Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Sorption of perfluorooctane sulfonate to carbon nanotubes in aquatic sediments

To date, sorption of organic compounds to nanomaterials has mainly been studied for the nanomaterial in its pristine state. However, sorption may be different when nanomaterials are buried in sediments. Here, we studied sorption of Perfluorooctane sulfonate (PFOS) to sediment and to sediment with 4% multiwalled carbon nanotubes (MWCNTs), as a function of factors affecting PFOS sorption; aqueous concentration, pH and Ca²⁺ concentration. Sorption to MWCNT in the sediment–MWCNT mixtures was assessed by subtracting the contribution of PFOS sorption to sediment-only from PFOS sorption to the total sediment–MWCNT mixture. PFOS Log K_D values ranged 0.52–1.62 L kg^?1 for sediment and 1.91–2.90 L kg^?1 for MWCNT present in the sediment. The latter values are relatively low, which is attributed to fouling of MWCNT by sediment organic matter. PFOS sorption was near-linear for sediment (Freundlich exponent of 0.92 ± 0.063) but non-linear for MWCNT (Freundlich exponent of 0.66 ± 0.03). Consequently, the impact of MWCNT on sorption in the mixture was larger at low PFOS aqueous concentration. Effects of pH and Ca²⁺ on PFOS sorption to MWCNT were statistically significant. We conclude that MWCNT fouling and PFOS concentration dependency are important factors affecting PFOS–MWCNT interactions in sediments.     

Perfluorinated compounds in Haihe River and Dagu Drainage Canal in Tianjin, China

In this study, nine perfluorinated compounds (PFCs) were investigated in water and sediment of Haihe River (HR) and Dagu Drainage Canal (DDC), Tianjin, China. The total PFCs in water samples from DDC (40-174 ng L⁻¹) was much greater than those from HR (12-74 ng L⁻¹). PFC contamination was severe at lower reaches of HR due to industry activities, while high PFCs were found in the middle of DDC due to the effluents from wastewater treatment plants. Perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the predominant PFCs in aqueous phase. The total PFCs in sediments from DDC (1.6-7.7 ng g⁻¹ dry weight) were lower as compared to HR (7.1-16 ng g⁻¹), maybe due to the dredging of sediment in DDC conducted recently. PFOS was the major PFC in HR sediments followed by PFOA; while PFHxA was the major PFC in DDC sediments. Organic carbon calibrated sediment-water distribution coefficients (K_OC) were calculated for HR. The Log K_OC ranged from 3.3 to 4.4 for C7-C11 perfluorinated carboxylic acids, increasing by 0.1-0.6 log units with each additional CF₂ moiety. The log K_OC for 8:2 fluorotelomer unsaturated acid was reported for the first time with a mean value of 4.0. The log Koc of PFOS was higher than perfluoronanoic acid by 0.8 log units.     

Sorption of perfluoroalkyl substances in sewage sludge

The sorption behaviour of three perfluoroalkyl substances (PFASs) (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonic acid (PFBS)) was studied in sewage sludge samples. Sorption isotherms were obtained by varying initial concentrations of PFOS, PFOA and PFBS. The maximum values of the sorption solid–liquid distribution coefficients (K_d,max) varied by almost two orders of magnitude among the target PFASs: 140–281 mL g^?1 for PFOS, 30–54 mL g^?1 for PFOA and 9–18 mL g^?1 for PFBS. Freundlich and linear fittings were appropriate for describing the sorption behaviour of PFASs in the sludge samples, and the derived K_F and K_d,linear parameters correlated well. The hydrophobicity of the PFASs was the key parameter that influenced their sorption in sewage sludge. Sorption parameters and log(K_OW) were correlated, and for PFOS (the most hydrophobic compound), pH and Ca?+?Mg status of the sludge controlled the variation in the sorption parameter values. Sorption reversibility was also tested from desorption isotherms, which were also linear. Desorption parameters were systematically higher than the corresponding sorption parameters (up to sixfold higher), thus indicating a significant degree of irreversible sorption, which decreased in the sequence PFOS?>?PFOA?>?PFBS.     

