Dioxin/POPs legacy of pesticide production in Hamburg: Part 1—securing of the production area

α-Hexachlorocyclohexane (HCH), β-HCH, and γ-HCH (lindane) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention. Therefore, the chemicals need to be globally addressed, including the disposal of historic wastes. At most sites, the approximately 85 % of HCH waste isomers were dumped. At a former lindane factory in Hamburg and some other factories the HCH, waste was recycled producing residues with high polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) levels. The soil and ground water under the former pesticide factory was/is highly contaminated with HCH (260 tons), chlorobenzenes (550 tons), and PCDD/PCDF (6 kg toxic equivalents (TEQ)). This contamination did not result from disposal operations but from spillages and leakages during the 30 years of the factory's production history. A containment wall has been constructed around the production area to prevent the dispersal of the pollutants. The ground water is managed by a pump and treat system. Over the last 15 years, approximately 10–30 tons of this pollution reservoir has been pumped and incinerated. For the contaminated production buildings, specific assessment and demolition technologies have been applied. In addition to their HCH waste isomer deposition, former lindane/HCH productions need to be assessed for possible recycling practice of HCH and related PCDD/PCDF contamination of the production area and buildings. Since such recycling activities have taken place at several factories in different countries, the experience of assessment and management of the described production area and contaminated buildings could be valuable. Such assessment could be addressed within the frame of the Stockholm Convention.     

Perfluorooctanesulfonate and perfluorooctanoate in raw and treated tap water from Osaka, Japan

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as emerging environmental pollutants because of their ubiquitous occurrence in the environment, biota, and humans. PFOS and PFOA have been detected in water in Japan. Nevertheless, occurrence of PFOS and PFOA in potable water from municipal water treatment plants is not clearly known. We analyzed PFOS and PFOA in raw and tap water samples collected from 14 drinking water treatment plants in winter and summer seasons in Osaka to determine the concentrations of PFOS and PFOA in raw and potable tap water samples. PFOS and PFOA were detected in all raw water samples. Concentration ranges of PFOS and PFOA in raw water were 0.26-22 ng/l and 5.2-92 ng/l, respectively. Whereas the concentrations PFOS in raw water from Osaka were similar to those in other areas in Japan, the concentrations of PFOA were higher than in other areas. Concentration ranges of PFOS and PFOA in potable tap water were 0.16-22 ng/l and 2.3-84 ng/l, respectively. There were positive correlations between PFC concentrations in raw water and tap water samples. Therefore, the removal efficiency of PFCs by the present water treatment may be low. Based on the current action value reported by U.S. Environmental Protection Agency, PFOA concentrations found in tap water in Osaka is not expected to pose health risks.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

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.     

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.     

The dioxin/POPs legacy of pesticide production in Hamburg: Part 2—waste deposits and remediation of Georgswerder landfill

α-HCH, β-HCH, and γ-HCH (lindane) were listed as persistent organic pollutants in the Stockholm Convention. Therefore, they need to be globally addressed including the wastes remaining from historic use and production. While at most lindane production sites the unintentionally produced 85 % HCH waste isomers have been deposited, at a former pesticide factory in Hamburg-Moorfleet HCH waste isomers have been recycled from 1953 to 1984 by thermal decomposition to chlorobenzenes and resulted in high polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/PCDF)-contaminated residues. The management of the PCDD/PCDF-contaminated waste from the former pesticide factory in Hamburg has been assessed and quantified. Based on past accredited PCDD/PCDF measurements, the registered 3,700 tonnes of disposed thermal HCH decomposition residue contained 333 to 854 kg of PCDD/PCDF toxicity equivalent (I-TEQ) in 53–102 tonnes total sum of PCDD/PCDF. The wastes have been deposited together with other wastes in landfills in Hamburg and other parts of Germany. For the Georgswerder landfill (Hamburg), where approximately 50 % of the PCDD/PCDF is disposed, current and previous situation and remediation activities are described. While PCDD/PCDF leaching from the landfill is controlled and incinerated, more water soluble organochlorines (vinyl chloride, cis-1,2-dichlorethene, chlorobenzenes) and benzene remain as a challenge for groundwater management. A comprehensive aftercare program has been established and will need to be operated by future generations including renewal of containment systems. Former lindane/HCH productions need—in addition to HCH deposits—to be assessed for possible recycling practice of HCH and related PCDD/PCDF-containing deposits. This could systematically be addressed within the Stockholm Convention implementation.     

