Di- and tribromoindoles in the common oyster (Crassostrea virginica)

The sources/origins, fate and impacts of naturally occurring organobromine compounds in the marine environment are largely unknown. Soft tissue composites of the common oyster (Crassostrea virginica) collected from coastal Georgia (USA) were analyzed for organobromines by gas chromatography. Three simple bromoindoles (BIs)--two dibromo- and one tribromo congener--were detected and their molecular formulas elucidated by electron and negative chemical ionization GC-MS. Semi-quantitative estimates of BI concentrations in these samples using GC-ECD indicated that oysters sampled in November 1999 contained 5-10 times more BIs than those sampled in August 2000 and March 2001. Although their bromine substitution patterns are presently unknown, this first ever report of bromoindoles in C. virginica, a prolific and important commercial and ecological species, underscores its potential utility as a bioindicator of organobromines in the coastal marine environment.     

Determination of toxaphenes in fish and marine mammals

An analytical method for the determination of toxaphene in biological materials using gas chromatography with an electron capture detector (GC-ECD) has been established and validated for three single congeners (chlorinated bornanes (CHB) 26, 50 and 62). The analytical method was based on a method for determination of PCB, DDT and other chlorinated pesticides. To include toxaphene congeners an extra step, adsorption chromatography on silica columns, was introduced to separate the pesticides from PCB. The recovery of CHB-26, 50 and 62 were 97+/-11%, 94+/-10% and 99+/-12%, respectively. Samples from cod, ringed seal and polar bear from the Norwegian arctic environment have been analysed. The levels of CHB-26 and 50 found were 13-55 ng/g fat in cod, 1.3-7.7 ng/g fat in ringed seal and 0.4-119 ng/g fat in polar bear. The levels of CHB-62 were 2.0-13, 0.8-3.4, 0.2-11 ng/g fat in cod, ringed seal and polar bear, respectively.     

Organochlorine pesticides,PCBs and heavy metals in tissues of the mullet Liza aurata in lake Ganzirri and Straits of Messina (Sicily,Italy)

The aim of this research was to investigate the presence of organochlorine pesticides, PCBs and heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in fish living in lake Ganzirri and the Straits of Messina, using the mullet Liza aurata as a "biological indicator". Different tissues of Liza aurata, which include the muscle, gill and vertebral column, were taken for analyses. Quantitative determination of the organochlorine compounds was performed by GC-ECD and confirmed with GC-MS. The concentrations of "essential" and "toxic" heavy metals were determined by Atomic Absorption Spectrophotometry. For the mullets of lake Ganzirri, the study showed DDE in three samples of gills and one of muscle, at concentrations below the MRL; no appreciable residues of PCBs (Aroclor 1232 series) were found. The concentrations of Zn and Cu were much higher than those of the "toxic" metals. No traces of organochlorine pesticides and PCBs were found in the individuals from the Straits of Messina. Therefore, these results indicate that these two environments are not at toxicological risk.     

Bulk atmospheric deposition of persistent toxic substances (PTS) along environmental gradients in Brazil

Bulk atmospheric deposition measurements for selected persistent toxic substances (PTS) were performed along environment gradients (urban–suburban–rural–background sites) in Brazil. The aim with this work is to investigate the fate of PTS and their emissions in South America, particularly along environment transects. Bulk sampler systems (polyurethane foams, 1?×?1 m²) were fixed along environment gradients (urban–suburban–rural–background) over summer and winter periods (2005–2007) at sites of different climate zones of Brazil. Organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) were analyzed by gas chromatography coupled to electron capture detector (Shimadzu 2010, 20i GC-ECD). Urban sites reported the highest deposition rates for all PTS, ranging from tens to thousands of pictograms per square meter per day. Basically, there were no obvious seasonal differences in deposition rate concentrations for PTS along the urban–suburban–rural–background gradient. Dichlorodiphenyltrichloroethane (DDT) and its metabolites were the OCs most frequently detected at relatively high deposition rate levels (>1,000 pg m^?2 day^?1). Other legacy and current-use pesticides such as hexachlorocyclohexanes, endosulfans, hexachlorcyclobenzine, dieldrin, aldrin, metoxichlor, and chlodanes were also detected at lower deposition rate levels (10–100 pg m^?2 day^?1). PCBs were detected at extremely high deposition rate levels (1,000–10,000 pg m^?2 day^?1) with highest contributions from the tetra-PCBs (PCB-52, PCB-44, PCB-66, PCB-81, and PCB-77) and penta-PCB congeners (PCB-101, PCB-105, PCB-114, PCB-118, and PCB-126). The greatest deposition rate concentrations for total PCBs were mainly detected at urban sites in connection with high population densities. The observed high deposition rate concentrations for PCBs and DDTs at urban sites are probably associated with old PTS stocks emissions. For PCBs in particular, the high levels are strongly associated with local population densities, highlighting the effect of local/regional urban sources on these target PTS. These results are important to show that even though the use of PTS is regulated, the deposition of selected PTS is still impacted by local and regional emissions in Brazil and may be related to the historical and continued emissions from old PTS stocks.     