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.     

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.     

Effective sorption of perfluorooctane sulfonate (PFOS) on hexadecyltrimethylammonium bromide immobilized mesoporous SiO2 hollow sphere

The hexadecyltrimethylammonium bromide (HDTMAB) immobilized hollow mesoporous silica spheres were prepared for the efficient removal of perfluorooctane sulfonate (PFOS) from aqueous solution. Besides the traditional sorption behavior including sorption kinetics as well as effect of solution pH and temperature, the effect of increasing volume which simulated the natural river where the rate of solute and solvent was relatively constant and solution volume was always changing was investigated. The result indicated that the residual PFOS concentrations in aqueous phase decreased with increasing solution pH and ionic strength, whereas they increased with increasing temperature. The HDTMAB immobilized material still maintained high efficiency after increasing volume, that is, the removal kept more than 99% after the treatment when the initial PFOS concentration was 1 mg L^?1. The uptake behavior and morphology of spheres which was characterized by transmission electron microscopy (TEM) revealed that the additional HDTMAB and mesoporous shell were responsible for the enhanced sorption of PFOS. It was concluded that electrostatic interaction and Ca-bridge role played an important role in the sorption of PFOS on the mesoporous SiO₂ hollow spheres, whereas, hydrophobic interaction contributed to the nice sorption performance of PFOS on the HDTMAB immobilized sorbent.     

River water contaminated with perfluorinated compounds potentially posing the greatest risk to young children

Although, humans are exposed to perflourinated compounds (PFCs) from various media, water consumption could be an important source for the residents living near to contaminated areas. Since comprehensive multimedia exposure model has not been developed for PFCs, assessment of the potential risk due to exposure to PFCs through direct water consumption could be a conservative estimate. The human health risks derived from the exposure to PFCs through water consumption were assessed for different age groups of general population in Taiwan using probabilistic approach. Based on available data on concentrations of PFCs in river water, exposure to PFOS, PFOA and PFDA via water consumption for different age groups were calculated using deterministic and probabilistic risk assessment methods. The oral non-cancer risks from PFOS, PFOA and their combination, expressed as a Hazard Index (HI), was determined by comparing oral exposure dose (through water intake) with the oral Reference Dose (RfD). The average exposure to PFOS, PFOA and PFDA via water consumption for adults ranged from 0.16 to 220.15, 0.43 to 12.5 and 0.43 to 2.36 ng kg-bw^?1 d^?1 and for children 0.13–354.3, 0.35–20.17 and 0.35–3.79 ng kg-bw^?1 d^?1, respectively. Probabilistic values of total HIs for all age groups reside near to Keya River exceed the RfD 2.4–4.8 times, corresponding mainly to PFOS with a percentage of 97%. In conclusions, children aged 1–3 years old and the residents reside near to Keya River are at the highest risk of exposure to PFCs via water consumption.     

A rapid and high-throughput quantum dots bioassay for monitoring of perfluorooctane sulfonate in environmental water samples

Currently HPLC/MS is the state of the art tool for environmental/drinking water perfluorooctane sulfonate (PFOS) monitoring. PFOS can bind to peroxisomal proliferator-activated receptor-alpha (PPARα), which forms heterodimers with retinoid X receptors (RXRs) and binds to PPAR response elements. In this bioassay free PFOS in water samples competes with immobilized PFOS in ELISA plates for a given amount of PPARα-RXRα. It can be determined indirectly by immobilizing PPARα-RXRα-PFOS complex to another plate coated with PPARα antibody and subsequent measuring the level of PPARα-RXRα by using biotin-modified PPARα-RXRα probes-quantum dots-streptavidin detection system. The rapid and high-throughput bioassay demonstrated a detection limit of 2.5 ng L⁻¹ with linear range between 2.5 ng L⁻¹ and 75 ng L⁻¹. Detection results of environmental water samples were highly consistent between the bioassay and HPLC/MS.     