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.     

The impact of semiconductor, electronics and optoelectronic industries on downstream perfluorinated chemical contamination in Taiwanese rivers

This study provides the first evidence on the influence of the semiconductor and electronics industries on perfluorinated chemicals (PFCs) contamination in receiving rivers. We have quantified ten PFCs, including perfluoroalkyl sulfonates (PFASs: PFBS, PFHxS, PFOS) and perfluoroalkyl carboxylates (PFCAs: PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA) in semiconductor, electronic, and optoelectronic industrial wastewaters and their receiving water bodies (Taiwan's Keya, Touchien, and Xiaoli rivers). PFOS was found to be the major constituent in semiconductor wastewaters (up to 0.13 mg/L). However, different PFC distributions were found in electronics plant wastewaters; PFOA was the most significant PFC, contributing on average 72% to the effluent water samples, followed by PFOS (16%) and PFDA (9%). The distribution of PFCs in the receiving rivers was greatly impacted by industrial sources. PFOS, PFOA and PFDA were predominant and prevalent in all the river samples, with PFOS detected at the highest concentrations (up to 5.4 μg/L).     

HCH contamination from former pesticide production in Brazil—a challenge for the Stockholm Convention implementation

Hexachlorocyclohexane (HCH) isomers (α-, β- and γ- HCH [lindane]) were recently added to the list of persistent organic pollutants regulated by the Stockholm Convention, and therefore, the legacy of HCH and lindane production has become an issue of global relevance. The production of lindane with the much larger quantities of associated waste isomers has generated large waste deposits and contaminated sites. This article presents an overview of HCH-polluted sites in Brazil as a basis for further activities related to the Stockholm Convention. The locations of HCH stockpiles and contaminated sites in Brazil arising from production and formulation have been compiled and mapped. This shows that the measures taken over the past 25 years have not resulted in remediation of the HCH pollution. An exposure risk study has been summarised for one major site and is included to demonstrate the contemporary relevance of the contamination. Major site remediation efforts are planned at one site but people live close to several other sites, and there is an urgent need of further assessments and remediation to ensure the protection of human health and the environment. The Stockholm Convention requires a systematic approach and should be adopted for the assessment of all sites and appropriate isolation/remediation measures should be facilitated. The appropriate planning of these activities for the production site in Rio de Janeiro could be a positive contribution for Rio+20 highlighting that green economy and sustainable production also include the appropriate management of legacies of historic production of an industrial sector (here the organochlorine industry).     

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.     

Determination and partitioning behavior of perfluoroalkyl carboxylic acids and perfluorooctanesulfonate in water and sediment from Dianchi Lake, China

Perfluorinated compounds (PFCs) have received much attention on their distribution in various matrices including water bodies, precipitations, sediment and biota in different areas globally, however, little attention has been paid to their occurrence and distribution in urban lakes. In this study, water and sediment samples collected from 26 sites in Dianchi Lake, a plateau urban lake in the southwestern part of China were analyzed via high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for ten analytes involving nine perfluoroalkyl carboxylic acids (PFOAs) and perfluorooctanesulfonate (PFOS). Total levels of PFCs were 30.98 ± 32.19 ng L(-1) in water and 0.95 ± 0.63 ng g(-1) in sediment. In water samples PFOA was the dominant PFC contaminant, with concentrations ranging from 3.41 to 35.44 ng L(-1), while in sediments PFOS was the main PFC contaminant at levels from 0.07-0.83 ng g(-1) dry weight. Field-based sediment water distribution coefficients (K(D)) were calculated and corrected for organic carbon content (K(oc)), which reduced variability among samples. The log K(oc) ranged from 2.54 to 3.57 for C8-C12 perfluorinated carboxylic acids, increasing by 0.1-0.4 log units with each additional CF2 moiety. The log K(oc) of PFOS was 3.35 ± 0.32. Magnitudes and trends in log K(D) or log K(oc) appeared to agree well with previously published laboratory data. Results showed that different PFC composition profiles were observed for samples from the lake water and sediments, indicating the presence of dissimilar characteristics of the PFCs compounds, which is important for PFC fate modeling and risk assessment.     

