Illicit drugs as new environmental pollutants: cyto-genotoxic effects of cocaine on the biological model Dreissena polymorpha

The increase in global consumption of illicit drugs has produced not only social and medical problems but also a potential new environmental danger. Indeed, it has been established that drugs consumed by humans end up in surface waters, after being carried through the sewage system. Although many studies to measure concentrations of several drugs of abuse in freshwater worldwide have been conducted, no data have been available to evaluate their potentially harmful effects on non-target organisms until now. The present study represents the first attempt to investigate the cyto-genotoxic effects of cocaine, one of the primary drugs consumed in Western Countries, in the biological model Dreissena polymorpha by the use of a biomarker battery. We performed the following tests on Zebra mussel hemocytes: the single cell gel electrophoresis (SCGE) assay, the apoptosis frequency evaluation and the micronucleus assay (MN test) for the evaluation of genotoxicity and the lysosomal membranes stability test (neutral red retention assay; NRRA) to identify the cocaine cytotoxicity. We exposed the molluscs for 96 h to three different nominal concentrations in water (40 ng L⁻¹; 220 ng L⁻¹; and 10 μg L⁻¹).Cocaine caused significant (p < 0.05) primary DNA damage in this short-term experiment, but it also caused a clear increase in micronucleated cells and a marked rise in apoptosis, which was evident in samples from even the lowest environmental cocaine concentration. Because cocaine decreased the stability of lysosomal membranes, we also highlighted its cytotoxicity and the possible implications of oxidative stress for the observed genotoxic effects.     

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.     

Effects of estrone on the early life stages and expression of vitellogenin and estrogen receptor genes of Japanese medaka (Oryzias latipes)

The fertilized eggs of Japanese medaka (Oryzias latipes) were exposed to estrone (E1) at 5–5000 ng L⁻¹ for 15 d, and the hatched fry were exposed continuously to the same concentrations for the additional 15 d. Adverse effects on hatchability, time to hatching, and gross abnormalities occurred at 50 ng L⁻¹ or above. Then the fry were divided into a continual exposure group, and a water recovery group. When the fry were exposed to E1 for another 60 d, there was a decrease in the hepatosomatic index (HSI) of males and the influence disappeared in the water recovery group. The gonadosonatic index (GSI) of females at 500 ng L⁻¹ decreased significantly in another 60 d exposure. While the fry were maintained in dechlorinated tap water for 60 d, a significant decrease in female GSI was observed at 50 ng L⁻¹ or above. An increased GSI was found in males in both continual exposure and water recovery groups at all E1 treatments. Quantitative RT-PCR showed that vitellogenin-I (Vtg-I) gene expressions in the female liver were significantly down-regulated at 50 ng L⁻¹ in the continual exposure group, and at 500 ng L⁻¹ in the water recovery group, while male Vtg-I genes were significantly up-regulated for all E1 treatments. In addition, all E1 treatments caused sex reversal of males. These results suggest that E1 at 5 ng L⁻¹ or above have unrecoverable impacts on the gonadal growth and development of medaka, even if only early life stages were exposed to E1.     

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.     

Risk assessment of xenoestrogens in a typical domestic sewage-holding lake in China

Release of domestic sewage leads to accumulation of xenoestrogens in holding waters, especially in closed or semi-enclosed waters such as lakes. In the study, the occurrence, distribution, estrogenic activity and risk of eight xenoestreogens were evaluated in Lake Donghu, China. Nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were identified as the main xenoestrogens ranging from tens of ng L⁻¹ (in the surface water) or ng g⁻¹ dw (in the suspended particles and sediment) to tens of μg L⁻¹ or μg g⁻¹ dw. The sum of 17β-estradiol equivalents (∑EEQs) ranged from 0.32 to 45.02 ng L⁻¹ in the surface water, 0.53 to 71.86 ng g⁻¹ dw in the suspended particles, and 0.09 to 24.73 ng g⁻¹ dw in the sediment. Diethylstilbestrol (DES) was determined as the main contributor to ∑EEQs followed by NP. The risk assessment showed a higher risk in the surface water than in the suspended particles and sediment in such domestic sewage-holding lake.     

