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The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.

A major part of sheep livers contains levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) above the former but to some extent also the new maximum levels (MLs) in the EU. In order to investigate the relationship between the intake of these contaminants and their accumulation in livers, kidney fat and meat, young blackhead sheep were fed with grass pellets containing PCDD/Fs at 2.5 times the maximum level. Levels of PCDD/Fs in livers were already quite high at the start of the exposure but increased 3-fold within 56d, exceeding the new product based MLs. Levels in meat and fat also increased but did not exceed the MLs. Although less elevated in the grass, both dl- and ndl-PCB levels also increased in liver and fat. Their kinetics in the tissues was less clear, potentially caused by increased levels in the straw given to the sheep during the whole experimental period. There was a clear difference in the behavior of the various congeners, the PCDFs and especially the higher chlorinated PCDFs and PCDDs showing a higher accumulation in the liver. In the case of the PCBs, this was particularly true for PCB 126. When switched to clean grass after 56d, the levels in livers and other tissues decreased to about the levels in the control sheep within 56d. This offers a potential solution for decreasing the intake of consumers., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Geophagy, the practice of consuming clay or soil, is encountered among pregnant women in Africa, Eastern Asia and Latin America, but also in Western societies. However, certain types of clay are known to contain high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The aim of this study was to determine the PCDD/F contents of orally consumed clays purchased from Dutch and African markets. Congener patterns were compared with those of pooled human milk samples collected in eight African countries, to investigate a possible relationship with clay consumption. From the Dutch market thirteen clay products were examined, seven of African and six of Suriname origin. From seven African countries, twenty clay products were collected. All 33 clay products were screened with a cell-based bioassay and those showing a high response were analyzed by GC/HRMS. High PCDD/F concentrations were measured in three clay products from the Dutch market, ranging from 66 to 103 pg TEQ g(-1), whereas clay products from African countries were from 24 to 75 pg TEQ g(-1). Patterns and relatively high concentrations of PCDD/Fs in human milk samples from the Democratic Republic of the Congo and Côte d'Ivoire suggest a relationship with the consumption of contaminated clay. Frequent use of PCDD/F contaminated clay products during pregnancy may result in increased exposure of the mother and subsequently the developing fetus and new-born child. The use of these contaminated clays during pregnancy should be carefully considered or even discouraged., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In this study, representative occurrence data for PCDD/Fs and dioxin-like PCBs in food were obtained and used to estimate dietary exposure of the Dutch population. Food composite samples were analyzed as well as single fish and vegetables samples. Total dioxin concentrations in animal products ranged from 0.05 pg TEQ/g product in poultry to 2.5 pg TEQ/g product (using TEF(2006)) in fish (shrimp), with 0.12pg TEQ/g product being the lowest concentrations measured in fish (tuna). In vegetable products, concentrations ranged from 0.00002 pg TEQ/g product (white kale) to 0.19 pg TEQ/g (oils and fats). A long-term dietary exposure distribution was calculated using Monte Carlo Risk Assessment software. The lower bound median exposure of the Dutch population to PCDD/Fs and dioxin-like PCBs was estimated at 0.8 pg WHO-TEQ/kgbw/d, half of which were dioxin-like PCBs. Dairy was the main source (38%) due to its high consumption. Time-trend analysis shows that the exposure to dioxins has further decreased by 35% over the past five years. This is due to lower levels of dioxin-like compounds in most of the foods, mainly influenced by lower levels in meat and milk. The use of the new TEFs gives an exposure reduction of 10% with respect to TEF(1998). Still, 4% of the Dutch population exceeds the exposure limit of 14 pg/kgbw/week as set by the EU.

Incidents with dioxins and PCBs have resulted in a strategy within the EU to reduce the exposure of the population to these compounds. Maximum levels were set for food and feed products and criteria were developed for the analytical methods (both confirmatory and screening) used for official control measurements. Ideally, any analysis performed with the aim of comparing the result with the legal limits should be performed according to these criteria. It should also apply to monitoring, performed to estimate human exposure and trend analysis rather than compliance with limits, since risk assessments and EU-policies rely heavily on these data. In recent years, analytical capacity has largely increased to complement the additional testing. In line with the responsibility of producers for the safety of their products, self-control has strongly increased and has played an important role in the discovery of several of the incidents. However, the increased monitoring seems not to have resulted in a clear further decrease in the levels reported for food and feed in the last decade. This may in part be due to a lack of follow up when elevated levels (above action levels) are found, which would lead to a reduction of output from remaining sources. It may also be related to the sensitivity of applied methods and the data collected in databases. This paper reviews the incidents and developments that have taken place within the EU over the last 15 years in the area of dioxins and PCBs, including the role of applying screening and confirmatory methods for achieving the desired further reduction in the levels. [ABSTRACT FROM AUTHOR]

Chicken and duck eggs collected from three different areas in Vietnam were examined for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). These regions included a background area, an area sprayed with Agent Orange and the Bien Hoa airbase area where Agent Orange was handled by the US Army. The latter area now is inhabited and people keep their own laying hens. Egg samples were first screened with an in vitro reporter gene bioassay and a selection was analyzed by GC/HRMS. Samples from Bien Hoa airbase showed very high PCDD/F levels, up to 249pg dioxin-equivalents (TEQ)/g fat, mainly due to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). In the sprayed areas, levels (3.2-8.2pgTEQg−1) were comparable to those observed in background areas (3.2-8.2pgTEQg−1 fat). The estimated average consumption of 22gd−1 of the highly contaminated eggs will result in a 2-fold exceedance of the current exposure limits for adults and 5-fold for children, even without considering other contaminated food sources. This indicates a potential health risk from consumption of these highly contaminated eggs, which were not yet considered as a source for exposure to PCDD/Fs of people living in the highly contaminated areas. [ABSTRACT FROM AUTHOR]

Polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), dioxin-like and non-dioxin-like (indicator) polychlorinated biphenyls (PCBs) and polybrominated diphenylethers (PBDEs) were monitored in butterfat obtained from 18 different areas in Turkey, both rural and industrial. The results obtained both at RIKILT in the Netherlands and in a food control laboratory in Turkey for PCDD/Fs and PCBs were in good agreement. The sum of PCDD/Fs+dl-PCBs, total indicator PCBs and PBDEs were in the range 0.26-3.82 pg TEQ g-1 fat, 0.20-3.04 ng g-1 fat and 0.18-5.00 ng g-1 fat, respectively. Despite the very low levels measured, slightly elevated PCDD/F and PCB levels were found in Izmir-Aliağa, Kocaeli, Denizli, and Zonguldak. The only result exceeding the EU action level was the dl-PCB concentration in Izmir-Aliağa. Ratios of PCDD/Fs and PCBs indicate that contamination in the elevated areas originated from different sources. High BDE 209 levels were detected in Mersin and Bursa. For the 18 regions analysed, the average total daily intake of total TEQ (dioxins and dl-PCBs) from butterfat was 0.09 pg TEQ(1998) (0.08 pg TEQ(2005)) kg-1 body weight, while those for indicator PCBs and PBDEs were 58.8 and 35.1 pg kg-1 body weight, respectively. The average total daily intake from dairy products were 0.26 pg TEQ(1998) (0.20 pg TEQ(2005)), 183 and 103 pg kg-1 body weight, respectively. [ABSTRACT FROM AUTHOR]

Fires and improper drying may result in contamination of feed with PCDD/Fs and PCBs. To predict the impact of elevated feed levels, it is important to understand the carry-over to edible products from food producing animals. Therefore, a carry-over study was performed with maize silage contaminated by a fire with PVC materials, and with sugar beet pulp contaminated by drying with coal, containing particles from a plastic roof. Levels of PCDD/Fs and dl-PCBs in the maize silage were 0.93 and 0.25 ng TEQ kg −1 , those in beet pulp 1.90 and 0.15 ng TEQ kg −1 (both on 88% dry matter (DM)). Dairy cows (3 per treatment) received either 16.8 kg DM per day of maize silage or 5.6 kg DM per day of sugar beet pellets for a 33-d period, followed by clean feed for 33 days. This resulted in a rapid increase of PCDD/F levels in milk within the first 10 days with levels at day 33 of respectively 2.6 and 1.7 pg TEQ g −1 fat for maize silage and beet pulp. Levels of dl-PCBs at day 33 were lower, 1.0 and 0.5 pg TEQ g −1 fat. In the case of the maize silage, the carry-over rates (CORs) at the end of the exposure were calculated to be 25% and 32% for the PCDD/F- and dl-PCB-TEQ, respectively. For the dried beet pulp the CORs were 18% and 35%. This study shows that the carry-over of PCDD/Fs and dl-PCBs formed during drying processes or fires can be substantial. [ABSTRACT FROM AUTHOR]

Abstract: At the end of 2004, during a routine monitoring project, high levels of PCDDs in milk from two farms were found. Using a bioassay and the congener patterns obtained by HRGC/HRMS, the source was traced back to the use of kaolinic clay for sorting potatoes in a production process of French fries. Rest products, especially peelings after scrubbing, were used as feed for dairy cows. Levels of PCCD/Fs in this product amounted to 44ng WHO1998-TEQkg−1 (88% dw). The maximum level observed in milk was 20pg WHO1998-TEQ g−1 fat. A Physiologically Based PharmacoKinetic (PB-PK) model was used to model three data obtained before eliminating the source in order to estimate the starting time of the contamination of the cows, the steady-state level after prolonged contamination and the kinetics of the decrease in the levels after removal of the source. Samples of milk were continuously collected for several months showing a decrease to levels below the product limit of 3pg WHO1998-TEQg−1 fat within 2months, in excellent agreement with the decrease predicted by the PB-PK model. Different batches of clay were sampled and analysed, showing varying levels of especially PCDDs. All clays were confirmed to be kaolinic clay using X-ray analysis. Other by-products used for animal feed were also contaminated and led to precautionary measures at a few hundred farms, especially pig farms. However, levels in other animal derived products like pig meat did not exceed the product limits. [Copyright &y& Elsevier]

During the last six years several incidents have occurred with dioxins in feed, stressing the need for rapid screening methods for these compounds. The most recent incident was the contamination of bakery waste used for animal feed due to the use of waste wood for drying of the material. In addition to Germany, the material was also shipped to the Netherlands. Levels up to 12 ng TEQ/kg have been detected, being about 15 times over the current limit of 0.75 ng TEQ/kg. In the Netherlands a combined strategy of screening with the CALUX-bioassay and the HRGC/HRMS confirmatory method was used to rapidly control the incident. Pigs were contaminated by the incident but only to a very limited extent. Despite the rather low limits for pig meat, the CALUX bioassay showed excellent performance, once again confirming the value of this assay. [Copyright &y& Elsevier]