Perfluorinated acids as novel chemical tracers of global circulation of ocean waters

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.     

How seasonality affects the flow of estrogens and their conjugates in one of Japan's most populous catchments

A detailed study of the free and conjugated estrogen load discharged by the eight major sewage treatment plants into the Yodo River basin, Japan was carried out. Sampling campaigns were focused on the winter and autumn seasons from 2005 to 2008 and the free estrogens estrone(E1), 17β-estradiol(E2), estriol(E3), 17α-ethynylestradiol(EE2) as well as their conjugated (sulfate and glucuronide) forms. For both sewage effluent and river water E2 and E1 concentrations were greatest during the winter period (December-March). This coincides with the period of lowest rainfall and lowest temperatures in Japan. E1 was the dominant estrogenic component in effluent (means of 10-50 ng/L) followed by E2 (means of 0.5-3 ng/L). The estrogen sulfate conjugates were found intermittently in the 0.5-1.7 ng/L concentration range in the sewage effluents. The greatest estrogen exposure was found to be in the Katsura River tributary which exceeded 1 ng/L E2-equivalents during the winter period.     

The environmental photolysis of perfluorooctanesulfonate,perfluorooctanoate, and related fluorochemicals

A field study on the photolysis of perfluoroalkyl substances (PFASs) was conducted at high altitudes in Mt. Mauna Kea (Hawaii, USA; 4200 m) and Mt. Tateyama (Toyama, Japan; 2500 m). Results of photolysis of PFASs in the field were further confirmed in laboratory studies. Perfluorooctanesulfonate (PFOS), which is perceived as a non-degradable chemical in the environment, can undergo photolysis. Long chain PFASs can be successively dealkylated to short chain compounds such as perfluorobutyric acid (PFBA) and perfluorobutane sulfonate (PFBS), but the short chain compounds were relatively more resistant to photodegradation. These results suggest that environmental levels of short chain PFASs would increase both due to their formation from photolysis of long chain PFASs and from direct releases. Earlier studies on photolysis of PFASs were focused on the formation of perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs) from precursor compounds (such as fluorotelomer alcohols) under laboratory conditions. Our study suggests that PFSAs and PFCAs themselves can undergo photodegradation in the environment.     

Embryonic abnormalities and organochlorine contamination in double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes in 1988

Persistent organochlorine contaminants including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were determined in eggs with normal and deformed embryos collected in 1988 from different colonies during an epizootiological survey of double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes. PCBs and p,p'-DDE were found in the highest concentrations in eggs of both species. The residue pattern of PCB isomers and chlordane compounds suggested that double-crested cormorants have greater metabolic capacity to degrade contaminants than Caspian terns. According to the toxicity evaluation using the 2,3,7,8-TCDD equivalents (TEQs) approach, non-ortho coplanar PCBs contributed much more toxicity than PCDDs and PCDFs. Total TEQ of dioxin-like compounds was likely associated with occurrence of live-deformed embryos in double-crested cormorants eggs. The toxic effects of these contaminants were also estimated in Caspian tern eggs, where elevated levels of coplanar PCBs, PCDDs and PCDFs were observed in concordance with increased rate of anomalies in eggs during a breeding season in the Great Lakes.     

High-performance liquid chromatography with conductimetric detection of perfluorocarboxylic acids and perfluorosulfonates

A rapid and simple method for separating and determining various environmentally harmful perfluorocarboxylic acids and perfluorosulfonates was successfully developed using high- performance liquid chromatography with conductimetric detection, for product and waste management of these compounds at manufacturing and processing sites. Compounds having C(3)-C(8) perfluoroalkyl groups were separated using a Tosoh TSKgel Super-ODS column and a mobile phase consisting of a mixture of methanol and aqueous NaH(2)PO(4) at several mixing ratios. The best detection limits for the compounds ranged from 0.12 to 0.66 mg l(-1) (ppm), and linear calibration graphs were obtained up to 87-109 mg l(-1). The combination of this method with concentration of the sample by solid-phase extraction with cartridges based on styrene-divinylbenzene-copolymer enabled the determination of approximately 50 microg l(-1) (ppb) for compounds with C(4)-C(8) perfluoroalkyl groups. This method was successfully used to monitor the artificial decomposition of the perfluorocarboxylic acid n-C(4)F(9)COOH induced by a photocatalyst.     

