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The European Commission asked EFSA to update its 2012 risk assessment on brominated phenols and their derivatives in food, focusing on five bromophenols and one derivative: 2,4,6-tribromophenol ( 2,4,6-TBP ), 2,4-dibromophenol ( 2,4-DBP ), 4-bromophenol ( 4-BP ), 2,6-dibromophenol ( 2,6-DBP ), tetrabrominated bisphenol S ( TBBPS ), tetrabromobisphenol S bismethyl ether ( TBBPS-BME ). Based on the overall evidence, the CONTAM Panel considered in vivo genotoxicity of 2,4,6-TBP to be unlikely. Effects in liver and kidney were considered as the critical effects of 2,4,6-tribromophenol ( 2,4,6-TBP ) in studies in rats. A BMDL 10 of 353 mg/kg body weight (bw) per day for kidney papillary necrosis in male rats was identified and was selected as the reference point for the risk characterisation. The derivation of a health-based guidance value was not considered appropriate due to major limitations in the toxicological database. Instead, the margin of exposure (MOE) approach was applied to assess possible health concerns. Around 78,200 analytical results for 2,4,6-TBP in food were used to estimate dietary exposure for the European population. Considering the resulting MOE values, all far above an MOE of 6000 that does not raise a health concern, and accounting for the uncertainties affecting the exposure and hazard assessments, the CONTAM Panel concluded with at least 95% probability that the current dietary exposure to 2,4,6-TBP does not raise a health concern. Due to lack of occurrence data, no risk assessment could be performed for breastfed or formula-fed infants. No risk characterisation could be performed for any of the other brominated phenols and derivatives included in the assessment, due to lack of data both on the toxicity and occurrence., Competing Interests: If you wish to access the declaration of interests of any expert contributing to an EFSA scientific assessment, please contact interestmanagement@efsa.europa.eu., (© 2024 European Food Safety Authority. EFSA Journal published by Wiley‐VCH GmbH on behalf of European Food Safety Authority.)

The European Commission asked EFSA to update its 2011 risk assessment on tetrabromobisphenol A (TBBPA) and five derivatives in food. Neurotoxicity and carcinogenicity were considered as the critical effects of TBBPA in rodent studies. The available evidence indicates that the carcinogenicity of TBBPA occurs via non-genotoxic mechanisms. Taking into account the new data, the CONTAM Panel considered it appropriate to set a tolerable daily intake (TDI). Based on decreased interest in social interaction in male mice, a lowest observed adverse effect level (LOAEL) of 0.2 mg/kg body weight (bw) per day was identified and selected as the reference point for the risk characterisation. Applying the default uncertainty factor of 100 for inter- and intraspecies variability, and a factor of 3 to extrapolate from the LOAEL to NOAEL, a TDI for TBBPA of 0.7 μg/kg bw per day was established. Around 2100 analytical results for TBBPA in food were used to estimate dietary exposure for the European population. The most important contributors to the chronic dietary LB exposure to TBBPA were fish and seafood, meat and meat products and milk and dairy products. The exposure estimates to TBBPA were all below the TDI, including those estimated for breastfed and formula-fed infants. Accounting for the uncertainties affecting the assessment, the CONTAM Panel concluded with 90%-95% certainty that the current dietary exposure to TBBPA does not raise a health concern for any of the population groups considered. There were insufficient data on the toxicity of any of the TBBPA derivatives to derive reference points, or to allow a comparison with TBBPA that would support assignment to an assessment group for the purposes of combined risk assessment., Competing Interests: If you wish to access the declaration of interests of any expert contributing to an EFSA scientific assessment, please contact interestmanagement@efsa.europa.eu., (© 2024 European Food Safety Authority. EFSA Journal published by Wiley‐VCH GmbH on behalf of European Food Safety Authority.)

