Occurrence of polybrominated diphenylethers, polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in coastal sediments from Spain

Fifteen sediment samples were analysed in order to determine their content of polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). Samples were collected from several hot spots on the Spanish coast, such as the harbours of Almeria and Tarragona, and the mouths of the Besos and Llobregat rivers in Barcelona. A generic analytical procedure based on Soxhlet extraction followed by an automated cleanup system and gas chromatography-ion trap-mass spectrometry was employed for determining the toxic congeners of PCDDs and PCDFs, as well as dioxin-like PCBs. As regards PBDE determinations, a rapid method based on the use of selective pressurized liquid extraction followed by gas chromatography-negative ion chemical ionization-mass spectrometry was applied. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. WHO-TEQ values ranged from 0.3 to 75 pg/g dry weight (dw), with PCB contribution on the toxicity of the samples between 1 and 84%. Total PBDE levels ranged from 2.7 to 134 ng/g dw, with BDE-209 contribution on the total PBDE contamination between 50 and 99%.     

Simultaneous quantification of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) in Mississippi river water, in New Orleans, Louisiana, USA

An effective analytical method for simultaneously determining 16 polycyclic aromatic hydrocarbons (PAHs), 28 polychlorinated biphenyl (PCBs), and 12 pharmaceuticals and personal care products (PPCPs) has been developed to measure their concentrations in the Mississippi river waters in New Orleans, Louisiana, USA. The method involves the simultaneous extraction of the selected PAHs, PCBs, and PPCPs, from the aqueous phase by solid phase extraction using two-layer disks consisting of C(18) and SDB-XC, and collection of suspended solid in water samples by 0.2-0.6 microm filter in a single step. Target compounds adsorbed on the extraction disks were eluted with methanol, acetone, and dichloromethane. The suspended particles retained by the filter were sonically extracted using the same solvents. GC/MS was used for quantification of PAHs and PCBs directly and of PPCPs after derivatization. The analytical method was used in a 6-month field study of the Mississippi river water for contamination by PAHs, PCBs, and PPCPs and the following concentrations (ng/l) have been obtained: clofibric acid (3.2-26.7), ibuprofen (0-34.0), acetaminophen (24.7-65.2), caffeine (0-38.0), naproxen (0-135.2), triclosan (8.8-26.3), bisphenol A (0-147.2), carbamazepine (42.9-113.7), estrone (0-4.7), 17beta-estradiol (0-4.5), total PAHs (62.9-144.7), and total PCBs (22.2-163.4).     

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.     

Levels of PCBs, PCDDs and PCDFs in commercial butter samples in Spain

Feasibility of three different extraction methods for the simultaneous determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in butter is discussed. The method based on liquid-liquid extraction with water of the non fatty solids from butter dissolved in hexane was found to be the most efficient for the determination of the lipid content and the levels of the investigated pollutants. This method was used to evaluate the background levels of PCBs, PCDDs and PCDFs in butters commercially available in Spain. Broad ranges of PCB, specifically, PCDD and PCDF concentrations were found in the different brands analysed. Levels, profiles and patterns of these pollutants in butter were compared with those previously reported for different Spanish dairy products. The toxic tetra-equivalents of 2,3,7,8-TCDD (1-TEQ) averages for PCDDs and PCDFs in the 21 butter samples analysed were 0.41 and 0.70 pg/g fat basis, respectively. These values were similar or lower than those cited in the literature for other countries.     

