Evaluating toxicity risk in sediments after remediation at a Superfund megasite using a Triad approach.

The Pine River downstream of the Velsicol Superfund site has been contaminated with various hydrophobic organic pollutants for more than 50 years. Remediation and sediment dredging near the site began in spring of 1999, and was completed in 2006. In 2011, the Michigan Department of Environmental Quality completed a baseline assessment report long-term monitoring plan for the Pine River. However, there has been limited assessment of the benthic community since this evaluation. The objective of this research was to evaluate the risk of Pine River sediment to aquatic macroinvertebrates downstream from the Superfund site after decades of degradation and dredging using the Triad approach. Three sites were selected downstream from the Superfund site, and an upstream reference site was used. At each site, macroinvertebrates surveys were conducted and sediments were collected for chemical analysis of DDT (1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane) and its degradation products and for laboratory toxicity testing for mortality and sublethal effects using Hyalella azteca and Chironomus dilutus. Sediment concentrations of DDT, DDD, and DDE were below levels expected to cause toxicity, and there was no observed toxicity in laboratory tests. Additionally, there were no statistically significant differences in richness, richness of Ephemeroptera, Plecoptera, and Trichoptera (EPT) species, total EPT abundance, percent EPT, or percent dominant taxa between the reference site and the downstream sites. There was an observed decrease in abundance of macroinvertebrate taxa at all downstream sites and a shift in macroinvertebrate structure when comparing the reference with most impaired sites. Although the sites downstream of the Superfund site remain different than the upstream control, there are improvements in species composition and abundance. However, more research is needed to evaluate the potential effects on ecosystem function.

Mercury and Organochlorines in the Terrestrial Environment of Schirmacher Hills, Antarctica.

We report the levels of mercury (Hg) and nine organochlorine pesticides [OCPs: α-hexachlorocyclohexane (HCH), ß-HCH, γ-HCH, δ-HCH, α-Endosulfan, ß-Endosulfan, Endosulfan sulfate, p,p'-dichlorodiphenyldichloroethylene (DDE) and p,p'-dichlorodiphenyldichloroethane (DDD)] in the terrestrial environment (moss and soil) and water (OCPs only) of Schirmacher Hills, Antarctica. This area has never been studied for mercury and not for OCPs since 1988. Mercury levels in moss, 66 ± 37 ng/g dry weight (dw), are comparable to other Antarctic locations. Levels of α-HCH, below detection to 4.48 ng/g dw, and p,p'-DDE, below detection to 31 ng/g dw, in mosses are lower or marginally higher than other Antarctic locations. No other OCPs were detected in moss. None of the OCPs were detected in soil. This suggests that Schirmacher Hills may be considered as a background site with respect to mercury and analyzed OCPs, despite the operation of two old research stations (Maitri, est. 1989, and Novolazarevskaya, est. 1961) in the region.

Abilities of Co-cultures of Brown-Rot Fungus Fomitopsis pinicola and Bacillus subtilis on Biodegradation of DDT.

DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) is one of the pesticides that are hazardous for the environment and human health. Effective environmental-friendly treatment using co-cultures of fungi and bacteria is needed. In this study, the bacteria Bacillus subtilis at various volumes of 1, 3, 5, 7, and 10 mL (1 mL ≈ 6.7 × 108 CFU) were mixed into 10 mL of the brown-rot fungus Fomitopsis pinicola culture for degrading DDT during a 7-days incubation period. DDT was degraded by approximately 42% by F. pinicola during the 7-days incubation period. The addition of 10 mL of B. subtilis into F. pinicola culture showed the highest DDT degradation of approximately 86% during the 7-days incubation period. DDD (1,1-dichloro-2,2-bis(4-chlorophenyl)ethane), DDE (1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene), and DDMU (1-chloro-2,2-bis(4-chlorophenyl)ethylene) were detected as metabolic products from DDT degradation by co-cultures of F. pinicola and B. subtilis. Transformation pathway was proposed in which DDT was transformed into three pathways as follows: (1) dechlorination to DDD, (2) dehydrochlorination to DDE, and (3) formation of DDMU.

