucumber (Cucumis sativus L.). To investigate the mechanism for this uptake, we presented p,p'-dichlorodiphenyldichloroethylene (DDE) to these two species in hydroponics solution. A mixture of DDE bound to Tenax beads stirred with a solution of water passing through a reservoir provided a flowing solution containing DDE at approximately 2 microg/L for many weeks duration. Approximately 90% of the DDE supplied in solution was adsorbed on the roots of both cucumber and zucchini. Less than 10% of the sorbed DDE was released subsequently when clean solution flowed past these contaminated roots for 9 d. The shoots of both species accumulated DDE, but the fraction that moved from the roots to the shoot in zucchini, ranging from 6 to 27% in various trials, was 10-fold greater than that in cucumber, 0.7 to 2%. The gradient in DDE concentration in zucchini tissues was in the order root more more than stem > petiole > leaf blade, indicating the movement was through the xylem in the transpiration stream. Some DDE in leaf blades might have been absorbed from the air, because the concentration in this tissue varied less with time, position in trough, or species, than did DDE in stems and petioles. The remarkable ability of zucchini to translocate DDE could not be attributed to differences in tissue composition, growth rate, distribution of weight among plant parts, or in the leaf area and rate of transpiration of water from leaves. Some other factor enables efficient translocation of hydrophobic organic contaminants in the xylem of zucchini.

Effect of mycorrhizal fungi on the phytoextraction of weathered p,p-DDE by Cucurbita pepo.

Field experiments were conducted to assess the impact of inoculation with mycorrhizal fungi on the accumulation of weathered p,p'-DDE from soil by three cultivars of zucchini (Cucurbita pepo spp. pepo cv Costata Romanesco, Goldrush, Raven). Three commercially available mycorrhizal products (BioVam, Myco-Vam, INVAM) were inoculated into the root system of the zucchini seedlings at planting. In agreement with our previous findings, plants not inoculated with fungi accumulated large but variable amounts of contaminant, with root bioconcentration factors (BCFs, ratio of p,p'-DDE, on a dry weight basis, in the root to that in the soil) ranging from 10 to 48 and stem BCFs ranging from 5.5 to 11. The total amount of contaminant phytoextracted during the 62 day growing season ranged from 0.72-2.9%. The effect of fungal inoculation on the release of weathered p,p'-DDE from soil and on the subsequent uptake of the parent compound by zucchini appeared to vary at the cultivar level. For Goldrush, fungal inoculation generally decreased tissue BCFs but because of slightly larger biomass, did not significantly impact the percent contaminant phytoextracted. Alternatively, for Costata, BioVam and Myco-Vam generally enhanced p,p'-DDE accumulation from soil, and increased the amount of contaminant phytoextracted by up to 34%. For Raven, BioVam reduced contaminant uptake whereas Myco-Vam and INVAM increased contaminant phytoextraction by 53 and 60%, respectively. The data show that fungal inoculation may significantly increase the remedial potential of C. pepo ssp. pepo. The apparent cultivar specific response to mycorrhizal inoculation is unexpected and the subject of ongoing investigation.

Soil amendments, plant age, and intercropping impact p,p'-DDE bioavailability to Cucurbita pepo.

Field experiments were conducted to optimize the phytoextraction of weathered p,p'-DDE (p,p'-dichlorodiphenyldichloroethylene) by Cucurbita subspecies. The effects of two soil amendments, mycorrhizae or a biosurfactant, on p,p'-DDE accumulation was determined. Also, p,p'-DDE uptake was assessed during plant growth (12, 26, 38, and 62 d), and cultivars that accumulate weathered p,p'-DDE were intercropped with cultivars known not to have that ability. Cucurbita pepo L. ssp. pepo accumulated large amounts of the contaminant, having stem bioconcentration factors, amounts of p,p'-DDE translocated, and contaminant phytoextraction that were 14, 9.9, and 5.0 times greater than C. pepo L. ssp. ovifera (L.) D.S. Decker, respectively. During 62 d, the stem BCF (bioconcentration factor) for p,p'-DDE in subspecies pepo remained constant and the total amount of contaminant accumulated was correlated with plant biomass (r(2) = 0.86). For subspecies ovifera, the stem BCF was highest at 12 d (1.5) but decreased to 0.39 by 62 d, and p,p'-DDE removal was not correlated with plant biomass. Mycorrhizal inoculation increased p,p'-DDE accumulation by both subspecies by an average 4.4 times. For subspecies pepo, mycorrhizae increased the percentage of contaminant extracted from 0.72 to 2.1%. Biosurfactant amendment also enhanced contaminant accumulation by both subspecies, although treatment reduced subspecies ovifera biomass by 60%. The biosurfactant had no effect on the biomass of subspecies pepo, increased the average contaminant concentration by 3.6-fold, and doubled the overall amount of p,p'-DDE removed from the soil. Soil amendments that enhance the mobility of weathered persistent organic pollutants will significantly increase the amount of contaminant phytoextraction by Cucurbita pepo.