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (alpha -HCH, beta -HCH, gamma -HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three S?o Paulo State cities: Araras, Araraquara and S?o Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (beta -HCH, gamma -HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, and p,p'-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

Application of automated mass spectrometry deconvolution and identification software for pesticide analysis in surface waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Induction of the P450 reporter gene system bioassay by polycyclic aromatic hydrocarbons in Ulsan Bay (South Korea) sediments

Polycyclic aromatic hydrocarbons (PAHs) and induction of the P450 reporter gene system (RGS) for 6- and 16-h exposure periods were determined in organic extracts of Ulsan Bay (South Korea) sediments to assess the utility of this bioassay as a screening tool for PAH contamination. The sum of the concentrations of 23 individual PAHs in 30 sediment samples (sigma PAH) based on GC-MS analysis ranged from 0.05 to 6.1 micrograms/g dry wt. P450 RGS fold induction ranged from 4.0 to 320 micrograms/g based on benzo[a]pyrene toxic equivalents (BaPEq). P450 RGS BaPEq and the 'chemical BaPEq', defined as the sum of the products of individual PAH concentrations and pre-determined toxic equivalency factors, exhibited very strong positive correlations with sigma PAH (r2 > 0.90; P < 0.001). Fold induction did not increase (and in some cases decreased) after the optimal incubation period (6 h) for PAHs, indicating that other compounds known to induce the P450 RGS (e.g. chlorinated organics) were not present at levels effecting significant induction. This was supported by GC-ECD analysis where non-ortho and mono-ortho polychlorinated biphenyls (PCBs) known to be strong P450 RGS inducers were found to be at very low or non-detectable levels in samples with the highest P450 RGS responses. The profound difference in PAH profiles for the two most contaminated sites suggested that this assay is especially sensitive for selected PAHs with greater than four rings. Combined with previous results, the P450 RGS shows promise as a useful screening tool for predicting deleterious biological effects resulting from CYP1A1-inducing, sediment-associated chemicals, particularly high molecular weight PAHs.     

Application of Automated Mass Spectrometry Deconvolution and Identification Software for Pesticide Analysis in Surface Waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg,France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.     

Development of GC capillary column for isomer-specific separation of toxic isomer of PCDDs and PCDFs in environmental samples

Analysis of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) has been performed using gas chromatography mass spectrometry (GC-MS). Analysis of the most toxic isomers, in particular, 2,3,7,8-substituted PCDD/PCDF in the presence of other isomers requires a special isomer specific capillary column or high performance liquid chromatography (HPLC) fractionation prior to GC-MS analysis. Commercially available long (>50 m) polar columns can separate 2,3,7,8-TCDD from other tetra isomers. However, those columns are not satisfactory for the analyses of total PCDD/PCDF in the environmental samples. Gas chromatography -high resolution mass spectrometry (GC-HRMS) and GC-MS/MS techniques are not helpful in the analysis of 2,3,7,8-TCDD unless it is separated from the other tetra isomers. The analysis of 2,3,7,8-TCDD and total PCDD and PCDF in a single GC-MS run can ease the laborious techniques presently used. In this study we have developed a new stationary phase for the GC capillary column. The capillary column developed using this new stationary phase showed unsurpassed selectivity for the separation of 2,3,7,8-TCDD from other tetra isomers. There are several advantages of the newly developed GC capillary column.     

Determination of pesticide residues in IPM and non-IPM samples of mango (Mangifera indica)

Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7-110.6%, at 0.1 and 1.0 microg g(-1) level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.     

Determination of pesticide residues in IPM and non-IPM samples of mango (Mangifera indica)

Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7 – 110.6%, at 0.1 and 1.0 μg g^{? 1} level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.     

