Pesticide Contamination in Native North American Crops, Part II-Comparison of Flower, Honey Bee Workers, and Native Bee Residues in Lowbush Blueberry.

In lowbush blueberry fields, we conducted residue analysis comparing flowers, trapped pollen (honey bee and Osmia spp.), and collected bees (honey bee workers, bumble bee queens, and non-Bombus spp. wild native bees). The study was conducted from 2012 to 2014. The number of pesticide residues, total concentrations, and risk to honey bees (Risk Quotient) on flowers were not significantly different from those determined for trapped honey bee pollen (except in one study year when residues detected in flower samples were significantly lower than residue numbers detected in trapped pollen). The compositions of residues were similar on flowers and trapped pollen. The number of residues detected in honey bee pollen was significantly greater than the number detected in Osmia spp. pollen, while the total concentration of residue was not different between the two types of pollen. The risk to honey bees was higher in trapped honey bee pollen than in trapped Osmia spp. pollen. The analysis of honey bee workers, native bumble bee queens, and native solitary bees showed that although more pesticide residues were detected on honey bee workers, there were no differences among the bee taxa in total residue concentrations or risk (as estimated in terms of risk to honey bees).

Pesticide Contamination in Native North American Crops, Part I-Development of a Baseline and Comparison of Honey Bee Exposure to Residues in Lowbush Blueberry and Cranberry.

A pesticide exposure baseline for honey bees was compiled for two New England cropping systems, the native North American plant species consisting of lowbush blueberry (Vaccinium angustifolium Aiton) and cranberry (Vaccinium macrocarpon Aiton). More unique pesticide compounds were applied in blueberry than cranberry, but the numbers of pesticides discovered in trapped honey bee pollen were similar between the two crop systems. Not all pesticides found in pollen were the result of the applications reported by growers of either crop. When comparing residues, number of pesticides detected, total concentration, and risk quotient varied between the two crops. Also, blueberry was dominated by fungicides and miticides (varroacides) and cranberry was dominated by insecticides and herbicides. When comparing reported grower applications that were matched with detection in residues, the proportion of pesticide numbers, concentrations, and risk quotients varied by crop system and pesticide class. In most cases, pesticide residue concentrations were of low risk (low risk quotient) to honey bees in these crops. Estimation of decay rates of some of the most common pesticide residues under field conditions could aid growers in selection of less persistent compounds, together with safe application dates, prior to bringing in honey bees for pollination.

Enzyme- and Relative Humidity-Responsive Antimicrobial Fibers for Active Food Packaging.

Active food packaging materials that are sustainable, biodegradable, and capable of precise delivery of antimicrobial active ingredients (AIs) are in high demand. Here, we report the development of novel enzyme- and relative humidity (RH)-responsive antimicrobial fibers with an average diameter of 225 ± 50 nm, which can be deposited as a functional layer for packaging materials. Cellulose nanocrystals (CNCs), zein (protein), and starch were electrospun to form multistimuli-responsive fibers that incorporated a cocktail of both free nature-derived antimicrobials such as thyme oil, citric acid, and nisin and cyclodextrin-inclusion complexes (CD-ICs) of thyme oil, sorbic acid, and nisin. The multistimuli-responsive fibers were designed to release the free AIs and CD-ICs of AIs in response to enzyme and RH triggers, respectively. Enzyme-responsive release of free AIs is achieved due to the degradation of selected polymers, forming the backbone of the fibers. For instance, protease enzyme can degrade zein polymer, further accelerating the release of AIs from the fibers. Similarly, RH-responsive release is obtained due to the unique chemical nature of CD-ICs, enabling the release of AIs from the cavity at high RH. The successful synthesis of CD-ICs of AIs and incorporation of antimicrobials in the structure of the multistimuli-responsive fibers were confirmed by X-ray diffraction and Fourier transform infrared spectrometry. Fibers were capable of releasing free AIs when triggered by microorganism-exudated enzymes in a dose-dependent manner and releasing CD-IC form of AIs in response to high relative humidity (95% RH). With 24 h of exposure, stimuli-responsive fibers significantly reduced the populations of foodborne pathogenic bacterial surrogates Escherichia coli (by ∼5 log unit) and Listeria innocua (by ∼5 log unit), as well as fungi Aspergillus fumigatus (by >1 log unit). More importantly, the fibers released more AIs at 95% RH than at 50% RH, which resulted in a higher population reduction of E. coli at 95% RH. Such biodegradable, nontoxic, and multistimuli-responsive antimicrobial fibers have great potential for broad applications as active and smart packaging systems.

