Levels of organochlorine pesticides in Amazon turtle (Podocnemis unifilis) in the Xingu River,Brazil

Abstract

Due to the toxicity and high environmental persistence of organochlorine pesticides in aquatic organisms, turtles have been studied as environment biomonitors. These animals are important sources of protein for the riverside and indigenous peoples of the Brazilian amazon. In the present study, organochlorine pesticide contamination was investigated in Podocnemis unifilis. Liver, muscle and fatty tissue samples were removed from 50 specimens collected from five sampling points located in the Xingu River basin. Fourteen organochlorine pesticides were analysed via gas chromatography with an electron capture detector (CG-ECD). Eight organochlorine pesticides were detected with average concentrations of ∑DDT, ∑Endossulfan and ∑HCH which were 26.17?±?26.35, 14.38?±?23.77 and 1.39?±?8.46?ng g^?1 in moisture content, respectively. DDT compounds were the most predominant, with a greater concentration of pp′-DDT in the liver and pp′-DDD in the muscle. Significant differences were noted between the types of tissues studied, and the concentration of OCPs varied between sampling sites.     

Residues levels of organochlorine pesticide in cow's milk from industrial farms in Hidalgo,Mexico

A survey was carried out from 2008 to 2010 to determine the concentrations of 16 organochlorine pesticide residues (OPRs) from Tizayuca, Hidalgo, Mexico. Organochlorine residue determinations were made from milk fat, using chromatographic cleanup and analysis by gas chromatography with an electron capture detector. The OPR concentrations found were from below the detection limit (DL) to 0.91 ng g^?1 in 2008, DL to 0.38 ng g^?1 in 2009 and DL to 0.59 ng g^?1 in 2010. In general concentrations of organochlorine pesticides were higher in the wet season (3.37 ng g^?1 and 4.79 ng g^?1) than the dry season (1.92 ng g^?1 and 2.71 ng g^?1) for 2009 and 2010, due to control of pests in the pasture and sheds. According to Codex Alimentarius regulations, individual pesticides did not exceed the permissible limits, which for example were 10 μg kg^?1 for alpha hexachlorocyclohexane (HCH) and endosulfan I, 20 μg kg^?1 for p,p’-DDT, and 6 μg kg^?1 for dieldrin, endrin and heptachlor. A reduction of organochlorine pesticide concentrations in cow's milk was noted, indicating that the Mexican government has achieved reduction or elimination of some organochlorine pesticides in response to global agreements on persistent organic pollutants.     

Persistent organochlorine pesticides in internal organs of coypu,Myocastor coypus

A highly selective and sensitive method based on gas chromatography-tandem mass spectrometry (GC-MS/MS) to identify and quantify persistent organochlorine pesticides, (18 compounds including primary compounds and metabolites), in animal internal organs (kidneys, liver, and brain) has been developed. Tandem mass spectrometric conditions were individually optimized for each target compound in Multiple Reaction Monitoring (MRM) mode to obtain maximum sensitivity. Prior to instrumental analysis, a sample preparation method based on matrix solid phase dispersion (MSPD) followed by acidic digestion with sulfuric acid to reduce matrix co-extractives was employed. Analyses of real samples were carried out on coypus (Myocastor coypus) from the autumn slaughter of 19 animals. In the analyzed samples, three of the target compounds, namely DDE-pp′ (DDT metabolite), HCB and lindane, were detected. Their concentration levels fell in the ranges of 0.003–0.007, 0.003–0.025, and 0.003–0.021 mg kg^?1 (0.005, 0.010, and 0.010 mg kg^?1 on average) in the case of DDE-pp′, HCB and lindane, respectively. Although low quantities of organochlorine pesticides do not pose an immediate danger to consumers' health, they should be of public health concern considering long-term, low-dose exposure.     

Commercial trials evaluating the novel use of ethyl formate for in-transit fumigation of shipping containers

Sediment samples from 25 sites in 17 rivers of the Pantanal (Brazil) were analyzed with the objective of evaluating pesticide contamination in sediments. Samples were extracted with an acetone, ethylacetate, and water mixture 2:2:1 (v/v/v). The extract was purified by flash chromatography with aluminum oxide and florisil. A multiresidue gas chromatography-mass spectrometry method was applied to monitor 23 pesticides of different chemical classes (organochlorine, organophosphorus, triazines, anilides and pyrethroids) with some of their degradation products. Compounds identified in sediment samples included λ -cyhalothrin (1.0 to 5.0 μ g kg^{? 1}), p,p′-DDT (3.6 μ g kg^{? 1}), deltamethrin (20.0 μ g kg^{? 1}) and permethrin (1.0 to 7.0 μ g kg^{? 1}).     

