气相色谱法同时测定水产品中12种多溴联苯醚

多溴联苯醚在水产品中的残留会危害人类健康。本文建立了水产品中12种多溴联苯醚的气相色谱测定方法。样品用30mL正己烷︰丙酮(1︰1)超声提取20min,60%硫酸脱脂,弗罗里硅土和中性氧化铝层析柱净化,5mL正己烷+5mL二氯甲烷按顺序洗脱,然后用配电子捕获检测器的气相色谱仪测定多溴联苯醚含量。多溴联苯醚在1~200μg/L浓度范围内线性关系良好,相关系数(r^2)>0.9972,检出限和定量限分别为0.2μg/kg和1.0μg/kg,样品的平均加标回收率为73.3%~98.4%,相对标准偏差<8.4%。本方法操作简便快速、灵敏、可靠,适用于水产样品中12种多溴联苯醚的测定。     

土壤中多溴联苯醚研究进展

多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)是一种新型的有机污染物,作为溴化阻燃剂被大量使用。目前,PBDEs在我国多处土壤介质中均有检出。同时由于其具有毒性、可持久性、生物蓄积性,近年来已成为环境领域关注的热点。本文分析了土壤中PBDEs的来源,总结了土壤中PBDEs的分布水平,介绍了土壤中PBDEs的迁移规律,讨论了土壤中PBDEs的降解途径,并对今后土壤中PBDEs的研究进行了展望。     

Polybrominated diphenyl ethers in seafood products of south China

South China is probably one of the heaviest polybrominated diphenyl ether (PBDE) polluted regions in the world, thanks to the presence of huge and rapidly growing electronics manufacturing industries, as well as several of the world's largest e-waste recycling sites in the region. In the present work, a wide variety of nonfish seafood products collected from South China was analyzed for PBDE residues. The concentrations of PBDEs in seafood products were highly species-specific, and the magnitude of PBDE pollution was moderate in South China compared to the global levels. Congener patterns of PBDEs in seafood samples suggested that seafood products are prone to accumulating low-brominated congeners, and possible metabolic debromination of BDE-99 to BDE-47 could occur in certain organisms, such as crabs and mantis shrimp. Generally, the congener profile was dominated by BDE-209, and to a lesser extent by BDE-47 and BDE-99, which was consistent with the fact that Deca-BDE is mass-produced in China and with previous sediment results from the same area. The occurrence of BDE-209 in aquatic species from South China suggests that BDE-209 appears to be more bioavailable than previously thought, and the environmental fate and safety of BDE-209 require further investigation and call for a thorough reassessment.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzofurans in commercial pentachlorophenols by combined gas chromatography-mass spectrometry.

Samples of commercial pentachlorophenol (PCP) and its sodium salt (PCP-Na) were examined for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), using a rapid, highly specific method of analysis. Phenolic compounds are removed by alkaline extraction, and the neutral components are fractionated on an alumina minicolumn. After gas chromatographic separation, individual PCDDs and PCDFs are detected by mass fragmentography and their presence is confirmed by complete mass spectral analysis. While some samples had only low amounts of PCDDs and PCDFs, others contained much higher amounts of these components. PCP-Na samples showed the unexpected presence of a tetrachlorodibenzo-p-dioxin. Re-analysis of PCP and PCP-Na samples with high PCDD contents on a high-resolution glass capillary column showed the presence of 3 hexa- and the 2 heptachlorodibenzo-p-dioxins with nearly constant isomeric ratios.     

Marine sponge: a potential source for methoxylated polybrominated diphenyl ethers in the Asia-Pacific food web

Marine sponges collected in Palau, Micronesia, were investigated for hydroxylated or methoxylated analogues of brominated diphenyl ethers (BDEs), brominated dibenzo-p-dioxin (BDD), and brominated biphenyls. The neutral fractions of Haliclona sp. and Callyspongia sp. contained 2'-methoxy-2,3',4,5'-tetraBDE, 6-methoxy-2,2',4,4'-tetraBDE, 2',6-dimethoxy-2,3',4,5-tetraBDE 2,2'-dimethoxy-3,3',5,5'-tetrabromobiphenyl, several methoxy-triBDEs, and dimethoxy-penta-/hexaBDEs. The methoxylated BDEs in sponges were strikingly similar to those of local fish living in the western Pacific Ocean. The total concentrations of these compounds (ΣMeO-PBDE) in both sponges were 63.5 μg/g extractable organic matter (EOM) for Haliclona sp. and 36.5 μg/g EOM for Callyspongia sp., which were about 2 orders of magnitude higher than the levels seen in tropical coral reef fish (unicornfish or surgeonfish) (280-290 ng/g lipid) and groupers (550 ng/g lipid) from Okinawan coastal waters. The phenolic fractions of both sponges contained hydroxy-methoxy tetra-/pentaBDEs as well as hydroxy-tetraBDD, in addition to the corresponding phenolic tetraBDE analogues. Although the total concentrations of phenolic products (27-80 μg/g EOM) in both sponges fell within a range comparable to the methoxylated products, ΣOH-PBDE in local fish were trace level (less than 10 ng/g lipid of) or undetectable. This survey indicates that marine sponges are a possible source of the MeO-PBDE analogues that biomagnify via the food chain to the higher trophic organisms in the western Pacific, whereas the distribution of the corresponding hydroxylated analogues is limited.     

