Low serum levels of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) in children and adults from Afghanistan

Applications of perfluorinated compounds (PFCs) have led to a PFC exposure of the general population worldwide. Most PFC human biomonitoring data are available from developed countries. Here we report for the first time PFC levels in serum from children and adults living in the low developed country of Afghanistan. Among a health cooperation project we had the chance to collect blood samples from 12 children (age 2.5-9 years) and 43 adults (age 20-65 years). 25 participants were from Kabul and 30 lived in a rural area. Drinking water samples were collected from 10 tap water and 16 well water sources. PFC levels were determined by HPLC and MS/MS detection after offline protein precipitation with acetonitrile. PFOS could be quantified in all blood samples (limit of quantification, LOQ: 0.1 µg/l). Median (range) was 1.2 µg/l (0.21-11.8 µg/l). Most PFOA (n = 43) and PFHxS levels (n = 42) were below LOQ of 0.5 µg/l. Maximum levels were 1.5 (PFOA) and 3.0 µg/l (PFHxS). All PFOS and PFOA concentrations in drinking water were below LOQ (PFOA 0.03 µg/l and PFOS 0.015 µg/l). It is concluded that exposure to PFCs also occurs in Afghanistan but on a very low level.     

Perfluoroalkyl sulfonates and perfluorocarboxylates in two wastewater treatment facilities in Kentucky and Georgia

Discharge of effluents from municipal wastewater treatment plants (WWTPs) is a route for the introduction of certain organic contaminants into aquatic environments. Earlier studies have reported the occurrence of perfluorochemicals in effluents from WWTPs. In this study, contamination profiles of perfluorinated compounds (PFCs), including perfluoroalkyl sulfonates (PFASs; PFOS, PFOSA, PFHxS) and perfluoroalkyl carboxylates (PFACs; PFOA, PFNA, PFDA, PFDoDA, PFUnDA), were determined in samples collected at various stages of wastewater treatment during different seasons. The two WWTPs selected for this study represent rural (Plant A, Kentucky) and urban (Plant B, Georgia) areas. PFOS was a major contaminant in samples from Plant A (8.2–990 ng/g dry wt in solid samples and 7.0–149 ng/L in aqueous samples), followed by PFOA (8.3–219 ng/g dry wt in solid samples and 22–334 ng/L in aqueous samples). PFOA was the predominant contaminant in samples from Plant B (7.0–130 ng/g dry wt in solid samples and 1–227 ng/L in aqueous samples), followed by PFOS (<2.5–77 ng/g dry wt in solid samples and 1.8–22 ng/L in aqueous samples). PFHxS, PFNA, PFDA, and PFOSA were detected in most of the samples, whereas PFUnDA and PFDoDA were detected in very few samples. Concentrations of some PFCs, particularly PFOA, were slightly higher in effluent than in influent, suggesting that biodegradation of some precursors contributes to the increase in PFOA concentrations in wastewater treatment processes. No large-magnitude seasonal variations in concentrations were found, although mass flow of PFCs was higher in winter than in summer. In general, samples from the rural plant in Kentucky contained greater concentrations of PFCs than did those from the urban plant in Georgia. Incineration of sludge reduced the PFC levels significantly. The mass flows of PFCs in these two plants were several hundreds of mg/day, comparable to flow values reported earlier.     

Perfluorinated contaminants in fur seal pups and penguin eggs from South Shetland, Antarctica

Perfluorinated compounds (PFCs) have emerged as a new class of global environmental pollutants. In this study, the presence of perfluorochemicals (PFCs) in penguin eggs and Antarctic fur seals was reported for the first time. Tissue samples from Antarctic fur seal pups and penguin eggs were collected during the 2003/04 breeding season. Ten PFC contaminants were determined in seal and penguin samples. The PFC concentrations in seal liver were in the decreasing order, PFOS > PFNA > PFHpA > PFUnDA while in Adélie penguin eggs were PFHpA > PFUnDA > PFDA > PFDoDA, and in Gentoo penguin eggs were PFUnDA > PFOS > PFDoDA > PFHpA. The PFC concentrations differed significantly between seals and penguins (p < 0.005) and a species-specific difference was found between the two species of penguins (p < 0.005). In our study we found a mean concentration of PFOS in seal muscle and liver samples of 1.3 ng/g and 9.4 ng/g wet wt, respectively, and a mean concentration in Gentoo and Adélie penguin eggs of 0.3 ng/g and 0.38 ng/g wet wt, respectively. PFCs detected in penguin eggs and seal pups suggested oviparous and viviparous transfer of PFOS to eggs and off-springs.     