Population characteristics of young African women influencing prenatal exposure to DDT (Manhiça, Mozambique)

The concentrations of dichlorodiphenyltrichloroethane (DDT) compounds in cord blood of 214 children born between 2003 and 2006 in Manhiça (Mozambique) have been determined. In this time interval, corresponding to the period before DDT reintroduction for indoor residual spraying, the observed values averaged 0.8 and 0.4 ng/ml for 4,4′-dichlorodiphenyldichloroethylene (4,4′-DDE) and 4,4′-DDT, respectively, and were similar to those found in western countries. However, the 4,4′-DDT/4,4′-DDE ratio was high indicating that the inputs of these compounds arriving to children in utero originated from recent uses of the insecticide. The strongest factor affecting DDT concentration was parity. A well-defined decreasing concentration trend was observed for the cord blood concentrations in the period of study. The trend was also observed for multiparae and primiparae mothers independently. Children from multiparae women showed much lower concentrations than primiparae women. Children from mothers with secondary school level exhibited lower concentrations of these pesticides than mothers with lower degree of education.     

Spatial distribution and partitioning of polychlorinated biphenyl and organochlorine pesticide in water and sediment from Sarno River and Estuary,Southern Italy

The Sarno River is nicknamed “the most polluted river in Europe”. The main goal of this study is to enhance our knowledge on the Sarno River water and sediment quality and on its environmental impact on the gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) in order to become a useful assessment tool for the regional administrations. For these reasons, 32 selected polychlorinated biphenyls (PCBs) and aldrin, α-BHC, β-BHC, δ-BHC, γ-BHC (lindane), 4,4′-DDD, 4,4′-DDE, 4,4′-DDT, dieldrin, endosulfan I, endosulfan II, endosulfan sulphate, endrin, endrin aldehyde, heptachlor, heptachlor epoxide (isomer B) and methoxychlor were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total concentrations of PCBs ranged from 1.4 to 24.9 ng L^?1 in water (sum of DP and SPM) and from 1.01 to 42.54 ng g^?1 in sediment samples. The concentrations of total organochlorine pesticides (OCPs) obtained in water (sum of DP and SPM) ranged from 0.54 to 7.32 ng L^?1 and from 0.08 to 5.99 ng g^?1 in sediment samples. Contaminant discharges of PCBs and OCPs into the sea were calculated in about 1,247 g day^?1 (948 g day^?1 of PCBs and 326 g day^?1 of OCPs), showing that this river should account as one of the main contribution sources of PCBs and OCPs to the Tyrrhenian Sea.     

Accumulation pattern of persistent organochlorine pesticides in liver tissues of various species of birds from India

As part of a large study on assessing the impact of environmental contaminants in Indian avifauna, the presence of organochlorine pesticides (OCPs) in liver tissues of 16 species of birds collected from Ahmedabad, India during 2005–2007 was quantified. The higher concentrations of total organochlorine pesticides were detected in livers of shikra Accipiter badius (3.43?±?0.99 μg/g wet wt) and the lower levels in white ibis Pseudibis papillosa (0.02?±?0.01 μg/g wet wt). Marked differences in the concentrations of total OCPs occurred among species (p?<?0.05). Concentrations of DDT and its metabolites, hexachlorocyclohexane (HCH) and isomers, dieldrin, and heptachlor epoxide were lower than the concentrations reported for various species of birds in India. Accumulation pattern of organochlorine pesticides in birds was, in general, in the order HCH > DDT > heptachlor epoxide > dieldrin. Among various pesticides analyzed, p,p′-DDE and β-HCH contributed maximum towards the total OCPs and study indicates the continuous use of lindane and DDT for agriculture and public health purpose, respectively. Although no serious threat is posed by any of the organochlorine pesticides detected in the present study species, continued monitoring is recommended.     