The European Commission asked EFSA to update its 2011 risk assessment on polybrominated diphenyl ethers (PBDEs) in food, focusing on 10 congeners: BDE-28 , - 47 , - 49 , - 99 , - 100 , - 138 , - 153 , - 154 , - 183 and ‑ 209 . The CONTAM Panel concluded that the neurodevelopmental effects on behaviour and reproductive/developmental effects are the critical effects in rodent studies. For four congeners ( BDE-47 , - 99 , - 153 , - 209 ) the Panel derived Reference Points, i.e. benchmark doses and corresponding lower 95% confidence limits (BMDLs), for endpoint-specific benchmark responses. Since repeated exposure to PBDEs results in accumulation of these chemicals in the body, the Panel estimated the body burden at the BMDL in rodents, and the chronic intake that would lead to the same body burden in humans. For the remaining six congeners no studies were available to identify Reference Points. The Panel concluded that there is scientific basis for inclusion of all 10 congeners in a common assessment group and performed a combined risk assessment. The Panel concluded that the combined margin of exposure (MOET) approach was the most appropriate risk metric and applied a tiered approach to the risk characterisation. Over 84,000 analytical results for the 10 congeners in food were used to estimate the exposure across dietary surveys and age groups of the European population. The most important contributors to the chronic dietary Lower Bound exposure to PBDEs were meat and meat products and fish and seafood. Taking into account the uncertainties affecting the assessment, the Panel concluded that it is likely that current dietary exposure to PBDEs in the European population raises a health concern., Competing Interests: If you wish to access the declaration of interests of any expert contributing to an EFSA scientific assessment, please contact interestmanagement@efsa.europa.eu., (© 2024 European Food Safety Authority. EFSA Journal published by Wiley‐VCH GmbH on behalf of European Food Safety Authority.)

The European Commission asked EFSA to update its 2011 risk assessment on hexabromocyclododecanes (HBCDDs) in food. HBCDDs, predominantly mixtures of the stereoisomers α-, β- and γ-HBCDD, were widely used additive flame retardants. Concern has been raised because of the occurrence of HBCDDs in the environment, food and in humans. Main targets for toxicity are neurodevelopment, the liver, thyroid hormone homeostasis and the reproductive and immune systems. The CONTAM Panel concluded that the neurodevelopmental effects on behaviour in mice can be considered the critical effects. Based on effects on spontaneous behaviour in mice, the Panel identified a lowest observed adverse effect level (LOAEL) of 0.9 mg/kg body weight (bw) as the Reference Point, corresponding to a body burden of 0.75 mg/kg bw. The chronic intake that would lead to the same body burden in humans was calculated to be 2.35 μg/kg bw per day. The derivation of a health-based guidance value (HBGV) was not considered appropriate. Instead, the margin of exposure (MOE) approach was applied to assess possible health concerns. Over 6,000 analytical results for HBCDDs in food were used to estimate the exposure across dietary surveys and age groups of the European population. The most important contributors to the chronic dietary LB exposure to HBCDDs were fish meat, eggs, livestock meat and poultry. The CONTAM Panel concluded that the resulting MOE values support the conclusion that current dietary exposure to HBCDDs across European countries does not raise a health concern. An exception is breastfed infants with high milk consumption, for which the lowest MOE values may raise a health concern., (© 2021 European Food Safety Authority. EFSA Journal published by John Wiley and Sons Ltd on behalf of European Food Safety Authority.)

A feasibility study for producing a matrix reference material for selected polycyclic aromatic hydrocarbons (PAHs) in baby food is reported. A commercially available baby food, containing carrots, potatoes, tomato, white beans and meat, was spiked with the so-called 15 + 1 PAHs included in the PAHs priority list for food of the EU, at a mass fraction level of 1 μg/kg. The contaminated baby food was further processed by autoclaving, freezing or freeze drying. The homogeneity of the three materials (bottle-to-bottle variation) and their short-term (4 weeks) and long-term (18 months) stability at different temperatures were assessed. To this end, an analytical method based on a solid-liquid extraction followed by cleaning up with gel permeation chromatography (GPC) and solid phase extraction (SPE) and GC-IDMS determination, was validated in-house. It could be demonstrated that the procedure fulfilled the demands for application to the homogeneity and isochronous stability studies for the candidate reference materials targeted here. All three materials proved to be sufficiently homogeneous for the intended use. Measurements on the autoclaved material provided the most promising results in terms of envisaged shelf life, although freeze drying was also found to be a suitable processing technique for most of the investigated PAHs. These results are an important step towards the development of a matrix reference material for PAHs in a processed food matrix in a presentation very similar to routine samples.

