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.     

Organochlorine pesticides in the ambient air of Chiapas, Mexico

Organochlorine (OC) pesticides were measured in the ambient air of Chiapas, Mexico during 2000-2001. Concentrations of some OC pesticides (DDTs, chlordanes, toxaphene) were elevated compared with levels in the Great Lakes region, while those of other pesticides were not (hexachlorocyclohexanes, dieldrin). While this suggests southern Mexico as a source region for the former group of chemicals, comparably high levels have also been reported in parts of the southern United States, where their suspected sources are soil emissions (DDTs, toxaphene) and termiticide usage (chlordane). Ratios of p,p'-DDT/p,p'-DDE and trans-chlordane/cis-chlordane/trans-nonachlor (TC/CC/TN) in Chiapas suggest a mixture of fresh and weathered sources, while congener profiles of toxaphene suggest emission of old residues from soils. This is supported by air parcel back trajectory analysis, which indicated that air masses over Chiapas at the time of sampling had previously passed over areas of continuing or recent use of some OC pesticides as well as areas of past use.     

Chlordane components and metabolites in seven species of Arctic seabirds from the Northwater Polynya: relationships with stable isotopes of nitrogen and enantiomeric fractions of chiral components

The Northwater Polynya (NOW) is a large area of year-round open water found in the high Arctic between Ellesmere Island and Greenland. NOW has high biological productivity compared with other arctic marine areas, and supports large populations of several seabird species. Seven species of seabirds, dovekie (Alle alle, DOVE), thick-billed murre (Uria lomvia, TBMU), black guillemot (Cepphus grylle, BLGU), black-legged kittiwake (Rissa tridactyla, BLKI), ivory gull (Pagophila eburnea, IVGU), glaucous gull (Larus hyperboreus, GLGU) and northern fulmar (Fulmaris glacialis, NOFU) were collected in May and June 1998 to determine chlordane concentrations in liver and fat and to examine species differences, relationships with stable isotopes of nitrogen, and enantiomeric fractions (EFs) of chiral components. sigma CHLOR concentrations varied over an order of magnitude among species, from a low of 176 +/- 19 ng/g (lipid corrected) in TMBU liver to a high of 3190 +/- 656 ng/g (lipid corrected) in NOFU liver. Lipid-corrected concentrations of chlordane did not vary between sex for any species or between fat and liver except for the DOVE, that had fat concentrations that were significantly greater than the liver. delta 15N values described a significant percentage of the variability of concentrations for most chlordane components, although less than what has been reported for whole food chains. Slopes of delta 15N versus concentration of chlordane components and sigma CHLOR were similar with the exception of those which were metabolized (trans-chlordane) or formed through biotransformation (oxychlordane). The relative proportions of chlordane components in seabirds were related to phylogeny; the procellariid (NOFU) had the greatest percentage of oxychlordane (> 70%), followed by the larids (BLKI, IVGU and GLGU; 40-50%) and the alcids (DOVE and BLGU; 10-20%). The exception was TBMU, an alcid, where oxychlordane made up > 40% of its chlordane. EFs of chiral components failed to predict concentration or trophic level, but did identify biotransformation differences between species and chlordane components. TBMU appeared to have a greater capacity to metabolize and eliminate chlordane, based on high proportions of oxychlordane, the highest EFs for oxychlordane and heptachlor epoxide, and a delta 15N-sigma CHLOR value which was well below the relationships developed for all seabird species.     

Degradation half-life times of PCDDs, PCDFs and PCBs for environmental fate modeling

Literature search of the knowledge on the degradation of persistent organic pollutants (POPs) in environmental compartments air, water, soil and sediment was done in purpose to find properties of POPs of interest for modeling. One degradation process, hydrolysis (chemical degradation), was omitted as negligibly slow for POPs studied. The other two, photolysis and biodegradation processes, were considered separately in purpose to develop estimation procedures. The estimates can be given as pseudo first-order rate constants kP for photolysis and kB for biodegradation. For each compartment, an overall degradation rate is k(tot) = kP + kB and lifetime t(1/2) = ln 2/k(tot). The latter values, lifetimes in each compartment, will be used as input parameters to the Baltic Sea model.     

