Optimisation and use of tandem-in-time mass spectrometry in comparison with immunoassay and HRGC/HRMS for PCDD/F screening

Rapid screening of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans using quadrupole ion storage tandem-in-time mass spectrometry (QISTMS) conjointly with polyclonal antibody immunoassay has been considered. The optimisation of the fragmentation of the parent ion in the trap has been completed. The analysis of fly ashes from a municipal waste incinerator contaminated at different levels has then been realised. Results obtained using QISTMS, HRMS and immunoassay are compared.     

Levels and profiles of PCDDs,PCDFs and cPCBs in Belgian breast milk. Estimation of infant intake

Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 20 non-pooled breast milk samples collected in or close to an industrial area of Wallonia (Belgium). PCDD/F concentrations ranged between 16.0 and 52.1 pg TEQ/g fat, with a mean value of 29.4 pg TEQ/g fat. If coplanar PCBs (77, 126, 169) are included in TEQ calculations, levels ranged between 22.2 and 100.2 pg TEQ/g fat, with a mean value of 40.8 pg TEQ/g fat. It appears that 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126 account for more than 90% of the TEQ. Estimated PCDD/F dietary intake is 76 pg TEQ/kg body weight (bw)/day. This value is almost 20 times higher than the World Health Organization tolerable daily intake. A value of 103 pg TEQ/kg bw/day represents the intake of PCDDs, PCDFs and cPCBs (no mono-ortho PCBs included).     

Levels of PCDDs, PCDFs and PCBs in Belgian and international fast food samples

Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were performed on twenty-eight non-pooled fast food samples collected in Belgium, Switzerland, Czech Republic, United States of America and Australia. PCDD/F and PCB concentrations for the four investigated types of meals were very low. PCDD/F values ranged from non-detected to 1.40 pg WHO-TEQ/g fat and from 0.79 to 2.08 pg WHO-TEQ/g fat for lower and upper bound, respectively. Major contributors to the PCDD/F TEQ were 1,2,3,4,7,8-HxCDD, 1,2,3,6,7,8-HxCDD, 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF. The relative contribution of PCBs to the total TEQ was 68%. For adults, an average estimated intake was 6.7 pg WHO-TEQ/kg bw/month, including consumption of all types of analyzed meals, representing 9.5% of the PTMI. For child, a value of 14.5 pg WHO-TEQ/kg bw/month was obtained, representing 20.6% of the PTMI.     

Increased risk of non-Hodgkin lymphoma and serum organochlorine concentrations among neighbors of a municipal solid waste incinerator

Organochlorine chemicals may contribute to an increased risk of non-Hodgkin lymphoma (NHL) within non-occupationally exposed populations. Among these chemicals, dioxins and furans were mainly released by municipal solid waste incinerators (MSWIs) until a recent past in France, a source of exposure that is of public concern. We investigated organochlorines and the risk of NHL among neighbors of a French MSWI with high levels of dioxin emissions (Besan?on, France), using serum concentrations to assess exposure. The study area consisted of three electoral wards, containing or surrounding the MSWI. Pesticides, dioxins, furans, and polychlorinated biphenyls (PCBs) were measured in the serum of 34 newly diagnosed NHL cases (2003-2005) and 34 controls. Risks of NHL associated with each lipid-corrected serum concentration were estimated using exact logistic regression. The pesticides β-hexachlorocyclohexane (odds ratio [OR]=1.05, 95% confidence interval [CI]=1.00-1.12, per 10 ng/g lipid) and p,p' dichloro-diphenyl-trichloroethane (DDT) (OR=1.20, 95% CI=1.01-1.45, per 10 ng/g lipid) were associated with NHL risk. Evidence indicated an increased NHL risk associated with cumulative WHO(1998)-toxic equivalency factor (TEQ) concentrations (dioxins, OR=1.12, 95% CI=1.03-1.26; furans, OR=1.16, 95% CI=1.03-1.35; dioxin-like PCBs, OR=1.04, 95% CI=1.00-1.07; and total TEQ, OR=1.04, 95% CI=1.01-1.05), as well as with non dioxin-like PCBs (OR=1.02, 95% CI=1.01-1.05, per 10 ng/g lipid). Most congener-specific associations were statistically significant. This study provides strong and consistent support for an association between serum cumulative WHO(1998)-TEQ concentrations, at levels experienced by people residing in the vicinity of a polluting MSWI, and risk of NHL.     