AhR-active compounds in sediments of the Haihe and Dagu Rivers, China

Total concentrations of compounds that can cause activation of the aryl hydrocarbon receptor (AhR) in extracts of river sediments from various locations in the Haihe and Dagu Rivers, Tianjin, China were determined by use of the in vitro H4IIE-luc cell line. AhR-active compounds were isolated from sediments by Soxhlet extraction, and the crude extracts were fractionated using a Florisil column into three Fractions. The response of samples was compared to the TCDD standard and expressed as 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TCDD-EQs). Significant dioxin-like activity was observed in each sample. The TCDD-EQs in crude extracts of sediments (SCEs), as determined with the bioassay were 2-4 times greater than the sum of the TCDD-EQs of the eluent from fractions separated with a Florisil column. The results also showed that Fractions 2 and 3 contained most of the AhR-mediated activity. The results obtained by using the bioassay were compared with those of previous measurements of the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and the structurally-similar AhR-active polychlorinated biphenyls (PCBs). It was determined that sediments from the Dagu River contained greater concentrations of TCDD-EQ than did sediments from the Haihe River except at Jingangqiao (location R3), which is associated with industrial activities in the adjacent densely populated area. The concentrations of TCDD-EQs, based on the EC20 and the relative potency ranges, of SCEs ranged from 330 to 930 and 1200 to 13,900 pg TCDD-EQ g(-1) dry wt in Haihe and Dagu Rivers, respectively.     

Extraction of organic contaminants from marine sediments and tissues using microwave energy.

In this study, we compared microwave solvent extraction (MSE) to conventional methods for extracting organic contaminants from marine sediments and tissues with high and varying moisture content. The organic contaminants measured were polychlorinated biphenyl (PCB) congeners, chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs). Initial experiments were conducted on dry standard reference materials (SRMs) and field collected marine sediments. Moisture content in samples greatly influenced the recovery of the analytes of interest. When wet sediments were included in a sample batch, low recoveries were often encountered in other samples in the batch, including the dry SRM. Experiments were conducted to test the effect of standardizing the moisture content in all samples in a batch prior to extraction. SRM1941a (marine sediment). SRM1974a (mussel tissue), as well as QA96SED6 (marine sediment), and QA96TIS7 (marine tissue), both from 1996 NIST Intercalibration Exercise were extracted using microwave and conventional methods. Moisture levels were adjusted in SRMs to match those of marine sediment and tissue samples before microwave extraction. The results demonstrated that it is crucial to standardize the moisture content in all samples, including dry reference material to ensure good recovery of organic contaminants. MSE yielded equivalent or superior recoveries compared to conventional methods for the majority of the compounds evaluated. The advantages of MSE over conventional methods are reduced solvent usage, higher sample throughput and the elimination of halogenated solvent usage.     

Occupational exposure

Concentrations of polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), hexachlorobenzene and methylsulphonyl metabolites of PCB were determined in blood plasma from potentially exposed workers and controls. Three of the potentially exposed subjects had worked with cable incineration and two were electricians. Extraction of the organochlorine compounds and lipids were performed using the lipophilic gel Lipidex. Different adsorbents and gel permeation chromatography were applied for further purification of the samples and separation of analytes. Determinations of the chlorinated compounds were made by using gas chromatography with electron-capture detection and gas chromatography-mass spectrometry. Only small differences in the concentrations of organochlorine compounds were found in the plasma from the three subject groups. Thus, specific exposure of the workers could not be confirmed.     

Optimization of selective pressurized liquid extraction for extraction and in-cell clean-up of PCDD/Fs in soils and sediments

This paper describes the development of methods for selective extraction of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from soils and sediments, using pressurized liquid extraction with in-cell clean-up (SPLE). Two binary solvent mixtures, viz. dichloromethane/n-heptane (DCM/Hp), and diethylether/n-heptane (DEE/Hp), were evaluated. The SPLE extraction conditions were optimized using central composite face (CCF) design. Three factors were investigated: extraction temperature (60–160 °C), number of extraction cycles (1–3) and time per cycle (2–18 min). The results showed that DCM/Hp (1/1, v/v) and DEE/Hp (1/2, v/v) were the best extraction solvent compositions and that the extraction temperature was a critical factor that needed careful optimization to achieve high extraction efficiency without co-extraction of sulfuric acid. Under the optimal conditions, the SPLE methods provided results with good accuracy and precision. For the sandy soil certified reference material (CRM-529) the quantification results ended up in the range 82–110% as compared to the concentrations obtained by a reference method based on Soxhlet extraction and external column clean-up. Furthermore, for a clay soil (CRM-530) and a sediment reference material (WMS-01), the accuracy (trueness) of the TEQ values were +11% (DCM/Hp) and +8% (DEE/Hp) for CRM-530, +8% and ?7% for WMS-01, respectively. The individual congener concentrations also agreed well with the certified values. These findings show that SPLE is a promising method for combined extraction and clean-up of PCDD/Fs in soil/sediment samples.     

