Soil sterilization affects aging-related sequestration and bioavailability of p,p′-DDE and anthracene to earthworms

Laboratory experiments investigated the effects of soil sterilization and compound aging on the bioaccumulation of spiked p,p′-DDE and anthracene by Eisenia fetida and Lumbricus terrestris. Declines in bioavailability occurred as pollutant residence time in both sterile and non-sterile soils increased from 3 to 203 d. Accumulation was generally higher in sterile soils during initial periods of aging (from 3-103 d). By 203 d, however, bioavailability of the compounds was unaffected by sterilization. Gamma irradiation and autoclaving may have altered bioavailability by inducing changes in the chemistry of soil organic matter (SOM). The results support a dual-mode partitioning sorption model in which the SOM components associated with short-term sorption (the ‘soft’ or ‘rubbery’ phases) are more affected than are the components associated with long-term sorption (the ‘glassy’ or microcrystalline phases). Risk assessments based on data from experiments in which sterile soil was used could overestimate exposure and bioaccumulation of pollutants.     

Influence of plant-earthworm interactions on SOM chemistry and p,p'-DDE bioaccumulation

Laboratory experiments assessed how bioaccumulation of weathered p,p′-DDE from soil and humic acid (HA) chemistry are affected by interactions between the plants Cucurbita pepo ssp. pepo and ssp. ovifera and the earthworms Eisenia fetida, Lumbricus terrestris, and Apporectodea caliginosa. Total organochlorine phytoextraction by ssp. pepo increased at least 25% in the presence of any of the earthworm species (relative to plants grown in isolation). Uptake of the compound by ssp. ovifera was unaffected by earthworms. Plants influenced earthworm bioaccumulation as well. When combined with pepo, p,p′-DDE levels in E. fetida decreased by 50%, whereas, in the presence of ovifera, bioconcentration by L. terrestris increased by more than 2-fold. Spectral analysis indicated a decrease in hydrophobicity of HA in each of the soils in which both pepo and earthworms were present. However, HA chemistry from ovifera treatments was largely unaffected by earthworms. Risk assessments of contaminated soils should account for species interactions, and SOM chemistry may be a useful indictor of pollutant bioaccumulation.     

Detection of DDT and its metabolites in two estuaries of South China using a SPME-based device: First report of p,p′-DDMU in water column

A solid-phase microextration-based sampling method was employed to determine the concentrations of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its metabolites, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD), 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (DDE) and 1-chloro-2,2-bis(p-chlorophenyl)ethene (DDMU), in two estuarine bays, Daya Bay and Hailing Bay, of South China. Six DDT components including p,p′-DDT, o,p′-DDD, p,p′-DDD, o,p′-DDE, p,p′-DDE, and p,p′-DDMU were detected in Hailing Bay, while only p,p′-DDD was found in Daya Bay. p,p′-DDD was the most abundant DDT component in both bays, sharply different from the previous finding in the water column of the Palos Verdes Shelf, California, USA that p,p′-DDE was prevalent. In addition, the occurrence of p,p′-DDMU (with a range of 0.047-0.21 ng/L in Hailing Bay) has not been reported around the globe, and its presence in our study region appeared to stem from dehydrochlorination of p,p′-DDD, favored under aerobic conditions, but further investigations are clearly needed to confirm the mechanism for generation of DDMU in estuarine environments.     

A study on As, Cu, Pb and Zn (bio)availability in an abandoned mine area (São Domingos, Portugal) using chemical and ecotoxicological tools

The aim of this study was to relate the results obtained by chemical methods, used to assess environmental (bio)availability, with the ecotoxic response and bioaccumulation of trace elements (TE) by the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils from a sulphide mine. The extracting solution 0.5 M NH₄CH₃COO, 0.5 M CH₃COOH and 0.02 M EDTA (pH 4.7), was able to predict environmental bioavailability of TE to E. fetida. However, the toxicological bioavailability could not be predicted from the results of the chemical extractions or from the bioaccumulation results: E. fetida reproduction was higher in soils where environmental bioavailability of TE and bioaccumulation values were also higher. In this study, the toxic response of the organism seemed to be more influenced by the overall nutritional status of the soil (e.g. pH, organic matter, plant nutrient availability and cation exchange capacity) than by its TE contamination. In the case of anthropogenic multi-contaminated sites, the different soil characteristics exert an important and confounding influence in the toxic response and the relationship between different bioavailable fractions cannot be easily established, emphasising the need to combine results from chemical methods with those from bioassays when evaluating the bioavailability of TE in these soils.     

