Diastereoisomer- and enantiomer-specific determination of hexabromocyclododecane in fish oil for food and feed

Fish oils are one of the main sources of ω-3 fatty acids. However, they can present elevated levels of some lipophilic pollutants, such as hexabromocyclododecanes (HBCDs). Since data about HBCDs in fish oil samples are very limited, in this study, 25 samples of fish oil for feed and food have been analyzed. Total HBCDs, as well as, α-, β- and γ-diastereoisomers have been determined. Total HBCDs ranged from 0.09 to 26.8 ng g⁻¹, with higher concentrations in fish oil for feed (average value of 9.69 ng g⁻¹) than those for food (1.14 ng g⁻¹). Concentrations of α-HBCD (average value of 4.12 ng g⁻¹ in feed samples and 0.48 ng g⁻¹ in food samples) and γ-HBCD (5.05 and 0.43 ng g⁻¹ respectively) were higher than that of β-HBCD (0.52 and 0.19 ng g⁻¹ respectively) in most of the samples. However, none of them was predominant in the samples. Concentrations of HBCDs were compared to concentrations of other pollutants and correlation between dioxin and dioxin-like PCBs levels and HBCDs levels were observed. Intake of HBCDs was calculated for fish oil with human consumption purposes and it ranged from 0.08 to 5.38 ng HBCDs d⁻¹, which could contribute significantly to HBCDs total intake. Enantiomeric fractions were also determined. No clear enrichment was observed for γ-HBCD, while (−)-α-HBCD enrichment was detected in some samples.     

Determinations of hexabromocyclododecane (HBCD) isomers in channel catfish, crayfish, hen eggs and fish feeds from China by isotopic dilution LC-MS/MS

HBCD is widely used brominated flame retardant, which is increasingly reported in the environment. A new isotopic dilution LC-MS/MS method was developed to determine three HBCD isomers, α-, β- and γ-HBCD in channel catfish, crayfish, hen eggs and fish feeds in this study, and especially for the first time HBCD isomers composition in crayfish, hen eggs and fish feeds. Soxhlet extractor and GPC cleanup were used, some important steps and crucial parameters were modified and intensified compared with other literatures, and LC and MS/MS conditions were optimized. The limits of quantitation values of 0.01, 0.005 and 0.005 ng g⁻¹ wet weight in channel catfish and crayfish were calculated for three HBCD isomers, respectively; so did 0.1, 0.05 and 0.05 ng g⁻¹ wet weight in eggs and 0.2, 0.1, 0.1 ng g⁻¹ wet weight in fish feeds. Recoveries of α-HBCD, β-HBCD and γ-HBCD were ranged between 75% and 105% for these productions at medium and high-level spiked samples, and between 60% and 85% at low-level spiked samples. The established methods were therefore suitable for the determinations of three HBCD isomers in these productions at trace contamination levels. Moreover, thirty commercial channel catfish, crayfish, hen eggs and fish feeds samples collected from local markets, and thirty home-produced hen eggs from private owners in Hubei province of China, were analyzed to determine whether these productions were contaminated by HBCD. Using the established methods, HBCD emerged in 4 of 30 fish feeds and 3 of 30 home-produced eggs, and in low-ng g⁻¹ wet weight.     

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

Hexabromocyclododecanes in limnic and marine organisms and terrestrial plants from Tianjin,China: Diastereomer- and enantiomer-specific profiles,biomagnification, and human exposure

To interpret the distribution of hexabromocyclododecanes (HBCDs) in various organisms, we measured the concentrations and diastereomer and enantiomer profiles of HBCDs in 21 different species of limnic and marine cohorts from Tianjin, China. The concentration ranges of HBCDs in limnic and marine organisms were 64.3–1111 ng g⁻¹ lw and 85.5–989 ng g⁻¹ lw, respectively. Living habitat and feeding habits had important impacts on HBCD diastereomer distribution. Most of the species appeared to preferentially select (+)-α-, (−)-β- and (−)-γ-HBCD. There is a tendency that the total and α-HBCDs were magnified as trophic level increased with trophic magnification factors (TMFs) around 2. The concentrations of HBCDs in the limnic and marine fishes were highest in the liver, followed by the gill, skin, and muscle. In terrestrial plants, the highest concentrations of HBCDs were observed in the leaf, followed by the root and the rhizosphere soil. Plants showed enantioselectivity for HBCD enantiomers, which varied with plant species and organs (leaf vs. root) of the same plant. Higher estimated daily intakes (EDIs) of HBCDs were observed from fish than from wheat.     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