Occupational exposure

Concentrations of polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), hexachlorobenzene and methylsulphonyl metabolites of PCB were determined in blood plasma from potentially exposed workers and controls. Three of the potentially exposed subjects had worked with cable incineration and two were electricians. Extraction of the organochlorine compounds and lipids were performed using the lipophilic gel Lipidex. Different adsorbents and gel permeation chromatography were applied for further purification of the samples and separation of analytes. Determinations of the chlorinated compounds were made by using gas chromatography with electron-capture detection and gas chromatography-mass spectrometry. Only small differences in the concentrations of organochlorine compounds were found in the plasma from the three subject groups. Thus, specific exposure of the workers could not be confirmed.     

Dependence of GC-RRTs on the solvent-accessible surface area of dioxins and related compounds

The correlation between gas chromatograph relative retention times (GC-RRTs) of dioxins and related compounds, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated naphthalenes (PCNs), and their solvent-accessible surface area (SAS) was analyzed for congeners and isomers. GC-RRTs were linearly dependent on SAS for congeners while there was little dependence for isomers. However, by using classification parameters, Nad-Cl, Nad-H, N1,9Cl, and NalphaCl, based on the substitution positions and patterns of chlorine and/or hydrogen atoms bound to the molecular skeleton, a linear relationship was found among isomers. Furthermore, the GC-RRTs of CDD, CDF, and CN isomers, which are planar, decreased despite increasing SAS, and this tendency was enhanced with the above classification. The retention behavior was explained in terms of the effective enhancement of molecular hydrophobicity caused by an increase in the number of adjacent chlorine pairs.     

Assays of dioxins and dioxin-like compounds in actually contaminated soils using transgenic tobacco plants carrying a recombinant mouse aryl hydrocarbon receptor-mediated β-glucuronidase reporter gene expression system

The transgenic tobacco plant XD4V-26 carrying the recombinant mouse aryl hydrocarbon receptor XD4V-mediated β-glucuronidase (GUS) reporter gene expression system was used for assay of dioxins and dioxin-like compounds consisting of polychlorinated dibenzeno-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls (Co-PCBs) in actually contaminated soils. The transgenic tobacco plant XD4V-26 showed a significant dose-dependent induced GUS activity when cultured on MS medium containing PCB126 [toxic equivalency factor (TEF) = 0.1]. In contrast, PCB169 and PCB180, which have 0.03 of TEF and unassigned TEF values, respectively, did not significantly induce GUS activity under the same conditions as with PCB126. When the tobacco plants were cultivated for up to 5 weeks on actually contaminated soils with dioxins and dioxin-like compounds collected from the periphery of an incinerator used for disposal of residential and industrial wastes, GUS activity in the leaves was dose-dependently increased. The plants clearly detected 360 pg-TEQ g(-1) of dioxins and dioxin-like compounds in this assay. There was a positive correlation between GUS activity and TEQ value of dioxins and dioxin-like compounds in the plants. This assay does not require any extraction and purification processes for the actually contaminated soil samples.     