New DDT inputs after 30 years of prohibition in Spain. A case study in agricultural soils from south-western Spain

This study provides information on the current status of contamination by DDT in agricultural soils in south-western Spain. A recent use of technical DDT in at least 17% of the soils was found based on the values (<1) of the ratio Rp,p^′/p,p^′=[p,p^′-DDE+p,p^′-DDD]/[p,p^′-DDT]. According to the ratio Ro,p^′/p,p^′=[o,p^′-DDT]/[p,p^′-DDT], a dicofol type contamination was detected in about 27% of the soils. A wide range of concentrations was observed (0.08-11.1 ng/g d.w.) regardless of the type of crop soil. Enantiomeric fractions (EFs), based on the chiral analysis of o,p′-DDT residues differed from the racemic value (0.500) in most soils but they were not correlated with the study variables [DDTs], SOM, Rp,p^′/p,p^′ and Ro,p^′/p,p^′. Given the health risks posed by DDT, our findings support how the environmental control of legacy pollutants such as DDT cannot be neglected.     

Sequestration of organochlorine pesticides in soils of distinct organic carbon content

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is not a reliable criterion for the identification of new DDT sources.     

Occurrence and levels of organochlorine compounds in human breast milk in Bangladesh

In low-income countries, the use of some organochlorine pesticides is still common in order to increase food production. Monitoring the chemical exposure is an important step in risk-reducing strategies. This is the first study to report concentrations of organochlorines in breast milk of women from Bangladesh where farming is the main income source.Organochlorines such as p,p′-DDT, o,p′-DDT, p,p′-DDE, p,p′-DDD (i.e., ∑DDT), HCB, α-, β- and γ-HCH, trans-chlordane, cis-chlordane, oxy-chlordane, trans-nonachlor, cis-nonachlor, mirex and polychlorinated biphenyls (CB 28, 52, 99, 101, 105, 114, 118, 123, 128, 138, 141, 149, 153, 156, 157, 163, 167, 170, 180, 183, 187, 189, 194) were analyzed in breast milk collected in 2002 from 72 first-time mothers (median age 20 years) living in the rural area Matlab, Bangladesh.While the concentrations of PCBs and many of the pesticides were low, the concentrations of p,p′-DDT and its metabolite p,p′-DDE were high (median 349 and 1645 ng g⁻¹ lipid, respectively) in comparison to other countries. The median value of ∑DDT was 2123 ng g⁻¹ lipid. The estimated daily exposure to p,p′-DDT, p,p′-DDE and ∑DDTs was 10, 30 and 42 μg kg⁻¹ body weight, respectively, in 3 months old infants. The p,p′-DDE/p,p′-DDT ratio ranged from 1 to 23, where 58% of the mothers had a ratio below 5 indicating recent or ongoing DDT exposure.This study reports infant exposure and maternal body burden of organochlorines through breast milk. Although the findings give no reason to limit breast-feeding, it is essential to identify the main exposure sources and find means to decrease the exposure.     

