Occurrence and distribution of atmospheric organic micropollutants in conifer needles

The distribution of some chlorinated hydrocarbons(p,p′-DDT, p,p′-DDE,α-HCH,γ-HCH,HCB) in spruce (Picea abies) needles was investigated. A comparision of concentrations in the wax with that of the remaining needle and time-resolved washing of the needle-surface shows the distribution behaviour of these substances.     

Global environmental cycling of γ-HCH and DDT in the 1980s – A study using a coupled atmosphere and ocean general circulation model

A coupled atmosphere–ocean general circulation model, ECHAM5-MPIOM, was used to study the multicompartmental cycling and long-range transport of persistent and semivolatile organics. Multiphase systems in air and ocean are covered by submodels for atmospheric aerosols, HAM, and marine biogeochemistry, HAMOCC5, respectively. The model, furthermore, encompasses 2D surface compartments, i.e. top soil, vegetation surfaces and sea-ice. The total environmental fate of γ-hexachlorocyclohexane (γ-HCH, lindane) and dichlorophenyltrichloroethane (DDT) in agriculture were studied.DDT is mostly present in the soils, the water-soluble γ-HCH in soils and ocean. DDT has the longest residence time in almost all compartments. Quasi-steady state with regard to substance accumulation is reached within a few years in air and vegetation surfaces. In seawater the partitioning to suspended and sinking particles contributes to the vertical transport of substances. On the global scale deep water formation is, however, found to be more efficient. Up to 30% of DDT but only less than 0.2% of γ-HCH in seawater are stored in particulate matter.On the time scale studied (1 decade) and on global scale substance transport in the environment is determined by the fast atmospheric circulation. The meridional transport mechanism, for both compounds, is significantly enhanced by multi-hopping. Net meridional transport in the ocean is effective only regionally, mostly by currents along the western boundaries of Africa and the Americas. The total environmental burdens of the substances experience a net northward migration from their source regions, which is more pronounced for DDT than for γ-HCH. Due to the application distribution, however, after 10 years of simulation 21% of the global environmental burden of γ-HCH and 12% of DDT have accumulated in the Arctic.     

Chlorinated hydrocarbon vapours and plant foliage: Kinetics and applications

Accumulation and release kinetics from azalea leaves exposed at vapours of (γ- and γ-HCH, p,p′-DDT and DDE, and a PCB mixture (Fenclor 64) are reported. The use of plant foliage as an air contamination indicator is discussed.     

Organochlorine pesticides in surface sediments and suspended particulate matters from the Yangtze estuary, China

Total HCHs' and total DDTs' levels in surface sediments (SS) ranged from 0.5 to 17.5 ng g⁻¹ and from 0.9 to 33.1 ng g⁻¹, averaged 6.0 and 8.2 ng g⁻¹, respectively. Total HCHs' and total DDTs' levels in suspended particulate matters (SPM) varied from 6.2 to 14.8 ng g⁻¹ with a mean value of 12.3 ng g⁻¹ and were from 3.4 to 25.7 ng g⁻¹ with an average of 16.4 ng g⁻¹, respectively. Lindane is the main HCHs' source and continuing use in the Yangtze Delta areas of ‘pure’ γ-HCH (lindane) rather than technical HCH (a mix of largely α- and some γ-HCH). DDTs in SS are mainly accumulated in history. However, high DDT fractions in SPM are indicators of new input of typical dicofol type DDT from 2002 to 2004. It can be seen that most samples from the Yangtze estuary were in ranges where adverse biological effects are expected, either occasionally or frequently.     

Serum levels of organochlorine pesticides in healthy adults from five regions of Spain

The aim of this study was to measure of serum levels of p,p′-dichlorodiphenyl trichloroethane (p,p′-DDT), p,p′-dichlorodiphenyl dichlorethylene (p,p′-DDE), β-hexachlorocyclohexane (β-HCH), and hexachlorobenzene (HCB) in healthy adults in Spain. Furthermore, we also analyzed these levels according to dietary, other lifestyle factors and anthropometric characteristics. We measured the concentrations of such organochlorine pesticides (OCPs) in serum samples collected during 1992–1996 from 953 subjects aged 35–64 years, they were residents of five Spanish regions, they were randomly selected from the European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. OCPs were determined by means of gas chromatography with electron-capture detection (GC-ECD). The most frequent compound found in serum was p,p′-DDE, present in 98% of the samples, followed by HCB and β-HCH, found in 89% and 77% of samples, respectively, while p,p′-DDT could be measured only in 26% of subjects. The geometric means of serum concentrations (ng/g lipid) were 822 for p,p′-DDE, 167 for β-HCH, and 379 for HCB. The concentrations of all OCPs were positively associated with age and body mass index, and decreased along the period of blood collection. No association was found between OCPs levels and dietary factors. The concentrations of p,p′-DDE and β-HCB were higher in Murcia, one of southern regions, most likely associated with intensive past use of pesticides related to agricultural practices, while higher levels of HCB were found in Navarra, located in the north, maybe due to industrial use rather than agricultural application.     