A preliminary investigation of persistent organic pollutants in ambient air in Hong Kong

Air samples were collected for characterisation of PCDD/Fs and other persistent organic pollutants (POPs) such as aldrin, alpha-HCH, beta-HCH, delta-HCH, gamma-HCH, o,p'-DDT, p,p'-DDT, o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, dieldrin, endrin, endosulfan I and II, heptachlor, heptachlor epoxide and hexachlorobenzene during the winter of 2000/2001 at the weather station of the Hong Kong Observatory at Tai Mo Shan (TMS), which is the highest point (approximately 957 m) in Hong Kong, besides the routine monitoring of PCDD/Fs and 200 other toxic air pollutants (TAPs) at two urban TAPs stations at Tsuen Wan and Central & Western. Concentrations of the pollutants detected at TMS station were evaluated and compared to those recorded at the urban stations. Though pesticides including alpha-HCH, hexachlorobenzene, DDT, DDE, heptachlor, and endosulfan I were detected, these pesticides were found at relatively low concentrations of about 0.02-0.23 ng/m3 and should not have any significant health effects. Concentrations of some of the monitored POPs were found to be higher whilst most of the monitored TAPs were at comparable levels to those measured at the urban stations during the same period. According to the Stockholm Convention on POPs (May 2001), the 12 chemicals labelled by the United Nations as the most dangerous are: aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, mirex, toxaphene, hexachlorobenzene, PCBs and dibenzo-p-dioxins/dibenzofurans (PCDDs)/(PCDFs). Given that there has not been any large scale use of organo-chlorine pesticides recorded since the decline of local farming activities in recent years, the results of the present study again show that pesticides and POPs such as PCDDs/PCDFs are ubiquitous environmental contaminants present in the atmosphere of Hong Kong. The findings also indicate that organo-chlorine pesticides and PCDDs/PCDFs are among the most prevalent chlorinated semi-volatile pollutants present in Hong Kong. Results obtained in the present study suggest that selected pesticides may be used as tracers for transport of pollutants for regional air quality study.     

Contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs): Application to Southeastern France

A modeling approach has been developed to estimate the contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs). It combines an Eulerian chemical transport model for atmospheric processes (Polair3D/Polyphemus) with a fate and transport model for soil and vegetation (Ourson). These two models were specifically adapted for POPs. Results are presented for benzo(a)pyrene (BaP). As expected no accumulation of BaP in leaf vegetables appears during the growth period for each harvest over the 10 years simulated. For BaP and leaf vegetables, this contamination depends primarily on direct atmospheric deposition without chemical transfer from the soil to the plant. These modeling results are compared to available data.     

Occurrence of persistent organic pollutants in sediments and biota from Portugal versus European incidence: A critical overview

Persistent organic pollutants (POPs) are widespread compounds, such as organohalogenated compounds, polycyclic aromatic hydrocarbons (PAHs) and pesticides, which can be found in all types of environmental compartments. Their presence in the aquatic environment is a worldwide problem, with emphasis on sediments which act as depository and consequently as a source of hydrophobic, recalcitrant and harmful compounds. Besides, these pollutants might affect the reproduction and mortality of living organisms, diverging in their potential to bioaccumulate in tissues. The present paper aims to review the occurrence of POPs in sediments and biota from the coastal, estuarine and river areas of Portugal. The list of the studied compounds comprises organohalogenated compounds, PAHs, organometallic compounds, pesticides, sterols, fatty acids and pharmaceutical compounds. The contamination of sediments by various pollutants is presented, such as PAHs up to 7,350 ng g^?1 found in Sado estuary and polychlorinated biphenyls up to 62.2 ng g^?1 in the case of sediments collected in Ria de Aveiro. The occurrence of these persistent toxic substances in sediments demonstrates aquatic contamination from agricultural, industrial and urban discharges and the concern about the potential risks to aquatic organisms, wildlife and humans. In fact, several classes of POPs have also been found in biota, such as polychlorinated biphenyls up to 810.9 ng g^?1 in sentinel fish from the Douro River estuary and pesticides in bivalves from the Sado River estuary. The importance of further systematic research on sediments and biota is here highlighted to compare the contamination of these two reservoirs; to assess their spatial and temporal variation; and to determine other classes of POPs that were not investigated yet (e.g., industrial compounds, estrogens and many classes of pharmaceuticals).     