Rapid determination of dichlorodiphenyltrichloroethane and its main metabolites in aqueous samples by one-step microwave-assisted headspace controlled-temperature liquid-phase microextraction and gas chromatography with electron capture detection

A rapid and sensitive analytical method for the determination of dichlorodiphenyltrichloroethane (DDT) and its main metabolites in environmental aqueous samples has been developed using one-step microwave-assisted headspace controlled-temperature liquid-phase micro-extraction (MA-HS-CT-LPME) technique coupled with gas chromatography-electron-capture detection (GC-ECD). In this study, the one-step extraction of DDT and its main metabolites was achieved by using microwave heating to accelerate the evaporation of analytes into the controlled-temperature headspace to form a cloudy mist vapor zone for LPME sampling. Parameters influencing extraction efficiency were thoroughly optimized, and the best extraction for DDT and its main metabolites from 10-mL aqueous sample at pH 6.0 was achieved by using 1-octanol (4-μL) as the LPME solvent, sampling at 34 °C for 6.5 min under 249 W of microwave irradiation. Under optimum conditions, excellent linear relationship was obtained in the range of 0.05-1.0 μg/L for 1-dichloro-2,2-bis-(p′-chlorophenyl)ethylene (p,p′-DDE), 0.1-2.0 μg/L for o,p′-DDT, 0.15-3.0 μg/L for 1,1-dichloro-2,2-bis-(p′-chlorophenyl)ethane (p,p′-DDD) and p,p′-DDT, with detection limits of 20 ng/L for p,p′-DDE, and 30 ng/L for o,p′-DDT, p,p′-DDD and p,p′-DDT. Precision was in the range of 3.2-11.3% RSD. The proposed method was validated with environmental water samples. The spiked recovery was between 95.5% and 101.3% for agricultural-field water, between 94% and 99.7% for sea water and between 93.5% and 98% for river water. Thus the established method has been proved to be a simple, rapid, sensitive, inexpensive and eco-friendly procedure for the determination of DDT and its main metabolites in environmental water samples.     

Organochlorine pesticides in soils of Mexico and the potential for soil-air exchange

The spatial distribution of organochlorine pesticides (OCs) in soils and their potential for soil-air exchange was examined. The most prominent OCs were the DDTs (Geometric Mean, GM = 1.6 ng g⁻¹), endosulfans (0.16 ng g⁻¹), and toxaphenes (0.64 ng g⁻¹). DDTs in soils of southern Mexico showed fresher signatures with higher F_DDTe = p,p′-DDT/(p,p′-DDT + p,p′-DDE) and more racemic o,p′-DDT, while the signatures in the central and northern part of Mexico were more indicative of aged residues. Soil-air fugacity fractions showed that some soils are net recipients of DDTs from the atmosphere, while other soils are net sources. Toxaphene profiles in soils and air showed depletion of Parlar 39 and 42 which suggests that soil is the source to the atmosphere. Endosulfan was undergoing net deposition at most sites as it is a currently used pesticide. Other OCs showed wide variability in fugacity, suggesting a mix of net deposition and volatilization.     

Eisenia fetida avoidance behavior as a tool for assessing the efficiency of remediation of Pb, Zn and Cd polluted soil

Remediation by means of soil leaching with ethylenediaminetetraacetic acid (EDTA) is capable of extracting the most labile soil fractions, leaving the residual metals in biologically non-available forms. We evaluated the feasibility of the standardized earthworm (Eisenia fetida) avoidance test for assessing the efficiency of soil remediation of Pb, Zn and Cd polluted soil. Chemical extraction tests (six-step sequential extraction, toxicity characteristic leaching procedure, physiologically based extraction test, diethylenediaminepentaacetic acid extraction) indicated that the mobility, oral bioaccessibility and phytoavailability of Pb, Zn and Cd were consistently reduced. However, the avoidance test showed no significant avoidance of polluted soil in favor of that which had been remediated. Pb, Zn and Cd accumulation in E. fetida mirrored the decreasing pattern of metal potential bioavailability gained by leaching the soil with increasing EDTA concentrations. The calculated bioaccumulation factors indicated the possibility of underestimating the metal bioavailability in soil using chemical extraction tests.     