Survey of commercial pasteurised cows' milk in Wallonia (Belgium) for the occurrence of polychlorinated dibenzo-p-dioxins,dibenzofurans and coplanar polychlorinated biphenyls

Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 35 samples of commercial long-life pasteurised cows' milk issued from eight different brands available in Walloon supermarkets (Belgium). The observed congener profile was characteristic of milk samples issued from industrialised countries with good inter and intra-brand reproducibility's. The PCDDs to PCDFs ratio was equal to 1.8 in concentration. The toxic equivalent (TEQ based on WHO-TEF) value for PCDD/Fs in all analysed milks was 1.09+/-0.30 pg TEQ/g fat (range 0.86-1.59), which is below the recommended EU non-commercialisation threshold value of 3 pg TEQ PCDD/Fs/g of milk fat. The mean TEQ value including cPCBs was 2.23+/-0.55 pg TEQ/g fat. These PCBs actually contributed for 49+/-8.6% of the total TEQ. Among PCDD/Fs and cPCBs, tetrachloro dibenzo-p-dioxin (TCDD), pentachloro dibenzo-p-dioxin (PeCDD), pentachloro dibenzofurans (PeCDFs) and 3,3',4,4',5-pentachloro biphenyl (PCB-126) were the most important contributors to the TEQ. Estimated daily intake (EDI) due to consumption of such milks was 0.34 pg TEQ/kg of body weight/day for PCDD/Fs and 0.69 pg TEQ/kg of body weight/day when cPCBs were included.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

Comprehensive two-dimensional gas chromatography time of flight mass spectrometry (GC×GC-TOFMS) for environmental forensic investigations in developing countries

The disposal and dumping of toxic waste is a matter of growing concern in developing countries, including South Africa. Frequently these countries do not possess access to gas chromatography-high resolution mass spectrometry (GC-HRMS) for the determination of persistent organic pollutants (POPs). This publication describes an alternative approach to the investigation of toxic waste using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS). The technology permits both comprehensive screening of toxic samples for numerous classes of organic pollutants and also quantitative analysis for the individual compounds. This paper describes the use of this technique by analysing samples obtained from a hazardous waste treatment facility in South Africa. After sampling and extraction the samples were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and four dioxin-like non-ortho substituted polychlorinated biphenyls (PCBs). The quantitative values, as well as detection limits, obtained using the GC × GC-TOFMS methodology compares well with those obtained using GC-HRMS; the accepted benchmark technology for this analysis. Although GC × GC-TOFMS is not a target compound analytical technique (as is GC-HRMS), it is possible to obtain information on numerous other classes of organic pollutants present in the samples in one analytical run. This is not possible with GC-HRMS. Several different column combinations have been investigated for handling very complex waste samples and suggestions are presented for the most suitable combination.     

Levels and trends of PCDD/Fs and PCBs in camel milk (Camelus bactrianus and Camelus dromedarius) from Kazakhstan