Influence of citric acid amendments on the availability of weathered PCBs to plant and earthworm species.

A series of small and large pot trials were conducted to assess the phytoextraction potential of several plant species for weathered polychlorinated biphenyls (PCBs) in soil (105 microg/g Arochlor 1268). In addition, the effect of citric acid on PCB bioavailability to both plants and earthworms was assessed. Under small pot conditions (one plant, 400 g soil), three cucurbits (Cucurbita pepo ssp pepo [zucchini] and ssp ovifera [nonzucchini summer squash], Cucumis sativus, cucumber) accumulated up to 270 microg PCB/g in the roots and 14 microg/g in the stems, resulting in 0.10% contaminant removal from soil. Periodic 1 mM subsurface amendments of citric acid increased the stem and leaf PCB concentration by 330 and 600%, respectively, and resulted in up to a 65% increase in the total amount of contaminant removed from soil. Although citric acid at 10 mM more than doubled the amount of PCB desorbed in abiotic batch slurries, contaminant accumulation by two earthworm species (Eisenia foetida and Lumbricus terrestris) was unaffected by citric acid at 1 and 10 mM and ranged from 11-15 microg/g. Two large pot trials were conducted in which cucurbits (C. pepo ssp pepo and ssp ovifera, C. sativus) and white lupin (Lupinus albus) were grown in 70 kg of PCB-contaminated soil White lupin was the poorest accumulator of PCBs, with approximately 20 microg/g in the roots and 1 microg/g in the stems. Both C. pepo ssp ovifera (summer squash) and C. sativus (cucumber) accumulated approximately 65-100 microg/g in the roots and 6-10 microg/g in the stems. C. pepo ssp pepo (zucchini) accumulated significantly greater levels of PCB than all other species, with 430 microg/g in the roots and 22 microg/g in the stems. The mechanism by which C. pepo spp pepo extracts and translocates weathered PCBs is unknown, but confirms earlier findings on the phytoextraction of other weathered persistent organic pollutants such as chlordane, p,p'-DDE, and polycyclic aromatic hydrocarbons.

Uptake by cucurbitaceae of soil-Bome contaminants depends upon plant genotype and pollutant properties.

Three Cucurbitaceae, Cucurbita pepo L. subsp. pepo (cv. Black Beauty, true zucchini), Cucurbita pepo L. intersubspecific cross (cv. Zephyr, summer squash), and Cucumis sativis (cv. Marketmore, cucumber), were grown in rhizotrons containing soil contaminated with three classes of highly weathered, hydrophobic organic contaminants: (1) technical chlordane, (2) dichlorodiphenylethanes (DDT and DDD) and -ethene (DDE), (3) polyaromatic hydrocarbons (PAHs), and heavy metal residues. Movement of the contaminants through the soil/plant system was studied by comparing contaminant concentration in the bulk soil, the rhizosphere soil pore water, the xylem sap, and aerial tissue. This permitted, for the first time, calculation of bioconcentration factors (BCFs) based on concentration in the xylem sap versus that in the rhizosphere soil pore water. The bioconcentration factors so determined for the sum of five chlordane residues (two enantiomers of trans-chlordane, TC; two enantiomers of cis-chlordane, CC; and achiral trans-nonachlor, TN) were 36, 40, and 23 for Black Beauty, Zephyr, and Marketmore, respectively. In addition, the xylem sap of each cultivar had a consistent enantioselective profile for some of the chiral chlordane components. For the sum of dichlorodiphenylethanes and -ethene, comparable BCF values were 19, 4, and 0.8, respectively. In the case of PAHs, different BCF patterns among the cultivars were noted for three- versus four-ring compounds. Similarly, movement of heavy metals was cultivar-dependent, with cadmium BCF values 9.5, 3.5, and 0.6for Black Beauty, Zephyr, and Marketmore, respectively; the analogous BCFs for zinc were 9, 11, and 2. Thus, passage from ex planta to in planta regions of the soil/plant system is dependent not only on properties of the plant, but also on those of the pollutant. Such data will provide insight into transport mechanisms of highly hydrophobic organic contaminants, as well as heavy metal contaminants, in the soil/plant system.

Accumulation of weathered polycyclic aromatic hydrocarbons (PAHs) by plant and earthworm species.