Nitrite is widely consumed from the diet by animals and humans. However the largest contribution to exposure results from the in vivo conversion of exogenously derived nitrate to nitrite. Because of its potential to cause to methaemoglobin (MetHb) formation at excessive levels of intake, nitrite is regulated in feed and water as an undesirable substance. Forages and contaminated water have been shown to contain high levels of nitrate and represent the largest contributor to nitrite exposure for food-producing animals. Interspecies differences in sensitivity to nitrite intoxication principally result from physiological and anatomical differences in nitrite handling. In the case of livestock both pigs and cattle are relatively susceptible. With pigs this is due to a combination of low levels of bacterial nitrite reductase and hence potential to reduce nitrite to ammonia as well as reduced capacity to detoxify MetHb back to haemoglobin (Hb) due to intrinsically low levels of MetHb reductase. In cattle the sensitivity is due to the potential for high dietary intake and high levels of rumen conversion of nitrate to nitrite, and an adaptable gut flora which at normal loadings shunts nitrite to ammonia for biosynthesis. However when this escape mechanism gets overloaded, nitrite builds up and can enter the blood stream resulting in methemoglobinemia. Looking at livestock case histories reported in the literature no-observed-effect levels of 3.3mg/kg body weight (b.w.) per day for nitrite in pigs and cattle were estimated and related to the total daily nitrite intake that would result from complete feed at the EU maximum permissible level. This resulted in margins of safety of 9-fold and 5-fold for pigs and cattle, respectively. Recognising that the bulkiness of animal feed limits their consumption, these margins in conjunction with good agricultural practise were considered satisfactory for the protection of livestock health. A human health risk assessment was also carried out taking into account all direct and indirect sources of nitrite from the human diet, including carry-over of nitrite in animal-based products such as milk, eggs and meat products. Human exposure was then compared with the acceptable daily intake (ADI) for nitrite of 0-0.07 mg/kg b.w. per day. Overall, the low levels of nitrite in fresh animal products represented only 2.9% of the total daily dietary exposure and thus were not considered to raise concerns for human health. It is concluded that the potential health risk to animals from the consumption of feed or to man from eating fresh animal products containing nitrite, is very low., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Humans are exposed to a number of "heavy metals" such as cadmium, mercury and its organic form methylmercury, uranium, lead, and other metals as wel as metalloids, such as arsenic, in the environment, workplace, food, and water supply. Exposure to these metals may result in adverse health effects, and national and international health agencies have methodologies to set health-based guidance values with the aim to protect the human population. This chapter introduces the general principles of chemical risk assessment, the common four steps of chemical risk assessment: hazard identification, hazard characterization, exposure assessment, risk characterization, and toxicokinetic and toxicity aspects. Finally, the risk assessments performed by international health agencies such as the World Health Organisation, the Environmental Protection Agency of the United States, and the European Food Safety Authority are reviewed for cadmium, lead, mercury, uranium, and arsenic.

