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.     

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.     

Occurrence and source characterization of perfluorochemicals in an urban watershed

Perfluorochemicals (PFCs) are used in numerous applications, mainly as surfactants, and occur ubiquitously in the environment as complex mixtures. This study was undertaken to characterize the occurrence and sources of commonly detected PFC compounds in surface waters of the Marina catchment, a watershed that drains an urbanized section of Singapore. Of the 19 target PFCs, 13 were detected with perfluorooctanoic acid (PFOA) (5-31 ng L⁻¹) and perfluorooctane sulfonate (PFOS) (1-156 ng L⁻¹) being the dominant components. Other compounds detected included perfluoroalkyl carboxylates (C7-C12) and perfluoroalkyl sulfonates (C6 and C8). Sulfonamide compounds detected 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA), 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), perfluorooctanesulfonamido acetic acid (FOSAA) and perfluorooctanesulfonamide (FOSA) were putative transformation products of N-EtFOSE and N-MeFOSE, the N-ethylated and N-methylated ethyl alcohol derivatives, respectively. Surface water concentrations were generally higher during dry weather than during storm water flow: the median concentrations of total PFCs in dry and wet weather were 57 and 138 ng L⁻¹ compared to 42 and 79 ng L⁻¹, respectively, at Stamford and Alexandra canal, suggesting the presence of a continuous source(s) which is subject to dilution during storm events. In rain water, median concentrations were 6.4 ng L⁻¹, suggesting rain contributed from 12-25% to the total PFC load for non-point source sites. The longitudinal concentration profile along one of the canals revealed a point source of sulfonated PFCs (PFOS), believed to originate from aqueous film-forming foam (AFFF). Sources were characterized using principal component analysis (PCA) and by plotting PFHxS/PFOA against PFOS/PFOA. Typical surface waters exhibit PFOS/PFOA and PFHxS/PFOA ratios below 0.9 and 0.5, respectively. PCA plots reveal waters impacted by “non-typical” PFC sources in Alexandra canal.     

Risk assessment for human consumption of perfluorinated compound-contaminated freshwater and marine fish from Hong Kong and Xiamen

Perfluorinated compounds (PFCs) are man-made fluoro-surfactants that are identified as global pollutants and can pose health risks to humans and wildlife. Two aspects of risk assessment were conducted in this study, including exposure and response. Exposure was estimated by using the concentrations of PFCs in fish and applying standard exposure factors. Among different PFCs, PFOS, PFOA, PFNA, PFDA, PFUdA and PFTrDA were detected. Total concentrations of PFC in fish ranged from 0.27-8.4 ng g⁻¹ to 0.37-8.7 ng g⁻¹ respectively in Hong Kong and Xiamen. The calculated hazard ratio (HR) of PFOS for all fish was less than 1.0. However, the HR for mandarin fish in Hong Kong and bighead carp, grass carp and tilapia in Xiamen, had HR values of approximately 0.5, indicating that frequent consumption of these 4 more contaminated fish species might pose an unacceptable risk to human health. Our data support the notion that the released/disposed chemical pollutants into water systems make fish a source of environmental toxicants to humans. The risks and potential effects of PFCs to health of coastal population in the Pearl River Delta are of concern.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.     

Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

Biogeochemical dynamics of perfluorinated alkyl acids and sulfonates in the River Seine (Paris, France) under contrasting hydrological conditions

The biogeochemical dynamics of 15 perfluorinated compounds (PFCs) were investigated in a heavily urbanised river (River Seine, Paris, France). The target compounds included C4-C10 sulfonates and C5-C14 acids; eleven PFCs were detected and ∑PFCs ranged between 31 and 91 ng L⁻¹ (median: 47 ng L⁻¹). The molecular pattern was dominated by the perfluoroalkyl sulfonates PFHxS and PFOS (>54% of ∑PFCs), which were the only PFCs quantified in both the dissolved and particulate phases. For these PFCs, the sorbed fraction positively correlated with suspended sediment levels. Total PFC levels negatively correlated with river flow rate, which varied between 150 and 640 m³ s⁻¹. This suggests the predominance of point sources (likely WWTP effluent discharge), but a contribution of non-point sources such as combined sewer overflow could not be excluded. The annual PFC mass flow was estimated at 500 kg, which is less than observed for other large European rivers.     

