Adsorption behavior of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on boehmite

Understanding the interaction of perfluorochemicals, persistent pollutants with known human health effects, with mineral compounds in surface water and groundwater environments is essential to determining their fate and transport. Kinetic experiments showed that adsorption equilibrium can be achieved within 48 h and the boehmite (AlOOH) surface is receptive to perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorption. The adsorption isotherms estimated the maximum adsorption capacities of PFOS and PFOA on boehmite as 0.877 μg m⁻² and 0.633 μg m⁻², respectively. Compared to the adsorption capacity on γ-alumina, the abundant hydroxyl groups on boehmite surfaces resulted in the 2-3 times higher adsorption of PFOS and PFOA. Increasing solution pH led to a moderate decrease in PFOS and PFOA adsorption, owing to an increase in ligand exchange reactions and the decrease of electrostatic interactions. The presence of NaCl and CaCl₂ in solution demonstrated negative effects for PFOS and PFOA adsorption on boehmite surfaces, with potential mechanisms being electrical double layer compression, competitive adsorption of chloride, and the Ca²⁺ bridging effect between perfluorochemicals.     

Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K_OC) decreased in the following order: PFOSA (log K_OC = 4.1 ± 0.35 cm³ g⁻¹) > PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Radiosynthesis of perfluorooctanesulfonate (PFOS) and perfluorobutanesulfonate (PFBS), including solubility, partition and adhesion studies

Here, we describe for the first time the synthesis of [³⁵S] PFOS and [³⁵S] PFBS with sulfur-35 enriched sulfur dioxide as the radiolabelled reagent, resulting in 2.5 and 2.3 mCi of product, respectively. Basic information concerning the physicochemical properties of perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate (PFBS) and perfluorooctanoic acid (PFOA) are still limited. Hence, we utilized these radiolabelled perfluoroalkanesulfonates (PFSAs), as well as carbon-14 labelled perfluorooctanoic acid ([¹⁴C] PFOA) to determine some basic characteristics of physiological and experimental significance.The solubility of PFOS in buffered aqueous solutions at pH 7.4 was found to be severely reduced in the presence of potassium and sodium ions, which, however, did not reduce the solubility of PFOA or PFBS. PFOS was found to adhere to a small extent to polypropylene and polystyrene, whereas no such adhesion of PFOA or PFBS was detected. The extents of adhesion of PFOS and PFOA to glass were found to be 20% and 10%, respectively. For the first time, the partition coefficients for PFOS, PFBS and PFOA between n-octanol and water were determined experimentally, to be −0.7, −0.3, and 1.4, respectively, reflecting the difference in the amphiphilic natures of these molecules.     

全氟辛烷磺酸盐(PFOS)在藻渣/小球藻上的吸附行为及机理

为了开发新型廉价生物吸附剂,以高效吸附去除水体中全氟辛烷磺酸盐(PFOS),对小球藻提取生物柴油后的藻渣吸附酸性水体中的PFOS进行了吸附行为及机理的研究。小球藻提取生物质柴油后,比表面积、孔容、孔径几乎没有变化;等电点由3.3降低至2.7;蛋白质含量由51.45%提高到57.35%。在酸性条件下(pH≤3),小球藻和藻渣对PFOS的吸附率均达到99%以上;随着pH值增加至7,二者的吸附去除率迅速降低,但仍保持在22%~26%。小球藻和藻渣对PFOS的最大吸附容量分别为353.69 mg/g和444.83 mg/g。Freundlich模型能较好地拟合二者对PFOS的吸附数据,表明为多层吸附,即小球藻以静电吸引的形式吸附PFOS阴离子,并疏水分配至所含蛋白质中;而藻渣中含量较高的蛋白质对PFOS的疏水性分配作用是导致藻渣吸附量增高的主要原因。     

Estimating the contribution of precursor compounds in consumer exposure to PFOS and PFOA