Multilaboratory Collaborative Study of a Nontarget Data Acquisition for Target Analysis (nDATA) Workflow Using Liquid Chromatography-High-Resolution Accurate Mass Spectrometry for Pesticide Screening in Fruits and Vegetables.

Nontarget data acquisition for target analysis (nDATA) workflows using liquid chromatography-high-resolution accurate mass (LC-HRAM) spectrometry, spectral screening software, and a compound database have generated interest because of their potential for screening of pesticides in foods. However, these procedures and particularly the instrument processing software need to be thoroughly evaluated before implementation in routine analysis. In this work, 25 laboratories participated in a collaborative study to evaluate an nDATA workflow on high moisture produce (apple, banana, broccoli, carrot, grape, lettuce, orange, potato, strawberry, and tomato). Samples were extracted in each laboratory by quick, easy, cheap, effective, rugged, and safe (QuEChERS), and data were acquired by ultrahigh-performance liquid chromatography (UHPLC) coupled to a high-resolution quadrupole Orbitrap (QOrbitrap) or quadrupole time-of-flight (QTOF) mass spectrometer operating in full-scan mass spectrometry (MS) data-independent tandem mass spectrometry (LC-FS MS/DIA MS/MS) acquisition mode. The nDATA workflow was evaluated using a restricted compound database with 51 pesticides and vendor processing software. Pesticide identifications were determined by retention time (tR, ±0.5 min relative to the reference retention times used in the compound database) and mass errors (δM) of the precursor (RTP, δM ≤ ±5 ppm) and product ions (RTPI, δM ≤ ±10 ppm). The elution profiles of all 51 pesticides were within ±0.5 min among 24 of the participating laboratories. Successful screening was determined by false positive and false negative rates of <5% in unfortified (pesticide-free) and fortified (10 and 100 µg/kg) produce matrices. Pesticide responses were dependent on the pesticide, matrix, and instrument. The false negative rates were 0.7 and 0.1% at 10 and 100 µg/kg, respectively, and the false positive rate was 1.1% from results of the participating LC-HRAM platforms. Further evaluation was achieved by providing produce samples spiked with pesticides at concentrations blinded to the laboratories. Twenty-two of the 25 laboratories were successful in identifying all fortified pesticides (0-7 pesticides ranging from 5 to 50 µg/kg) for each produce sample (99.7% detection rate). These studies provide convincing evidence that the nDATA comprehensive approach broadens the screening capabilities of pesticide analyses and provide a platform with the potential to be easily extended to a larger number of other chemical residues and contaminants in foods.

Effects of the neonicotinoid acetamiprid in syrup on Bombus impatiens (Hymenoptera: Apidae) microcolony development.

Worldwide, many pollinator populations are in decline. Population reductions have been documented for the agriculturally important honey bee (Apis mellifera), and other bee species such as bumble bees that are also critical for pollinating crops and natural landscapes. A variety of factors contribute to the observed population reductions, including exposure to agrochemicals. In recent decades, neonicotinoid pesticide use has dramatically increased, as have concerns regarding the safety of these chemicals for pollinator health. Here we assessed the toxicity of the neonicotinoid acetamiprid to the bumble bee Bombus impatiens, a species commercially available for use in agricultural settings in North America. Using the microcolony model, we examined nest growth, development and subsequent nest productivity as measured by drone production. We found that high concentrations of acetamiprid in syrup (11,300 µg/L) significantly impacted nest growth and development, and ultimately drone production, and exposure to 1,130 µg/L acetamiprid also significantly decreased drone production. The no observable adverse effect level was 113 µg/L. Overall, acetamiprid delivered in syrup can negatively impact B. impatiens nest development and productivity, however only at concentrations above which would be expected in the environment when used according to label rates.

Tracking Pesticide Residues to a Plant Genus Using Palynology in Pollen Trapped from Honey Bees (Hymenoptera: Apidae) at Ornamental Plant Nurseries.