Passive water sampling via semipermfable membrane devices (SPMDS) in concert with bivalves in the Sacramento/San Joaquin River Delta

Freshwater clams (Corbicula fluminea) and the Huckins et al. (1) semi-permeable membrane sampling device (SPMD) were simultaneously deployed at three sites on the Sacramento and San Joaquin rivers in 1990. Both clams and the SPMDs were analyzed for sequestered pesticides and polychlorinated biphenyls (PCBs) by gas chromatography with electron capture detection (GC/ECD). Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs were quantified by high resolution mass spectrometry (MS). In general, levels of organochlorine compounds were approximately 1.6 times higher in clams on a wet weight basis than in the SPMDs, and trends in accumulation were similar except where biofouling of the SPMD membranes decreased uptake rates. Comparisons between the normalized, average levels of PCDDs accumulated showed that while octachlorodibenzo-p-dioxin (OCDD) was most prevalent in both clams and SPMDs, much higher levels of 2,3,7,8 TCDD were found in the SPMDs than in the clams; 2,3,7,8 TCDD was 32% of the profile relative to the OCDD level for the SPMDs and <1% of the clam OCDD level. PCB levels showed the clams primarily accumulated hexachlorinated PCBs while the pentachlorinated and tetrachlorinated congeners were higher in the SPMDs. Differences in profiles for homologous series among the PCBs reveal that some congeners, especially those with 2,4,5 substitution, are more likely to bioaccumulate than those with lower chlorination or adjacent unsubstituted sites. GC/MS chromatograms indicate the SPMDs also sequestered several polyaromatic hydrocarbons. GC/ECD chromatograms indicate the presence of several unidentified, early eluting compounds in the SPMDs.     

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho substituted biphenyls in polar bear milk from Svalbard (Norway)

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g⁻¹ fat (0.2–1.6 pg ml⁻¹ milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.     

Organochlorine pesticides and polychlorinated biphenyls (PCBs) in eggs of red-legged frogs (Rana aurora) and northwestern salamanders (Ambystoma gracile) in an agricultural landscape

Organochlorine pesticides were widely used in the past in Sumas Prairie, British Columbia, Canada. In the 1990s, the hatching success of amphibians from agricultural sites was significantly depressed in the Sumas Prairie compared to reference sites. Therefore, in this study, organochlorine pesticides and polychlorinated biphenyls (PCBs) were measured in eggs of red-legged frogs (Rana aurora) and northwestern salamanders (Ambystoma gracile) from the Sumas Prairie. Egg masses were sampled from three agricultural sites that were exposed to agricultural runoff, and three reference sites that had lower agricultural runoff exposures. Not only was there little difference in contamination between agricultural and reference sites, but the levels of pesticides and PCBs found were lower than the concentrations reported to cause developmental or behavioural problems in amphibians.     

Analysis of some organochlorine pesticides in an urban atmosphere (Strasbourg, east of France)

High volume samples of urban air have been collected in Strasbourg, a big city situated in the east of France, for the evaluation of the contamination by organochlorine pesticides. Pesticides (p,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, dieldrin, endrin, gamma-HCH, cis-chlordane, trans-chlordane, alpha-endosulfan, beta-endosulfan, hexachlorobenzene, heptachlor and some of their metabolites: alpha-HCH, 2,4'-DDT, 2,4'-DDD and 2,4'-DDE) were analysed by GC-ECD. Prior to analysis, samples were Soxhlet extracted with a mixture of n-hexane/methylene chloride. The analysis of samples collected in 2001 (n = 6), 2002 (n = 7) and 2003 (n = 5) shows that alpha-HCH and gamma-HCH were detected in all samples (between 0.05 and 4 ng m(-3) and between 0.01 and 1 ng m(-3), respectively) along with aldrin and dieldrin at lower concentrations (between 0.01 and 0.08 ng m(-3) and between 0.02 and 0.09 ng m(-3), respectively). Other pesticides were detected very randomly at very low concentrations. The calculation of the alpha/gamma-HCH ratio shows that hexachlorocyclohexane measured in the atmosphere have a local origin and come probably from contaminated soil by volatilisation. alpha and beta-endosulfan were practically not detected in samples collected in 2001 and 2002 while they were always measured in the gas phase in samples from 2003. This observation can be explained by an increase of volatilisation with the increase of the air temperature. In July, temperature were higher (between 17 and 30 degrees C in climatic station) than in March-May 2001 and 2002 (between 2 and 19 and between 2 and 10, respectively).     

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.     

Age and seasonal variability of polybrominated diphenyl ethers in free-ranging East Greenland polar bears (Ursus maritimus)

Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean SigmaPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the SigmaPBDE concentration. The SigmaPBDE concentration had a highly significant correlation with SigmaPCB, SigmaCHL, dieldrin, HCB and SigmaHCH concentrations. We found a seasonal pattern of median SigmaPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression.     

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.