Organohalogenated contaminants in eggs of rockhopper penguins (Eudyptes chrysocome) and imperial shags (Phalacrocorax atriceps) from the Falkland Islands

In this study, we evaluated the use of seabird eggs of two common bird species from the Falkland Islands as bioindicators of contamination with organohalogenated contaminants (OHCs). We compared contamination levels and profiles of different OHCs between eggs of the rockhopper penguin (Eudyptes chrysocome) and the imperial shag (Phalacrocorax atriceps). In addition, laying order effects on OHC concentrations and profiles were also investigated in both species. For polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) as well as polybrominated diphenyl ethers (PBDEs), concentrations were significantly lower in eggs of rockhopper penguins (27.6 ± 0.70 ng/g lw, 56.5 ± 1.33 ng/g lw and 0.98 ± 0.04 ng/g lw, respectively) compared to the imperial shags (140 ± 5.54 ng/g lw, 316 ± 11.53 ng/g lw, 1.92 ± 0.15 ng/g lw, respectively). On the other hand, 2′MeO-BDE 68 and 6MeO-BDE 47, two brominated compounds of reported natural origin, were significantly higher in the penguin eggs (0.55 ± 0.05 ng/g lw and 7.01 ± 0.64 ng/g lw, respectively) compared to the shag eggs (0.17 ± 0.03 ng/g lw and 0.50 ± 0.06 ng/g lw, respectively). In addition, PCB, OCP and PBDE contamination profiles differed markedly between the two species. Various factors, such as diet, feeding behaviour, migratory behaviour and species-specific metabolism, may be responsible for the observed results. For both rockhopper penguins and imperial shags, PCB, OCP and PBDE concentrations and profiles did not significantly change in relation to the laying order. This suggests that, for both species, any egg of a clutch is useful as a biomonitoring tool for OHCs. Although our results showed that OHCs have also reached the Falkland Islands, concentrations were relatively low compared to other studies. However, future monitoring may be warranted to assess temporal trends of different OHCs.     

Evaluation of the fate of perfluoroalkyl compounds in wastewater treatment plants

Recent studies have shown that the wastewater treatment plant (WWTP) is a significant source of perfluoroalkyl compounds (PFCs) in natural water. In this study, 10 PFCs were analyzed in influent and effluent wastewater and sludge samples in 15 municipal, 4 livestock and 3 industrial WWTPs in Korea. The observed distribution pattern of PFCs differed between the wastewater and sludge samples. Perfluorooctane sulfonate (PFOS) was dominant in the sludge samples with a concentration ranging from 3.3 to 54.1 ng/g, whereas perfluorooctanoic acid (PFOA) was dominant in wastewater and ranged from 2.3 to 615 ng/L and 3.4 to 591 ng/L in influent and effluent wastewater, respectively. Principal component analysis (PCA) results provided an explanation for this variation in PFC distribution patterns in the aqueous and sludge samples. The fates of PFCs in the WWTPs were related with the functional groups. The PFOS concentrations tended to decrease after treatment in most WWTPs, whereas PFOA increased. The different fates of PFOA and PFOS in WWTPs were attributed to the higher organic carbon-normalized distribution coefficient of perfluoroalkylsulfonate (PFASs) than that of the carboxylate analog, indicating the preference of PFASs to partition to sludge. Although industrial WWTPs contained high concentration of PFCs, they are not the main source of PFCs in Korean water environment because of their small release amount. WWTPs located in big cities discharged more PFCs, suggesting household sewage is one of the significant sources of PFCs contamination in the environment.     