[Levels of dichlorodiphenyltrichloroethane internal exposure levels in pregnant women of Xiamen and influencing factors].

Objective: To investigate the level of and factors influencing internal exposure to dichlorodiphenyltrichloroethane (DDT) in pregnant women. Methods: In all, 1 064 pregnant women were recruited in a hospital of Xiamen. Participants were asked to complete a questionnaire to obtain data on sociodemographic characteristics and lifestyle. Peripheral venous blood and cord blood samples were collected. Of the 1 064 pregnant women, 600 were enrolled in this study after completing the questionnaire and providing peripheral venous blood and cord blood. Among those women, 150 were selected randomly using a systematic sampling method. A gas chromatography coupled electron capture detector was used to determine the concentration of six DDT homologues: p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), o,p'-dichlorodiphenyltrichloroethane (o,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), o,p'-dichlorodiphenyldichloroethane (o,p'-DDD), p,p'-dichlorodiphenylethylene (p,p'-DDE), and o,p'-dichlorodiphenylethylene (o,p'-DDE) . Pregnant women were divided into two groups according to DDT concentration: a low concentration group (detection value≤P50) and a high concentration group (detection value>P50). multivariate logistic regression was used to analyze the association between the DDT levels and potential influencing factors which investigated in the questionnaire. Results: The detection rates of p,p'-DDT, o,p'-DDT, p,p'-DDD, o,p'-DDD, p,p'-DDE and o,p'-DDE in the peripheral venous blood samples from the 150 pregnant women were 83.3% (125), 29.3% (44), 58.0% (87), 24.0% (36), 82.0% (123), and 34.7% (52), respectively. The median concentrations were 1.56, 0.03, 0.07, 0.03, 0.93 and 0.03 µg/ml, respectively. The detection rates of p,p'-DDT, o,p'-DDT, p,p'-DDD, o,p'-DDD, p,p'-DDE and o,p'-DDE in the cord blood samples were 69.3% (104), 10.7% (16), 29.3% (44), 20.7% (31), 81.3% (122) and 45.3% (68), and the median concentrations were 0.41, 0.03, 0.03, 0.03, 0.42 and 0.03 µg/ml, respectively. The concentration ranges in the low and high DDT concentration groups which contained 75 respondents respectively were 0-3.69 and 3.74-82.09 µg/ml, respectively. In the single-factor analysis, the number (percentage) of those who consumed seafood " rarely" , "less than twice a week" , and " twice a week or more" was 15 (20.3%), 22 (29.7%), and 37 (50.0%), respectively, in the low concentration group, and 4(5.3%), 20(26.7% ), and 51(68.0% ) in the high concentration group (χ2=8.69, P=0.013). The results of the multivariate logistic regression analysis indicate that pregnant women who consume seafood less than twice a week, twice a week or more have higher peripheral blood DDT concentrations compared with those who rarely consume seafood. The OR (95% CI) values were 1.14 (1.08-1.21), 2.11 (1.55-2.85), respectively. Conclusion: The exposure level of pregnant women to DDTs in the Xiamen area is higher than that of women in other regions. High seafood intake is a risk factor for internal exposure to DDTs.

Contaminants in the southern tip of South America: Analysis of organochlorine compounds in feathers of avian scavengers from Argentinean Patagonia.

The aim of this study was to assess the exposure to organochlorine compounds (OC) in 91 primary wing feathers of avian scavengers, Turkey vulture (Cathartes aura), American black vulture (Coragyps atratus) and Southern crested caracaras (Polyborus plancus) from the southern tip of South America, in the Argentinean Patagonia. We analyzed for a series of OC including hexachlorocyclohexane (HCH) isomers, endosulfan, aldrin, dieldrin, endrin, dichlorodiphenyltrichloroethane (p,p'-DDT), dichlorodiphenyldichloroethane (p,p'-DDD), dichlorodiphenyldichloroethylene (p,p'-DDE), heptachlor and heptachlor-epoxide. This is the first study on OC in feathers of three terrestrial top carnivores from South America. OC concentrations found in the studied species were much higher than those found in feathers of raptors from Europe and Asia, which likely indicate their high use in the region, specifically in agriculture, and other possible uses of OC in this area. ∑HCH had the highest median concentration, followed by ∑Drins, ∑DDT, ∑Heptachlor, and ∑Endosulfan, similar to those reported in several food samples in Argentina. On the other hand, differences in OC profiles between species and areas may be related to feeding and migratory habits, as well as the molt period. Three individuals showed ∑DDT (DDT, DDD and DDE) concentrations in feathers related to sublethal effects. However, this comparison should be used with caution due to problems with extrapolating such data across tissues and species.