Analysis of perfluoroalkyl carboxylates in vacuum cleaner dust samples in Japan

Perfluorooctanoic acid (PFOA) has long been an environmental contaminant of concern owing to its potential health risk. However, exposure to perfluorinated carboxylic acids (PFCAs) other than PFOA is not well understood. In this study, we investigated the concentrations of PFCAs in vacuum cleaner dust in Japan to measure the PFCAs contamination in an indoor environment. Most of the 77 samples contained PFCAs with 6-13 carbon atoms. The median concentration of perfluorononanoic acid (PFNA, 23.2 ng g⁻¹) was highest among PFCAs, followed by PFOA (20.8 ng g⁻¹) and perfluoroundecanoic acid (PFUnDA, 12.9 ng g⁻¹). The 90th percentile concentrations of PFNA, PFUnDA and perfluorotridecanoic acid (PFTrDA) were 948, 283 and 110 ng g⁻¹, respectively, and these were detected at greater concentrations than neighboring, even-numbered PFCAs. The proportion of long-chain PFCAs in vacuum cleaner dust from Japan was relatively higher than those reported for other countries. Factor analysis showed three independent factors. Odd-numbered long chain PFCAs (PFNA, PFUnDA and PFTrDA), which can correspond to factor 1, were major components of PFCAs in vacuum cleaner dust. Short chain PFCAs (factor 2) and even numbered long chain PFCAs (factor 3) were also statistically separated. These findings suggest that there are several sources of PFCAs with different origins in indoor environment. Further investigations into the origins of PFCAs are needed to evaluate indoor contamination with PFCAs.     

Reprint of: Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.     

Evaluation of the presence of drugs of abuse in tap waters

A total of seventy samples of drinking water were tested for non-controlled and illicit drugs. Of these, 43 were from Spanish cities, 15 from seven other European countries, three from Japan and nine from seven different Latin American countries. The most frequently detected compounds were caffeine, nicotine, cotinine, cocaine and its metabolite benzoylecgonine, methadone and its metabolite EDDP. The mean concentrations of non-controlled drugs were: for caffeine 50 and 19 ng L⁻¹, in Spanish and worldwide drinking water respectively and for nicotine 13 and 19 ng L⁻¹. Illicit drugs were sparsely present and usually at ultratrace level (<1 ng L⁻¹). For example, cocaine has mean values of 0.4 (Spain) and 0.3 ng L⁻¹ (worldwide), whereas for benzoylecgonine, these mean values were 0.4 and 1.8 ng L⁻¹, respectively. Higher concentrations of benzoylecgonine were found in Latin American samples (up to 15 ng L⁻¹). No opiates were identified in any sample but the presence of methadone and EDDP was frequently detected. Total mean values for EDDP were 0.4 ng L⁻¹ (Spain) and 0.3 ng L⁻¹ (worldwide). Very few samples tested positive for amphetamines, in line with the reactivity of chlorine with these compounds. No cannabinoids, LSD, ketamine, fentanyl and PCP were detected.     

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.     

Background levels of Persistent Organic Pollutants in humans from Taiwan: Perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently received attention due to their widespread contamination of the environment. PFOS and PFOA are stable in the environment and resistant to metabolism, hydrolysis, photolysis and biodegradation. PFOS and PFOA have been found in human blood and tissue samples from both occupationally exposed workers and the general worldwide population. This study aimed to determine the background levels of PFOS and PFOA in the Taiwanese population, investigate related factors, and compare exposure in Taiwan to that in other countries. The concentration of PFOS in the 59 serum samples collected from the general population in Taiwan ranged from 3.45 to 25.65 ng mL⁻¹ (median: 8.52), and the concentration of PFOA ranged from 1.55 to 7.69 ng mL⁻¹ (median: 3.22). There was a significant positive correlation (r = 0.51; p < 0.0001) between PFOS and PFOA concentrations. Males had higher concentrations of PFOA and PFOS than females. PFOS levels in serum increased with age. This study is the first investigation to reveal the PFOS and PFOA levels of serum samples in the general population of Taiwan. The levels of PFOS and PFOA in Taiwanese serum samples were comparable with those from other countries (PFOS: 5.0–35 ng mL⁻¹, PFOA: 1.5–10 ng mL⁻¹).     

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.     

Persistent organic pollutants associated to water fluxes and sedimentary processes in the Colorado River delta, Baja California, México

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in sediment cores from two distinctive modern channels of the Colorado River (CR) delta. Their abundance and temporal changes are associated with flood-flows from the CR across the USA-Mexico border. The CR channel is directly exposed to river flood-flows while the Hardy River (HR) is a local channel derived mainly from agricultural runoff, geothermal effluents, and treated urban wastewater. Different headwater compositions and degrees of exposure to flood-flows appear to be the factors controlling the composition of persistent organic pollutants (POPs). Enrichment of OCPs (46 ng g⁻¹ dwt in HR and 4.37 ng g⁻¹ dwt in CR) occurred during or a few years after flooding. PCB-138 (4.2 ng g⁻¹ dwt) is enriched in HR suggesting its origin in dielectric oils from the geothermal power plant. PCB-28 (2.1 ng g⁻¹ dwt) in CR may be related with atmospheric input and/or re-deposition of upstream sediments. In surficial sediments (0-3 cm), only HR exceeds international sediment quality guidelines (4,4′-DDE = 8.16 ng g⁻¹ dwt and ΣDDT = 8.34 ng g⁻¹ dwt).     