Occurrence and partition of perfluorinated compounds in water and sediment from Liao River and Taihu Lake, China

The concentrations of four perfluorinated sulfonate acids (PFSAs) and 10 perfluorinated carboxylate acids (PFCAs) were measured in water and sediment samples from Liao River and Taihu Lake, China. In the water samples from Taihu Lake, PFOA and PFOS were the most detected perfluorinated compounds (PFCs); in Liao River, PFHxS was the predominant PFC followed by PFOA, while PFOS was only detected in two of the samples. This suggests that different PFC products are used in the two regions. PFOS and PFOA in both watersheds are at similar level as in the rivers of Japan, but significantly lower than in Great Lakes. The contributions of PFOS and long chain PFCAs in sediments were much higher than in water samples of both watersheds, indicating preferential partition of these PFCs in sediment. The concentrations of PFOS and PFOA were three orders of magnitude of lower than that of polycyclic aromatic hydrocarbons in the same sediments. The average sediment-water partition coefficients (log K_oc) of PFHxS, PFOS and PFOA were determined to be 2.16, 2.88 and 2.28 respectively.     

Production and release of dimethylsulphide from an estuary in Portugal

The distribution of dimethylsuphide (DMS) and its precursor dimethylsulphoniopropionate, in both particulate (DMSP_p) and dissolved fractions (DMSP_d) was surveyed along estuarine water profiles of Canal de Mira (Ria de Aveiro, Portugal), on 45 occasions during one year. The field campaigns revealed pronounced gradients, which were to some extent interpreted with reference to supporting hydrographic parameters like salinity, temperature and chlorophyll a. Surface water concentrations showed a clear seasonal variation with peak values during the warmer months. Mean summer concentrations for DMS, DMSP_p and DMSP_d, were, respectively, a factor of 1.8, 1.9 and 2.9 times higher than winter concentrations. Surface water concentration was the main factor controlling DMS emissions into the atmosphere, which were estimated to be, as a mean, 5.4 and 27.3 nmol m^-2 h^-1 for winter and summer, respectively. In addition, DMS fluxes from two intertidal mud flat sites in Canal de Mira were examined monthly over a year. Average emission rates were a factor of 2–5 times higher than those estimated for estuarine waters and revealed strong seasonal variations, with summer peaks apparently related to ambient temperature. The relative contribution of estuarine waters and mud flats for local DMS budget is discussed in terms of tidal cycles and exposed surface area.     

Adaptation to osmotic stress provides protection against ammonium nitrate in Pelophylax perezi embryos

The negative effects of pollution on amphibians are especially high when animals are additionally stressed by other environmental factors such as water salinity. However, the stress provoked by salinity may vary among populations because of adaptation processes. We tested the combined effect of a common fertilizer, ammonium nitrate (0-90.3 mg N-NO₃NH₄/L), and water salinity (0-2‰) on embryos of two Pelophylax perezi populations from ponds with different salinity concentrations. Embryos exposed to the fertilizer were up to 17% smaller than controls. Survival rates of embryos exposed to a single stressor were always below 10%. The exposure to both stressors concurrently increased mortality rate (>95%) of embryos from freshwater. Since the fertilizer was lethal only when individuals were stressed by the salinity, it did not cause lethal effects on embryos naturally adapted to saline environments. Our results underscore the importance of testing multiple stressors when analyzing amphibian sensitivity to environmental pollution.     

A field survey—Staroe lake suffering from atmospheric deposition in the region north of the Arctic Circle