The exposure of humans to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) was quantified with emphasis on assessing the relative importance of metabolic transformation of precursor compounds. A Scenario-Based Risk Assessment (SceBRA) approach was used to model the exposure to these compounds from a variety of different pathways, the uptake into the human body and resulting daily doses. To capture the physiological and behavioral differences of age and gender, the exposure and resulting doses for seven consumer groups were calculated. The estimated chronic doses of a general population of an industrialized country range from 3.9 to 520 ng/(kg day) and 0.3 to 140 ng/(kg day) for PFOS and PFOA, respectively. The relative importance of precursor-based doses of PFOS and PFOA was estimated to be 2-5% and 2-8% in an intermediate scenario and 60-80% and 28-55% in a high-exposure scenario. This indicates that sub groups of the population may receive a substantial part of the PFOS and PFOA doses from precursor compounds, even though they are of low importance for the general population. Similar to a preceding study, uptake of perfluorinated acids from contaminated food and drinking water was identified as the most important pathway of exposure for the general population. The biotransformation yields of telomer-based precursors and to a lesser extent perfluorooctanesulfonylfluoride-based precursors were identified as influential parameters in the uncertainty analysis. Fast food consumption and fraction of food packaging paper treated with PFCs were influential parameters for determining the doses of PFOA.     

Occurrence of perfluorooctanoate and perfluorooctanesulfonate in the Korean water system: implication to water intake exposure

Perfluorinated compounds (PFCs) measured in surface running waters indicated the existence of different emission sources in eight main city basins. The tap water reflected the contamination pattern and levels in their corresponding source water basins. The daily intakes through tap water consumption ranged from <0.01 to 0.73 ng kg⁻¹ d⁻¹ for perfluorooctanoate (PFOA) and <0.01 to 0.08 ng kg⁻¹ d⁻¹ for perfluorooctanesulfonate (PFOS). Tap water intake-derived exposure accounted for 8.6%-101% (for PFOA) and while <10% (for PFOS) of total daily exposure, which was estimated from Korean serum concentrations using a pharmacokinetic model. Our findings indicate that tap water intake could be an important contributor to PFOA exposure in Korean populations; accordingly, additional efforts are necessary to improve the removal efficiency of perfluorinated compounds (PFCs) in the water purification process. However, more fundamentally the aim would be to reduce the discharge of PFCs from potential sources within the basin.     

Occurrence and dietary exposure assessment of PFOS and PFOA in cultured Trachinotus ovatus in China

In this study, investigation was conducted into concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in Chinese farmed Trachinotus ovatus between 2014 and 2015 using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) method. The tissue distribution (muscle, skin, liver, kidney and gill) in Trachinotus ovatus was also assessed. The detection frequencies of PFOS and PFOA in fish were 92% and 3%, respectively, and the mean concentrations were 0.392 and 0.015 μg/kg wet weight. The analysis of PFOS distribution in different tissues in Trachinotus ovatus showed the following trend: skin> gill> kidney> liver> flesh. Results revealeded farmed Trachinotus ovatus in China to generally be contaminated with PFOS. Moreover, the average daily intake for Chinese urban residents calculated on the basis of pollution content was 0.268 ng/kg body weight/d (PFOS) and 0.014 ng/kg body weight /d (PFOA), respectively. Both hazard ratio values were less than 1, indicating that exposure levels of PFOS and PFOA through Trachinotus ovatus consumption may not lead to adverse health effects in the Chinese population.     