Relative proportions of polycyclic aromatic hydrocarbons differ between accumulation bioassays and chemical methods to predict bioavailability

Chemical methods to predict the bioavailable fraction of organic contaminants are usually validated in the literature by comparison with established bioassays. A soil spiked with polycyclic aromatic hydrocarbons (PAHs) was aged over six months and subjected to butanol, cyclodextrin and tenax extractions as well as an exhaustive extraction to determine total PAH concentrations at several time points. Earthworm (Eisenia fetida) and rye grass root (Lolium multiflorum) accumulation bioassays were conducted in parallel. Butanol extractions gave the best relationship with earthworm accumulation (r² ≤ 0.54, p ≤ 0.01); cyclodextrin, butanol and acetone-hexane extractions all gave good predictions of accumulation in rye grass roots (r² ≤ 0.86, p ≤ 0.01). However, the profile of the PAHs extracted by the different chemical methods was significantly different (p < 0.01) to that accumulated in the organisms. Biota accumulated a higher proportion of the heavier 4-ringed PAHs. It is concluded that bioaccumulation is a complex process that cannot be predicted by measuring the bioavailable fraction alone.     

Assessing seasonal and spatial trends of persistent organic pollutants (POPs) in Indian agricultural regions using PUF disk passive air samplers

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m³): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p′-DDE and p,p′-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site).     

PCB153 and p,p′-DDE disorder thyroid hormones via thyroglobulin,deiodinase 2, transthyretin,hepatic enzymes and receptors

Polychlorinated biphenyls (PCBs) and DDT are widespread environmental persistent organic pollutants that have various adverse effects on reproduction, development and endocrine function. In order to elucidate effects of PCBs and DDT on thyroid hormone homeostasis, Sprague–Dawley rats were dosed with PCB153 and p,p′-DDE intraperitoneally (ip) for five consecutive days and sacrificed within 24 h after the last dose. Results indicated that after combined exposure to PCB153 and p,p′-DDE, total thyroxine , free thyroxine, total triiodothyronine, and thyroid-stimulating hormone in serum were decreased, whereas free triiodothyronine and thyrotropin-releasing hormone were not affected. Thyroglobulin and transthyretin levels in serum were significantly reduced. mRNA expression of deiodinases 2 (D2) was also suppressed, while D1 and D3 levels were not significantly influenced after combined exposure. PCB153 and p,p′-DDE induced hepatic enzymes, UDPGTs, CYP1A1, CYP2B1, and CYP3A1 mRNA expressions being significantly elevated. Moreover, TRα1, TRβ1, and TRHr expressions in the hypothalamus displayed increasing trends after combined exposure to PCB153 and p,p′-DDE. Taken together, observed results indicate that PCB153 and p,p′-DDE could disorder thyroid hormone homeostasis via thyroglobulin, deiodinase 2, transthyretin, hepatic enzymes, and hormone receptors.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

Influence of activated carbon amendment on the accumulation and elimination of PCBs in the earthworm Eisenia fetida

In this study we investigated the use of activated carbon (AC) as a soil amendment for reducing bioavailability of polychlorinated biphenyls (PCBs) to the earthworm Eisenia fetida. Artificial soil was contaminated with PCBs and used in bioaccumulation experiments fresh or after aging for 19 months. PCB bioaccumulation in earthworms was reduced by 68% when AC was placed as a layer without mixing and by 94% when AC was manually mixed into the soil. Aging of the same AC mixed soil for 19 months resulted in an overall reduction of 99% in PCB biouptake. AC-treated aged soil also showed two orders of magnitude lower equilibrium aqueous concentrations of PCBs compared to untreated aged soils. The findings from this study indicate that application of engineered sorbents like AC to PCB impacted soils may greatly reduce PCB uptake at the base of the terrestrial food chain.     

Bioaccumulation and depuration of anthracene in Penaeus monodon (Fibricius) through food ingestion