Contamination levels and spatial distribution of organochlorine pesticides in soils from India.

Organochlorine pesticides, dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH), are potential chemical pollutants extensively used for agriculture and vector control purposes due to low cost and high effectiveness. Concentrations of HCH and DDT were determined in 175 surface soil samples from different agricultural fields, fallow and urban lands of districts Nagaon and Dibrugarh, Assam, India. The mean concentrations of total HCH and total DDT were 825 ng/g (range: 98-1945 ng/g) and 903 ng/g (range: 166-2288 ng/g) in district Nagaon while 705 ng/g (range: 178-1701 ng/g) and 757 ng/g (range: 75-2296 ng/g) in district Dibrugarh, respectively. The soils from paddy fields contained highest amounts of HCH and DDT residues. Total organic carbon was found to be positively associated with soil HCH and DDT residues. Ratios of DDT/(DDD+DDE) were 1.25 and 1.82 while of α/γ HCH were 2.78 and 2.51 for districts Dibrugarh and Nagaon, respectively. Source identification revealed that soil residue levels have originated from long past and recent mixed source of technical HCH and Lindane for HCHs and mainly technical DDT for DDTs. Spatial distribution was also investigated to identify the areas with higher pesticide loadings in soil.

Comparison of bioaccumulation and biomarker responses in Dreissena polymorpha and D. bugensis after exposure to resuspended sediments.

The zebra mussel Dreissena polymorpha is widely used as sentinel organism for the assessment of environmental contamination in freshwater environments. However, in the River Rhine (Germany), the D. polymorpha population is declining, whereas the closely related quagga mussel D. bugensis is found in high numbers at some sites. In the present laboratory study, D. polymorpha and D. bugensis were exposed to resuspended native sediments for ≤2 weeks. Wet sediments (<63 µm, 100 mg l(-1) dry weight) were used as surrogate suspended particulate matter to mimic one of the mussels' main uptake route for chemicals. The sediments were sampled in (1) the River Elbe in Dessau, a site known to be highly polluted with, e.g., organochlorine (OC) pesticides and (2) at a relatively unpolluted site in Havelberg in the River Havel, one of the Elbe's tributaries. Chemical analysis of persistent OC compounds (seven polychlorinated biphenyls [PCBs], DDT and its metabolites (DDX), hexachlorocylohexanes [HCHs], and hexachlorobenzene [HCB]) in soft tissue of mussels showed significantly greater values of PCBs 101, 118, 153, 138, 180, the sum of seven PCBs, and p,p'-DDD in D. bugensis compared with D. polymorpha. Fourteen days of exposure to Dessau sediment increased the concentration of p,p'-DDE and p,p'-DDD, as well as the sum of DDX, in both species compared with Havelberg sediment. Interspecific differences were less pronounced when regarding chemical concentrations with lipid content instead of dry-weight of tissue because D. bugensis had greater levels of total lipid than D. polymorpha. DNA damage in gills, as measured with the comet assay, was greater in D. bugensis compared with D. polymorpha. Simultaneously, the content of heat-shock protein (hsp70) in gills was greater in D. polymorpha than in D. bugensis. DNA damage and hsp70 were not induced by exposure time or sediment type. This study shows that D. bugensis and D. polymorpha may differ in their bioaccumulation potential of OC pesticides as well as their levels of DNA damage and hsp70. Therefore, more investigations are needed before quagga mussel can be used as alternative test organism for the zebra mussel.