Mobility of polychlorinated aromatic compounds in soils contaminated with wood-preserving oil

Greater understanding of the mobility of polychlorinated aromatic compounds in soils is needed to investigate contamination and design suitable remediation strategies for sites contaminated with wood-preserving oil. The objectives of this study were (1) to develop a suitable aqueous batch extraction method for soil containing wood-preservative residues; (2) to determine partition coefficients for the primary contaminants [pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFS)] in oil, soil, and aqueous phases; and (3) to evaluate the potential soil migration of the primary contaminants. In a three-phase oil-soil-water mixture, PCP, PCDDs, and PCDFs were partitioned to the greatest extent in the oil phase. These results suggest that the migration of contaminants can occur in a saturated subsurface soil zone containing an oil phase at a wood-preserving site. In the absence of a free oil phase, PCDDs and PCDFs were highly partitioned onto soil and were considered non-leachable in the aqueous phase. However, PCP was considered highly leachable from contaminated soil containing only an aqueous liquid phase. Results from this study indicate that removal of any free oil phase present in subsurface soil should have highest priority during the cleanup of contaminated wood-preserving sites.     

Use of a column leaching test to study the mobility of chlorinated HOCs from a contaminated soil and the distribution of compounds between soluble and colloid phases

An equilibrium and recirculation column test for hydrophobic organic chemicals (ER-H test) was used to study the leaching behaviour of chlorophenols (CPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) from contaminated soil. A 50% increase in the pore water velocity was shown to have little or no effect on the mobility of CPs, PCDEs, PCDFs and PCDDs. The standard deviations of truly dissolved compounds, CPs, were between 19% and 65% between the tests. However, the repeatability of the ER-H test decreased with increases in the hydrophobicity of the studied compounds; the standard deviations for PCDEs, PCDFs and PCDDs ranged from 53% to 110%, 57% to 77% and 110% to 130%, respectively. The influence of colloids on the release of these compounds was also examined. Up to 30% of the CPs in the soil were leached, of which 1-3% were associated with colloids. The PCDEs, PCDFs and PCDDs were found to be preferably associated with the particulate fraction of the leachate, and less than 0.2% of these compounds were mobilised.     

Levels of dioxins and dioxin-like PCBs in food samples on the Greek market

Food intake is the main source of exposure to dioxin-like compounds for humans. The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) in 77 food samples from the Greek market and producers are presented. The study included the analyses of milk and dairy products, meat and meat products, fish, vegetable oil, eggs, fruit, vegetable and rice collected between August and December 2002. After extraction, extracts were cleaned up on a series of carbon column chromatography, silica gel, alumina chromatography, and then analysed by high resolution gas chromatography/high resolution mass spectrometry. All samples had a dioxin content far below the EC Regulation (2375/2001/EC) limits.     

Mobility of Polychlorinated Aromatic Compounds in Soils Contaminated With Wood-preserving Oil

Greater understanding of the mobility of polychlorinated aromatic compounds in soils is needed to investigate contamination and design suitable remediation strategies for sites contaminated with wood-preserving oil. The objectives of this study were (1) to develop a suitable aqueous batch extraction method for soil containing wood-preservative residues; (2) to determine partition coefficients for the primary contaminants [pentachlorophenol (PCP), polychlorinated dibenzo-p-dloxins (PCDDs), and polychlorinated dibenzofurans (PCDFS)] in oil, soil, and aqueous phases; and (3) to evaluate the potential soil migration of the primary contaminants. In a three-phase oil-soil-water mixture, PCP, PCDDs, and PCDFs were partitioned to the greatest extent in the oil phase. These results suggest that the migration of contaminants can occur in a saturated subsurface soil zone containing an oil phase at a wood-preserving site. In the absence of a free oil phase, PCDDs and PCDFs were highly partitioned onto soil and were considered non-leachable in the aqueous phase. However, PCP was considered highly teachable from contaminated soil containing only an aqueous liquid phase. Results from this study Indicate that removal of any free oil phase present in subsurface soil should have highest priority during the cleanup of contaminated wood-preserving sites.     

