A survey of perfluorooctane sulfonate and related perfluorinated organic compounds in water,fish, birds,and humans from Japan

Occurrence of perfluorooctane sulfonate (PFOS) in the tissues of humans and wildlife is well documented. In this study, concentrations and distribution of PFOS, perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) were determined in samples of surface water, fish and bird blood and livers, and human blood collected in Japan. Notable concentrations of PFOS were found in surface water and fish from Tokyo Bay. PFOS was found in all of the 78 samples of fish blood and liver analyzed. Based on the concentrations of PFOS in water and in fish livers, bioconcentration factors were calculated to range from 274 to 41 600. Concentrations of PFOS in the blood of Japanese human volunteers ranged from 2.4 to 14 ng/mL. PFHS was detected in 33% of the fishes analyzed, at concentrations severalfold less than those of PFOS.     

Tissue distribution of perfluorinated chemicals in harbor seals (Phoca vitulina) from the Dutch Wadden Sea

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.     

Accumulation of perfluorooctane sulfonate in marine mammals

Perfluorooctane sulfonate (PFOS) is a perfluorinated molecule that has recently been identified in the sera of nonindustrially exposed humans. In this study, 247 tissue samples from 15 species of marine mammals collected from Florida, California, and Alaskan coastal waters; and northern Baltic Sea; the Arctic (Spitsbergen); and Sable Island in Canada were analyzed for PFOS. PFOS was detected in liver and blood of marine mammals from most locations including those from Arctic waters. The greatest concentrations of PFOS found in liver and blood were 1520 ng/g wet wt in a bottlenose dolphin from Sarasota Bay, FL, and 475 ng/mL in a ringed seal from the northern Baltic Sea (Bothnian Sea), respectively. No age-dependent increase in PFOS concentrations in marine mammals was observed in the samples analyzed. The occurrence of PFOS in marine mammals from the Arctic waters suggests widespread global distribution of PFOS including remote locations.     

Global distribution of perfluorooctane sulfonate in wildlife

Here we report, for the first time, on the global distribution of perfluorooctanesulfonate (PFOS), a fluorinated organic contaminant. PFOS was measured in the tissues of wildlife, including, fish, birds, and marine mammals. Some of the species studied include bald eagles, polar bears, albatrosses, and various species of seals. Samples were collected from urbanized areas in North America, especially the Great Lakes region and coastal marine areas and rivers, and Europe. Samples were also collected from a number of more remote, less urbanized locations such as the Arctic and the North Pacific Oceans. The results demonstrated that PFOS is widespread in the environment. Concentrations of PFOS in animals from relatively more populated and industrialized regions, such as the North American Great Lakes, Baltic Sea, and Mediterranean Sea,were greaterthan those in animals from remote marine locations. Fish-eating, predatory animals such as mink and bald eagles contained concentrations of PFOS that were greater than the concentrations in their diets. This suggests that PFOS can bioaccumulate to higher trophic levels of the food chain. Currently available data indicate that the concentrations of PFOS in wildlife are less than those required to cause adverse effects in laboratory animals.     

Distribution of perfluorooctane sulfonate and other perfluorochemicals in the ambient environment around a manufacturing facility in China

Perfluorinated compounds (PFCs) can be released to the surrounding environment during manufacturing and usage of PFC containing products, which are considered as main direct sources of PFCs in the environment. This study evaluates the release of perfluorooctane sulfonate (PFOS) and other PFCs to the ambient environment around a manufacturing plant. Among the nine PFCs analyzed, only PFOS, perfluorooctanoic acid (PFOA), and perfluorohexane sulfonate (PFHxS) were found in dust, water, soil, and chicken eggs. Very high concentrations of PFOS and PFOA were found in dust from the production storage, raw material stock room, and sulfonation workshop in the manufacturing facility, with the highest value at 4962 μg/g (dry weight) for PFOS and 160 μg/g for PFOA. A decreasing trend of the three PFCs concentrations in soils, water, and chicken eggs with increasing distance from the plant was found, indicating the production site to be the primary source of PFCs in this region. Risk quotients (RQs) assessment for surface water >500 m away from the plant were less than unity. Risk assessment of PFOS using predicted no-effect concentration (PNEC, 3.23 ng/g on a logarithmic scale) indicated no immediate ecological risk of a reduction in offspring survival. PFOS concentrations in most egg samples did not exceed the benchmark concentration derived in setting a reference dose for noncancer health effects (0.025 μg/(kgxd)).     