Experiments were conducted to assess the bioavailability of polyclycic aromatic hydrocarbons (PAHs) in soil from a Manufactured Gas Plant site. Three plant species were cultivated for four consecutive growing cycles (28 days each) in soil contaminated with 36.3 microg/g total PAH. During the first growth period, Cucurbita pepo ssp. pepo (zucchini) tissues contained significantly greater quantities of PAHs than did Cucumis sativus (cucumber) and Cucurbita pepo ssp. ovifera (squash). During the first growth cycle, zucchini plants accumulated up to 5.47 times more total PAH than did the other plants, including up to three orders of magnitude greater levels of the six ring PAHs. Over growth cycles 2-4, PAH accumulation by zucchini decreased by 85%, whereas the uptake of the contaminants by cucumber and squash remained relatively constant. Over all four growth cycles, the removal of PAHs by zucchini was still twice that of the other species. Two earthworm species accumulated significantly different amounts of PAH from the soil; Eisenia foetida and Lumbricus terrestris contained 0.204 and 0.084 microg/g total PAH, respectively, but neither species accumulated measurable quantities 5 or 6 ring PAHs. Lastly, in abiotic desorption experiments with an aqueous phase of synthetically prepared organic acid solutions, the release of 3 and 4 ring PAHs from soil was unaffected by the treatments but the desorption of 5-6 ring constituents was increased by up to two orders of magnitude. The data show that not only is the accumulation of weathered PAHs species-specific but also that the bioavailability of individual PAH constituents is highly variable.

Influence of nutrient amendments on the phytoextraction of weathered 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene by cucurbits.

Field experiments were conducted to determine the impact of nutrient amendments on the phytoextraction of weathered 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene (p,p '-DDE) by eight cultivars of cucurbits over a single growing season. Four cultivars of Cucurbita pepo ssp pepo are accumulators and extract percent level quantities of persistent organic pollutants (POPs), whereas C. pepo ssp ovifera and Cucumis sativus are nonaccumulators. The nonamended accumulators phytoextracted 1.0% of the p,p'-DDE and had a translocation factor of 0.44; however, the nonaccumulators removed 0.16% of the contaminant and had a translocation factor value of 0.09. The accumulators also had 3.8 times greater inorganic element content than the nonaccumulators. Duplicate mounds of each cultivar also received weekly nutrient amendments of phosphorus (400 mg/L K2HPO4), nitrogen (200 mg/L KNO3), or nitrogen/phosphorus (400 mg/L K2HPO4, 200 mg/L KNO3); a minus phosphorus treatment involved a 1-L addition of 1 g/L AlSO4 to the soil before planting. When normalized to respective control values (unamended vegetation), the root and stem p,p'-DDE bioconcentration factors (BCF) of the accumulator cultivars were significantly greater than those of the nonaccumulator cultivars under most nutrient regimes. The biomass of accumulator cultivars decreased by up to 61% under certain nutrient regimes, resulting in mixed effects on the amount of p,p'-DDE extracted. Treatment with N and P increased nonaccumulator biomass by 40 to 100%, and increased p,p'-DDE extraction from soil by 75%. Although generally assumed that fertilizer amendments will enhance phytoremediation, as evidenced here by the nonaccumulators, additions of macronutrients may reduce the phytoextraction of weathered POPs by C. pepo ssp pepo. These findings support our hypothesis that the ability of C. pepo ssp pepo to remove sequestered organic contaminants is governed by unique nutrient-acquisition mechanisms.

Plant uptake and translocation of highly weathered, soil-bound technical chlordane residues: data from field and rhizotron studies.

It has been observed that plants are susceptible to uptake from soil and in planta transport of technical chlordane, in spite of its hydrophobicity and sequestration within the soil matrix due to weathering. Field and rhizotron studies were conducted with Cucurbitaceae planted in highly weathered, chlordane-contaminated soil to investigate details of soil-to-plant contaminant uptake. In the field-work, Cucurbita pepo L. (zucchini) was grown in soil at four levels of chlordane contamination: Clean (

Phytoextraction of weathered p,p'-DDE by zucchini (Cucurbita pepo) and cucumber (Cucumis sativus) under different cultivation conditions.