Dispersive liquid-phase microextraction using ionic liquid as extractant for the enrichment and determination of DDT and its metabolites in environmental water samples.

Ionic liquids are a kind of environmentally friendly solvents which have drawn great attention in many fields. The potential of ionic liquid as dispersive liquidphase microextraction (DLPME) solvent for the enrichment of typical persistent organic pollutants, dichlorodiphenyltrichloroethane (DDT), and its metabolites including 1,1-dichloro-2,2-bis-(4'-chlorophenyl)ethane and 1,1-dichloro-2,2-bis-(4'-chlorophenyl)ethylene has been investigated. Parameters that may influence the extraction efficiency, such as the type and volume of ionic liquid, the type and volume of disperser solvent, extraction time, and sample pH, were investigated and optimized in detail. The experimental results showed the excellent linear relationship between peak area and the concentration of DDT and its metabolites over the range of 1-50 µg L⁻¹, and the precisions (RSDs) were 5.27-6.73% under the optimal conditions. The limits of detection could reach 0.33-0.63 µg L⁻¹. Satisfied results were achieved when the proposed method was applied to determine the target compounds in real-world water samples with spiked recoveries over the range 94.4-115.3%. All these facts indicated that ionic liquid DLPME coupled to HPLC was an environmentally friendly alternative for the rapid analysis of DDT and its metabolites at trace level in environmental water samples.

Organochlorine residual concentrations in cattle egret from the Punjab Province, Pakistan.

In this study, residual concentration of organochlorine pesticides (OCPs) in the sediments, prey, and eggs of Bubulcus ibis were measured from three breeding heronries from the Punjab province of Pakistan. Pattern of contamination in eggs followed the order: DDTs>HCHs>heptachlor>aldrin. Overall, pesticide residual concentrations were greater in eggs of cattle egrets collected from heronry on the River Ravi. Among HCHs, γ-HCH was more prevalent in eggs, whereas DDTs followed the order: DDD>DDE>p,p'-DDT>o,p'-DDT. Eggshell thinning was detected which showed negative relationship with residual concentration of DDE. In prey samples, residual concentration of POPs followed the order: DDTs>HCHs>dicofol>heptachlor; however, contamination pattern in sediments followed a slightly different order: DDTs>heptachlor>dicofol>HCHs>dieldrin>aldrin. Concentration of ß-HCH was more prevalent in sediments and comparatively greater concentrations of POPs were measured in sediments collected from the River Ravi. Dicofol was found for the very first time in the biological samples from Pakistan, and its concentration was measured as relatively high in eggs from heronry from the River Chenab. Residual concentrations measured in eggs were below the levels that could affect egret populations. Biomagnification of the total OCPs through the food chain was evident in three breeding heronries. The concentration of DDE measured in eggs of the cattle egret suggests the need for monitoring this contaminant in other bird species at different trophic levels.

Distribution of organochlorine pesticides in sediments and mussels from the Istanbul Strait.

This study was conducted to determine the status and trends of organochlorine pesticide (OCP) compounds in the sediment and mussel samples collected along the Istanbul Strait and from the coasts of an island in the Marmara Sea. The total concentrations of OCPs were found in the range of 40-13,852 pg g(-1) dry weight for sediments and 5,195-12,322 pg g(-1) wet weight for mussels. The levels of OCPs in both sediments and mussels were dominated by DDTs and HCHs; ß-HCH, 4,4(')-DDD and 4,4(')-DDE were the major pollutants. The degree of sediment pesticide contamination was more severe in the inner part of the strait. OCP concentrations in sediments and mussels were compared with the sediment guideline values and legal limits for human health, respectively. The results showed that OC pesticide contamination in the strait might not pose a serious threat to the health of the marine inhabitants at most of the stations.

Survey of organochlorine pesticides and polychlorinated biphenyls in commercial pasteurized milk in Iran.