Residue levels of organochlorine pesticides in cattle meat and organs slaughtered in selected towns in West Shoa Zone,Ethiopia

Residue levels of organochlorine pesticides (OCP) in a total of 90 cattle samples comprising meat, liver and kidney collected from carcasses slaughtered in six towns in West Shoa Zone, Ethiopia, (Ambo, Guder, Ginchi, Gedo, Holeta and Tikur Inchini), have been determined. The pesticides were extracted by solid phase extraction (SPE) and quantification was carried out using gas chromatography-mass spectrometry (GC-MS). A good linearity (r² > 0.998) was found in the range 0.001–7.00 mg/kg for the samples studied. Most of the pesticides had recoveries in the range 81–99% and values of relative standard deviation (RSD) <7.2% for repeatability and reproducibility, showing good accuracy and precision of the method. The concentration level of the studied organochlorines followed the order: p, p’ dichloro-diphenyl-trichloroethane (DDT) > endosulfan>o,p′-DDT >lindane>dieldrin>endrin>aldrin>chlorothanolin while the order of contamination in the analyzed organs was liver > kidney > meat. Heat treatment of the meat, kidney and liver samples (boiling for 90 min.) produced an overall reduction of 62.2%, 44.5%, 37.7%, 29%, 31%, 34.3% and 30.8% in lindane, o, p′-DDT, endosulfan, p, p′-DDT, chlorothanolin, aldrin, dieldrin, and endrin, respectively. Although the residual contents of the organochlorines detected in all the contaminated samples analyzed from the six cities were below the respective maximal permissible levels set by international organizations, samples from Holeta town were more contaminated and may necessitate effective monitoring as bioaccumulation of these residues may pose health problems in human beings.     

Organochlorine pesticides and polychlorinated biphenyls in soils surrounding the Tanggu Chemical Industrial District of Tianjin, China

The spatial distribution of persistent organic pollutants (POPs) was examined in soils surrounding the Tanggu Chemical Industrial District in Tianjin, China. The concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzenes (HCBs), and polychlorinated biphenyls (PCBs) were determined in 70 surface soils using accelerated solvent extraction and gas chromatography with electron capture detection. The results showed that the ranges of ∑HCH, ∑DDT, ΣHCB, and ∑PCB concentrations in soils were 2.1–12,549 μg?kg^?1 (average, 965 μg?kg^?1), n.d.–2,033 μg?kg^?1 (average, 88.4 μg?kg^?1), n.d.–1,924 μg?kg^?1 (average, 349 μg?kg^?1), and n.d.–373 μg?kg^?1 (average, 46.2 μg?kg^?1), respectively. Of these, HCHs were the dominant POPs, accounting for 75 % of the total organochlorine pesticide (OCP) residues. Overall, the spatial distribution of OCP concentrations showed a decreasing trend from the center of the Tanggu District to the surrounding areas. Two major pollution sources were Tianjin Dagu Chemical Co., Ltd. in the district center and the Tianjin Chemical Plant in Hangu District. In contrast, PCB concentrations were relatively high in the Haihe estuary to the east and low to the west of the study area. Component analysis of OCPs in these soils showed that they mainly came from industrial point sources. Compared with soils in other regions, soil DDT pollution was at a medium level in the Tanggu Chemical Industrial District, but associated HCH, HCB, and PCB pollution was relatively heavy. By multivariate statistical analyses, Tianjin Dagu Chemical Co., Ltd. was recognized as the main source of POPs, and soil properties were clarified to play an important role on the distribution and composition of POPs, especially the organic carbon content.     

Lead accumulation and elimination in tissues of Prussian carp, Carassius gibelio (Bloch, 1782), after long-term dietary exposure, and depuration periods

We studied the bioaccumulation of lead in selected tissues of Prussian carp Carassius gibelio (Bloch, 1782) during 12 and 24 months exposure to different doses of this metal in feed and the elimination of lead from tissues during the following 12-month depuration period. Lead concentration was determined using atomic absorption spectrometry method. The highest lead concentrations were observed at 2.0?±?0.54 to 7.4?±?1.1 mg?kg^?1 in the kidney, 3.0?±?0.13 to 5.2?±?0.17 mg?kg^?1 in the bone, and 4.5 (±0.4)?mg?kg^?1 in the hepatopancreas of fish from groups exposed to lead dietary concentration from 8 to 49 mg?kg^?1 for 24 months. The rate of accumulation were generally the highest at the beginning of exposure as evidenced by the highest monthly increments of bioaccumulation observed after 3 months of contamination for muscles, hepatopancreatic gland, intestine, and gills. Also analysis of the monthly increments of lead bioaccumulation in bone tissue and the highly significant coefficients of correlation indicate that the dynamics of accumulation are clearly dependent on dose of exposure. Depuration of accumulated lead from the organs depended mainly on tissue and duration of elimination period. Very rapid depuration was observed in soft tissues such as the intestine or muscles. Very low elimination was observed for scales and bones where until the end of the experiment highly significant lead concentration differences were observed in all groups in relation to the control group. Chronic dietary exposure in the range of 8–49 mg Pb?kg^?1 resulted in no significant effects on the growth and survival of Prussian carp females.     