Determination of polybrominated biphenyl residues in dairy products.

A method for the determination of polybrominated biphenyls (PBBs) in dairy products is described. Fat is extracted from the products by the official AOAC method. The PBB residues are separated from the fatty material by gel permeation chromatography prior to gas-liquid chromatographic (GLC) quantitation. An additional cleanup using petroleum ether elution through a miniature Florisil column is necessary for thin layer chromatographic (TLC) confirmation. Recoveries of PBBs from samples fortified at levels from 0.1 to 0.5 ppm ranged from 94 to 104% with an average of 99%. GLC sensitivity permits the estimation of PBB residue levels as low as 0.007 ppm. Routine TLC confirmation is limited by sensitivity to greater than or equal to 0.2 ppm.     

Identification and quantification of polybrominated hexahydroxanthene derivatives and other halogenated natural products in commercial fish and other marine samples

During routine analysis of commercial fish on halogenated pollutants, an unknown tribromo component (TriBHD) was initially detected as an abundant peak in sample extracts from the Mediterranean Sea. The molecular formula was established to be C16H19Br3O by gas chromatography with electron ionization high-resolution mass spectrometry (GC/EI-HRMS). GC/EI-MS data were virtually identical with a polybrominated hexahydroxanthene derivative (PBHD) previously isolated from an Australian sponge species known to occur in the Mediterranean Sea as well. A tetrabromo isomer (TetraBHD) was also found in the fish samples. The concentrations of TriBHD and other halogenated compounds in commercial fish (sea bass, gilt head bream, anchovy, sardine, and salmon) were estimated with GC/electron capture detection (ECD). Using the ECD response of trans-nonachlor, the concentration of TriBHD reached up to 90 ng/g lipid weight and accounted for up to >90% of the concentration of p,p'-DDE, which was the most abundant peak in the most samples investigated. On the basis of the GC/ECD response, TetraBHD amounted for approximately 1/7 of TriBHD in all fish samples investigated. The sample with the highest content was a green-lipped mussel from New Zealand (236 ng/g lipid weight). The halogenated natural products TBA, Q1, and MHC-1 were also present in most of the samples. We assume that the bulk of the residues in fish from aquaculture may originate from algae and sponges living in proximity of the fish farms. Detection of TriBHD and TetraBHD in blubber of a monk seal (Monachus monachus) suggests that both HNPs may reach the top predators of food webs and thus also humans.     

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans in food of animal origin. The Swiss dioxin monitoring program

Between 1997 and 1999, several cases of dioxin contaminations in foodstuffs of animal origin occurred in Europe due to feed contaminated by several independent sources: citrus pulp pellets, fat containing polychlorinated biphenyls (PCB), and kaolinitic clay as anti-caking agent in feedingstuffs. As a consequence of the latter, a survey on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in food of animal origin was initiated by the Swiss authorities to assess the extent of PCDD/F contamination and to document the efficiency of the measures taken to ensure the decontamination of the food supply. Investigation of a total of 128 samples of cow's milk, poultry, eggs, and meat revealed several cases of residue levels distinctly above the background exposure limit of approximately 2.5 ng of I-TEQ/kg (fat basis). Particularly, elevated concentrations were found in eggs (maximum 13 ng of I-TEQ/kg), poultry (maximum 3.9 ng of I-TEQ/kg), and pork (maximum 7.5 ng of I-TEQ/kg). On the basis of the observed PCDD/F congener pattern, the contamination could be attributed to PCDD/F-contaminated kaolin that was used as an anti-caking agent in particular feedstuffs.     