Sonochemical decomposition of perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are shown to be globally distributed, environmentally persistent, and bioaccumulative. Although the toxicities of these compounds were reported, the cleanup procedure from the environment is not developed because of their inertness. In this report the sonochemical degradations of PFOS and PFOA to the products through the fission of the perfluorocarbon chains were observed and the half-life times of the PFOS and PFOA degradations under an argon atmosphere determined to be 43 and 22 min, respectively. The shortening of perfluorocarbon chain of PFOS and PFOA leads to the lowering of the toxicity in view of the decrease of the persistence, and the technique would contribute to the remediation of the environmental pollution by these compounds.     

气相色谱法测试纺织品中PFOS

以30 mL甲醇/水(体积比1:1)为萃取剂,使用微波辅助萃取-气相色谱-微电子捕获检测器测定纺织品中全氟辛烷磺酰基化合物(PFOS),并通过正交试验对测定条件进行优化.该方法的最低检出限可达0.002 74～0.006 52 μg/g,精密度为2.31%～10.56%,加标回收率为93.31%～102.99%(n=6).该方法操作简单、快速、准确,灵敏度高,适用于对纺织品中残留痕量PFOS的监测分析.     

Levels and enantiomeric signatures of methyl sulfonyl PCB and DDE metabolites in livers of harbor porpoises (Phocoena phocoena) from the Southern North Sea

The concentration of 26 methyl sulfonyl metabolites of polychlorinated biphenyls (MeSO2-PCBs) and of p,p'-DDE (MeSO2-DDE) were determined in 19 liver samples from harbor porpoises (Phocoena phocoena) stranded between 1997 and 2000 on the Belgian and French North Sea Coasts. The total concentration of MeSO2-PCBs ranged from 39 to 4221 ng/g lipid weight (lw) and were generally higher in adults (age > 2 yr, range 969-4,221 ng/g lw) than in juveniles (age < 2 yr, range 39-1815 ng/g lw). The concentrations of MeSO2-DDE were generally also higher in adults (21-96 ng/g lw) than in juveniles (0.5-60 ng/g lw). Congeners 3- and 4-MeSO2-CB101 were the dominating metabolites in all samples. Due to their preferential retention in the liver, the MeSO2-PCB congeners could be divided into two groups. The first group was dominated by the 3-MeSO2-PCB congeners and consisted of MeSO2-CB31, -CB49, -CB52, -CB87, and -CB101, which all have a 2,5-chlorine substitution in the phenyl ring containing the methyl sulfonyl group. The second group was dominated by the 4-MeSO2-PCB congeners and consisted of MeSO2-CB64, -CB91, -CB110, and -CB132, which all have a 2,3,6-chlorine substitution. The ratios of sum of PCBs/sum of MeSO2-PCBs and p,p'-DDE/MeSO2-DDE differed greatly between individual subjects and ranged from 15 to 419 and from 17 to 1088, respectively. The ratio between the precursor PCB congeners and their corresponding metabolites ranged from 0.6 (CB49) to 175 (CB174). Enantiomeric fractions (EFs) for MeSO2-PCB atropisomers, which include 3-MeSO2-CB132, 3-MeSO2-CB149, 4-MeSO2-CB149, 3-MeSO2-CB174, and 4-MeSO2-CB174, were also measured in 8 out of the 19 subjects. High enantiomeric excess (EF > 0.73 or EF < 0.23) for the measured chiral MeSO2-PCB congeners was found in all samples. This result may suggest that one atropisomer may be preferentially formed in harbor porpoises or that the atropisomers are retained in a highly selective manner.     