European legislation has recently established a list of 15 priority polycyclic aromatic hydrocarbons (PAHs) to be monitored in foodstuff. Thus, the accurate determination of these compounds has become a highly relevant issue. The fact that some of these European Union (EU) PAHs differ from those typically analysed, requires the re-evaluation of the instrumental conditions for the proper determination of the new target compounds. In this study, the influence of the stationary phase and dimensions of the GC capillary column on the chromatographic resolution of the 15 EU PAHs has been investigated. Apolar (DB-5 type) and medium polar (DB-17 type) stationary phases with different lengths and film thickness have been evaluated for the separation of the target compounds, with special emphasis on those coelutions involving isomers such as the three benzofluoranthenes included in the EU PAHs. In addition, the influence of the injection technique and the column dimensions on the recovery of the high molecular mass PAHs has been studied. A programmable temperature vaporising (PTV) injector has been used in three different operational modes and the results were compared to those obtained using on-column injection. The experimental parameters involved in the injection step were optimised by using experimental design.

Separations of eight persistent organohalogenated classes of pollutants, organochlorinated pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated naphthalenes (PCNs), polychlorinated terphenyls (PCTs) and toxaphene (CTT) by comprehensive two-dimensional gas chromatography (GC x GC) were evaluated. Columns with different polarity and selectivity, including ZB-5, HT-8, DB-17 and BP-10, were selected as first dimension and combined with columns of increasing polarity in the second dimension, i.e. HT-8, BPX-50 and Carbowax (or Supelcowax-10). In total nine column combinations were tested. Because the main interest of the study was fast screening of the test xenobiotic families in complex matrices, in all cases, attention was primarily focussed on group-type separation. Nevertheless, within-group separation was also considered, especially for those classes containing particularly toxic congeners, such as PCBs and PCDD/Fs. Although none of the assayed column sets allowed the simultaneous and complete separation of all pollutants classes, some column combinations provided satisfactory separations among selected families and the rest of pollutants investigated. That was, for instance, the case of HT-8 x BPX-50 for PBDEs and PCDD/Fs, DB-17 x HT-8 for PCNs and OCPs and BP-10 x BPX-50 for CTT, PCDD/Fs and PBDEs. The feasibility of the proposed approach for the fast screening of the target classes of pollutants in complex samples was illustrated by the analysis of food and marine fat samples prepared using simplified miniaturised sample treatment methods.

The concentration of the most relevant polychlorinated biphenyl (PCB) congeners has been determined in milk and dairy products (i.e., cheese and yogurt, from cow, goat, and ewe). In addition, the enantiomeric composition of 11 atropisomeric PCB has been determined for the first time in this type of product, using heart-cut multidimensional gas chromatography and 2 enantioselective columns for the unambiguous determination of both enantiomers. Results showed a deviation from the racemic composition for PCB 135, 136, 176, 171, and 183 in the samples analyzed. Whereas PCB 135, 136, and 176 showed an enrichment of the first eluted enantiomer, congeners 171 and 183 showed an enrichment of the first or second eluted enantiomer depending on the dairy product and species. The remaining congeners analyzed (PCB 84, 91, 95, 132, 149, and 174) did not present a clear enrichment of any of the enantiomers. Therefore, differences in the enantiomeric composition of some of the target atropisomeric PCB have been found among the 3 species and among the milk samples and the related dairy products analyzed. Enantioselective species-dependent processes, as well as enantioselective processes carried on by microorganisms during the fermentation and ripening in the latter could be possible explanations for the differences observed. However, changes in the enantiomeric composition are still not well understood, and further investigation in this direction is recommended.

Concentrations and congener specific profile of DDTs, PCBs and PCDD/Fs have been determined in a number of Spanish breast milk samples. The concentrations found indicate a decreasing tendency compared to previous data from the 1990s. Mean concentrations of 238 ng/g fat weight, 111 ng/g fat weight and 82.1 pg/g fat weight were found for DDTs, PCBs and 2,3,7,8-PCDD/Fs, respectively. When the WHO-TEQs were calculated, PCDD/Fs was the family contributing with the highest percentage to the total (62-84%), followed by the non-ortho PCBs (10-25%) and the mono-ortho PCBs (5-24%). The congener specific accumulation patterns found were comparable to those reported in other studies in industrialised countries. In addition, the levels of 9 PBDEs congeners have been also determined in the breast milk samples. The concentrations ranged from 0.04 to 1.38 ng/g fat weight. The enantiomeric enrichment of a number of chiral PCBs in the breast milk samples, including congeners 84, 91, 95, 132, 135, 149, 171, 174, 176 and 183, has also been studied, for some of them for the first time in this matrix.