Development of an In-Line System for the Analysis of 4,4′-DDT in Water

An in-line system for trace persistent organic pollutants (POPs) in water was developed by using a laboratory-made hollow fiber membrane (HFM) unit connected with a high-resolution gas chromatograph-mass spectrometer (HRGC-MS). The semivolatile organic compound, 4,4′-Dichlorodiphenyl trichloroethane (4,4′-DDT), was chosen as a representative of a persistent organic compound. The synthetic water contaminated with 4,4′-DDT was passed through the HFM unit, the extraction occurred by the analyte pervaporated and permeated, then stripped into HRGC-MS. Several factors were investigated for the high extraction efficiency. The best performance was obtained at sample and stripping gas flow rates of 6 and 9 mLmin^?1, respectively, and desorption temperature of 60°C. At this temperature, the diffusion rate was enhanced by 15 times over 25°C. A wide linear dynamic range was obtained, i.e., 0.10–1.0 mgL^?1, with a limit of detection (LOD) of 90 μgL^?1. The extraction efficiency of 4,4′-DDT in real water samples was in the range of 83–94%. Real water samples were analyzed and 0.6 μgL^?1 of 4,4′-DDT was found in unregistered bottled water and 7.0 μgL^?1 in tap water.     

Assessment of Organochlorine Pesticide Residues in Water,Sediment, and Fish of the Songhua River,China

This study examined residual concentrations and associated ecological risks of the organochlorine pesticides (OCPs) hexa- chlorocyclohexane (HCH) and dichloro-diphenyl-trichloroethane (DDT) in water, sediment, and fish of the Songhua River in Zhaoyuan County, China. In June 2012, 10 water, 10 sediment, and 20 fish samples were collected. Residual concentrations of ΣHCH and ΣDDT ranged from 10.0–35.59 ng L^?1 (mean 28.03 ± 11.66 ng L^?1) and 5.12–39.66 ng L^?1 (mean 32.36 ± 11.58 ng L^?1) for water. Residual concentrations of ΣHCH and ΣDDT ranged from 0.52–3.00 ng g^?1 (mean 2.04 ± 0.73 ng g^?1) and 0.34–3.41 ng g^?1 (mean 2.38 ± 0.92 ng g^?1) for sediment. The ratios of α-HCH/γ-HCH were close to 1 at the majority of sampling points, indicating considerable new pollution from the use of lindane. The ratios of p,p′-DDE + p,p′-DDD/ΣDDT were less than 0.5, indicating recent inputs from DDT impurities in dicofol. All HCH and DDT isomers except for p,p′-DDD were detected in fish tissue samples, but the associated ecological risks were estimated to be below levels of concern. The study revealed a historical usage of OCPs in the Zhaoyuan section of the Songhua River and new OCP from the use of lindane and dicofol.     

Solid phase extraction with silicon dioxide microsphere adsorbents in combination with gas chromatography-electron capture detection for the determination of DDT and its metabolites in water samples

The goal of the present study was to investigate the feasibility of silicon dioxide (SiO₂) microspheres without special modification to enrich dichlorodiphenyltrichloroethane (DDT) and its main metabolites, p,p′-dichlorodiphenyl-2,2-dichloroethylene (p,p′-DDD) and p,p′-dichlorodiphenyldichloroethylene (DDE) in combination with gas chromatography-electron-capture detection. The experimental results indicated that an excellent linear relationship between the recoveries and the concentrations of DDT and its main metabolites was obtained in the range of 0.2–30 ng mL^?1 and the correlation coefficients were in the range of 99.96–99.99%. The detection limits based on the ratio of signal to the baseline noise (S/N = 3) were 2.2, 2.9, 3.8 and 4.1 ng L^?1 for p,p′-DDD, p,p′-DDT, o,p′-DDT, and p,p′-DDE, respectively. The precisions of the proposed method were all below 10% (n = 6). Four real water samples were utilized for validation of the proposed method, and satisfactory spiked recoveries in the range of 72.4–112.9% were achieved. These results demonstrated that the developed method was a simple, sensitive, and robust analytical method for the monitoring of pollutants in the environment.     