全氟辛烷磺酰基化合物及全氟辛酸测试技术

为遏制全氟辛烷磺酰基化合物(PFOS)和全氟辛酸(PFOA)的全球性污染及对人类健康的危害,美、欧等国的有关部门及相关组织相继提出了禁止PFOS和PFOA生产及使用的规定.随着欧盟等对PFOS禁令的颁布和实施,PFOS和PFOA监测技术及分析方法研究倍受关注.然而,对于这些全氟化合物的定量测定,目前国际上尚无统一的标准...     

Monitoring of perfluorinated compounds in edible fish from the Mediterranean Sea

Perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS) are environmental contaminants belonging to a chemical group known as perfluorinated compounds (PCFs). The United States Environmental Protection Agency (US EPA) considers both compounds to be carcinogenic. The goal of the present study was to evaluate the contamination levels of PFOS and PFOA in edible fish of the Mediterranean Sea. Twenty six fish muscles, 17 fish livers, five series of cephalopods (each composed of ten specimens) and thirteen series of bivalves (each composed of about 50 specimens) were used for the investigation. A fast sample treatment, followed by an LC–ESI–MS/MS method is described for the identification, and quantification of PFOA and PFOS in fish. The method was in-house-validated through the determination of precision, accuracy, specificity, calibration curve, decision limit (CCα), and detection capability (CCβ). The results showed PFOA and PFOS levels in fishes and molluscs lower than those reported for analogue matrices in different geographic areas. Therefore, our biomonitoring results did not show that the Mediterranean Sea had any particularly alarming pollution by PFCs, although it is located in a semi-closed basin with scarce water change. Nonetheless, a worrying element is that a few fish showed extremely high contamination by PFOA and PFOS. This finding needs further clarification in order to assess whether such unusual contamination is linked to “dot-like” pollutant release, which could explain the anomaly.     

Photodegradation of perfluorooctane sulfonate by UV irradiation in water and alkaline 2-propanol

Perfluorooctane sulfonate (PFOS) is the environmentally concerned compound because of its persistence and bioaccumulative properties. Since photodegradation of PFOS is not yet experimentally confirmed, photodegradation study of PFOS in water and alkaline 2-propanol solution was conducted. Aqueous and alkaline 2-propanol solution of PFOS (40 microM) was irradiated with a low-pressure mercury lamp (254 nm, 32 W) by internal irradiation for 10 d, and then PFOS, fluoride and sulfate ions, and the other degradation products were analyzed. Photodegradation of PFOS was confirmed in both media. PFOS was degraded by 8% after 1 day and by 68% after 10 days irradiation compared to the initial concentration in water. In alkaline 2-propanol, 76 and 92% of PFOS was degraded after 1 and 10 days irradiation, respectively. Photodegradation of PFOS in alkaline 2-propanol was much faster and effective than in water, as the photodegradation rate constants were 0.93 days(-1) in alkaline 2-propanol and 0.13 days(-1) in water, respectively. Formation of fluoride and sulfate was also confirmed by ion chromatography and X-ray diffraction analysis. From observation of the degradation products, two major degradation pathways of PFOS were considered: via C8HF17 and C8F17OH, respectively, resulting in short-chain fluorinated compounds such as C7HF15 and C7F15OH by stepwise removal of CF2. Formation of short-chain fluorocarbons such as CF4, C2F6, and C3F8 were also confirmed. This is the first study to confirm photodegradation of PFOS in water and alkaline 2-propanol.     