Human health risk assessment of organochlorines associated with fish consumption in a coastal city in China

Food consumption is an important route of human exposure to organochlorines (OCs). In order to assess the potential health risks associated with these contaminants due to fish consumption, five species of fish were collected from a local market in Zhoushan City, an island in the East China Sea. Dioxin-like compounds, such as polychlorinated dibenzo-p-dioxins/ dibenzofurans, in the fish samples were screened by H4IIE-luc cell bioassay, and the concentrations of specific organochlorines were measured by gas chromatograph-electron capture detector (GC-ECD). The bioassay results indicated that concentrations of dioxin-like compounds in the fish samples were below detection limit (0.64 pg/mL). The concentrations of OC pesticides and PCBs ranged from 0.67 to 13 and 0.24 to 1.4 ng/g wet wt., respectively. Significantly, concentrations of p,p'-DDE in fish meat were comparatively high (average 3.9 ng/g wet wt.) compared with the other OC pesticides. The daily fish consumption, based on a dietary survey conducted among 160 local healthy residents, was determined to be 105 g/person. The relevant cancer benchmark concentrations of HCB, dieldrin, chlordane, DDTs and PCBs were 0.36, 0.04, 1.6, 1.7, and 0.29 ng/kg per day, respectively, based on the local diet. The hazard ratios (HRs), based on non-cancer endpoints were all less than 1.0, while the HRs based on cancer were greater than 1.0 for certain contaminants based on the 95th centile concentration in fish tissue.     

Perfluorinated organic compounds in human blood serum and seminal plasma: a study of urban and rural tea worker populations in Sri Lanka

Concentrations and accumulation of 13 fluorinated organic compounds (FOCs) in human sera and seminal plasma were measured in an Asian developing country, Sri Lanka. Six of the FOCs, PFOS (perfluorooctanesulfonate), PFHS (perfluorohexanesulfonate), PFUnA (perfluoroundecanoic acid), PFDA (perfluorodecanoic acid), PFNA (perfluorononanoic acid) and PFOA (perfluorooctanoic acid), were detected in all of the sera samples. Measurable quantities of two main perfluorosulfonates, PFOS and PFHS, were found in all seminal plasma samples. The detection frequency of the predominant perfluoroalkylcarboxylate, PFOA, in seminal plasma was >70%. Accumulation of PFOS in sera was significantly positively correlated with PFOA, PFHS and PFNA. Positive linear regressions were also found between PFNA and PFUnA and PFNA and PFDA suggesting that these compounds may have a similar origin of exposure and accumulation. Significantly positive associations were observed for partitioning of both PFOS and PFNA between sera and seminal plasma. The accumulation of FOCs was not significantly different in sera from Colombo (urban population) and Talawakele (rural conventional tea workers). However, the Haldummulla population (rural organic tea workers) had relatively lower exposure to FOCs compared to the other two groups, urban and rural conventional tea workers. Concentrations of FOCs in Sri Lanka were similar to those reported for industrialized countries suggesting that human exposure to such chemicals is widespread even in developing countries. The novel finding of FOCs in human seminal plasma implies that further studies are needed to determine whether long-term exposure in humans can result in reproductive impairments.     

Source determination of highly chlorinated biphenyl isomers in pine needles - comparison to several PCB preparations

The isomer specific composition of 13 technical PCB formulations of different origin and of pine needles was analyzed using GC/MS and HRGC/HRMS. Nonachlorinated biphenyls were identified in 11 among 13 formulations analyzed, with the highest abundance found for highly chlorinated ones (Aroclors 1268 and 1260, Chlorofen, Sovol, Kanechlors 600 and 500, Delor 106, Clophen A60). Decachlorobiphenyl was identified only in Aroclor 1268, Clophen A60, Aroclor 1260 and Chlorofen, comprising, respectively, 8.9, 2.8, 1.3 and 0.82% of the total bulk of nona- and decaCBs detected. Nona- and decaCB were detected in pine needles in Poland with the highest concentrations found at the sites neighboring to a former production sites of the Polish PCB formulations, while in pine needles collected around the Tokyo Bay nona- and decacCB were detected only in four of 10 sites and the concentrations corresponded to those found at the rural areas of Poland.