Background, aim, and scope  The Arctic holds large stores of minerals, and extracted materials are provided to the world’s economy; in this sense, the Arctic issue associated with mining is not local but global. In a part of the Arctic region (the Kola Peninsula, 66–70° N and 28–41° E), metal levels are generally elevated in the lake sediment. There is a question as to what results in elevated metal levels—a natural process (naturally abundant minerals) or an anthropogenic process (mining and metallurgy). In terms of solving this question, Staroe lake located on the Kola Peninsula was researched as a case study. Materials and methods  The following parameters were determined in relation with Staroe lake: (1) the current quality of the lake’s water—each 1,000-ml sample was collected at a surface point and a deep point (near the bottom layer), and the collected samples were directly analyzed after filtration; (2) atmospheric bulk deposition—bulk deposition was collected using a set of three rainwater samplers near the lake. In addition, bulk deposition was collected in a background site (250 km to the southwest of the smelter complex) as a reference; and (3) sediment profile (plus principal component analysis)—lake-bottom sediment was collected by an open-gravimetric column sampler equipped with an automatic diaphragm. After collection, the sample columns were cut at a 1-cm interval for analysis. Eigenvalues and variances by factor were calculated from the correlation coefficients. Results  The obtained data show that (1) naturally poor elements (Cu, Ni, Si, and SO₄ ²⁻) dominantly influence the lake’s water quality; (2) they are transported from the anthropogenic sources to the study lake through the atmospheric pathway; (3) mainly the contents of Cu, Ni, Sr, and Ca have influenced the sediment quality since the 1950s, corresponding to the industrial movement; and (4) Cu, Ni, and Sr originate from an anthropogenic source (smelter), and Ca originates from both natural and anthropogenic sources. Discussion  As compared with the Russian standard (San Pin 2.1.980–00), the contents of NO₃ ⁻ (50.3 ± 0.1 mg l⁻¹) and particulates (2.3 ± 0.2 mg l⁻¹) exceeded the standard levels (0.7 mg l⁻¹ NO₃ ⁻ and 45 mg l⁻¹ particulates); Staroe lake may be slightly contaminated. However, the contamination factor (comparison with the background data) implies that Staroe lake is considerably contaminated. There is a strong possibility that fine overburden detritus (<0.1 mm diameter) may be transported from an open pit to the study lake by natural forces such as wind. Although it is difficult to suppose that one factor dominantly affects the sediment quality, it follows from a factor analysis that factors 1 and 2 account for about 70% of the total variance: Factor 1 is the most dominant, and factor 2 is the second most dominant in the variability of sediment quality. It is considered that Cu, Sr, and Ni in factor 1 originate from anthropogenic sources because they are poor in sediment rocks. Conclusions  The field survey conducted in Staroe lake can give the following answers to the key objectives: (1) The present water quality is affected by Cu, Ni, Si, and SO₄ ²⁻ in light of the contamination factor, and these elements originate from anthropogenic sources (the smelter and the open pit) and are transported to the lake through the atmospheric pathway; (2) the sediment profile and statistic analysis show that the lake quality has been influenced by deposition of metals since the 1950s; and (3) Cu, Ni, Sr, and Ca have influenced the sediment quality in light of the most dominant factor—Cu, Ni, and Sr originate from an anthropogenic source, whereas Ca comes from both natural and anthropogenic sources. Recommendations and perspectives  The presented lake survey shows that the dispersion of human-related pollutants via the atmospheric pathway takes place in the Arctic region. If the current pollution continues without countermeasures, the high-latitude environment may lose its original characteristics; hence, this subject is important when considering how to implement a wide range of environmental protection measures in the Arctic.     

Impact of permanent inundation on methane emissions from a Spartina alterniflora coastal salt marsh

To understand the effect of water level on CH₄ emissions from an invasive Spartina alterniflora coastal brackish marsh, we measured CH₄ emissions from intermittently and permanently (5 cm water depth) inundated mesocosms with or without N fertilizer added at a rate of 2.7 g N m^?2. Dissolved CH₄ concentrations in porewater and vertically-profiled sediment redox potential were measured, as were aboveground biomass and stem density of S. alterniflora. Mean CH₄ fluxes during the growing season in permanently inundated mesocosms without and with N fertilizer were 1.03 and 1.73 mg CH₄ m^?2 h^?1, respectively, which were significantly higher than in the intermittently inundated mesocosms. This response indicates that prolonged submergence of sediment, up to a water depth of 5 cm, stimulated CH₄ release. Inundation did not greatly affect aboveground biomass and stem density, but did significantly reduce redox potential in sediment, which in turn stimulated CH₄ production and increased the CH₄ concentration of porewater, resulting in higher CH₄ emission in the mesocosm. Our data showed that the stimulatory effect of shallow, permanent inundation on CH₄ emission in S. alterniflora marsh sediment was due primarily to an improved methanogenic environment rather than an increase in plant-derived substrates and/or the number of gas emission pathways through the plant’s aerenchymal system.     