To date, despite the fact it represents a very important part of the national dairy production, no data are available concerning the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in camel milk from the Republic of Kazakhstan. Selected PCDDs, PCDFs, and PCBs were measured in pools of milk from camels (n=15) located in various places of Kazakhstan (Almaty, Atyrau, Aralsk, Shymkent) and sampled at two different seasons for two different species (Camelus bactrianus and Camelus dromedarius). Non-dioxin-like (NDL-)PCB concentrations (6.3±2.7 ng g(-1) fat, median 5.1 ng g(-1) fat, range 0.6-17.4 ng g(-1) fat) were far below the maximum value of 40 ng g(-1) fat proposed by the EU. Dioxin-like (DL-)PCB concentrations (1.7±0.7 ng g(-1) fat, median 1.5 ng g(-1) fat, range 0.3-4.2 ng g(-1) fat) and the NDL-PCB to DL-PCB ratio (4.3) were similar to what is reported in EU for cow-based dairy products. PCB 52 and PCB 101 appeared to be proportionally more present in Kazakh camel milk samples (>60% of the sum of the 6 indicator NDL-PCBs) than in European cow milk samples (<10% of the sum of the 6 indicator NDL-PCBs), indicating possible differences in the route of exposure to PCBs in Kazakhstan. PCB 105 and PCB 118 appeared to be present at higher concentrations in camel milk (>80% of the sum of the 12 DL-PCBs). PCB 105, PCB 118 and PCB 156 were the major congeners for DL-PCBs, accounting for 92% of the sum of concentrations of DL-PCBs (88% for Belgian cows). In terms of TEQ, PCB 126 and PCB 118 are the major contributors and represent, respectively, 80% and 14% of the DL-PCB TEQWHO05 concentrations. No significant interracial or geographical trends were observed for NDL- and DL-PCB profiles. However, concentrations of all DL-PCBs appeared to be significantly higher for samples collected in Atyrau region. 2,3,7,8-TCDD level (mean 0.08±0.07 pg g(-1) fat, median 0.08 pg g(-1) fat, range 0.00-0.18 pg g(-1) fat, 60%>LOQs) were very low for all samples and 2,3,4,7,8-PeCDF was the major contributor (27%) to the PCDD/F TEQWHO05. Considering the total TEQWHO05 (sum of DL-PCBs and PCDD/Fs), DL-PCB and PCDD/F contributed for 73% and 27%, respectively. A decrease of only 1% of the total TEQ was observed when using the TEFWHO05 scale instead of the TEFWHO98 scale. Two samples collected in the region of Atyrau exceeded the EU maximum level value of 6.00 pg TEQWHO98 g(-1) fat (6.4 pg TEQWHO05 g(-1) fat and 6.9 pg TEQWHO05 g(-1) fat). Both samples exceeded the EU action level for the sum of DL-PCBs. Based on the fact that camel milk is used to prepare popular traditional fermented drinks like shubat, this suggests that the human exposure in the Caspian Sea region of Atyrau should be expected to be higher than in the other regions studied here.     

Levels and congener distributions of PCDDs,PCDFs and non-ortho PCBs in Belgian foodstuffs--assessment of dietary intake

Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 197 foodstuffs samples of animal origin from Belgium during years 2000 and 2001. All investigated matrices (except horse) present background levels lower than the Belgian non-commercialization value of 5 pg TEQ/g fat. Pork was the meat containing the lowest concentration of both PCDD/Fs and cPCBs. The mean background concentration of 2,3,7,8-TCDD toxicity equivalent in milk was 1.1 pg/g of fat, with a congener distribution typical of non-contaminated milk. The relative contribution of 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF to the PCDD/Fs TEQ was 85+/-7.9% for all investigated matrices. The cPCBs contribution to the total TEQ was 47+/-19.0% for products of terrestrial species and 69+/-20.0% for aquatic species. Once the contribution of cPCBs was added to the TEQ, few foodstuffs such as horse, sheep, beef, eggs and cheese presented levels above the future European guidelines that currently only include PCDD/Fs but will be re-evaluated later in order to include 'dioxin-like' PCBs. Based on levels measured in the samples, the estimation of the dietary intake was 65.3 pg WHO-TEQ/day for PCDD/Fs only (1.00 pg WHO-TEQ/kg bw/day, for a 65 kg person) and 132.9 pg WHO-TEQ/day if cPCBs were included (2.04 pg WHO-TEQ/kg bw/day, for a 65 kg person). Meat (mainly beef), dairy products, and fish each account for roughly one third of the intake.