Worldwide studies have used the technique of pollen trapping, collecting pollen loads from returning honey bee (Apis mellifera L.) (Hymenoptera: Apidae) foragers, to evaluate the exposure of honey bees to pesticides through pollen and as a biomonitoring tool. Typically, these surveys have found frequent contamination of pollen with multiple pesticides, with most of the estimated risk of acute oral toxicity to honey bees coming from insecticides. In our survey of pesticides in trapped pollen from three commercial ornamental plant nurseries in Connecticut, we found most samples within the range of acute toxicity in a previous state pollen survey, but a few samples at one nursery with unusually high acute oral toxicity. Using visual sorting by color of the pollen pellets collected in two samples from this nursery, followed by pesticide analysis of the sorted pollen and palynology to identify the plant sources of the pollen with the greatest acute toxicity of pesticide residues, we were able to associate pollen from the plant genus Spiraea L. (Rosales: Rosaceae) with extraordinarily high concentrations of thiamethoxam and clothianidin, and also with high concentrations of acephate and its metabolite methamidophos. This study is the first to trace highly toxic pollen collected by honey bees to a single plant genus. This method of tracking high toxicity pollen samples back to potential source plants could identify additional high-risk combinations of pesticide application methods and timing, movement into pollen, and attractiveness to bees that would be difficult to identify through modeling each of the contributing factors.

Co-exposure to the food additives SiO2 (E551) or TiO2 (E171) and the pesticide boscalid increases cytotoxicity and bioavailability of the pesticide in a tri-culture small intestinal epithelium model: Potential health implications.

Many toxicity investigations have evaluated the potential health risks of ingested engineered nanomaterials (iENMs); however, few have addressed the potential combined effects of iENMs and other toxic compounds (e.g. pesticides) in food. To address this knowledge gap, we investigated the effects of two widely used, partly nanoscale, engineered particulate food additives, TiO2 (E171) and SiO2 (E551), on the cytotoxicity and cellular uptake and translocation of the pesticide boscalid. Fasting food model (phosphate buffer) containing iENM (1% w/w), boscalid (10 or 150 ppm), or both, was processed using a simulated in vitro oral-gastric-small intestinal digestion system. The resulting small intestinal digesta was applied to an in vitro tri-culture small intestinal epithelium model, and effects on cell layer integrity, viability, cytotoxicity and production of reactive oxygen species (ROS) were assessed. Boscalid uptake and translocation was also quantified by LC/MS. Cytotoxicity and ROS production in cells exposed to combined iENM and boscalid were greater than in cells exposed to either iENM or boscalid alone. More importantly, translocation of boscalid across the tri-culture cellular layer was increased by 20% and 30% in the presence of TiO2 and SiO2, respectively. One possible mechanism for this increase is diminished epithelial cell health, as indicated by the elevated oxidative stress and cytotoxicity observed in co-exposed cells. In addition, analysis of boscalid in digesta supernatants revealed 16% and 30% more boscalid in supernatants from samples containing TiO2 and SiO2, respectively, suggesting that displacement of boscalid from flocculated digestive proteins by iENMs may also contribute to the increased translocation.

Exposure of Honey Bee (Apis mellifera L.) Colonies to Pesticides in Pollen, A Statewide Assessment in Maine.

In 2015, we conducted a statewide assessment of honey bee exposure to pesticides with assistance of volunteer beekeepers. Pollen trapping was conducted at 32 sites in the spring, summer, and early fall. Apiary locations ranged from unmanaged natural landscapes to managed agricultural or urban landscapes. Pollen samples at each site were aggregated over the collection dates and chemical residue analysis was conducted on each pollen sample for 190 pesticides and metabolites using HPLC/MS. Twenty-five different residues were detected for an average of 2.9 detections per site. Detections were dominated by fungicides, but risk, calculated as: ppb residue concentration/LD50, was mostly due to insecticides. Beekeeper perceived land-use in the vicinity of each apiary was associated with significant differences in the number of detections and residue concentrations, agricultural landscapes greater than nonagricultural. However, there was no significant difference in oral or contact risk quotients due to land-use type. The landscape composition surrounding apiaries, derived with GIS, determined pesticide exposure for honey bees when total detections, log pesticide residue concentration, and log contact risk quotients were used as measures. Partial least squares explained 43.9% of the variance in pesticide exposure due to landscape composition. The best predictors describing pesticide exposure were: area (ha) of blueberry, coniferous forest, and urban/developed land cover types. Maine is the most forested state in the United States (as determined by % land area forested, 93%) and a negative exponential decay was observed between land area in conifer forest and the number of pesticide detections per apiary.

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.

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.

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.

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.

Correction: Using a Hazard Quotient to Evaluate Pesticide Residues Detected in Pollen Trapped from Honey Bees (Apis mellifera) in Connecticut.

[This corrects the article DOI: 10.1371/journal.pone.0077550.].

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.

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.

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.

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.

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 (

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.