Fluctuating wing asymmetry and hepatic concentrations of persistent organic pollutants are associated in European shag (Phalacrocorax aristotelis) chicks

In aquatic birds, high body burdens of persistent organic pollutants (POPs) have been associated with developmental effects related to growth, increased fluctuating wing asymmetry, and disruption of the thyroid hormone, vitamin A (retinol) and vitamin E (tocopherol) homeostasis. The aim of the present study was to examine if morphological variables (body mass, liver mass, wing length, tarsus length and head length), fluctuating asymmetry of the wings and tarsus, growth rates and endocrine variables (thyroid hormones, retinol and tocopherol) were associated with hepatic levels of POPs (PCBs, OCPs and PBDEs) in 21 day old chicks of European shag (Phalacrocorax aristotelis). Partial Least Squares (PLS) analysis showed that fluctuating asymmetry of wing bone length (FA_WBL) was affected by PCB-105, -118, -138, -153, and -180 (r²x = 0.88, r²y = 0.35, q² = 0.29). Bivariate correlation confirmed significant positive relationships between FA_WBL and each of these PCB congeners. In the PLS model no other biological variables were significantly affected by any of the POPs. Levels of POPs were much lower in the shag chicks than in eggs and in hatchlings from the same breeding colony, most likely due to growth dilution of the compounds. We suggest that the effects of the PCBs on FA_WBL may be due to effects of these compounds on bone growth and bone structure. FA_WBL may have functional effects on the fitness if it persists after fledging.     

Levels and patterns of Persistent Organic Pollutants (POPS) in selected food items from Northwest Russia (1998-2002) and implications for dietary exposure

Residues of persistent organic pollutants (POPs) were analysed in 70 selected food items from Northwest Russia in 1998-2002. Levels of PCBs ranged from 0.2 to 16 ng/g wet weight (ww) in dairy products and fats, 0.2 to 23 ng/g ww in meat products, 0.5 to 16 ng/g ww in eggs and 0.3 to 30 ng/g ww in fish. High levels of DDT (16 ng/g ww) were found in locally produced butter from Kola Peninsula, in pork fat from Arkhangels region (10 to 130 ng/g ww) and in some fish samples from White Sea and Kargopol region (17 and 30 ng/g ww). Findings of low DDE/DDT ratios in many of the studied food items indicated recent contamination to DDTs. Mean levels of sum TEQs_WHO1998 of dioxin-like mono-ortho PCBs: PCBs 105, 118, 156 and 157 (∑ mo-PCBs-TEQs_WHO1998) were highest in dairy products, chicken eggs and fish, with levels of 0.292, 0.245 and 0.254 pg/g ww, respectively. The estimated daily intake (EDI) for ∑ mo-PCBs-TEQs_WHO1998 was 0.74 pg/kgbw/day and in the same range as in Sweden and Denmark. Fish, dairy products, eggs and meat were the main contributors to the EDI of ∑ mo-PCBs-TEQs_WHO1998. The EDIs of DDTs, HCHs and HCB were several times higher than in Sweden and Denmark. Consumption of meat and poultry were important sources for intake of DDTs and HCHs, respectively. Contamination of animal feed and agricultural practice were assumed the most important causes for the results in the present study. However, increased control on maximum residue levels in food and feed may have resulted in large changes on levels and patterns of POPs in food in the studied areas.     

Perfluorinated compounds in surface waters and WWTPs in Shenyang, China: mass flows and source analysis