Analysis of biomagnification of persistent organic pollutants in the aquatic food web of the Mekong Delta, South Vietnam using stable carbon and nitrogen isotopes

The present study elucidated the biomagnification profiles of persistent organic pollutants (POPs) through a tropical aquatic food web of Vietnam based on trophic characterization using stable nitrogen analysis. Various biological samples collected from the main stream of the Mekong Delta were provided for the analysis for both POPs, and stable nitrogen and carbon isotope ratios. Of the POPs analyzed, dichlorodiphenyltrichloroethane and its metabolites (DDTs) were the predominant contaminants with concentrations ranging from 0.058 to 12 ng/g wet weight, followed by polychlorinated biphenyls (PCBs) at 0.017-8.9 ng/g, chlordane compounds (CHLs) at 0.0043-0.76 ng/g, tris-4-chlorophenyl methane (TCPMe) at N.D.-0.26 ng/g, hexachlorocyclohexane isomers (HCHs) at N.D.-0.20 ng/g and hexachlorobenzene (HCB) at 0.0021-0.096 ng/g. Significant positive increases of concentrations in DDTs, CHLs, and TCPMe against the stable nitrogen ratio (delta(15)N) were detected, while, concentrations of HCHs and HCB showed no significant increase. The slopes of the regression equations between the log-transformed concentrations of these POPs and delta(15)N were used as indices of biomagnification. The slopes of the POPs for which positive biomagnification was detected ranged from 0.149 to 0.177 on a wet weight basis. The slopes of DDTs and CHLs were less than those reported for a marine food web of the Arctic Ocean, indicating that less biomagnification had occurred in the tropical food web. Of the isomers of CHLs, unlike the studies of the Arctic Ocean, oxychlordane did not undergo significant biomagnification through the food web of the Mekong Delta. This difference is considered to be due to a lack of marine mammals, which might metabolize cis- and trans-chlordane to oxychlordane, in the Mekong Delta ecosystem. The biomagnification profile of TCPMe is reported for the first time in the present study.     

Uptake of polychlorinated biphenyls and organochlorine pesticides from soil and air into radishes (Raphanus sativus)

Uptake of organochlorine pesticides and polychlorinated biphenyls from soil and air into radishes was measured at a heavily contaminated field site. The highest contaminant concentrations were found for DDT and its metabolites, and for β-hexachlorocyclohexane. Bioconcentration factor (BCF, defined as a ratio between the contaminant concentration in the plant tissue and concentration in soil) was determined for roots, edible bulbs and shoots. Root BCF values were constant and not correlated to log K_OW. A negative correlation between BCF and log K_OW was found for edible bulbs. Shoot BCF values were rather constant and varied between 0.01 and 0.22. Resuspended soil particles may facilitate the transport of chemicals from soil to shoots. Elevated POP concentrations found in shoots of radishes grown in the control plot support the hypothesis that the uptake from air was more significant for shoots than the one from soil. The uptake of POPs from air was within the range of theoretical values predicted from log K_OA.     

Henry's law constants for hexachlorobenzene, p,p'-DDE and components of technical chlordane and estimates of gas exchange for Lake Ontario

The Henry's law constants (HLC) for trans- and cis-chlordane (TC, CC), trans-nonachlor (TN), hexachlorobenzene (HCB) and p,p'-DDE were determined by the gas-stripping method over a temperature range of 5-35 degrees C. The HLC variation versus temperature (K) was described by logH=m/T+b. Parameters of this equation were (with standard deviations) TC: m=-1524+/-158, b=6.58+/-0.54; CC: m=-1786+/-209, b=7.42+/-0.71; TN m=-2068+/-284, b=8.44+/-0.97; HCB: m=-3013+/-174, b=11.60+/-0.59 and p,p'-DDE: m=-2043+/-240, b=8.37+/-0.82. The HLCs (Pa m3 mol(-1)) at 25 degrees C (298.15 K) were: TC=29; CC=27; TN=32; p,p'-DDE=33 and HCB=35. These HLCs values were used to calculate fugacity ratios from paired air and water data from Lake Ontario, July 1998. The resulting fugacity ratios predict that volatilization was occurring for all compounds during that month.     

Strategies for including vegetation compartments in multimedia models

The incentives for including vegetation compartments in multimedia Level I, II and III fugacity calculations are discussed and equations and parameters for undertaking the calculations suggested. Model outputs with and without vegetation compartments are compared for 12 non-ionic organic chemicals with a wide variety of physical-chemical properties. Inclusion of vegetation compartments is shown to have a significant effect on two classes of chemicals: (1) those that are taken up by atmospheric deposition and (2) those that are taken up by transpiration through the plant roots. It is suggested that uptake from the atmosphere is important for chemicals with logK(OA) greater than 6 and a logK(AW) of greater than -6. Plant uptake by transpiration is important for chemicals with logK(OW) less than 2.5 and a logK(AW) of less than -1. At logK(OA) > 9 atmospheric uptake is dominated by particle-bound deposition and the importance of partitioning to vegetation is largely dependent on the relative magnitude of the particle deposition velocities to soil and vegetation. These property ranges can be used to determine if a chemical will significantly partition to vegetation. If the chemical falls outside the property ranges of the two classes it will probably be unnecessary to include vegetation in models for assessing environmental fate. The amount of chemical predicted to partition to vegetation compartments in the model is shown to be highly sensitive to certain model assumptions. Further experimental research is recommended to obtain more reliable equations describing equilibrium partitioning and uptake/depuration kinetics.     