Previous studies have shown that zucchini (Cucurbita pepo) and cucumber (Cucumis sativus) under field conditions are good and poor accumulators, respectively, of persistent organic pollutants from soil. Here, each species was grown under three cultivation regimes: dense (five plants in 5 kg soil): nondense (one plant in 80 kg soil): and field conditions (two to three plants in approximately 789 kg soil). p,p'-DDE and inorganic element content in roots, stems, leaves, and fruit were determined. In addition. rhizosphere, near-root, and unvegetated soil fractions were analyzed for concentrations of 11 low-molecular-weight organic acids (LMWOA) and 14 water-extractable inorganic elements. Under field conditions, zucchini phytoextracted 1.3% of the weathered p,p'-DDE with 98% of the contaminant in the aerial tissues. Conversely, cucumber removed 0.09% of the p,p'-DDE under field conditions with 83% in the aerial tissues. Under dense cultivation, cucumber produced a fine and fibrous root system not observed in our previous experiments and phytoextracted 0.78% of the contaminant, whereas zucchini removed only 0.59% under similar conditions. However. cucumber roots translocated only 5.7% of the pollutant to the shoot system, while in zucchini 48% of the p,p'-DDE in the plant was present in the aerial tissue. For each species, the concentrations of LMWOA in soil increased with increasing impact by the root system both within a given cultivation regime (i.e., rhizosphere > near-root > unvegetated) and across cultivation regimes (i.e., dense > nondense > field conditions). Under dense cultivation, the rhizosphere concentrations of LMWOAs were significantly greater for cucumber than for zucchini; no species differences were evident in the other two cultivation regimes. To enable direct comparison across cultivation regimes, total in planta p,p'-DDE and inorganic elements were mass normalized or multiplied by the ratio of plant mass to soil mass. For cucumber, differences in total p,p'-DDE and inorganic element content among the cultivation regimes largely disappear upon mass normalization, indicating that greater uptake of both types of constituents in the dense condition is due to greater plant biomass per unit soil. Conversely, for zucchini the mass normalized content of p,p'-DDE and inorganic elements is up to two orders of magnitude greater under field conditions than under dense cultivation, indicating a unique physiological response of C. pepo in the field. The role of cultivation conditions and nutrient availability in controlling root morphology, organic acid exudation, and contaminant uptake is discussed.

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.

Subspecies-level variation in the phytoextraction of weathered p,p'-DDE by Cucurbita pepo.

Previous studies indicate that Cucurbita pepo can phytoextract highly weathered persistent organic pollutants (POPs) from soil and translocate large quantities to aerial tissues. To investigate intraspecific variability in uptake potential, a field study was conducted to quantify the phytoextraction of weathered p,p'-DDE by 21 cultivar varieties of summer squash from two distinct subspecies, C. pepo ssp texana and C. pepo ssp pepo. Significant differences exist between the two subspecies, with average root and stem to soil bioconcentration factors (BCF, dry weight ratio of contaminant concentration in the vegetation to that in the soil) of 7.22 and 5.40 for ssp pepo and of 2.37 and 0.454 for spp texana, respectively. The amounts of weathered p,p-DDE extracted from the soil by ssp pepo and ssp texana were 0.301 and 0.065%, respectively, with maximum values within each subspecies of 0.780 and 0.182%, respectively. The quantities of 14 inorganic elements were determined in both the soil and tissues (roots, stems, leaves, and fruit) of all 21 cultivar varieties. Phosphorus concentrations in the tissues of ssp pepo were 14 (fruit)-73% (stems) greater than those of ssp texana. These data support our hypothesis that the unique ability of certain cultivars of C. pepo to phytoextract highly weathered POPs from soil is the result of low molecular weight organic acid exudation as a unique phosphorus acquisition mechanism.

Plant uptake and translocation of air-borne chlordane and comparison with the soil-to-plant route.

In order to assess fully the impact of persistent organic pollutants (POPs) on human health, pollutant exchange at the interface between terrestrial plants, in particular food crops, and other environmental compartments must be thoroughly understood. In this regard, transfers of multicomponent and chiral pollutants are particularly informative. In the present study, zucchini (Cucurbita pepo L.) was planted in containerized, uncontaminated soil under both greenhouse and field conditions and exposed to air-borne chlordane contamination at 14.0 and 0.20 ng/m(3) (average, greenhouses), and 2.2 ng/m(3) (average, field). Chiral gas chromatography interfaced to an ion trap mass spectrometer was used to determine the chiral (trans-chlordane, TC, and cis-chlordane, CC) and achiral (trans-nonachlor, TN) chlordane components in vegetation, air, and soil compartments. The chlordane components of interest were detected in all vegetation tissues examined--root, stem, leaves, and fruits. When compared with the data from a soil-to-plant uptake study, the compositional profile of the chlordane components, i.e. the component fractions of TC, CC, and TN, in plant tissues, showed significantly different patterns between the air-to-plant and soil-to-plant pathways. Changes in the enantiomer fractions of TC and CC in plant tissues relative to the source, i.e. air or soil, although observed, were not markedly different between the two routes. This report provides the first comprehensive comparison between two distinct plant uptake routes for POPs and their subsequent translocation within plant tissues.