Concentrations of PFOS, PFOA and other perfluorinated alkyl acids in Australian drinking water

Perfluorinated alkyl acids (PFAAs) are persistent environmental pollutants, found in the serum of human populations internationally. Due to concerns regarding their bioaccumulation, and possible health effects, an understanding of routes of human exposure is necessary. PFAAs are recalcitrant in many water treatment processes, making drinking water a potential source of human exposure. This study was conducted with the aim of assessing the exposure to PFAAs via potable water in Australia. Sixty-two samples of potable water, collected from 34 locations across Australia, including capital cities and regional centers. The samples were extracted by solid phase extraction and analyzed via liquid chromatography/tandem mass spectrometry for a range of perfluoroalkyl carboxylates and sulfonates. PFOS and PFOA were the most commonly detected PFAAs, quantifiable in 49% and 44% of all samples respectively. The maximum concentration in any sample was seen for PFOS with a concentration of 16 ng L⁻¹, second highest maximums were for PFHxS and PFOA at 13 and 9.7 ng L⁻¹. The contribution of drinking water to daily PFOS and PFOA intakes in Australia was estimated. Assuming a daily intake of 1.4 and 0.8 ng kg⁻¹ bw for PFOS and PFOA the average contribution from drinking water was 2-3% with a maximum of 22% and 24% respectively.     

Removal of PFOS, PFOA and other perfluoroalkyl acids at water reclamation plants in South East Queensland Australia

This paper examines the fate of perfluorinated sulfonates (PFSAs) and carboxylic acids (PFCAs) in two water reclamation plants in Australia. Both facilities take treated water directly from WWTPs and treat it further to produce high quality recycled water. The first plant utilizes adsorption and filtration methods alongside ozonation, whilst the second uses membrane processes and advanced oxidation to produce purified recycled water. At both facilities perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) were the most frequently detected PFCs. Concentrations of PFOS and PFOA in influent (WWTP effluent) ranged up to 3.7 and 16 ng L⁻¹ respectively, and were reduced to 0.7 and 12 ng L⁻¹ in the finished water of the ozonation plant. Throughout this facility, concentrations of most of the detected perfluoroalkyl compounds (PFCs) remained relatively unchanged with each successive treatment step. PFOS was an exception to this, with some removal following coagulation and dissolved air flotation/sand filtration (DAFF). At the second plant, influent concentrations of PFOS and PFOA ranged up to 39 and 29 ng L⁻¹. All PFCs present were removed from the finished water by reverse osmosis (RO) to concentrations below detection and reporting limits (0.4-1.5 ng L⁻¹). At both plants the observed concentrations were in the low parts per trillion range, well below provisional health based drinking water guidelines suggested for PFOS and PFOA.     

Perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish blood collected near the outfall of wastewater treatment plant (WWTP) in Beijing

Perfluorinated compounds (PFCs) were measured in zooplankton and five fish species collected from Gaobeidian Lake, which receives discharge from wastewater treatment plant (WWTP) in Beijing, China. The mean total PFCs in five fish were in the order: crucian carp > common carp > leather catfish > white semiknife carp > tilapia. Perfluorooctane sulfonate (PFOS) occurred at the greatest concentrations, with mean concentrations ranging from 5.74 to 64.2 ng/ml serum. Perfluorodecanoic acid (PFDA) was the second dominant PFC in fish samples except for common carp in which perfluorooctane sulfonamide (PFOSA) was dominant. A positive linear relationship (r² = 0.85, p < 0.05) was observed between ln PFOS concentrations (ln ng/ml) and trophic level (based on δ¹⁵N) if tilapia was excluded. The risk assessment showed that PFOS might not pose an immediate risk to fish in Gaobeidian Lake.     

Serum concentrations of perfluorooctanesulfonate and other fluorochemicals in an elderly population from Seattle, Washington