Modification of UNIFAC parameter table Revision 5 for representation of aqueous solubility and 1-octanol/water partition coefficient for POPs

In order to represent aqueous solubility and 1-octanol/water partition coefficient for POPs (persistent organic pollutants) by the UNIFAC model, two pairs of group interaction parameters in Revision 5 of the UNIFAC parameter table were modified. First, the pair of interaction parameters between the aromatic carbon-chloride (ACCl) and water (H2O) groups were corrected by minimizing the deviation between the experimental and calculated values of these properties for chlorinated benzenes, polychlorinated biphenyls, and polychlorinated dibenzo-p-dioxins and dibenzofurans. The corrected interaction parameters provided a better representation of both properties than the calculation results obtained in early works using the UNIFAC model. Second, the unknown pair of interaction parameters between the chloroalkene (Cl(C=C)) and H2O groups, which are required for calculating those properties of the other five POPs (aldrin, chlordane, endrin, dieldrin, and heptachlor), were newly determined from the experimental data on their properties. Finally, this study shows that Revision 5 could also predict solubility of POPs in some organic solvents. The modified parameter table is first suggested as the UNIFAC parameter table applicable to various phase equilibria including aqueous or nonaqueous solubility and partition coefficient of POPs.     

Air Pollution Research Needs: Herbaceous and Ornamental Plants and Agriculturally Generated Pollutants

Effects of various air pollutants on economically important crops and ornamentals have been studied since before the turn of the century.

Summaries of this research on the effects of air pollutants, that have appeared in criteria documents developed by the Environmental Protection Agency, should be reviewed with respect to differences in plant susceptibility found in various regions of the country. These susceptibility differences are associated with variations in both environmental conditions and distribution of pollutants. Research efforts on air pollution injury to vegetation have often been poorly coordinated leaving many gaps in our knowledge. A better assessment of the impact of air pollution on vegetation is required to attain realistic controls for pollutants affecting agriculture. Research areas of major concern include: baseline information on effects of pollutants on agricultural productivity; dose-response information to support predictive mathematical models for acute and chronic studies of growth, yield, and quality effects; effects of pollutants interacting with other pollutants and with insects and plant diseases; mechanisms of pollutant action; genetic changes related to pollutant effects; effects of environmental stresses on plant response to pollutants; evaluation of plants including soil microbes as pollutant sinks; development of techniques to minimize pollutant effects; and, the effects of agricultural chemicals as air pollutants. There is a need for studies that consider the whole plant in its natural environment. Conceptual models interrelating pollutant effects and their interactions and ultimately mathematical models will be needed to develop an intelligent approach to land management. The effects of agriculturally produced pollutants on plants and other receptors must be identified and quantified.     

Reliable QSAR for estimating Koc for persistent organic pollutants: correlation with molecular connectivity indices

Several recent studies have shown that n-octanol/water partition coefficients may not be a good predictor for estimating soil sorption coefficients of persistent organic pollutants (POPs), defined here as chemicals with log Kow greater than 5. Thus, an alternative QSAR model was developed that seems to provide reliable estimates for the soil sorption coefficients of persistent organic pollutants. This model is based on a set of calculated molecular connectivity indices and evaluated soil sorption data for 18 POPs. The chemical's size and shape, quantified by 1chi, 3chiC and 4chiC(v) indices, have a dominant effect on the soil sorption process of POPs. The developed QSAR model was rationalized in terms of potential hydrophobic interactions between persistent organic pollutants and soil organic matrix. Its high predictive power has been verified by an extensive internal and external validation procedure.     

Residues of organochlorinated pesticides in soils from the Czech Republic

National POPs inventories carried out currently in many countries as a part of the implementation of Stockholm Convention revealed the need for detailed information about a distribution of pollutants in various regions. Screening for the residues of selected organochlorinated pesticides (chlordane, heptachlor, dieldrin, aldrin, endrin, isodrin, endosulfan I, endosulfan II, methoxychlor, mirex) in soil and biotic samples from the Czech Republic was performed. Although these pesticides have never been used in large quantities in this region, results indicate that their residues still persist in the top layer soils more than 20 years after they have been banned. The fact that their soil concentrations in the mountains are generally higher than those in agricultural areas, and detection of the traces of pesticides that have never been used in this region suggest on their occurrence in soils due to the atmospheric redistribution rather than as a result of direct application.     