Role of organic acids in enhancing the desorption and uptake of weathered p,p'-DDE by Cucurbita pepo.

Experiments were conducted to assess the effect of seven organic acids [succinic, tartaric, malic, malonic, oxalic, citric, ethylene-diaminetetraacetic (EDTA)] over a concentration range of two orders of magnitude (0.001-0.10 M) on the abiotic desorption of weathered p,p'-DDE and the extraction of polyvalent inorganic ions from soil. At 0.05 M all organic acids significantly increased contaminant desorption by 19-80%. Organic acids also increased the aqueous concentration of eight inorganic constituents extracted from soil, with at least a six-fold increase in the release of Al, Fe, Mn, and P at 0.001 M. Zucchini seedlings grown for 28 d in soil containing weathered p,p'-DDE (300 ng/g, dry weight) were periodically amended with distilled water, citric or oxalic acids (0.01 M). Plants receiving water removed 1.7% of the p,p'-DDE from the soil. Seedlings amended with citric or oxalic acids removed 2.1 and 1.9% of the contaminant, respectively, and contained up to 66% more contaminant in the shoot system than unamended vegetation. A second crop of untreated (distilled water) zucchini in the same soil removed more contaminant than the first crop (2.5%), although the addition of organic acids did not further enhance contaminant uptake. The data indicate that the addition of low molecular weight organic acids causes the partial dissolution of the soil structure through the chelation of inorganic structural ions, potentially enhancing bioavailability and having implications for the phytoremediation of persistent organic pollutants in soil.

Persistent organic pollutants in the environment: chlordane residues in compost.

The half-lives of some persistent organic pollutants (POPs) in environmental compartments such as soil and air can be as long as decades. In spite of the hydrophobicity of many POPs, the literature contains reports of their uptake by, and translocation through, a variety of plants. Both these observations prompt the investigation of whether a vegetation-based environmental compartment such as compost contains significant residues of POPs. Previous reports imply that residues of technical chlordane will be found in compost. Due to its physicochemical properties, technical chlordane provides insights into the fate of POPs in the environment, which are not accessible through determinations of other pollutants in this group. Accordingly, we undertook the first comprehensive examination of technical chlordane residues in a variety of composts, specifically, 13 commercial and 39 municipal compost products, to both characterize and quantify the magnitude of this point source of contamination. Using chiral gas chromatography interfaced to ion trap mass spectrometry, the concentration and the compositional and enantiomeric profiles of chlordane components were determined. Of the 13 commercial products, 9 contained detectable chlordane concentrations, ranging from 4.7 to 292 microg/kg (dry wt.), while all 39 municipal products contained chlordane residues ranging from 13.9 to 415 microg/kg (dry wt.). The residue concentrations and profiles suggest possible feedstock sources for the chlordane in the finished compost product. The data also support the conclusion that some composts contribute to anthropogenic cycling of POPs through the biosphere.

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.

Cycling of weathered chlordane residues in the environment: compositional and chiral profiles in contiguous soil, vegetation, and air compartments.

Technical chlordane, a synthetic organic pesticide composed of 147 separate components, some of which exhibit optical activity, was used as an insecticide, herbicide, and termiticide prior to all uses being banned in the United States in 1988. It has been shown that food crops grown in soil treated decades earlier with technical chlordane translocate the weathered chlordane residues from the soil into root and aerial plant tissues. A rigorous analytical method is presented for the simultaneous, quantitative determination of both achiral and chiral components of technical chlordane in soil, plant, and air compartments using chiral gas chromatography interfaced to ion trap mass spectrometry and internal standard calibration. Using this method, we have observed differences in both the absolute and the relative amounts of trans- and cis-chlordane enantiomers and achiral trans-nonachlor between the soil compartment and various plant tissue compartments for several field-grown food crops. Changes in the relative amounts of the (+) and (-) enantiomers of trans- and cis-chlordane indicate enantioselective processes are in effect in the contiguous compartments of soil, plant roots, and aerial plant tissues. The data for zucchini (Cucurbita pepo L.), in particular, show an approximate fivefold enhancement in absolute concentration for total trans-chlordane, an eightfold concentration enhancement for total cis-chlordane, and a 2.5-fold enhancement for trans-nonachlor in the root relative to the soil matrix, the largest enhancements of any crop studied. This is the first comprehensive report of enantioselective processes into and through plant tissues for a variety of field-grown food crops. The selectivity will be related to observed insect toxicities of the enantiomers.