Spatial distribution of lindane in topsoil of Northern France

Lindane is a persistent organochlorine insecticide and the use of this insecticide in agriculture was banned in France in 1998. In this study we investigated the concentrations of lindane in topsoil in Northern France and used robust geostatistics to map the geographical distribution of lindane. The study was based on a 16 km × 16 km grid covering an area of ca 25 000 km². Lindane was found in all soils, even those from non-agricultural-application areas. Very low ratios of α-/γ-HCH and δ-/γ-HCH suggested that a long time had passed since technical HCH was used in the studied area, or that emission sources of lindane were still present. A strong gradient in lindane concentration was observed, with the highest lindane concentrations in an area located in the northern region. Results suggested that some of the lindane observed in the high concentration area may have come from volatilization of old lindane applied to intensively cultivated areas, which was then transported by prevailing winds coming from the south-west and deposited in a densely inhabited depression.     

Organochlorine pesticides and polybrominated diphenyl ethers in irrigated soils of Beijing, China: Levels, inventory and fate

Limited information on the levels, inventory and fate of Organochlorine pesticides (OCPs) and Polybrominated diphenyl ethers (PBDEs) in the soils irrigated by sewage or wastewater is available. In this study, variation in concentrations, profiles and fate of OCPs and PBDEs were investigated using soil samples collected from a region irrigated by sewage, mixed water and clean water in the east of Beijing, China. No significant variation was observed among groups, except for penta-BDEs. The measured ΣOCPs and ΣPBDEs residues ranged from 6.4 to 171.2 ng g⁻¹ (dw) and 501.9 to 3310.7 pg g⁻¹ (dw), respectively. ΣDDTs and BDE-209 were the most abundant congeners accounting for about 76% of ΣOCPs and 93% of ΣPBDEs. Concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDTs) and its major degradation products, and hexachlorobenzene (HCB) ranged from 1.2 to 11.4 ng g⁻¹ (dw), 4.0 to 155.6 ng g⁻¹ (dw) and 0.3 to 3.4 ng g⁻¹ (dw), respectively. The major DDT degradation products were p,p′-DDT and p,p′-DDE. The major hexachlorocyclohexane (HCH) isomer in irrigated soils is β-HCH, reflecting its higher affinity to solids and resistance to degradation than other isomers. Both α-HCH/β-HCH and p,p′-DDT/p,p′-DDE ratios were log-normally distributed and negatively correlated to log(ΣHCHs) and log(ΣDDTs), respectively, suggesting no significant recent application of OCPs. Individual BDE congeners, ΣPBDEs and ΣOCPs were significantly correlated with total organic carbon (TOC). Moreover, a good correlationship between ΣPBDEs and black carbon (BC) was obtained but not between ΣOCPs and BC. Sewage irrigation did not have obvious effect on their contaminant levels and inventory of OCPs and PBDEs.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain)

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC–ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers β-HCH and -HCH in all samples whereas δ-HCH and γ-HCH were at lower levels. Some other pesticides such as p,p′-DDT, p,p′-DDD and p,p′-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC–MS.     

Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir

For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis^® HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70–103% and 71–103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0–7.0%, 4.0–8.0% for water and sediment, respectively. Thirty one pesticides (-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p′-DDD, o,p′-DDT, p,p′-DDT, p,p′-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, -chlordane, γ-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g⁻¹ on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l⁻¹ for pore waters and from 48.8 to 890 ng l⁻¹ for water samples, respectively, with a mean concentration of 10.7 ng g⁻¹ in sediment, 735 ng l⁻¹ in pore water and 295 ng l⁻¹ in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.     

Persistent organic pollutants (PCB, DDT, HCH, HCB & BDE) in eels (Anguilla anguilla) in Scotland: Current levels and temporal trends

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.     