Perfluorinated contaminants in sediments and aquatic organisms collected from shallow water and tidal flat areas of the Ariake Sea, Japan: environmental fate of perfluorooctane sulfonate in aquatic ecosystems

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorohexane sulfonate (PFHS), and perfluorooctane sulfonamide (PFOSA) are widely distributed in aquatic ecosystems. Despite studies reporting the occurrence of PFCs in aquatic organisms, the fate of PFCs in tidal flat and marine coastal ecosystems is not known. In this study, we determined concentrations of PFOS, PFOA, PFNA, PFHS, and PFOSA in sediments; benthic organisms, including lugworm, mussel, crab, clam, oyster, and mudskipper fish from tidal flat; and shallow water species, such as filefish, bream, flounder, shark, finless porpoise, gull, and mallard collected from the Ariake Sea, Japan. PFOS and PFOA were detected in most of the samples analyzed, followed by PFNA, PFOSA, and PFHS. In shallow water species, PFOS was the dominant contaminant, and elevated concentrations were found in higher trophic level species, such as marine mammals and omnivorous birds. These results suggest biomagnification of PFOS through the coastal food chain. In contrast, PFOA was the most abundant compound in tidal flat organisms and sediments. PFOA concentrations in sediments, lugworms, and omnivorous mudskippers in tidal flat were approximately 1 order of magnitude greater than the levels of PFOS. This indicates differences in exposure pattern and bioavailability of PFOS and PFOA between shallow water and tidal flat organisms. The accumulation profiles of PFCs were compared with those of organochlorines (polychlorinated biphenyls, PCB), organotin (tributyltin,TBT), and polycyclic aromatic hydrocarbons (PAHs) in tidal flat and shallow water samples collected from the Ariake Sea. Concentrations of PFCs in sediments and in tidal flat organisms were significantly lower than that found for PCBs, TBT, and PAHs. Nevertheless, PFOS concentrations in shallow water species were comparable to and/or significantly greater than those of other classes of contaminants. This implies that the aqueous phase is a major sink for PFCs, which is different from what was observed for nonpolar organic pollutants.     

Use of reverse osmosis membranes to remove perfluorooctane sulfonate (PFOS) from semiconductor wastewater

Perfluorooctane sulfonate (PFOS) and related substances are persistent, bioaccumulative, and toxic, and thus of substantial environmental concern. PFOS is an essential photolithographic chemical in the semiconductor industry with no substitutes yet identified. The industry seeks effective treatment technologies. The feasibility of using reverse osmosis (RO) membranes for treating semiconductor wastewater containing PFOS has been investigated. Commercial RO membranes were characterized in terms of permeability, salt rejection, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and membrane surface zeta potential (streaming potential measurements). Filtration tests were performed to determine the membrane flux and PFOS rejection. Over a wide range of feed concentrations (0.5 - 1500 ppm), the RO membranes generally rejected 99% or more of the PFOS. Rejection was better for tighter membranes, but was not affected by membrane zeta potential. Flux decreased with increasing PFOS concentration. While the flux reduction was severe for a loose RO membrane probably due to its higher initial flux, very stable flux was maintained for tighter membranes. At a very high feed concentration (about 500 ppm), all the membranes exhibited an identical stable flux. Isopropyl alcohol, present in some semiconductor wastewaters, had a detrimental effect on membrane flux. Where present it needs to be removed from the wastewater prior to using RO membranes.     