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.     

Stability considerations of aspartame in the direct analysis of artificial sweeteners in water samples using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

A HPLC-MS/MS method is presented for the simultaneous determination of frequently used artificial sweeteners (ASs) and the main metabolite of aspartame (ASP), diketopiperazine (DKP), in environmental water samples using the direct-injection (DI) technique, thereby achieving limits of quantification (LOQ) of 10 ng L⁻¹. For a reliable quantification of ASP pH should be adjusted to 4.3 to prevent formation of the metabolite. Acesulfame (ACE), saccharin (SAC), cyclamate (CYC) and sucralose (SUC) were ubiquitously found in water samples. Highest concentrations up to 61 μg L⁻¹ of ACE were found in wastewater effluents, followed by surface water with concentrations up to 7 μg L⁻¹, lakes up to 600 ng L⁻¹ and groundwater and tap water up to 70 ng L⁻¹. The metabolite DKP was only detected in wastewater up to 200 ng L⁻¹ and at low detection frequencies.     

Determination of anti-anxiety and anti-epileptic drugs in hospital effluent and a preliminary risk assessment

In this study, an analytical methodology was developed for the determination of psycho-active drugs in the treated effluent of the University Hospital at the Federal University of Santa Maria, RS – Brazil. Samples were collected from point A (Emergency) and point B (General effluent). The adopted methodology included a pre-concentration procedure involving the use of solid phase extraction and determination by liquid chromatography coupled to mass spectrometry. The limit of detection for bromazepam and lorazepam was 4.9 ± 1.0 ng L⁻¹ and, for carbamazepine, clonazepam and diazepam was 6.1 ± 1.5 ng L⁻¹. The limit of quantification was 30.0 ± 1.1 ng L⁻¹, for bromazepam, clonazepam and lorazepam; for carbamazepine was 50.0 ± 1.8 ng L⁻¹ and was 40.0 ± 1.0 ng L⁻¹ for diazepam. The mean concentrations in the Emergency and General effluent treated currents were as follows: for bromazepam, 195 ± 6 ng L⁻¹ and 137 ± 7 ng L⁻¹; for carbamazepine, 590 ± 6 ng L⁻¹ and 461 ± 10 ng L⁻¹; for diazepam, 645 ± 1 ng L⁻¹ and 571 ± 10 ng L⁻¹; for lorazepam, 96 ± 7 ng L⁻¹ and 42 ± 4 ng L⁻¹; and for clonazepam, 134 ± 10 ng L⁻¹ and 57 ± 10 ng L⁻¹. A preliminary risk assessment was conducted: carbamazepine and diazepam require considerable attention owing to their environmental toxicity. The occurrence of these psychoactive-drugs and the environmental risks that they pose demonstrated the need for a more efficient treatment system. As far we are aware, there have been no comparable studies to this on the hazards of hospital effluents in Brazil, and very few that have carried out a risk assessment of psycho-active drugs in hospital effluent in general.     

Endocrine disrupting activities in sewage effluent and river water determined by chemical analysis and in vitro assay in the context of granular activated carbon upgrade

As part of endocrine disruption in catchments (EDCAT) programme, this work aims to assess the temporal and spatial variations of endocrine disrupting chemicals (EDCs) in River Ray, before and after the commissioning of a full-scale granular activated carbon (GAC) plant at a sewage treatment works (STW). Through spot and passive sampling from effluent and river sites, estrogenic and anti-androgenic activities were determined by chemical analysis and in vitro bio-assay. A correlation was found between chemical analyses of the most potent estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethinylestradiol (EE2)) and yeast estrogen screen (YES) measurement, both showing clearly a reduction in estrogenic activity after the commissioning of the GAC plant at the STW. During the study period, the annual average concentrations of E1, E2 and EE2 had decreased from 3.5 ng L⁻¹, 3.1 ng L⁻¹ and 0.5 ng L⁻¹ to below their limit of detection (LOD), respectively, with a concentration reduction of at least 91%, 81% and 60%. Annual mean estrogenic activity measured by YES of spot samples varied from 1.9 ng L⁻¹ to 0.4 ng L⁻¹ E2 equivalent between 2006 and 2008 representing a 79% reduction. Similarly, anti-androgenic activity measured by yeast anti-androgen screen (anti-YAS) of spot samples was reduced from 148.8 to 22.4 μg flutamide L⁻¹, or by 85%. YES and anti-YAS values were related to each other, suggesting co-existence of both types of activities from chemical mixtures in environmental samples. The findings confirm the effectiveness of a full-scale GAC in removing both estrogenic and anti-androgenic activities from sewage effluent.     

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.