The objective of this study was to investigate the presence of organochlorine pesticides (α-HCH, ß-HCH, γ-HCH, HCB, dieldrin, o,p'-DDE, p,p'-DDE, p,p'-DDD, p,p'-DDT) and polychlorinated biphenyl (PCBs) congeners (28, 52, 101, 138, 153, 180) in pasteurized and sterilized milk containing 1.5%, 2.5%, and 3% fat from Tehran province (Iran). Considering the importance of milk and dairy products for human nutrition and the toxicity of these compounds, their daily intake (DI) through milk was also determined. The compounds γ-HCH (13.49 ng g(-1) fat), ß-HCH (11.7 ng g(-1) fat), and PCB180 (7.56 ng g(-1) fat) were found at highest concentrations. The DI for all compounds was less than the acceptable daily intake established by FAO/WHO except for Σ PCBs which was more than the minimal risk level.

Bioaccumulation of organochlorine pesticides in aquatic system--an overview.

In recent years, various environmental issues have aroused a concern on the pollution of pesticides in rivers and in their various intercompartments. Multiple residues of pesticides discharged from industries or as a result of extensive use of agrochemicals in agriculture have been monitored. These pesticide residues contaminate the river ecosystem and its intercompartments such as sediments, and aquatic biota, and make it harmful to humans when they contaminate food and drinking water. The pesticide contamination in water, sediments, and aquatic biota has been reported to be beyond the acceptable range. The most commonly found pesticides are organochlorine, namely, dichlorodiphenyltrichloroethane, hexachlorocyclohexane, endosulfan, heptachlor, lindane, dieldrin, aldrin, endrin, and others. The paper discusses the general description, classification, and toxicity of pesticides; it also aims to create public awareness among people and appraise them with various alternate methods to combat the problem of pesticide contamination. An attempt has also been made to elucidate the findings of various works on pesticides in aquatic system and to highlight the challenging aspects of pesticide contamination, which have not attracted the attention of investigators yet.

Intersex in feral indigenous freshwater Oreochromis mossambicus, from various parts in the Luvuvhu River, Limpopo Province, South Africa.

This study reports on intersex in Oreochromis mossambicus, an indigenous fish species inhabiting most aquatic systems throughout South Africa (SA). Male fish were collected from three sites in the Luvuvhu River, Limpopo Province, SA: Albasini Dam (AD), Nandoni Dam (ND), and Xikundu Weir (XW). The latter two sites are situated in a currently dichloro-diphenyl-trichloroethane (DDT) sprayed area. A laboratory-bred reference group (Aq R) were included for a histological comparison. 48% of the fish at AD were intersex individuals compared with 63% at ND, and 58% at XW. The Aq R fish had no cases of intersex. o,p'- and p,p'-DDT and metabolites dichlorodiphenyldichloroethane (DDD) and -dichlorodiphenyldichloroethylene (DDE) were detected in fat samples, indicative of contamination of the aquatic environment and subsequent exposure of fish to these chemicals. Although some of the fat samples contained levels of DDTs no association could be established between intersex and chemical contaminants in fish.

Bioremediation of chlorinated pesticide-contaminated soil using anaerobic sludges and surfactant addition.

Methanogenic granular sludge and wastewater fermented sludge were used as inocula for batch tests of anaerobic bioremediation of chlorinated pesticide contaminated soil. Results obtained for both types of biomass were similar: 80 to over 90% of gamma -hexachlorocyclohexane (gamma-HCH), 1,1,1-trichloro-2,2-bis-(4-methoxyphenyl)ethane (methoxychlor) and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) removed in 4-6 weeks. Residual fractions of these pesticides persisted till the end of the 16-week experiment. DDT was degraded through 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethane (DDD). Accumulation of this product corresponded stoichiometrically only to 34-53% of removed DDT, supposedly due to its further transformations, finally resulting in formation of detected 4,4'-dichlorobenzophenone (DBP). Addition of 0.5 mM Tween 80 nonionic surfactant resulted in about a twofold decrease of gamma -HCH and methoxychlor residual concentrations, as well as considerably lower DDD accumulation (7-29%) and higher DBP production. However, 1.25 mM dose of this surfactant applied together with granular sludge brought DDD levels back to that observed for treatments with the sludge alone, also impairing DBP formation.