Influence of environmental factors on the response of a natural population of Daphnia magna (Crustacea: Cladocera) to spinosad and Bacillus thuringiensis israelensis in Mediterranean coastal wetlands

The present study was undertaken to assess the impact of a candidate mosquito larvicide, spinosad (8, 17 and 33 μg L⁻¹) on a field population of Daphnia magna under natural variations of water temperature and salinity, using Bti (0.16 and 0.50 μL L⁻¹) as the reference larvicide. Microcosms (125 L) were placed in a shallow temporary marsh where D. magna was naturally present. The peak of salinity observed during the 21-day observation period may have been partly responsible for the decrease of daphnid population density in all the microcosms. It is also probably responsible for the absence of recovery in the microcosms treated with spinosad which caused a sharp decrease of D. magna abundance within the first two days following treatment whereas Bti had no effect. These results suggest that it may be difficult for a field population of daphnids to cope simultaneously with natural (water salinity and temperature) and anthropogenic (larvicides) stressors.     

Distribution of perfluorinated compounds in surface water from Hanjiang River in Wuhan,China

This study provided the first spatial distribution of perfluorinated compounds (PFCs) in Hanjiang River in Wuhan, China (HR). Surface water samples, collected from 23 sites in HR were analyzed for eight PFCs. The total concentrations of PFCs ranged from 8.90 to 568 ng L⁻¹, while perfluoropentanoic acid (PFOA, <LOQ − 256 ng L⁻¹) and perfluorooctane sulfonate (PFOS, <LOQ − 88.9 ng L⁻¹) dominated. All data were found to be normally distributed in the river. Similar spatial distribution tendencies were found among perfluorocarboxylates (PFCAs) and significant correlations were observed among PFCAs, while no significant correlations were found between PFOS and PFCAs. The distributions of PFCs were highly influenced by the industrial discharge and urban activities. The flux of PFCs from HR to the Yangtze River was estimated in the range of 16.9–127 kg yr⁻¹. More than a half of the samples studied could not meet the drinking water standards and avian wildlife values, suggesting further studies of characterizing PFCs and their potential risk to human were needed.     

Partitioning behaviour of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France)

This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C₄-C₁₀ sulfonates and C₅-C₁₄ carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L⁻¹ in water and 8.4 ± 0.5 ng g⁻¹ in sediment. They were in the range 43.1-4997.2 ng g⁻¹ in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (log K_d) and bioaccumulation factors (log BAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. log BSAF ranged between −1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids.     

Influence of water quality parameters on occurrence of polybrominated diphenyl ether in sediment and sediment to biota accumulation

Polybrominated diphenyl ether (PBDE) concentrations in sediment and fish from 12 principal rivers in Taiwan were investigated to determine their association with water quality parameters as well as the biota-sediment accumulation factor (BSAF) in fish with different living patterns. The highest PBDE concentration in sediment was found in the Bajhang River (261 ng g^?1 dry weight (d.w.)) and the lowest in the Beinan River and the Da-an River (0.17 ng g^?1 d.w.). The PBDE concentrations in fish samples ranged from 1.28 ng g^?1 d.w. (Oreochromis niloticus niloticus) in the Yanshuei River to 33.7 ng g^?1 d.w. (Varico rhinos barbatulus) in the Da-an River. We conclude that PBDEs contamination in sediment was significantly affected by NH₃–N, pH, and DO. The BSAF results showed a parabolic trend from low- to high-brominated BDEs. Fish easily accumulated the congeners BDE-47, -100, -119, -126, and -154 from sediment. The BSAF decreased in the following order: PeBDE > HxBDE > TeBDE > other BDEs. Principle component analysis showed that demersal fish have different PBDE sources than do pelagic fish. We conclude that living and feeding habits are critical factors affecting PBDE accumulation in fish.