Atmospheric deposition of organochlorine pesticides by precipitation in a coastal area

Wet deposition fluxes of organochlorine pesticides (OCPs) were determined for rain samples collected in a coastal area of Turkey. Seventeen precipitation samples were collected over a 1-year period from 2008 to 2009. Rainwater was accumulated at the beginning of rain events using real time monitoring. Atmospheric concentrations were also measured in parallel with deposition samples. Both atmospheric concentrations and deposition fluxes were determined as particle and gas phases. The particle phase and dissolved phase deposition fluxes were 794.26?±?756.70 ngm^?2 day^?1 and 800.77?±?672.63 ngm^?2 day^?1, respectively. The washout ratios for OCP compounds were calculated separately for the particle and dissolved phases using the atmospheric concentrations and rain concentrations. The minimum washout ratio for the particle phase was 2339.47 for Endrin aldehyde, whereas the maximum washout ratio was 497593.34 for Methoxychlor. The maximum washout ratio for the dissolved phase was 247523.89 for Endosulfan beta, whereas the minimum washout ratio was 10169.69 for p,p′-DDT. The dry deposition velocities ranged from 0.01 to 1.67 cms^?1. The partitioning of wet deposition between the particle and dissolved phases was 50 % in terms of total OCP deposition.     

Photocatalytic degradation of p,p′-DDT under UV and visible light using interstitial N-doped TiO2

1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (or p,p′-DDT) is one of the most persistent pesticides. It is resistant to breakdown in nature and cause the water contamination problem. In this work, a major objective was to demonstrate the application of N-doped TiO₂ in degradation and mineralization of the p,p′-DDT under UV and visible light in aqueous solution. The N-doped TiO₂ nanopowders were prepared by a simple modified sol–gel procedure using diethanolamine (DEA) as a nitrogen source. The catalyst characteristics were investigated using XRD, SEM, TEM, and XPS. The adsorption and photocatalytic oxidation of p,p′-DDT using the synthesized N-doped TiO₂ under UV and visible light were conducted in a batch photocatalytic experiment. The kinetics and p,p′-DDT degradation performance of the N-doped TiO₂ were evaluated. Results show that the N-doped TiO₂ can degrade p,p′-DDT effectively under both UV and visible lights. The rate constant of the p,p′-DDT degradation under UV light was only 0.0121 min^?1, whereas the rate constant of the p,p′-DDT degradation under visible light was 0.1282 min^?1. Under visible light, the 100% degradation of p,p′-DDT were obtained from N-doped TiO₂ catalyst. The reaction rate of p,p′-DDT degradation using N-doped TiO₂ under visible light was sixfold higher than that under UV light. According to Langmuir-Hinshelwood model, the adsorption equilibrium constant (K) for the N-doped TiO₂ under visible light was 0.03078 L mg^?1, and the apparent reaction rate constant (k) was 1.3941 mg L^?1-min. Major intermediates detected during the p,p′-DDT degradation were p,p′-DDE, o,p′-DDE, p,p′-DDD and p,p′-DDD. Results from this work can be applied further for the breakdown of p,p′-DDT molecule in the real contaminated water using this technology.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.     

Atmospheric monitoring of organochlorine pesticides across some West African countries

Most African countries have ratified the Stockholm Convention on persistent organic pollutants (POPs) and are expected to reduce emissions of POPs such as organochlorine pesticides (OCPs) to the atmosphere. Emerging evidence, however, suggests that there are contemporary sources of OCPs in African countries despite the global ban on these products. This study investigated the atmospheric contamination from OCPs in four West African countries—Togo, Benin, Nigeria, and Cameroon—to ascertain the emission levels of OCPs and the characteristic signatures of contamination. Polyurethane foam (PUF) disk passive air samplers (PAS) were deployed in each country for ca. 55 days in 2012 and analyzed for 25 OCPs. Hexachlorocyclohexanes (HCHs) and DDTs constituted the highest burden of atmospheric OCPs in the target countries, at average concentrations of 441 pg m^?3 (range 23–2718) and 403 pg m^?3 (range 91–1880), respectively. Mirex had the lowest concentration, ranged between 0.1 and 3.3 pg m^?3. The concentration of OCPs in rainy season was higher than in dry season in Cameroon, and presupposed inputs from agriculture during the rainy season. The concentrations of ∑25 OCPs in each country were in the following order: Cameroon > Nigeria > Benin > Togo. There was significant evidence, based on chemical signatures of the contamination that DDT, aldrin, chlordane, and endosulfan were recently applied at certain sites in the respective countries.     