Effects of amendments on the uptake and distribution of DDT in Cucurbita pepo ssp pepo plants

The effects of soil amendments on the phytoextraction of ∑DDT (DDT + DDD + DDE) from soil ([∑DDT] ∼ 1500 ng/g) by a pumpkin variety of Cucurbita pepo ssp pepo were tested and the patterns of ∑DDT storage throughout the plant shoot were examined. The soil amendments did not increase the total amount of ∑DDT extracted into plant shoots, but new information about ∑DDT distribution in the plants was obtained. As observed previously, the ∑DDT concentration in plant leaves (mean 290 ng/g) was significantly lower than in plant stems (mean 2600 ng/g). Further analysis revealed that ∑DDT composition was consistent throughout the plant shoot and that ∑DDT concentration in leaves and stems decreased exponentially as distance from the root increased, which was previously unknown. This new information about the patterns of ∑DDT uptake and translocation within pumpkin plants highlights the need for appropriate plant sampling strategies in future POPs phytoextraction research.     

Relationships between pesticides and organic carbon fractions in sediments of the Danshui River estuary and adjacent coastal areas of Taiwan

In order to understand the fate of pesticides in marine environments, concentrations of pesticides and different carbonaceous fractions were determined for surface sediments in the Danshui River and nearby coastal areas of Taiwan. The major compounds detected were tetrachlorobenzene, HCHs, chlordane, aldrin, DDDs, DDEs and DDTs. Total concentrations of pesticides in the sediments ranged from not detectable to 23 ng g(-1), with the maximum value detected near the discharge point of the marine outfall from the Pali sewage treatment plant. These results confirm that pesticides persist in estuarine and nearby coastal environments of the Danshui River well after their ban. Concentrations of total pesticides significantly correlate with concentrations of total organic carbon and black carbon in these sediments, suggesting that total organic carbon and black carbon regulate the distribution of trace organic pollutants in fluvial and coastal marine sediments.     

Vertical distributions of persistent organic pollutants (POPs) caused from organochlorine pesticides in a sediment core taken from Ariake bay, Japan

Persistent organic pollutants (POPs) of organochlorine pesticides such as dichlorodiphenyl trichloroethane (DDTs) and its metabolites, hexachlorobenzene (HCB), heptachlor, chlordane compounds (CHLs), aldrin, dieldrin, endrin, mirex and isomers of hexachlorocyclohexane (HCHs), were analyzed in sediment cores collected from Ariake Bay, Japan. Although Chikugo River has the largest flow in Ariake Bay, the total concentration of POPs in surface sediment was found in St.3, mouth of the Yabe River, where that level was two times higher than St.1, mouth of the Chikugo River. It could be assumed that the potential source of POPs contamination is relatively close to this study area. Relatively high residue levels of HCB, HCHs and DDTs in sediment core were found during the period from 1967 to 1970. In this layer, the HCB concentration investigated in sediment cores of Ariake Bay was maximum, 2.6 ng g(-1) dry weight and higher than that of Tokyo Bay and subsequently detected in deeper sediment cores. The ratio of (DDD+DDE)/SigmaDDTs was high in top sediments (0-2 cm). Although there was a concentration of DDTs in the top sediment, it was noticed that DDT emission did not cause direct input of DDT recently. The HCHs determined in upper sediment cores might be originated from long-range accumulation in environment after dispersing of technical-grade HCH. Moreover, the CHLs, dieldrin and heptachlor concentrations were detected and recently increased in sediment core. POPs in sediment cores of Ariake Bay based on the possibility of PCP contamination during the early 1960s were reflected.     

Modelling the fate of organic chemicals in the soil plant environment: Model study of root uptake of pesticides

The fate of organic chemicals in the soil-plant-atmosphere environment and the governing processes were studied with a coupled dynamic soil transport and plant compartment model. Scenarios with applications of pesticides on sand and loam soils with chemical uptake in barley and wheat were used in the model calculations. Root uptake and concentrations in the plant compartments stem, leave and fruit were calculated for the pesticides terbuthylazine, isoproturon and carbofuran.

The effectivity of uptake from soils with different soil sorption coefficients had been shown for sand and loam soils. The processes degradation in plant and volatilization from leaves to atmosphere are especially effective for carbofuran and terbuthylazine. Although the concentrations in corn at harvest are lower than the maximum allowed concentrations, the peak concentrations in the course of the vegetation period are significantly higher (factor ≤ 200).