Occurrence and sources of perfluorinated surfactants in rivers in Japan

We analyzed perfluorinated surfactants (PFSs) in 20 river samples and 5 wastewater secondary effluent samples in Japan to reveal their occurrence and sources. Nine PFS species were determined: perfluorooctanesulfonate (PFOS), perfluorooctane sulfonamide (FOSA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), perfluorododecanoate (PFDDA), and perfluorotridecanoate (PFTDA). PFSs were detected in all rivers, revealing nationwide contamination of rivers. In particular, 11 out of 20 river samples exceeded New Jersey guidance for PFOA in drinking water (40 ng/L). PFOS, PFHpA, PFOA, and PFNA were major species in Japan. Concentrations of PFOS, PFHpA, and PFNA in rivers were strongly correlated with population density, suggesting that the chemicals were derived from urban activities. PFOA showed a significant but weak correlation. We used crotamiton, a marker of sewage effluent, for further source analysis. Concentrations of PFOS, PFHpA, and PFNAwere strongly correlated with those of crotamiton, and plots of secondary effluents fell near the regression lines of rivers, indicating that the PFOS, PFHpA, and PFNA in rivers were derived from sewage effluent. On the other hand, PFOA was found at remarkably high levels (54-192 ng/L) in seven river samples containing low levels of crotamiton, suggesting that it was derived from nonsewage point sources, as well as sewage effluent. The total fluxes of sewage-derived PFOS, PFHpA, PFOA, and PFNA from Japan were estimated to be 3.6, 2.6, 5.6, and 2.6 t/year, respectively. This is the first report to identify PFOA in several rivers, derived from nonsewage point sources, by using a marker of sewage effluent.     

水产品中全氟辛酸和全氟辛烷磺酸检测技术 及污染现状

全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)是环境中广泛存在、较为典型的两种全氟化合物。针对水产品中PFOA和PFOS的检测技术和污染现状进行研究,进而研究其暴露途径、生物富集规律等内容,并基于此预测污染物环境分布、环境行为,以及相应地制定环境水和水产品质量安全标准,对于确保消费者食用安全具有重要意义。本文总结、分析了水产品中PFOA和PFOS的检测技术研究进展,及水环境和水产品中污染情况,对目前存在的问题及今后的研究方向进行了讨论和展望,以期为中国水产品中全氟化合物的监控和质量安全风险评估提供参考。     

High accumulation of perfluorooctane sulfonate (PFOS) in marine tucuxi dolphins (Sotalia guianensis) from the Brazilian coast

Perfluorooctane sulfonate (PFOS) and other perfluoroalkyl compounds (PFCs) were measured in liver samples from 29 marine tucuxi dolphins from Rio de Janeiro state (RJ), Brazil. PFC measurement combined liquid chromatography and mass spectrometry, using a CapLC system connected to a Quadrupole-LIT mass spectrometer. PFOS was the only PFC detected and it was so in all samples. PFOS concentrations (ng x g(-1) dw) of dolphins (n=23) from the highly contaminated Guanabara Bay (in RJ) varied between 43 and 2431 as well as between 76 and 427 from areas of RJ other than the quoted bay (n=6). Concentrations of three fetuses and one neonate varied between 664 and 1590. Fetus/mother ratios were calculated in two situations (2.75 and 2.62). It seems that mother-to-calf transference plays important role for relationships between PFOS and age. When a one-year-old male calf presenting 2431 ng x g(-1) dw was excluded from the test, significant correlations were observed between PFOS concentrations and both age and total length. Despite the placental transference, PFOS concentrations were not significantly lower in females than in males. PFOS levels in marine tucuxi dolphins from Guanabara Bay are among the highest detected to date in cetaceans, and this may represent a threat to the small population concerned.     

食品中全氟烷基化合物的污染现状

全氟烷基化合物（Perflurorinated alkylated substances, PFASs）是一类人工合成的脂肪烃类化合物,自上个世纪50年代合成以来,该类化合物以其优良的稳定性及表面活性作为加工助剂被应用于多种民用及工业领域,如纺织品、灭火器和油漆等行业。近年来的研究发现,在空气、沉积物、饮用水、海水和食品等多种基质中均可检测出全氟类化合物,说明其已在生态系统中造成较为严重的污染。作为一类新型持久性污染物,全氟烷基化合物已引起了科学和法规上的研究兴趣。目前对食品中PFASs的污染调查主要集中在动物源性食品中,而对植物源性食品的调查尚缺乏。本文综述了中国及其他国家市场食品中全氟化合物的污染水平,比较国内外各种食品中全氟化合物污染水平的差异,并通过文献报道的污染水平对当地居民存在的健康风险进行评估,为全面了解并控制PFASs污染提供基础依据。     