The feasibility of heart-cut MDGC-ECD and GCxGC-muECD for the separation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) has been evaluated. Among the different column combinations tested, the best results were obtained when using either a DB-5 type or an HT-8 column as the first dimension combined with a mid-polar stationary phase (50% phenyl) as the second dimension. The co-elutions between the target PCBs and PBDEs in the first dimension were satisfactorily resolved once transferred to the second column. Repeatability and intermediate precision were satisfactory in both systems, considering retention times in both dimensions. Nevertheless, peak area/volume precision was better for heart-cut MDGC since software for the data analysis in the case of GCxGC was still under development. The need for multiple injections of the same extract on the heart-cut MDGC system was the main drawback since the analysis time it increased. GCxGC becomes then a valuable alternative able to achieve the same performance in one injection. However, the GCxGC data analysis is still very time-consuming and needs further development. The applicability of both separation techniques was shown using a human breast milk sample with low concentrations of PCBs (0.2-227 pg/g fresh weight) and PBDEs (1.2-41 pg/g fresh weight).

Comprehensive two-dimensional gas chromatography with micro electron-capture detection (GC x GC-microECD) has been evaluated for the enantioseparation of five chiral toxaphenes typically found in real-life samples (Parlar 26, 32, 40, 44 and 50). From the two enantioselective beta-cyclodextrin-based columns evaluated as first dimension column, BGB-176SE and BGB-172, the latter provided the best results and was further combined with three non-enantioselective columns in the second dimension: HT-8, BPX-50 and Supelcowax-10. The combination BGB-172 x BPX-50 was finally selected because it provided a complete separation among all enantiomers. A satisfactory repeatability and reproducibility of the retention times in both the first and the second dimension were observed for all target compounds (RSDs below 0.8%, n = 4). Linear responses in the tested range of 10-200 pg/microl and limits of detection in the range of 2-6 pg/microl were obtained. The repeatability and reproducibility at a concentration of 100 pg/microl, evaluated as the RSDs calculated for the enantiomeric fraction (EF), was better than 11% (n = 4) in all instances. The feasibility of the method developed for real-life analyses was illustrated by the determination of the enantiomeric ratios and concentration levels of the test compounds in four commercial fish oil samples. These results were compared to those obtained by heart-cut multidimensional gas chromatography using the same enantioselective column.

Concentrations and congener specific profiles of PCDD/Fs and PCBs were determined in edible fish and seafood species from the Coast of Huelva, in the Spanish southwest Atlantic coast. Five fish species, namely wegde sole (Dicologoglossa cuneata), common sole (Solea vulgaris), white seabream (Diplodus sargus), sardine (Sardina pilchardus), angler fish (Lophius piscatorius), two shellfish species (Donax trunculus and Chamelea gallina), common cuttlefish (Sepia officinalis) and prawns (Parapenaeus longirostris), frequently found and consumed in the area were analysed. Concentrations ranged from 861 to 23787pg/g wet weight for total PCBs, while 2,3,7,8-PCDD/Fs showed concentrations ranging from 0.2 to 1.18pg/g wet weight. WHO-TEQ concentrations ranged from 0.038 to 0.186pg WHO-TEQ(PCDD/Fs)/g wet weight, values well below the maximum concentrations established by the EU. When non- and mono-ortho PCBs were included the values increased to a maximum of 0.99pg WHO-TEQ(PCDD/Fs+PCBs)/g wet weight. The PCB and PCDD/F accumulation pattern found in the samples analysed showed a distribution typically reported for marine samples, and no remarkable differences were found between species. The PCBs were the ones contributing with the highest percentage to the total TEQ content in most species studied. Concerning the seafood, specially prawns and shellfish, the opposite was observed and PCDD/Fs were found to contribute with a higher percentage than PCBs. The congener specific contribution to the TEQ showed PCB 126 followed by 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF as the most abundant ones.