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.     

Persistence,variance and toxic levels of organochlorine pesticides in fluvial sediments and the role of black carbon in their retention

The present study assesses the persistence and variation of organochlorine pesticides (OCPs) and their regulation by total organic carbon (TOC) and black carbon (BC) in freshwater sediment. Sediment samples from the Yamuna River, a major tributary of the Ganges (one of the most populated and intensively used rivers in Asia), had high levels of Σ₂₀OCPs (21.41 to 139.95 ng g^?1). β-Hexachlorocyclohexane (β-HCH) was the most predominant component. ΣHCH and Σdichloro-diphenyl-trichloroethane (DDT) constituted ~86 % of Σ₂₀OCPs. Isomer ratios indicated fresh usage of lindane, DDT and technical-grade HCH. Toxicological comparison with freshwater sediment quality guidelines showed γ-HCH and DDT at high levels of concern. β-HCH, α-HCH, endrin, heptachlor epoxide, dichloro-diphenyl-dichloroethane (DDD), dichloro-diphenyl-dichloroethylene and chlordane were above some of the guideline levels. TOC and BC had mean concentrations of 1.37?±?0.51 % and 0.46?±?0.23 mg g^?1, respectively. BC constituted 1.25 to 10.56 % of TOC. We observed low to moderate correlations of BC with isomers of HCH, p,p′-DDT and methoxychlor while of TOC with Σ₂₀OCPs, γ-HCH, endosulfan sulfate and methoxychlor. Principal component analysis enabled correlating and clustering of various OCPs, BC and TOC. OCP distribution was related with pH, electrical conductivity, soil moisture and finer fractions of sediment. OCPs with similarity in properties that determine their interactions with carbonaceous components of sediment clustered together. A number of factors may, thus, be involved in the regulation of interactive forces between BC and OCPs. BC in this study may be more important than TOC in the retention of some OCPs into fluvial sediments, thereby reducing their bioavailability. The finding is probably the first of its kind to report and emphasises the role of BC in the persistence of OCPs in fluvial sediments.     

Presence of DDT metabolites in water,sediment and fish muscle tissue from Lake Prespa,Republic of Macedonia

Organochlorine pesticides were determined in water and sediment samples collected from the littoral zone of Lake Prespa, as well as from its three main tributaries (the rivers Golema, Brajcinska and Kranska), during the period 2004 to 2006. In addition, muscle tissue samples of barbus fish (Barbus prespensis Karaman, 1928) collected from the littoral zone of Lake Prespa were also analysed. The obtained results give an overview of the contamination levels of these problematic compounds at their potential sources in the river mouths, in the potentially affected, species-rich littoral section of the lake and in the muscle tissue of one selected fish species, collected near the rivers’ deltas. Special attention was paid to the presence of some DDT metabolites (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p′–DDE); (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDD) and 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDT). The extraction of pesticides from water samples was done by liquid-liquid partition in dichloromethane. For the sediment and fish tissue we used solid-liquid extraction. The extracted residues were analyzed on a gas chromatograph equipped with an electron capture detector (GC-ECD). The results of the respective studies indicated the presence of DDT metabolic forms in the samples of the three analysed matrixes. The highest levels of presence for these pollutants were found in the muscle tissue of the fish samples. The total DDTs content in the analysed muscle tissue samples range from 11.67 to 13.58 μg kg^?1of fresh tissue. The average total DDTs content for the sediment samples were within the range of 2.32 to 4.17 μg kg^?1 of dry sediment. Higher DDT metabolites content were found in the sediments collected from the rivers than in the samples from the littoral zone. The lowest average total concentrations of DDTs, on the other hand, were recorded in the water samples and ranged between 0.036 and 0.057 μg L^?1. The obtained results indicated that the dominant metabolic form in the samples of the three investigated matrixes (water, sediment and fish tissue) from Lake Prespa was p,p′-DDE. There was a very good linear correlation in this study between the content of DDT's (total DDT metabolites) detected and the percentage of total organic material in the sediment. The detected concentrations are clearly below the toxicity thresholds; consequently, severe effects on the endemic species of Lake Prespa are not very likely.