Potential occupational exposures in the Reiss-Engelhorn-Museen Mannheim/Germany.

The Reiss-Engelhorn-Museen in Mannheim, Germany requested support from a toxicological laboratory in evaluating occupational exposures before a cleanup and renovation period in 2006. Samples of dust and dirt and scrapings of exhibits were collected from several locations. Following toxicologically relevant compounds could be identified by gas chromatography - mass spectrometry (GC/MS) by comparison with a mass spectra library: dichlorodiphenyl trichloroethane (DDT) and its breakdown product dichlorodiphenyl dichloroethane (DDD) as well as dichlorodiphenyl dichlorethylene (DDE), methoxychlor, nicotine, and camphor. In recent times various insecticides have been used to protect museum artefacts against moths, woodborers and other insect pests. Caution has to be made because the presence of hazardous compounds can result in security problems for museum staff as well as for visitors.

Changes of various insecticides during in vitro human digestion.

This study was performed to determine the effects of in vitro human digestion on the concentrations of five insecticides, namely 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD), 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene (DDE), bifenthrin, and fipronil. In vitro models included all the steps of human digestion, i.e., passage through the mouth, stomach, small intestine, and large intestine (with enteric bacteria). The concentrations of DDT and fipronil did not change (P > 0.05) until small intestinal digestion, whereas those of DDD, DDE, and bifenthrin decreased (P < 0.05) at each digestion step. The concentrations of all the insecticides decreased (P < 0.05) during the large intestinal digestion step with enteric bacteria, Lactobacillus sakei and Escherichia coli. In conclusion, the concentrations of all the tested insecticides decreased during all the steps of in vitro human digestion and were especially reduced by enteric bacteria during the large intestinal digestion step.

DDT residues in marine phytoplankton: increase from 1955 to 1969.

Phytoplankton samples collected in Monterey Bay, California, from 1955 to 1969 contained compounds identified as p,p'-DDT, p,p'-DDD, and p,p'-DDE. Total concentrations of these compounds were approximately three times greater in the later samples. Lower concentrations throughout the period were associated with higher densities of standing crop.

DDT residues: distribution of concentrations in Emerita analoga (stimpson) along coastal California.

The total concentrations (tDDT) of DDT [1,1,1-trichloro-2,2-bis(pchlorophenyl)ethane], DDD [1,1-dichloro-2,2-bis(p-chlorophenyl)ethanel, and DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene] in Emerita analoga from 19 California beaches reflect tDDT contamination nearby. Animals near the Los Angeles County sewer outfall contain over 45 times as much tDDT as animals near major agricultural drainage areas. Sediments near the outfall probably contain over 100 metric tons of tDDT-a reservoir for input into marine organisms. The effluent from a plant that manufactures DDT is a probable source.

DDT residues in an east coast estuary: a case of biological concentration of a persistent insecticide.

DDT residues in the soil of an extensive salt marsh on the south shore of Long Island averaged more than 13 pounds per acre (15 kilograms per hectare); the maximum was 32 pounds per acre (36 kilograms per hectare). A systematic sampling of various organisms from the vicinity showed concentrations of DDT increasing with trophic level through more than three orders of magnitude from 0.04 part per million in plankton to 75 parts per million in a ring-billed gull. Highest concentrations occurred in scavenging and carnivorous fish and birds, although birds had 10 to 100 times more than fish. These concentrations approach those in animals dying from DDT poisoning, which suggests that many natural populations in this area are now being affected, possibly limited, by DDT residues. Similar concentrations have been reported elsewhere in North America.

DDT residues and declining reproduction in the Bermuda petrel.

Residues of DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane] averaging 6.44 parts per million in eggs and chicks of the carnivorous Bermuda petrel indicate widespread contamination of an oceanic food chain that is remote from applications of DDT. Reproduction by the petrel has declined during the last 10 years at the annual rate of 3.25 percent; if the decline continues, reproduction will fail completely by 1978. Concentrations of residues are similar to those in certain terrestrial carnivorous birds whose productivity is also declining. Various considerations implicate contamination by insecticides as a probable major cause of the decline.