A method based on gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITD-MS/MS), using isotope dilution, was developed for the determination of ten native polybrominated diphenyl ethers (PBDEs) and four (13)C(12)-labeled congeners in biological (fat tissue and human serum) and food samples. The highest-mass fragment ions were used as precursor ions for those congeners with molecular ions with m/z values higher than the maximum of the instrument. In these cases (hepta-BDEs and (13)C(12)-hexa-BDEs) no fragmentation was achieved under the experimental conditions employed. Repeatability (lower than 9%) and reproducibility (lower than 13%), expressed as relative standard deviation (RSD, n = 3 and 4, respectively), were satisfactory. Similarly, the coefficient of variation (n = 4) of the isotopic ratio between the two most abundant product ions was lower than 10 and 6% for native and labeled congeners, respectively. To evaluate the feasibility of the method, the optimized isotope dilution GC/ITD-MS/MS method was used for the quantitation of selected PBDE congeners in different samples including adipose tissue, human serum and foodstuff samples, from three inter-laboratory comparative exercises, covering a wide range of concentrations. A solid-phase extraction procedure, previously developed for PCB determination in small-size bird serum samples, was successfully applied to quantification of PBDEs in 1 mL samples of human serum.

The polychlorinated dibenzo-p-dioxin (PCDD), dibenzofuran (PCDF), and polychlorinated biphenyl (PCB) contents of 123 Spanish commercial salmon, tuna fish, sardine, oyster, mussel, and clam samples from 1995 to 2003 were investigated. A significant decrease of dioxin and non-ortho PCB concentrations in the studied species was found over the years. The decrease was greater in the case of dioxins than in that of non-ortho PCBs, especially during the early years of the study. PCB and PCDD/F concentrations in the years 2001-2003 were comparable to those reported in the literature for similar species collected after 1999. Mean PCB concentrations ranged from 3.46 ng/g of fresh weight (fw) in clams to 100 ng/g of fw in tuna fish. PCDD/F mean current levels ranged from 0.62 pg/g of fw in clams to 2.89 pg/g of fw in oysters. Toxic equivalent quantities (WHO-TEQ) ranged from 0.05 pg of WHO-TEQ(PCDD/Fs)/g of fw in clams to 0.5 pg of WHO-TEQ(PCDD/Fs)/g of fw in salmon (in the upper bound determination levels). When coplanar PCBs were included, the WHO-TEQ(PCDD/Fs+cop) (PCBs) values increased by a range of 1.7 times in oysters to 14.1 times in tuna fish. The decrease in dioxin concentrations suggests that efforts to control dioxin emissions and to reduce human exposure through foodstuffs are succeeding. The high contribution of PCBs to total WHO-TEQs in the fish and shellfish species investigated suggests that it is important to determine PCBs in foodstuffs, and especially in fish products, and they should be included in further research and future legislation.

The Biobio River basin, located in central Chile, is one of the most important freshwater resources for a population of 1 million inhabitants. The river receives discharges of pulp mills, sewage treatment plants and there is a diffuse input of materials coming from the drainage basin. Previous studies reported high levels of etoxyresorufin-O-deethylase (EROD) induction in fish from the lower stretch of the river, mainly due to polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) exposure. The present study investigates polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) levels as well as EROD induction in fish livers from Central Chile's Biobio River. Dioxin and furan levels in fish livers are reported for the first time in three areas of the Basin. In all samples the highest concentrations were found for the octachlorodibenzo-p-dioxin (OCDD) and PCDD/F TEQ concentrations ranged from 2.83 to 6.33 ppt (wet weight). The results indicate a clear induction of EROD activity in different fish species as the river mouth is approached, although this induction is not clearly related with dioxin and furan levels found in the fish livers. Our results clearly show that other pollutants might be acting as EROD inductors in the Biobio Basin.