Characterization of polychlorinated biphenyls and brominated flame retardants in sludge,sediment and fish from municipal dumpsite at Surabaya,Indonesia

We investigated the PCBs, PBDEs and HBCDs contamination in sludge, sediments and fish from various locations including raw leachate pond, leachate treatment plans (LTPs), control wells and reference site at open landfill of municipal dumpsite, Surabaya City, Indonesia. 62 PCBs and 14 PBDEs congeners, and 3 HBCDs isomers were identified and quantified using GC–MS and LC–MS/MS, respectively. Concentration ranges and median (value in parentheses) of PCBs, PBDEs and HBCDs were from not detected (ND) to 60 (3.9) ng g⁻¹ dw, 0.0075 to 45 (4.5) ng g⁻¹ dw and ND to 2.8 (0.052) ng g⁻¹ dw in sludge and sediments, respectively. While in two polled of fish samples were 30–55 ng g⁻¹ lw, 6.6–11 ng g⁻¹ lw and 1.6–3.3 ng g⁻¹ lw, respectively. Among the sampling sites, the highest level of PCBs and PBDEs were detected in sludge from raw leachate pond. However, PCBs and PBDEs levels were showing decreased in LTP-1 that could be due to the bacterial degradation but not in LTP-2, HBCDs were more stable in both LTPs. Levels of PCBs and BFRs in sludge at the present study were lower than those reported in sewage sludge reported from some other countries. PCBs profiles were mainly composed in that order by CB-138, -153, -180, -101, -118 and -28, while by BDE-47, -99, -100, -153, -154 and -28 for PBDEs in sludge, sediments and fish. Profiles of HBCDs were predominantly composed by γ- and α-isomers in sludge and fish, respectively. Debromination, dechlorination, commercial formulations used and congener-specific accumulation of those contaminants are the factors influenced the profiles.     

Temporal trend (1988-2008) of hexabromocyclododecane enantiomers in herring gull eggs from the German coastal region

Levels of α-, β-, and γ-hexabromocyclododecane (HBCD) were determined in pooled eggs from herring gulls (Larus argentatus) sampled on three bird sanctuaries near the German North Sea coast between 1988 and 2008 (Mellum and Trischen) and the German Baltic Sea coast between 1998 and 2008 (Heuwiese) and archived by the German Environmental Specimen Bank. Pressurized fluid extraction, gel permeation chromatography, and LC-MS/MS using ¹³C₁₂-labelled isotope standards and a chiral column were applied. α-HBCD was the dominating diastereomer and ranged between 3.7 and 107 ng g⁻¹ lw while β- and γ-HBCD were throughout close to LOQ. The highest α-HBCD concentration was found in eggs from Mellum sampled in the year 2000. Interestingly, HBCD in eggs from the three islands displayed similar time courses with levels increasing to a peak contamination around 2000 and decreasing levels ever since. Chiral signatures of α-HBCD in eggs differed among the islands but indicated a preferential enrichment of the first eluting enantiomer (−)-α-HBCD.     

Dietary intake of hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCD) in the Belgian adult population

A study was performed to assess exposure of the Belgian population to HBCD diastereoisomers. Measurements of HBCD were performed by UPLC-MS/MS, on 45 composite samples from 5 major food groups: dairy (products), meat (products), eggs, fish (products) and a group of “other” products. The medium bound estimated average daily intake (EDI) of ΣHBCD in the Belgian population was 0.99 ng kg⁻¹ bw d⁻¹. The diastereoisomer contribution to the mean EDI showed a predominance of γ-HBCD at 67%, followed by α-HBCD at 25% and 8% for β-HBCD. These results are consistent with the pattern found in the two food groups contributing the most to the EDI: meat (products) and the group of “other” products. Anyway, it has to be noted that diastereomeric distribution of HBCD can change due to bioisomerisation in biological material. Levels of HBCD diastereoisomers found in Belgian food samples of animal origin were low in comparison with those found in other EU countries and the resulting EDI was substantially below the proposed thresholds.     