Coexposure of dioxin-like polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and dibenzofurans in free-range hens and implications derived from congener profile analysis

The consumption of free-range eggs is becoming more popular worldwide. We analyzed the levels of 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and their congener profiles from 6 free-range and 12 caged egg samples. The mean levels of dl-PCBs in the free-range samples were 5.4 times higher than those in caged eggs. All egg samples exhibited at least two characteristic dl-PCB congener patterns, which reflected distinctive contamination sources. Additionally, for the first time, we demonstrated that the dl-PCB levels in the free-range eggs were highly correlated with elevated levels of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) (r = 0.986; p < 0.001), indicating a coexposure scenario in free-range hens. Cluster analysis of congener patterns implied that this coexposure scenario could be attributed to distinct dl-PCB and PCDD/F sources. This congener profile information provides insights from a different perspective for further identifying potential dl-PCB and PCDD/F sources in the polluted free-range eggs.     

Polybrominated diphenyl ethers in retail fish and shellfish samples purchased from Canadian markets

Fish and shellfish retail samples (n = 122) were purchased from three Canadian cities in the winter of 2002 and analyzed for a total of 18 polybrominated diphenyl ether (PBDE) congeners. The samples (salmon, trout, tilapia, Arctic char, mussels, oysters, shrimp, and crab) represented the range of fish and shellfish commercially available to Canadian consumers at the time of purchase. Trout and salmon (geometric mean SigmaPBDE = 1600 and 1500 pg/g, wet weight, respectively) were found to contain significantly higher amounts of PBDEs than the mussel, tilapia, and shrimp groups (geometric mean SigmaPBDE = 260, 180, and 48 pg/g, wet weight, respectively). These differences in SigmaPBDE concentrations among fish and shellfish products were partly driven by differences in lipid content among the samples. Mean SigmaPBDE concentrations in domestic samples were also significantly greater than in imported samples, possibly reflecting global environmental distribution of PBDEs. These concentration differences will contribute to variations in dietary exposure to PBDEs when assorted fish and shellfish items from various origins are consumed.     

Ion-trap tandem mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in food

This paper reports on the applicability of gas chromatography coupled to ion-trap tandem mass spectrometry (GC/ITMS/MS) for the analysis of polychlorinated dibenzo- p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in food. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for food analysis. Good precision (RSD=5-18% for PCDD/Fs and 6-14% for dl-PCBs) and low limits of detection for PCDD/Fs (0.1-0.93 pg/g of fat) and dl-PCBs (0.1-0.89 pg/g of fat) were obtained. A comparative study of the congener-specific determination using both GC/ITMS/MS and GC-high resolution mass spectrometry (GC/HRMS) was performed by analyzing several matrices such as milk, fish oil, chicken, pork, fish, eggs, and a chicken compound feed, at low pg/g levels. The results using GC/ITMS/MS were in good agreement with those obtained by GC/HRMS. Consequently, GC/ITMS/MS is proposed for the analysis of PCDD/Fs and dl-PCBs in food and feed samples.     

Toxic potency of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and polychlorinated biphenyls in food samples from Catalonia (Spain)

A surveillance program on polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in 29 foodstuff samples produced all over the four provinces in Catalonia (Spain) is presented. The study included the analyses of milk, egg, meat (beef, chicken, and pork), mussel, and olive oil samples. A previously developed method for the simultaneous analysis of the 2,3,7,8-substituted PCDDs/PCDFs and the dioxin-like PCBs, as well as the indicator PCBs, was employed. Total toxicity equivalent (TEQ) values were calculated using the toxicity equivalent factors (TEFs) proposed by the World Health Organization (WHO) for dioxin-like PCBs, PCDDs, and PCDFs. The TEQ(PCDD/F) levels were below the limits proposed in the draft of the EC regulation for food commercialization in the European countries. These limits are the following: 2 pg WHO-TEQ/g fat for pork, 3 pg WHO-TEQ/g fat for milk and chicken, 5 pg WHO-TEQ/g fat for egg and beef, and 3 pg WHO-TEQ/g whole product for fish. The contributions of PCDDs/Fs and dioxin-like PCBs in the total toxicity of the samples were calculated for each matrix. The results showed that the TEQ(PCB) contribution varied from 27% in olive oil samples to 81% in mussel samples. These findings suggest that the regulation of TEQ contents in food should include not only the TEQ(PCDD/F), but also the TEQ(PCB).     