The population of peregrine falcon (Falco peregrinus sbs. brookei) inhabiting the Regional Park of southeastern Madrid (RPSM), Spain, has experienced an increase of unsuccessful pairs (from 15% among a total of 20 pairs in 1995 to 55% among a total of 18 pairs in 2001). Traditionally, this area has been known to be contaminated with organochlorine compounds and toxic metals, which are known to be deleterious to the reproductive system of birds. During the breeding seasons of 2000 and 2001, contaminant residues were measured in unhatched eggs of peregrine falcons and liver of their main prey, to determine if they could be affecting the survival of the population. The most abundant contaminants were ortho-polychlorinated biphenyls (ortho-PCBs), ranging from 202.56 to 3,335.16 ng/g (wet wt) in falcon eggs and from 10.25 to 53.51 ng/g (wet wt) in pigeon livers. In all samples, the 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were detected, although these levels never exceeded 20 pg/g (wet wt). The major contributor to total toxic equivalent quantities (TEQs) were non-ortho-PCBs. Organochlorine levels found in this study may contribute to the entire suite of stressors that are negatively affecting the peregrine population.

The feasibility of comprehensive two-dimensional gas chromatography with electron-capture detection (GC x GC-ECD) for the enantioseparation of chiral PCBs from other possible interfering compounds has been evaluated. Three commercially available enantioselective beta-cyclodextrin-based capillary columns (Chirasil-Dex, BGB-172 and BGB-176SE) have been tested as first-dimension columns. Three non-enantioselective stationary phases (HT-8, BPX-50 and Supelcowax-10) were combined with the enantioselective columns to allow the unambiguous determination of the enantiomers of the target chiral PCBs. Each enantioselective first-dimension column tested was able to separate into enantiomers different PCB congeners, but in all cases, the use of Supelcowax-10 as second-dimension column provided the most satisfactory results. The Chirasil-Dex x Supelcowax-10 column combination allowed the determination of the enantiomeric fraction (EF) of PCBs 84, 91, 95, 132, 136, 149, 174 and 176 in the working standard solution, while that of congener 135 was hindered. The BGB-172 x Supelcowax-10 column set allowed a proper EF determination of congeners 45, 84, 131, 132, 135, 171, 174 and 183, while that of PCB 91 was interfered with co-elutants. The column combination BGB-176SE x Supelcowax-10 allowed the determination of all congeners that this enantioselective stationary phase was able to separate into enantiomers, i.e. PCBs 45, 91, 95, 136, 149 and 176. These column combinations have also been evaluated for the simultaneous determination of the 12 congeners with a toxic equivalency factor assigned by the WHO (PCBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) and the seven indicator congeners (PCBs 28, 52, 101, 118, 138, 153 and 180), and evaluated for the analysis of food samples.

Three commercially available chiral capillary columns, Chirasil-Dex, BGB-176SE, and BGB-172, have been evaluated for the separation into enantiomers of the 19 chiral polychlorinated biphenyls (PCB) congeners stable at room temperature. The enantiomers of 15 chiral PCBs were, at least to some extent, separated using these beta-cyclodextrin based columns. Multidimensional techniques, such as heart-cut multi-dimensional gas chromatography (heart-cut MDGC) and comprehensive two-dimensional gas chromatography (GC x GC), were investigated for their ability to solve coelution problems with other PCBs present in commercial mixtures and real-life samples. Heart-cut MDGC improved the separation as compared to one-dimensional GC, and enantiomeric fractions of the investigated chiral PCBs could be determined free from interferences. However, limitations on the number of target compounds that can be transferred to the second column in a single run and, therefore, the time consumption, have led to the evaluation of GC x GC as an alternative for this type of analysis. With GC x GC, two column set-ups were tested, both having a chiral column as first-dimension column, and two different polar stationary phase columns in the second dimension. On using both column combinations, congeners 84, 91, 95, 132, 135, 136, 149, 174, and 176 could be determined free from coelutions with other PCBs. Results on the application of heart-cut MDGC to food samples such as milk and cheese are given, as well as the first results on the application of GC x GC to this type of samples.