Concentrations of 10 perfluorinated chemicals (PFCs) were investigated in the Hun River (HR), four canals, ten lakes, and influents and effluents from four main municipal wastewater treatment plants (WWTPs) in Shenyang, China. Mass flows of four main PFCs were calculated to elucidate the contribution from different sections of the HR. Overall, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the major PFCs in the HR, with ranges of 2.68-9.13 ng/L, and 2.12-11.3 ng/L, respectively, while perfluorooctane sulfonate (PFOS) was detected at lower levels, ranging from 0.40 to 3.32 ng/L. The PFC concentrations in the HR increased after the river passes through two cities (Shenyang and Fushun), indicating cities are an important contributor for PFCs. Mass flow analysis in the HR revealed that PFC mass flows from Fushun are 1.65-5.50 kg/year for C6-C8 perfluorinated acids (PFCAs) and 1.29 kg/year for PFOS, while Shenyang contributed 2.83-5.18 kg C6-C8 PFCAs/year, and 3.65 kg PFOS/year. The concentrations of PFCs in four urban canals were higher than those in the HR, with the maximum total PFCs of 240 ng/L. PFOA and PFOS showed different trends along these canals, suggesting different sources for the two PFCs. Total PFCs in ten lakes from Shenyang were at low levels, with the greatest concentration (56.2 ng/L) detected in a heavily industrialized area. The PFC levels in WWTP effluents were higher than those in surface waters with concentrations ranging from 18.4 to 41.1 ng/L for PFOA, and 1.69-3.85 ng/L for PFOS. Similar PFC profiles between effluents from WWTPs and urban surface waters were found. These results indicate that WWTPs are an important PFC source in surface water. Finally, we found that the composition profiles of PFCs in surface waters were similar to those in tap water, but not consistent with those in adult blood from Shenyang. The calculation on total daily intake of PFOS by adults from Shenyang showed that the contribution of drinking water to human exposure was minor.     

Effects of laying order and experimentally increased egg production on organic pollutants in eggs of a terrestrial songbird species, the great tit (Parus major)

In this study, concentrations and profiles of organic pollutants were investigated in a passerine species with a large clutch size, the great tit (Parus major). In the first clutches, mean egg concentrations decreased significantly in relation to the laying order from 3025 ± 416 ng/g lw to 2267 ± 386 ng/g lw for sum PCBs and from 989 ± 339 ng/g lw to 695 ± 320 ng/g lw for sum DDTs. Sum PBDE concentrations also decreased in relation to the laying order from 68 ± 10 ng/g lw to 53 ± 11 ng/g lw, but not significantly. Although laying order effects were found, variation in concentrations within clutches was smaller than among clutches. To further investigate the impact of laying large numbers of eggs on levels and profiles of organic pollutants, initiation of replacement clutches was experimentally induced. Mean sum PCB and sum PBDE concentrations were significantly lower in eggs of replacement clutches compared to first clutches. In addition, first clutches had a higher contribution of the higher chlorinated and more persistent PCB congeners, CB 170, 180 and 183, and a lower contribution of CB 52, 95 and 149 compared to replacement clutches. Because of the differences in concentrations and profiles between the first and replacement clutches, the combined use of eggs from both the first and replacement clutches for monitoring purposes is not recommended. In conclusion, we suggest that, due to the larger variation among clutches compared to the variation within clutches, one randomly collected great tit egg from a first clutch is useful as a biomonitoring tool for organic pollutants. To our knowledge, this is the first study in which the impact of an experimentally increased clutch size on the levels and profiles of contaminants in eggs has been investigated.     

Adsorption of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on alumina: influence of solution pH and cations

The persistent nature of perfluorochemicals (PFCs) has attracted global concern in recent years. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are the most commonly found PFC compounds, and thus their fate and transport play key roles in PFC distribution in the natural environment. As most solid phases in natural water contain alumina, an investigation of PFOS and PFOA adsorption behavior on alumina should prove useful in evaluating the environmental impact of this type of persistent pollutant. Systematic experiments were carried out in this study to investigate the adsorption behavior of PFOS and PFOA onto alumina. The results of adsorption kinetics on alumina show that it takes 48 h to reach equilibrium. The adsorption isotherms reveal maximum adsorption capacities of 0.252 μg/m² for PFOS and 0.157 μg/m² for PFOA at pH = 4.3, with the difference primarily due to their different functional groups. An increase in pH leads to a decrease in PFOS and PFOA adsorption on alumina, which may be attributed to the reduction in electrostatic interaction. The adsorption of both PFOS and PFOA decreases with an increase in ionic strength for all four types of cations (Na⁺, K⁺, Mg²⁺, and Ca²⁺), due to the compression of the electrical double layer. Furthermore, the results also indicate that both Ca²⁺ and Mg²⁺ can form bridges with PFOA anions in solution, whereas only PFOS can be bridged by Ca²⁺ due to the higher covalent nature of magnesium.