Perfluoroalkyl substances (PFASs) in food and water from Faroe Islands

Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.     

Determinants of maternal and fetal exposure and temporal trends of perfluorinated compounds

In recent years, some perfluorinated compounds (PFCs) have been identified as potentially hazardous substances which are harmful to the environment and human health. According to limited data, PFC levels in humans could be influenced by several determinants. However, the findings are inconsistent. In the present study, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were measured in paired maternal and cord serum samples (N?=?237) collected between 1978 and 2001 in Southern Sweden to study the relationship between these and to investigate several potential determinants of maternal and fetal exposure to PFCs. Time trends of PFCs in Swedish women were also evaluated. The study is a part of the Fetal Environment and Neurodevelopment Disorders in Epidemiological Research project. PFOS, PFOA, and PFNA levels (median) were higher in maternal serum (15, 2.1, and 0.24 ng/ml, respectively) than in cord serum (6.5, 1.7, and 0.20 ng/ml, respectively). PFC levels were among the highest in women originating from the Nordic countries and the lowest in women from the Middle East, North Africa, and sub-Saharan Africa. Multiparous women had lower serum PFOA levels (1.7 ng/ml) than primiparous women (2.4 ng/ml). Maternal age, body mass index, cotinine levels, and whether women carried male or female fetuses did not affect serum PFC concentrations. Umbilical cord serum PFC concentrations showed roughly similar patterns as the maternal except for the gestational age where PFC levels increased with advancing gestational age. PFOS levels increased during the study period in native Swedish women. In summary, PFOS levels tend to increase while PFOA and PFNA levels were unchanged between 1978 and 2001 in our study population. Our results demonstrate that maternal country of origin, parity, and gestational age might be associated with PFC exposure.     

Evaluation of hexachlorocyclohexane contamination from the last lindane production plant operating in India

Purpose

??-Hexachlorocyclohexane (HCH), ??-HCH, and lindane (??-HCH) were listed as persistent organic pollutants by the Stockholm Convention in 2009 and hence must be phased out and their wastes/stockpiles eliminated. At the last operating lindane manufacturing unit, we conducted a preliminary evaluation of HCH contamination levels in soil and water samples collected around the production area and the vicinity of a major dumpsite to inform the design of processes for an appropriate implementation of the Convention.

Methods

Soil and water samples on and around the production site and a major waste dumpsite were measured for HCH levels.

Results

All soil samples taken at the lindane production facility and dumpsite and in their vicinity were contaminated with an isomer pattern characteristic of HCH production waste. At the dumpsite surface samples contained up to 450?g?kg^?1 ?? HCH suggesting that the waste HCH isomers were simply dumped at this location. Ground water in the vicinity and river water was found to be contaminated with 0.2 to 0.4?mg?l^?1 of HCH waste isomers. The total quantity of deposited HCH wastes from the lindane production unit was estimated at between 36,000 and 54,000?t.

Conclusions

The contamination levels in ground and river water suggest significant run-off from the dumped HCH wastes and contamination of drinking water resources. The extent of dumping urgently needs to be assessed regarding the risks to human and ecosystem health. A plan for securing the waste isomers needs to be developed and implemented together with a plan for their final elimination. As part of the assessment, any polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) generated during HCH recycling operations need to be monitored.     

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.     

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.     

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs��a global perspective on the management of Lindane and its waste isomers

Purpose

Hexachlorocyclohexane (HCH) isomers (??-, ??- and ??- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries.

Results

In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tonnes of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tonnes, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs?? contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production.

Conclusion

It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilisation. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.     

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/l and <0.01–14 ng/l in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0–260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9–26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions.     

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.