Understanding on the bioaccumulation and depuration of PAHs (polycyclic aromatic hydrocarbons) in Penaeus monodon is important in seafood safety because it is one of the most popular seafood consumed worldwide. In this study, we used anthracene as the precursor compound for PAHs accumulation and depuration in the shrimp. Commercial feed pellets spiked with anthracene were fed to P. monodon. At 20 mg kg⁻¹ anthracene, P. monodon accumulated 0.1% of the anthracene from the feed. P. monodon deputed the PAH two times faster than its accumulation. The shrimp reduced its feed consumption when anthracene content in the feed exceeded 20 mg kg⁻¹. At 100 mg kg⁻¹ anthracene, P. monodon started to have necrosis tissues on the posterior end of their thorax. The bioaccumulation factor (BAF), uptake rate constant (k₁) and depuration rate constant (k₂) of anthracene in P. monodon were 1.15 × 10⁻³, 6.80 × 10⁻⁴ d⁻¹ and 6.28 × 10⁻¹ d⁻¹, respectively. The depuration rate constant is about thousand times higher than the uptake rate constant and this indicated that this crustacean is efficient in depurating hydrocarbons from their tissue.     

Concentrations of organochlorine pesticides and polychlorinated biphenyls in human serum and their relation with age,gender, and BMI for the general population of Bizerte,Tunisia

Human serum samples (n?=?113) from Bizerte, northern Tunisia, collected between 2011 and 2012 were analyzed for 8 organochlorine pesticides (OCPs) including p,p′-dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers, dieldrin, and heptachlor and 12 polychlorinated biphenyls (PCBs) congeners. Concentrations of these residues in serum were determined by gas chromatography with electron capture detector and total cholesterol (CHOL) and triglycerides (TG) levels were evaluated by enzymatic colorimetric method. HCB, p,p′-DDE, PCB-138, PCB-153, and PCB-180, were the most abundant organochlorine compounds (OCs) detected in >95 % of the study subjects. The mean levels of p,p′-DDE and HCB in serum were 168.8 and 49.1 ng?g^?1 lipid, respectively. The sum PCBs concentrations ranged from 37.5 to 284.6 ng?g^?1 lipid in the samples, with mean and median value of 136.1 and 123.2 ng?g^?1 lipid, respectively. The PCB profile consisted of persistent congeners, such as PCB-138, PCB-153, and PCB-180 which contributed for approximately 82.7 % to the ∑PCBs. Statistical analysis showed that most OCs correlated significantly with age, considering all samples together or with gender differentiation. The present study shows that the levels of p,p′-DDE and ∑DDTs were significantly higher in females than in males (p?<?0.05), while PCBs levels were significantly higher in male (p?<?0.05) than in females. No statistically significant association was found between body mass index and concentration of any organochlorine pesticide or PCB congeners 153, 138, 180, or ∑PCBs.     

Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida

To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.     

Analysis of organochlorine pesticide residues in human and cow’s milk in the towns of Asendabo,Serbo and Jimma in South-Western Ethiopia

The level of some OCPs in human and cow milk collected from Asendabo, Serbo and Jimma in South-West Ethiopia were analyzed using GC–ECD. Results of the analysis indicated that all samples contained detectable quantities of p,p′-DDT and its metabolites, p,p-DDE and p,p-DDD, but none of the other OCPs analyzed. Mean levels of total DDT in the human and cow milk samples in the three areas were 12.68 and 0.389 μg g^?1 respectively. The distributions of p,p-DDT, p,p-DDE and p,p-DDD in the human milk samples from the three locations followed the same trend in which the proportion of p,p-DDT was the highest in all the three cases, comprising 55–71% of total DDT, followed by p,p-DDE, 26–39%, and the least, p,p-DDD of 2–5%. The mean ratio of DDT/DDE concentration for the three areas was calculated to be 2.01. This value was much higher than the values reported from other countries in earlier studies and indicates the existence of a higher quantity of DDT from a fresh input in the three study areas. The mean estimated daily intake of DDT by infants from mother’s milk in the three locations was found to be 62.17 μg kg^?1 body weight, which is about three times higher than the acceptable daily intake set by WHO/FAO for total DDT, 20 μg kg^?1 of body weight. This alarmingly high daily intake value is a cause for concern, since children are highly susceptible to effects from such environmental contaminants. The study has revealed that people in the study areas are facing exposure to DDT from recent use. The observed contamination of mother’s milk and the possible transfer of the contaminant from mother to child is an obvious risk associated with breast-feeding in the study areas and possibly in other parts of the country too.