PCDDs and PCDFs in sewage sludges from two wastewater treatment plants in Beijing, China

The levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were analyzed by an isotope-dilution high-resolution mass spectrometric in 16 sewage sludges, sampled from 2004 to 2009, from two municipal wastewater treatment plants (WWTPs) in Beijing. Total toxicity equivalent (TEQ) values were evaluated using the toxicity equivalent factors proposed by International for PCDD/Fs. The I-TEQs for these sewage sludges were from 0.97 to 15.0 pg g⁻¹ dry weight (dw) with a mean value 4.43 pg g⁻¹ dw, indicating that all I-TEQs were below Chinese legislation limit value regulated for agricultural use in soils.The results from limited samples (16 samples) showed that the levels of PCDD/Fs might be correlated with the sludge age. Meanwhile, the temporal trends of PCD/Fs suggested that the I-TEQs may correlate with rainfall in the present study.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.     

The impact of production type and region on polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in Canadian chicken egg yolks

Chicken eggs from five different production types (conventional, omega-3 enriched, free range, organic and free run) were collected, when available, from three regions (west, central and east) of Canada to determine persistent organic pollutant (POP) concentrations. Total polychlorinated biphenyl (PCB) concentrations (∑37 congeners) in yolks from the eggs ranged from 0.162 ng g⁻¹ lipid to 24.8 ng g⁻¹ lipid (median 1.25 ng g⁻¹ lipid) while the concentration of the sum of the 6 indicator PCBs ranged from 0.100 ng g⁻¹ lipid to 9.33 ng g⁻¹ lipid (median 0.495 ng g⁻¹ lipid). Total polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) concentrations ranged from 2.37 pg g⁻¹ lipid to 382 pg g⁻¹ lipid (median 9.53 pg g⁻¹ lipid). The 2005 WHO toxic equivalency (TEQ) ranged from 0.089 pg TEQ_{PCDD/F+dioxin-like[DL]-PCB} g⁻¹ lipid to 12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid (median 0.342 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). PCB and PCDD/F concentrations were significantly different (p < 0.001) in egg yolks from different regions of collection. In contrast to observations in Europe, PCB and PCDD/F concentrations in Canadian egg yolks were not impacted solely by the production type (e.g., conventional, free range, organic, etc.) used to maintain the laying chickens. Additionally, only one Canadian free range yolk from western Canada (12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). This differs from observations in Europe where free range/home produced eggs frequently have higher POP concentrations than eggs from other production types. Median PCB dietary intake estimates based on consumption of eggs were less than 10 ng d⁻¹ while median PCDD/F intakes were less than 45 pg d⁻¹.     

Hexabromocyclododecanes (HBCDs) in marine fishes along the Chinese coastline

This study reports concentrations of hexabromocyclododecanes (HBCDs) in two species of marine fish, large yellow croaker (Pseudosciaenacrocea) and silver pomfret (Pampusargenteus) (n = 46), from nine Chinese coastal cities (Dalian, Tianjin, Qingdao, Shanghai, Zhoushan, Wenzhou, Fuzhou, Quanzhou and Xiamen). HBCDs were detectable in all samples analyzed, indicating ubiquitous contamination of these compounds in the Chinese coastal environment. The average total HBCD concentration was 3.7 ng g⁻¹ lipid weight (range: 0.57-10.1 ng g⁻¹ lipid weight), which is relatively lower than other regions of the world, especially Europe, where HBCDs are intensively used. Among the three individual HBCD isomers (α-, β- and γ-HBCD) in all fish samples, the α-isomer showed a remarkable predominance (from 87.5% to 100% of total contribution), indicating its higher bioaccumulative potential. Geographically, the highest HBCD level present in fish was found in Dalian in northern China, and the lowest occurred in Wenzhou. Estimated daily intakes of HBCDs via fish consumption for the Chinese population were 0.004-1.00 ng kg body weight⁻¹ d⁻¹. These exposure levels were much lower than the effect levels.     