Tissue distribution of perfluorinated surfactants in common guillemot (Uria aalge) from the Baltic Sea

Perfluorinated alkyl surfactants (PFAS) were investigated in tissues and organs of the common guillemot (Uria aalge) from the Baltic Sea. Concentrations of 11 perfluorinated carboxylates, four perfluorinated sulfonates, and perfluorooctane sulfonamide were determined in egg, liver, kidney, and muscle of adult guillemot, as well as in liver from chicks, all sampled in 1989. Additionally, whole herring homogenates from 2005 were analyzed, herring comprising a large part of guillemot's diet. Quantifiable concentrations of PFAS were found in all samples. Perfluorooctane sulfonate (PFOS) was predominant, followed by perfluorotridecanoate (PFTriDA) and perfluoroundecanoate (PFUnDA). The median concentration of PFOS was highest in eggs (325 ng/g wet weight (w wt)) followed by chick liver (309 ng/g w wt), kidney (127 ng/g w wt), adult liver (121 ng/g w wt), and muscle (14 ng/g w wt). Comparatively low levels of PFOS were found in herring, leaving a blurred picture of uptake routes. PFAS concentrations in livers of male and female guillemots did not differ significantly. Some PFAS showed higher concentrations in eggs than in female livers. The ratio of levels in egg/female liver, indicating mother-to-egg transfer capacity, increased with increasing PFAS chain length. PFOS showed a higher tendency for transfer than carboxylates of carbon chain lengths C9-C13.     

Occurrence of Vibrio and other pathogenic bacteria in Mytilus galloprovincialis (mussels) harvested from Adriatic Sea, Italy.

Sixty-two samples of Mytilus galloprovincialis (mussels) harvested from approved shellfish waters in the Adriatic Sea were examined for the presence of Vibrio, Salmonella, Campylobacter, and verocytotoxin producing Escherichia coli. Vibrio spp. were isolated from 48.4% of samples; the species most frequently found were V. alginolyticus (32.2%) and V. vulnificus (17.7%), followed by V. cincinnatiensis (3.2%), V. parahaemolyticus (1.6%), V. fluvialis (1.6%) and V. cholerae non-O1 (1.6%). V. parahaemolyticus resulted negative to Kanagawa-phenomenon and to PCR amplification of tdh gene. V. cholerae resulted negative to PCR amplification of sto gene. No Salmonella, Campylobacter, or E. coli verocytotoxin-producing strains were isolated. The results of this study suggest the potential risk of ingesting raw or undercooked mussels due to the frequent presence of potentially pathogenic Vibrio species.     

液相色谱串联质谱法检测一次性纸杯中全氟辛酸和全氟辛烷磺酸的迁移量

目的 建立液相色谱串联质谱法检测一次性纸杯中全氟辛酸、全氟辛烷磺酸向食品模拟物中的迁移量。方法 待测样品经前处理后, 通过C18色谱柱进行分离, 以乙腈-水为流动相进行梯度洗脱、流速 0.2 mL/min、柱温为30 ℃、进样量2 μL, 由三重四级杆质谱进行定性和定量分析。结果 全氟辛酸和全氟辛烷磺酸在0.1~2.0 ng/mL范围内线性关系良好, 相关系数均≥0.999; 低、中、高3个添加水平的平均加标回收为81.27%~97.12%; 相对标准偏差为2.9%~7.4%。应用建立的方法对一次性纸杯进行模拟迁移试验, 初步得到了这2种物质在不同模拟状态下的迁移量。结论 该方法选择性强、灵敏性和准确度高, 适用于一次性纸杯中全氟辛酸和全氟辛烷磺酸的确证和定量分析。