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant were analyzed by GC/ECD and GC/MS. Wax and the rest of the needles were analyzed separately. As a rule the concentrations of -HCH (0.5–13.6 ng/g), γ-HCH (0.4–7.3 ng/g), HCB (0.2–3.4 ng/g), PCB congeners (0.2–67 ng/g), PCDDs and PCDFs were higher in the older needles. The ratio of the concentration in the wax to the concentration in the rest of the needles was higher in the younger needles. The concentrations of PCB congeners, TeCDDs and TeCDFs were higher in the needles collected in the area nearest to the plant. The samples, obviously, contained tri- and tetrachlorodibenzothiophenes but these were not determined quantitatively due to interfering peaks in GC/MS.     

Enantioselective toxicokinetics study of the bioaccumulation and elimination of α-hexachlorocyclohexane in loaches (Misgurnus anguillicaudatus) and its environmental implications

The enantioselective bioaccumulation and elimination of α-hexachlorocyclohexane (α-HCH) in loaches (Misgurnus anguillicaudatus) were studied for the first time. Valid chiral residue analysis methods for α-HCH enantiomers in water and loach samples were established using gas chromatography coupled with electron capture detector and a BGB-172 chiral column. A rapid accumulation process was found during the 39-d bioaccumulation experiment. The α-HCH in loaches reached its maximum on the fourth day, after which it fluctuated slightly, reflecting a balance between elimination and reuptake. The maximum bioaccumulation factor was 728 at the 10 μg L^?1 exposure level. The enantiomeric fraction (EF) values showed that the bioaccumulation was enantioselective with enantioenrichment of (+)-α-HCH in the loaches. The elimination experiment indicated that the degradation kinetics of α-HCH fitted a typical first-order kinetics model, and the half-life was about 5 d. Significant enantioselectivity was observed during the elimination process, with the EFs declining from higher than 0.5–0.39, suggesting (+)-α-HCH is preferentially biotransformed than (?)-α-HCH in loaches. The results reveal a high capacity for α-HCH bioconcentration by loaches and that biotransformation is the main route of decontamination.     

Distribution and bioaccumulation of organochlorine pesticides in surface sediments and benthic organisms from Taihu Lake, China

The spatial distribution and bioaccumulation of organochlorine pesticides (OCPs) in surface sediments and benthic organisms from Taihu Lake were studied. OCPs were detected in all sediment samples with total concentrations ranging from 4.22 to 461 ng g⁻¹ dry weight (dw). The ratios of certain metabolites to their parent compounds indicated there are still new inputs of parent DDT (dichlorodiphenyltrichloroethane) to Taihu Lake, while the highest residues of HCHs (hexachlorocyclohexanes) mainly came from earlier usage and fresh γ-HCH (lindane). No positive correlation was found between the distribution of OCPs and organic matter contents in sediments. Concentrations of OCPs and lipids in typical large benthic organisms, Bellamya aeruginosa (B. aeruginosa) and Corbicula fluminea (C. fluminea), increased with body weight. HCHs, DDTs, chlordanes and heptachlors were the dominant compounds detected in organisms and C. fluminea accumulated much more OCP than B. aeruginosa. Higher values of biota-sediment accumulation factor (BSAF) were detected in C. fluminea, which was both affected by biological characteristics of the organisms and physicochemical properties of the compounds.     

Distribution pattern of PCBs,HCB and PeCB using passive air and soil sampling in Estonia

Background, aim, and scope  

Passive air sampling survey of the Central and Eastern Europe was initiated in 2006. This paper presents data on toxic organic compounds such as polychlorinated biphenyls (PCB 28, 52, 101, 118, 153, 138, and 180), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), hexachlorocyclohexane compounds (α-HCH, β-HCH,γ-HCH, δ-HCH), and dichloro-diphenyl-trichloroethane (DDT) compounds (p,p′DDE, p,p′DDD, p,p′DDT, o,p′DDE, o,p′DDD, and o,p′DDT) determined in ambient air and soil samples collected at Estonian monitoring stations.     