Assays of dioxins and dioxin-like compounds in actually contaminated soils using transgenic tobacco plants carrying a recombinant mouse aryl hydrocarbon receptor-mediated β-glucuronidase reporter gene expression system

The transgenic tobacco plant XD4V-26 carrying the recombinant mouse aryl hydrocarbon receptor XD4V-mediated β-glucuronidase (GUS) reporter gene expression system was used for assay of dioxins and dioxin-like compounds consisting of polychlorinated dibenzeno-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls (Co-PCBs) in actually contaminated soils. The transgenic tobacco plant XD4V-26 showed a significant dose-dependent induced GUS activity when cultured on MS medium containing PCB126 [toxic equivalency factor (TEF) = 0.1]. In contrast, PCB169 and PCB180, which have 0.03 of TEF and unassigned TEF values, respectively, did not significantly induce GUS activity under the same conditions as with PCB126. When the tobacco plants were cultivated for up to 5 weeks on actually contaminated soils with dioxins and dioxin-like compounds collected from the periphery of an incinerator used for disposal of residential and industrial wastes, GUS activity in the leaves was dose-dependently increased. The plants clearly detected 360 pg-TEQ g^?1 of dioxins and dioxin-like compounds in this assay. There was a positive correlation between GUS activity and TEQ value of dioxins and dioxin-like compounds in the plants. This assay does not require any extraction and purification processes for the actually contaminated soil samples.     

Organochlorine compounds,nitro musks and perfluorinated substances in breast milk – Results from Bavarian Monitoring of Breast Milk 2007/8

The aim of the Bavarian Monitoring of Breast Milk (BAMBI) project was to examine 10 organochlorine pesticides (OPs), 3 nitro musks, 6 indicator polychlorinated biphenyls (PCBs), 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), 12 dioxin-like PCBs (dl-PCBs) and several perfluorinated alkyl compounds in breast milk samples. A total of 516 breast milk samples were collected from seven regions in Bavaria and were analyzed by means of GC/ECD, GC/HRMS, and LC/MS-MS.     

Isolation and identification of intermediates from biodegradation of low chlorinated biphenyls (Delor-103)

Microorganism Pseudomonas species P2 metabolizes polychlorinated biphenyls (PCBs) and biphenyl, producing the whole spectrum of intermediates, among them coloured intermediates, which are suitable for the monitoring of PCBs degradation by optical sensors. Knowledge of chemical structures and conditions of development of colour metabolites is necessary for application of optical analytical methods. The main goal of this work was the isolation and identification of intermediates from the biodegradation of the mixture of low chlorinated biphenyls (Delor-103), which is based on the solid phase extraction (SPE) of the whole mixture using LiChrolut EN cartridges, then silylation of the extract as one way to the identification of one part of intermediates by GC-MS, and acetylation of the extract as a way for the further concentration and analysis of more polar chlorobiphenylols and chlorobiphenyldiols. The combination of SPE and following acetylation allows to obtain chlorobiphenylols and chlorobiphenyldiols as an almost pure fraction. The acetylation method could be also used instead SPE procedure with the same final concentration effect. Using the simulation mass spectrometry program, two new compounds, dihydrodihydroxytrichloro- and tetrahydrodihydroxytrichlorobiphenyl, as silylderivatives, were identified.     

Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.     

Assessment of human exposure to PCDDs,PCDFs and Co-PCBs using hair as a human pollution indicator sample I: Development of analytical method for human hair and evaluation for exposure assessment

Dioxins including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (Co-PCBs) are highly toxic. Even at environmental pollution levels, they cause hormonal damage in women, and they have been shown to induce immunosuppression and genital function damage in humans. In this study, a new method using isotope dilution was established to detect PCDDs, PCDFs and Co-PCBs in human hair. This method, comprised of washing and cutting of hair, alkaline decomposition, hexane extraction, multilayer silica gel column chromatography, high performance liquid chromatography with a porous graphite carbon column and analysis by high resolution gas chromatography/high resolution mass spectrometry, enabled us to analyze PCDDs, PCDFs and Co-PCBs at trace levels of less than pg/g with good reproducibility. In addition, there was a correlation between some isomers in human hair and blood collected from identical donors. Human hair analysis is useful to evaluate human risk assessment including that due to environmental pollution.