Complete mass balance of dietary polychlorinated dibenzo-p-dioxins and dibenzofurans in dairy cattle and characterization of the apparent synthesis of hepta- and octachlorodioxins

Mass balances of 2,3,7,8-substituted dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were measured in cows following administration of pentachlorophenol (PCP)-treated wood. Fecal excretion accounted for the major fraction of all congeners. Recovery in feces increased with increasing chlorination, while storage in body fat and excretion in milk decreased with increasing chlorination. The PCDFs with no chlorines in the 4- and 6-positions were apparently metabolized because residues were not detected in milk and body fat. Storage and excretion of 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8,9-OCDD exceeded intake by factors of 1.7 and 3.4, but recovery of other PCDD/Fs did not exceed intake significantly. Excess excretion of OCDD, but not HpCDD, was confirmed in a follow-up study. Synthesis of HpCDD and OCDD did not occur when PCP-treated wood was fermented with rumen microorganisms, and enhanced concentrations of HpCDD and OCDD were not found in gastrointestinal tract contents of dosed animals. Formation of OCDD during incubation of feces spiked with PCP-treated wood led to the conclusion that synthesis was postexcretion during sample preparation.     

Human exposure to polychlorinated diphenyl ethers through the diet in Catalonia, Spain

Although polychlorinated diphenyl ethers (PCDEs) are recognized environmental pollutants, information concerning human exposure to these organic substances is very scarce. For the present study the concentrations of PCDEs in a number of foodstuffs acquired in Catalonia, Spain, were determined. The dietary intake of PCDEs was estimated for various age groups of the general population living in this Spanish region. With the exception of fish and shellfish, PCDE concentrations were under the limit of detection in the 10 remaining food groups analyzed. For an adult (20-65 years old) male of 70 kg average body weight, the estimated total dietary intake of PCDEs was 41 ng/day. It was assumed that if a PCDE congener was below the detection limit, the concentration was equal to half of the limit of detection. The highest exposure to PCDEs through the diet corresponded to the group aged 51-65 years, whereas the lowest intake corresponded to the youngest group (4-9 years). With the exception of the group aged >65 years, PCDE intake was always higher in males than in females. The results of this study should be of interest for future assessments of time trends in human exposure to PCDEs through the diet.     

Polybrominated diphenyl ethers (PBDEs) in foodstuffs: human exposure through the diet

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a variety of materials, including synthetic polymers and textiles. Although these chemicals have been detected in environmental samples and human tissues, there is little information about human exposure to PBDEs through the diet. In the present study, we determined the concentrations of PBDEs in a number of food samples acquired in Catalonia (Spain) during 2000. The dietary intake of PBDEs was estimated for the general population living in this Spanish region. The highest PBDE concentrations were found in oils and fats, fish and shellfish, meat and meat products, and eggs, while the lowest levels corresponded to fruits, vegetables, and tubers. The dietary intake of PBDEs for an adult male was 97.3 ng/day (assuming not detected (ND) = (1)/(2) limit of detection (LOD)) or 81.9 ng/day (assuming ND = 0) The greatest contribution to these values corresponded to fish and shellfish, with approximately one-third of the total intake. TetraBDEs and pentaBDEs were the homologues showing the highest percentages of contribution to the sum of total PBDEs. The comparison of the current dietary intake with the suggested lowest observed adverse effect level value of 1 mg/kg/day for the most sensitive endpoints for toxic effects of PBDEs results in a safety factor over 5 orders of magnitude in relation to PBDE exposure from food.     

Determination of polybrominated biphenyl residues in dry animal feeds.

A new procedure is described for the determination of polybrominated biphenyls (PBBs) in dry animal feeds and developmental results are discussed. Finely ground feed is packed into a chromatographic column containing Celite and then eluted with methylene chloride. The concentrated extract is cleaned up by elution with petroleum ether through Florisil before gas-liquid chromatographic quantitation. Chromatograms thus obtained were essentially free of the interfering peaks encountered when using AOAC methods for pesticide residues in dry products. Results of feed analyses by the proposed procedure averaged 30% higher than those obtained by AOAC procedures. Recoveries of PBBs from samples fortified at levels of 0.04 to 0.4 ppm ranged from 90 to 104%, with an average of 98%.     

Determination of cerium in marine sediments

Marine sediments carry almost all the radioactive Ce that enters the ocean with the effluents released from the nuclear industry. The uptake of radioactive¹⁴⁴Ce by the sedentary organisms is influenced by the amount of stable Cc present in the sediment. A method has been described for the determination of stable Cc in the sediments, based on ion exchange separation and colorimetric measurement with Arsenazo I reagent. The effect of diverse cations on the recovery of Cc is discussed. Lanthanum, Y, Th and Zr which form colored complexes with Arsenazo I, do not interfere under the conditions of the experiment. The recovery of stable Ce ranges from 95 to 98% Using the method, the stable Ce content in some sediments from coastal Bombay was observed to range from 20 to 99 ppm. The same method with minor changes is described for the determination of radioactive Ce in the sediments and illustrated with the analysis of a sediment sample.