Perfluorooctanesulfonyl fluoride (POSF, C₈F₁₇SO₂F) related-materials have been used as surfactants, paper and packaging treatments, and surface (e.g., carpet, textile, upholstery) protectants. A metabolite, perfluorooctanesulfonate (PFOS, C₈F₁₇SO₃⁻), has been identified in the serum and liver of non-occupationally exposed humans and wildlife. Because of its persistence, an important question was whether elderly humans might have higher PFOS concentrations. From a prospective study designed to examine cognitive function in the Seattle (WA) metropolitan area, blood samples were collected from 238 dementia-free subjects (ages 65–96). High-pressure liquid chromatography-electrospray tandem mass spectrometry determined seven fluorochemicals: PFOS; N-ethyl perfluorooctanesulfonamidoacetate; N-methyl perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamide; perfluorooctanoate; and perfluorohexanesulfonate. Serum PFOS concentrations ranged from less than the lower limit of quantitation (3.4 ppb) to 175.0 ppb (geometric mean 31.0 ppb; 95% CI 28.8–33.4). An estimate of the 95% tolerance limit was 84.1 ppb (upper 95% confidence limit 104.0 ppb). Serum PFOS concentrations were slightly lower among the most elderly. There were no significant differences by sex or years residence in Seattle. The distributions of the other fluorochemicals were approximately an order of magnitude lower. Similar to other reported findings of younger adults, the geometric mean serum PFOS concentration in non-occupational adult populations likely approximates 30–40 ppb with 95% of the population’s serum PFOS concentrations below 100 ppb.     

Linear and branched perfluorooctane sulfonate (PFOS) isomer patterns differ among several tissues and blood of polar bears

Perfluorooctane sulfonate (PFOS) is a globally distributed persistent organic pollutant that has been found to bioaccumulate and biomagnify in aquatic food webs. Although principally in its linear isomeric configuration, 21–35% of the PFOS manufactured via electrochemical fluorination is produced as a branched structural isomer. PFOS isomer patterns were investigated in multiple tissues of polar bears (Ursus maritimus) from East Greenland. The liver (n = 9), blood (n = 19), brain (n = 16), muscle (n = 5), and adipose (n = 5) were analyzed for linear PFOS (n-PFOS), as well as multiple mono- and di-trifluoromethyl-substituted branched isomers. n-PFOS accounted for 93.0 ± 0.5% of Σ-PFOS isomer concentrations in the liver, whereas the proportion was significantly lower (p < 0.05) in the blood (85.4 ± 0.5%). Branched isomers were quantifiable in the liver and blood, but not in the brain, muscle, or adipose. In both the liver and blood, 6-perfluoromethylheptane sulfonate (P6MHpS) was the dominant branched isomer (2.61 ± 0.10%, and 3.26 ± 0.13% of Σ-PFOS concentrations, respectively). No di-trifluoromethyl-substituted isomers were detectable in any of the tissues analyzed. These tissue-specific isomer patterns suggest isomer-specific pharmacokinetics, perhaps due to differences in protein affinities, and thus differences in protein interactions, as well transport, absorption, and/or metabolism in the body.     

PFOS and PFC releases and associated pollution from a PFC production plant in Minnesota (USA)

Perfluorooctane sulfonate (PFOS) and PFOS-related substances have been listed as persistent organic pollutants in the Stockholm Convention. From August 2012, Parties to the Convention needed to address the use, storage, and disposal of PFOS—including production sites and sites where PFOS wastes have been deposited—in their national implementation plans. The paper describes the pollution in Minnesota (USA) caused by the 3M Company at one of the largest per/polyfluorinated chemical (PFC) production facilities. From early 1950s until the end of 2002, when 3M terminated PFOS and perfluorooctanoic acid (PFOA) production, PFOS, PFOA, and other PFC production wastes were disposed around the plant and in local disposal sites. Discharges from the site and releases from deposits caused widespread contamination of ground and surface waters including local drinking water wells. Fish in the river downstream were contaminated with PFOS to levels that led to fish consumption advisories. Human exposures resulted from ingesting contaminated drinking water, requiring installation of water treatment facilities and alternate water supplies. The critical evaluation of the assessments done revealed a range of gaps in particular of human exposure where relevant exposure pathways including the entire exposure via food have not been taken into consideration. Currently, the exposure assessment of vulnerable groups such as children or Hmong minorities is inadequate and needs to be improved/validated by epidemiological studies. The assessment methodology described for this site may serve—with highlighted improvements—as a model for assessment of other PFOS/PFC production sites in the Stockholm Convention implementation.     

Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands

Extensive screening analyses of perfluorooctane sulfonate (PFOS) and related perfluorinated compounds in biota samples from all over the world have identified PFOS as a global pollutant and have shown its bioaccumulation into higher trophic levels in the food chain. Perfluorinated compounds have been found in remote areas as the Arctic. In this study a preliminary screening of PFOS and related compounds has been performed in liver samples of fish, birds and marine mammals from Greenland and the Faroe Islands. PFOS was the predominant fluorochemical in the biota analyzed, followed by perfluorooctane sulfonamide (PFOSA). PFOS was found at concentrations above LOQ (10 ng/g wet weight) in 13 out of 16 samples from Greenland and in all samples from the Faroe Islands. The results from Greenland showed a biomagnification of PFOS along the marine food chain (shorthorn sculpin < ringed seal < polar bear). The greatest concentration of PFOS was found in liver of polar bear from east Greenland (mean: 1285 ng/g wet weight, n = 2). The geographical distribution of perfluorinated compounds in Greenland was similar to that of persistent organohalogenated compounds (OHCs), with the highest concentrations in east Greenland, indicating a similar geographical distribution to that of OHCs, with higher concentrations in east Greenland than in west Greenland.     

Sediment-water distribution of perfluorooctane sulfonate (PFOS) in Yangtze River Estuary

Analysis of Perfluorooctane sulfonate (PFOS) distribution in water and sediment in Yangtze River Estuary showed that the estuary was a sink for PFOS. Salinity was an important parameter in controlling the sediment-water interactions and the fate or transport of PFOS in the aquatic environment. As the salinity (S‰) increased from 0.18 to 3.31, the distribution coefficient (K_d) between sediment and water linearly increased from 0.76 to 4.70 L g⁻¹. The study suggests that PFOS may be carried with the river water and transported for long distances before it reaches to the sea and largely scavenged to the sediment in the estuaries due to the dramatic change in salinity.     

Characterisation of perfluorooctane sulfonate (PFOS) in a terrestrial ecosystem near a fluorochemical plant in Flanders,Belgium

Bioaccumulation of perfluorooctane sulfonate (PFOS) in a restricted terrestrial food chain was investigated with the omnivorous wood mouse (Apodemus sylvaticus) on top of the studied food chain. The levels detected are very high compared with literature as a result of the presence of fluorochemical plant in the immediate vicinity of the study area. Soil, surface water, fruits of European elder and common blackberry, invertebrates, bank vole and wood mouse were collected at two sites, e.g. Blokkersdijk, adjacent to the fluorochemical plant, and Galgenweel, a reference site 2 km further away. In wood mouse, the highest PFOS concentrations were found in the liver followed by the pancreas, lungs and kidneys, with the spleen having the lowest levels. In the liver, the concentrations ranged from 787 to 22,355 ng/g ww at Blokkersdijk and these were significantly correlated with those detected in the kidneys (13.7–4,226 ng/g ww). If current results are compared to the findings of a previous study conducted in 2002 at the same sites, a significant decrease of PFOS in livers of wood mouse is observed. To the best of our knowledge, so far no studies reported levels of PFOS in terrestrial invertebrates under field conditions. At Blokkersdijk, PFOS was detected in all invertebrate species ranging from 28 to 9,000 ng/g. Soil and water were also contaminated with levels of respectively 68 ng/g and 22 ng/L. Biota-to-soil accumulation factors ranged from 0.11 to 68 for earthworms. Biomagnification factors (BMFs) of liver wood mouse/berries were as high as 302. BMFs for invertebrates were remarkably lower (up to 2).     

Effects of anionic hydrocarbon surfactant on the transport of perfluorooctanoic acid (PFOA) in natural soils

Environmental Science and Pollution Research - The widespread usage of per- and polyfluoroalkyl substances (PFASs) has led to their ubiquitous co-existence with hydrocarbon surfactants in the...