Congener-specific analyses of seventeen 2,3,7,8-substituted PCDD/Fs, three non-ortho and 8 mono-ortho dioxin-like polychlorinated biphenyls (PCBs) were performed on 258 Spanish foodstuff samples, mainly of animal origin, for 2000--03. Daily dietary intakes of PCDD/Fs and PCBs, expressed as toxic equivalents (WHO-TEQs), were estimated by combining food consumption data from the Spanish National Institute Statistics survey and concentration levels measured in individual samples, using upper bound determination values (not detectable = limit of detection). The calculated dietary intake of PCDD/Fs for a person weighing 70 kg was 1.35+/-0.11pg WHO-TEQs kg(-1) bw day(-1), and 3.22+/-0.75 pg WHO-TEQs kg(-1) bw day(-1) if dioxin-like PCBs (non- and mono-ortho PCBs) were included, showing the importance of their inclusion in monitoring studies. Both values were within the range of tolerable daily intake (TDI) proposed by the WHO (1-4pg WHO-TEQs kg(-1) bw day(-1)). The current levels are lower than earlier intakes estimates conducted in Spain. Meat and meat products accounted for more than 35% of the intake, followed by milk and milk products (29%), vegetables oils (19%), fish and seafood (11%) and eggs (4%). Dioxin-like PCBs are an important component in the total WHO-TEQs in foodstuffs. This is particularly true for the fish food group, where the total WHO-TEQs is dominated by dioxin-like PCBs (up to 80% of WHO-TEQs in some cases).

Concentrations of PCBs, PCDDs, and PCDFs, heavy metals (Cu, Cd, Zn, Pb, and Hg), and arsenic have been determined in a great variety of food samples purchased in different markets across the city of Huelva, located in southwestern Spain and under strong industrial activity. All samples analyzed presented concentrations below the maximum allowed by the European Community regarding PCDD/Fs, with the exception of samples within the meat group. An estimation of the daily intake resulted in 1.15 pg of WHO(PCDD/Fs)-TEQ/kg of body weight/day for a 70 kg person and 2.63 pg of WHO-TEQ/kg of body weight/day when PCBs were included, therefore accounting for a similar or even higher percentage than PCDD/Fs and showing the importance of their inclusion in monitoring studies. Meat and meat products, together with vegetable oils and dairy products, were the major food groups contributing to the estimated daily intake. For heavy metals and arsenic, the concentrations found were under the value proposed by European regulations, and estimated daily intakes were well below those proposed by the WHO for all metals investigated. PAHs have been analyzed in food samples from marine origin, values ranging from 8.22 to 71.4 ng/g of fresh weight. Pyrene was the most abundant compound, accounting for >80% in the samples investigated. The most carcinogenic PAHs, such as benzo[a]pyrene and dibenz[a,h]anthracene, were in all cases below the limits of detection. Therefore, the samples analyzed in this survey can be considered as safe with regard to the levels obtained and the in-force legislation.

In this study samples of common trout, European eel and barbel have been analysed for the levels of heavy metals such as lead (Pb), cadmium (Cd), zinc (Zn), copper (Cu), and the metalloid arsenic (As). Polychlorinated biphenyls (PCBs), including three non-ortho substituted PCBs, 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and DDT and its two main metabolites were also analysed in some selected samples, in order to evaluate the extent of contamination of the River Turia basin. All samples presented detectable levels of the elements analysed, presenting zinc the highest concentrations. European eel was the species found to highly accumulate these contaminants. Regarding organochlorinated compounds, seven samples exhibited detectable levels of the most toxic PCDD/Fs congener, the 2,3,7,8-TCDD. Non-ortho PCBs were not detected or not quantified in almost all samples and the sum of the individual PCB congeners determined were low compared to other aquatic ecosystems with similar fish species.