Levels,profile and distribution of Dechloran Plus (DP) and Polybrominated Diphenyl Ethers (PBDEs) in the environment of Pakistan

No scientific data is available on emerging contaminants including Polybrominated Diphenyl Ethers (PBDEs) and Dechloran Plus (DP) levels in the environment in Pakistan. Levels of PBDEs and DP were determined in the soil, sediment and atmospheric samples along the stretch of River Ravi in Punjab Province. Average concentrations of ΣPBDEs in atmosphere, soils and sediments were 36 pg m⁻³, 40 ng g⁻¹ and 640 ng g⁻¹. BDE-209 was the most abundant PBDE congener, showing that deca-BDE accounts for most of the total PBDE emitted in the environment of Pakistan. Total DP levels were calculated as 88 pg m⁻³, 0.8 ng g⁻¹ and 1.9 ng g⁻¹ in air, soil and sediment samples, respectively. The lower average fractions of anti-DP showed significant differences to those of the technical mixtures, indicating the lack of DP production source in Pakistan.     

Spatial distribution of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs) in an e-waste dismantling region in Southeast China: Use of apple snail (Ampullariidae) as a bioindicator

Fengjiang is a large e-waste dismantling site located in southeast China. In this paper, apple snail and soil samples were collected from this e-waste dismantling site and 25 vicinal towns to investigate the contamination status, spatial distributions and congener patterns of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs). Total PCB concentrations in apple snails (3.78-1812 ng g⁻¹ dry weight (dw)) were significant higher than that in soil samples (0.48-90.1 ng g⁻¹ dw). PBDE (excluding BDE 209) concentrations in apple snail and soil samples ranged from 0.09 to 27.7 ng g⁻¹ dw and 0.06 to 31.2 ng g⁻¹ dw, respectively. Concentrations of PCBs and PBDEs in snails and soils correlated negatively with the distance from Fengjiang. Both the concentrations and profiles of the pollutants were significantly correlated (p < 0.05) between the snail and soil samples, indicating the suitability of apple snail as a reliable bioindicator for PCBs and PBDEs contamination in this region. Relatively high concentrations of PCBs and PBDEs at locations far from e-waste dismantling sites implied that these pollutants have been transported to surrounding regions.     

Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947 ng kg⁻¹ dw (0.02-49.9 ng WHO-TEQ kg⁻¹ dw) for 17 PCDD/Fs, 17.5-66 761 μg kg⁻¹ dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29 604 μg kg⁻¹ dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618 μg kg⁻¹ dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.     

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in seven different marine bird species from Iceland

Data on distribution, concentration and trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) is scarce in biota from the sub-Arctic region of the Atlantic. The present study is an investigation on PBDE and HBCD concentrations in eggs from seven marine bird species from Iceland, i.e. common eider (Somateria mollissima), arctic tern (Sterna paradisaea), guillemot (Uria aalge), fulmar (Fulmarus glacialis), lesser black-backed gull (Larus fuscus), great black-backed gull (Larus marinus) and great skua (Stercorarius skua). Concentrations of sum PBDEs ranged from 44 ng g⁻¹ fat in eider eggs to 2400 ng g⁻¹ fat in great skua eggs. The contribution of different PBDE congeners to the sum concentration differed between species. Concentration of HBCDs (sum of α−,β⁻ and γ−HBCD) ranged from 1.3 ng g⁻¹ fat in arctic tern eggs to 41 ng g⁻¹ fat in great black-backed gull. PCA on PBDE and HBCD shows different trends between the two BFR groups, further indicating different sources/usage. Investigations on any potential health or population effects of environmental pollutants on the great skua are advised since both the PBDE and HBCD concentrations are high.     