Sorption of alpha and beta hydrophobic endosulfan in a Vertisol from southeast region of Turkey

Endosulfan has been applied to control numerous insects in a variety of food and non-food crops. Limited information is available on dynamics of this pesticide in the soil. The objective of this research was to determine the adsorption–desorption behavior of the alpha (α) and beta (β) endosulfan in a Vertisol from the southeast region of Turkey, where cotton is the main crop in the large irrigated lowlands. The α and β endosulfan were adsorbed considerably and Freundlich adsorption–desorption isotherms fitted the α and β endosulfan data (R² > 0.98). Freundlich adsorption coefficients (K_f) for the α endosulfan ranged between 21.63 and 16.33 while for the β endosulfan they were between 14.01 and 17.98 for the Ap and Bw2 horizons. The difference of K_f values of α and β endosulfan for two horizons were explained with the slight difference in the amount of organic matter and clay, but considerable difference in Fe contents of the two horizons. Alpha and β endosulfan K_fd values were 118.03 and 45.81 for the Ap and 48.08 and 68.71 for the Bw2 horizons. Higher adsorption and desorption behavior of the endosulfan isomers for the same horizon was attributed to poor physical bonding between the endosulfan molecule and the surfaces of fundamental soil particles. This fact is thought to increase the effective use of endosulfan in agriculture with a possibility of its movement to the surface and groundwater in the Vertisol studied.     

Application of simple soil-water flow models to the transfer of surface-applied solutes to streams

In the context of leaching of surface-applied nitrate fertilizer to runoff, this paper evaluates the performance of five simple predictive models, based upon: (1) field capacity; (2) uniform displacement; (3) wetting front; (4) by-passing (preferential) flow; and (5) soil-water domains. Predicted behaviour and observed on an 85-cm depth soil are compared for leaching depth and outflow response. Predictive success of outflow by the models for 40 monitored rainfall events were: (1) 60%; (2) 52%; and (3) 76%. For the by-passing flow model (4), simple prediction of pedal excess flow (4a) gave a success of 80%; where calculations of the operational volume in preferential flow were involved (4b), variations from 20 to 100% success occurred for a range of operational volumes, the lowest volumes giving the greatest success (4c). The soil-water domain model (5) is a simple, predictive scheme involving the classification of outflow events according to antecedent soil moisture (θ_a); the method uses the mobile: retained water content (θ_r) at 2 bars and field capacity (θ_fc). Using soil-water domains alone was of limited success but when the domains were combined with rainfall intensity, the scheme specified outflow exactly. Thus, for θ_a < θ_r, no soil-water outflow occurred, even at high rainfall intensity; for θ_a >θ_fc outflow always occurred, even at low rainfall intensity and for θ_a >θ_r < θ_fc the simple by-passing model (4a) achieved 100% predictive success. The implications for fertilizer application are discussed.     

Organochlorine pesticides in Avicennia marina from the Mumbai mangroves, India

This paper examines the concentration levels of organochlorine pesticides (OCPs) such as hexachlorocyclohexane (HCH) (α, β and γ), Aldrin, Endosulfan (α, β), DDE, DDD, and DDT in the leaf, root and sediment part of Avicennia marina, a dominantly distributed mangrove species in Mumbai. The overall pattern of accumulation of OCPs was observed as ∑HCH > ∑DDT > ∑Endosulfan > Aldrin. The occurrence of αHCH was found to be frequent in all the samples. The leaf and root samples showed better uptake of organochlorine pesticides whereas lower concentration levels of OCPs was observed in case of sediment samples. The mean concentration of OCPs was observed highest in case of root samples. This study indicated towards the capability of A. marina in bioaccumulation of the OCPs. The present data will serve as the baseline against which future study of OCPs uptake in the mangrove plant species may be assessed.     

Accumulation levels and characteristics of some pesticides in human adipose tissue samples from Southeast China

This paper presents a comprehensive study of pesticide levels and bio-accumulation characteristics in human adipose tissues among residents of Southeast China. A large number of adipose samples (n = 633) were selected for 58 pesticides and were analyzed by high sensitive Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS). The results showed that POPs pesticides were frequently detected, including 2,4′-DDD, 2,4′-DDE, 2,4′-DDT, 4,4′-DDD, 4,4′-DDE, 4,4′-DDT, α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), and mirex. Other detected pesticide species were dicofol, methamidophos and chlordimeform, which have rarely been reported. Comparing to different countries, the concentrations of total DDT and HCH in these three Chinese southeastern sites were in the middle range, whereas the HCB and mirex were in the lower end. A significant correlation was observed between region as well as age and POPs pesticide levels. Some pesticide residue levels were also found significantly correlated to occupation. However, there was no significant correlation between gender and pesticides. Meanwhile, it is interesting to find that mortality of malignant tumors tends to associate with the pesticides levels in human adipose tissue. More importantly, the measured data presented in this study provide realistic information which is useful for assessing human exposure to pesticides in the general population of Southeast China.