Environ. Sci. Technol. 2006, 40, 3742-3748
Levels of 12 Perfluorinated Chemicals in Pooled Australian Serum, Collected 2002-2003, in Relation to Age, Gender, and Region A N N A K A¨ R R M A N , * , † J O C H E N F . MUELLER,‡ BERT VAN BAVEL,† FIONA HARDEN,‡ LEISA-MAREE L. TOMS,‡ AND GUNILLA LINDSTRO ¨ M† Man-Technology-Environment (MTM) Research Centre, O ¨ rebro University, SE-701 82 O ¨ rebro, Sweden, and National Research Centre for Environmental Toxicology, The University of Queensland, Brisbane, Australia
Pooled serum samples from 3802 Australian residents were analyzed for four perfluoroalkylsulfonates, seven perfluoroalkylcarboxylates, and perfluorooctanesulfonamide (PFOSA). Serum was collected from men and women of five different age groups and from rural and urban regions in Australia. The highest mean concentration was obtained for perfluorooctane sulfonate (PFOS, 20.8 ng/mL) followed by perfluorooctanoic acid (PFOA, 7.6 ng/mL), perfluorohexane sulfonate (PFHxS, 6.2 ng/mL), perfluorononanoic acid (PFNA, 1.1 ng/mL), and PFOSA (0.71 ng/mL). Additional four PFCs were detected in 5-18% of the samples at concentrations near the detection limits (0.1-0.5 ng/mL). An increase in PFOS concentration with increasing age in both regions and genders was observed. The male pool levels of some of the age groups compared to females were higher for PFOS, PFOA, and PFHxS. In contrast, PFNA concentrations were higher in the female pools. No substantial difference was found in levels of PFCs between the urban and rural regions. The levels are equal or higher than previously reported serum levels in Europe and Asia but lower compared to the U.S.A. These results suggest that emissions from production in the Northern Hemisphere are of less importance for human exposure.
Introduction The presence and levels of perfluorinated chemicals (PFCs) have been determined in biota, wildlife and humans in several countries worldwide including in the Arctic region (1-4). Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are generally the most prevalently found PFCs in the environment and human blood. No adverse effects of PFOS and PFOA on humans have been shown. However, laboratory studies on rodents and primates indicate that PFOS and PFOA may disturb the fatty acid metabolism, affect the reproductive system and/or cause liver damages (5, 6). These effects together with their stability and bioaccumulation properties suggest that PFCs are potentially harmful to humans and the * Corresponding author phone: +46 19 30 14 01; fax: +46 19 303566; e-mail:
[email protected]. † Man-Technology-Environment (MTM) Research Centre, O ¨ rebro University. ‡ National Research Centre for Environmental Toxicology, The University of Queensland. 3742
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 12, 2006
environment. Assessments of PFC distribution and levels have so far been focused on the Northern Hemisphere from where almost all published data on biota, air, ocean water, and human levels originate. Present and historical manufacturing, usage, and emission of PFCs are most likely to have occurred in the Northern Hemisphere due to larger industrial density and population. To the best of our knowledge, no PFCs have been produced in Australia or in any other country in the Southern Hemisphere. Long-range transport in the atmosphere has been shown to occur for precursors to PFOA and PFOS, e.g., telomer alcohols and sulfonamides (7), and it has been suggested that long-range ocean transport is likely to occur for perfluorocarboxylates (8). However, long range transport in the atmosphere and in oceans across the equator is expected to be relatively slow. To date, little is known about the fate of PFCs in the environment and which exposure pathways are most important for humans. Emissions from production facilities, secondary use of products in industries or consumer articles, as well as subsequent waste disposal can result in release to air and water. PFCs have been found in the environment close to humans; for example, in drinking water, indoor air, and household dust (9-11). Previous studies have shown that humans living in more industrialized areas or urban areas in Japan and Sri Lanka have higher PFOS and PFOA levels compared to those living outside industrialized cities (12, 13). A limited number of studies have shown the presence of PFCs in food (14). Fish was suggested to be a PFC source for humans living on the Baltic coast in Poland (15). Accumulation and trends in humans are largely unknown. However it is evident that unlike the classical, more lipophilic POPs, PFCs are not typically accumulating in the lipid. PFOS and PFOA associate with proteins (16, 17) and have been found in the liver and kidney as well as in the blood of different species (18, 19). So far there is little evidence of an age-related trend in the concentrations of PFCs in humans, but it has been suggested that the levels of PFOS are higher in males (12, 20, 21). The present study is the first survey of PFCs in the Australian population. Levels of other POPs have historically been relatively low in Australia, which is a typical industrialized country with approximately 20 million residents. Serum from 3802 residents was collected from men and women living in the area around Sydney (urban) and regions outside major metropolitan centers (rural) in 2002-2003. The samples were pooled into five different age groups (60 years). Serum concentrations of four perfluoroalkylsulfonates (C4, C6, C8, C10), seven perfluoroalkylcarboxylates (C6, C8, C9, C10, C11, C12, C14), and perfluorooctanesulfonamide (PFOSA) were measured in order to evaluate the presence of PFCs and how age, gender, and region influence the levels in Australian blood.
Materials and Methods Samples. An Australian nationwide pathology company (Sullivan and Nicolaides Pathology) pooled the serum samples from stored serum that had been collected as part of their routine testing procedures. The oldest sample included in this study was collected on 27 November 2002, and the most recent sample was collected on 15 April 2003. Age, gender, and region stratified the 40 pools from 3802 individual samples, with 2 pools prepared for each stratum. An overview of the sample material is given as Supporting Information. The samples were obtained from men and women representing the following age groups: 60 years. The samples representing the 10.1021/es060301u CCC: $33.50
2006 American Chemical Society Published on Web 05/19/2006
TABLE 1. Target PFCs and the SPE-LC/MS Method Performance
d
compound
abbreviation
perfluorobutane sulfonate perfluorohexane sulfonate perfluorooctane sulfonate perfluorodecane sulfonate perfluorohexanoic acid perfluorooctanoic acid perfluorononanoic acid perfluorodecanoic acid perfluoroundecanoic acid perfluorododecanoic acid perfluorotetradecanoic acid perfluorooctanesulfonamide perfluoroheptanoic acidc 7H-perfluoroheptanoic acidd 1H,1H,2H,2H-perfluorooctanesulfonic acidc
PFBuS PFHxS PFOS PFDS PFHxA PFOA PFNA PFDA PFUnDA PFDoDA PFTDA PFOSA PFHpA 7H-PFHpA THPFOS
instrument detection limit (ng/mL)
recovery (% (CVb %)) n ) 3
0.5 a 0.3 0.1 0.5 0.3 0.5 0.1 0.1 0.1 0.3 0.1 0.1
14 (10) 102 (11) 122 (15) 69 (17) 86 (16) 85 (8) 109 (10) 73 (13) 73 (15) 67 (17) 70 (7) 131 (13)
a Method detection limit estimated to 2 ng/mL due to low recovery. b CV ) coefficent of variation. c Internal standard, i.e., added before extraction. Performance standard, i.e., added before injection.
urban population were obtained from the Southeast of Australia (Sydney, Canberra, Wollongong, Newcastle, and other major population centers from New South Wales). The rural samples were obtained from the Northern Territory and areas in all states with postcodes outside metropolitan or major regional centers. For all groups except the