Concentration of DL-PCBs in fish from market of Parma city (north Italy): estimated human intake

The concentrations of 12 congeners of non-ortho and mono-ortho dioxin-like polychlorinated biphenyls (ΣDL-PCB) were measured in 30 fish samples from Parma markets by GC/MS technique. The samples were randomly purchased, choosing the species commonly found in supermarkets. The concentration of DL-PCBs estimated remained under the fixed Italian limit of 4 pg g⁻¹ ww WHO-TEQ (World Health Organization-Toxic Equivalent) in the major part of the samples, so the situation seems to be not at a level sufficient to pose a risk to human health of the Parma population. The medium daily intake for DL-PCBs for Italian consumers (Parma) was also estimated. This value generally resulted minor than 2 pg g⁻¹ ww WHO-TEQ kg⁻¹ body weight, exceeding only in four cases: eel, smooth hound, starry smooth hound and tuna.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

Congener profile, occurrence and estimated dietary intake of dioxins and dioxin-like PCBs in foods marketed in the Region of Valencia (Spain)

During 2006-2008, a monitoring program was conducted on 29 target compounds, including PCDD/Fs and dl-PCBs, comprising 150 randomly collected individual food samples marketed in the Region of Valencia, Spain, grouped into 8 categories (vegetables, cereals, fats and oils, eggs, milk and dairy products, fish products, meat and meat products and fish oil). For PCDD/Fs, the highest frequency of detection corresponds to 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF; and PCBs 118, 105 and 156 were the more frequent dl-PCBs. The food groups presenting higher contamination, expressed as toxic equivalents (WHO-TEQs), were fish oil (6.38 pg WHO-TEQ g⁻¹ fat), fish (1.21 pg WHO-TEQ g⁻¹ w.w.) and milk and dairy products (0.90 pg WHO-TEQ g⁻¹ fat). Of all analysed samples, only two fish oils presented levels higher than the EU limits for total WHO-TEQ. The average PCDD/Fs and dl-PCBs intakes were estimated as 2.86 pg WHO-TEQ kg⁻¹ b.w. d⁻¹ and 4.58 pg WHO-TEQ kg⁻¹ b.w. d⁻¹, for adults and children, respectively, using the deterministic method for chronic exposure. The main contributors to total intake for adults were fish (59%), milk and dairy products (19%), and fat and oils (9%). The average daily intake for adults (2.86 pg WHO-TEQ kg⁻¹ b.w. d⁻¹) is within range of TDI recommended by the WHO (1-4 pg WHO-TEQ kg⁻¹ b.w. d⁻¹), and slightly above the TWI and PTMI adopted by SCF and JECFA respectively.     

Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) from a refinery process for zinc oxide used in feed additives: a source of dioxin contamination in Chilean pork

The Republic of Korea found dioxin at concentrations exceeding the Korean maximum residue limit (MRL) in pork (2 pg TEQ g⁻¹ fat) imported from Chile in June 2008. Korea and Chile collaborated and investigated to find out the sources of contamination. An isotope dilution method and high resolution gas chromatography/mass spectrometry (HR-GC/MS) were used for the analysis of PCDD/Fs. PCDD/Fs were found from 2.17 to 36.7 pg TEQ g⁻¹ fat from Chilean pork. 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF were found as the major congeners in pork samples. 2,3,4,7,8-PeCDF showed the highest concentration and contributed about 30% among the congeners in most of the samples. 2,3,7,8-TCDD, 1,2,3,7,8,9-HxCDD, OCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 1,2,3,7,8,9-HxCDF, and OCDF were not detected or exist at background levels in the less contaminated samples. Remarkably high concentrations of PCDD/Fs were found in samples of zinc oxide (17 147 pg TEQ g⁻¹), zinc oxide based premix (6673 pg TEQ g⁻¹), and the residue crust (800 pg TEQ g⁻¹) in a mixing chamber in the feed mill. From the results of various investigations, this case concluded that zinc oxide in the feed was the major source of the dioxin contamination in pork. The dioxins were formed from a metal refinery process to collect zinc oxide.