Atmospheric partitioning and the air–water exchange of polycyclic aromatic hydrocarbons in a large shallow Chinese lake (Lake Chaohu)

The residual levels of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere and in dissolved phase from Lake Chaohu were measured by (GC–MS). The composition and seasonal variation were investigated. The diffusive air–water exchange flux was estimated by a two-film model, and the uncertainty in the flux calculations and the sensitivity of the parameters were evaluated. The following results were obtained: (1) the average residual levels of all PAHs (PAH16) in the atmosphere from Lake Chaohu were 60.85 ± 46.17 ng m⁻³ in the gaseous phase and 14.32 ± 23.82 ng m⁻³ in the particulate phase. The dissolved PAH16 level was 173.46 ± 132.89 ng L⁻¹. (2) The seasonal variation of average PAH16 contents ranged from 43.09 ± 33.20 ng m⁻³ (summer) to 137.47 ± 41.69 ng m⁻³ (winter) in gaseous phase, from 6.62 ± 2.72 ng m⁻³ (summer) to 56.13 ± 22.99 ng m⁻³ (winter) in particulate phase, and 142.68 ± 74.68 ng L⁻¹ (winter) to 360.00 ± 176.60 ng L⁻¹ (summer) in water samples. Obvious seasonal trends of PAH16 concentrations were found in the atmosphere and water. The values of PAH16 for both the atmosphere and the water were significantly correlated with temperature. (3) The monthly diffusive air–water exchange flux of total PAH16 ranged from −1.77 × 10⁴ ng m⁻² d⁻¹ to 1.11 × 10⁵ ng m⁻² d⁻¹, with an average value of 3.45 × 10⁴ ng m⁻² d⁻¹. (4) The results of a Monte Carlo simulation showed that the monthly average PAH fluxes ranged from −3.4 × 10³ ng m⁻² d⁻¹ to 1.6 × 10⁴ ng m⁻² d⁻¹ throughout the year, and the uncertainties for individual PAHs were compared. (5) According to the sensitivity analysis, the concentrations of dissolved and gaseous phase PAHs were the two most important factors affecting the results of the flux calculations.     

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.     

The distribution of 4-nonylphenol in marine organisms of North American Pacific Coast estuaries

One of the chemical breakdown products of nonylphenol ethoxylates, 4-nonylphenol (4-NP), accumulates in organisms and is of concern as an environmental pollutant due to its endocrine disrupting effects. We measured 4-NP levels in the seawater, sediment, and twelve organisms within the California estuary, Morro Bay, and examined biomagnification of 4-NP using stable isotope abundances (δ¹⁵N and δ¹³C) to quantify trophic position. 4-NP concentrations in organisms from Morro Bay included 25000 ± 8600 ng g⁻¹ lw in liver of California sea lion, 14000 ± 5600 ng g⁻¹ lw in liver of harbor porpoise, 138000 ± 55000 ng g⁻¹ lw in liver of sea otters, 15700 ± 3600 ng g⁻¹ lw in liver of seabirds, 36100 ± 6100 ng g⁻¹ lw in arrow goby fish, 62800 ± 28400 ng g⁻¹ lw in oysters, and 12700 ± 1300 ng g⁻¹ lw in mussels. 4-NP levels generally showed a pattern of trophic dilution among organisms in Morro Bay, with exceptions of biomagnification observed between three trophic links: mussel to sea otter (BMF 10.9), oyster to sea otter (BMF 2.2), and arrow goby to staghorn sculpin (BMF 2.7). Our examination of other west coast estuaries of USA and Canada revealed that mean 4-NP concentrations in gobies and mussels from Morro Bay were significantly higher than those from a more urbanized estuary, San Francisco Bay (goby: 11100 ± 3800 ng g⁻¹ lw) and from a remote estuary, Bamfield Inlet, Canada (goby: 9000 ± 900 ng g⁻¹ lw, mussel: 6100 ± 700 ng g⁻¹ lw). Relative to other estuaries worldwide, 4-NP levels in seawater (0.42 ± 0.16 μg L⁻¹) and sediment (53 ± 14 ng g⁻¹ dw) of Morro Bay are low, but gobies and oysters have higher 4-NP levels than comparable fauna.     

Effects of wavelength and water quality on photodegradation of N-Nitrosodimethylamine (NDMA)

N-Nitrosodimethylamine (NDMA) is a potent carcinogen that yields a cancer risk of 10⁻⁶ at concentrations as low as 0.7 ng L⁻¹. Tentative guideline values are set at 3 ng L⁻¹ in California, USA; 9 ng L⁻¹ in Ontario, Canada; 40 ng L⁻¹ nationwide in Canada; and 100 ng L⁻¹ by the World Health Organization. NDMA is a great concern in treating reclaimed water as well as drinking water. UV degradation can be considered effective degradation method. A 1-log reduction of NDMA is achieved by 1000 mJ cm⁻² of a 254-nm low pressure (LP) mercury UV lamp. However, a higher degradation efficiency than that provided by LP lamps is desired in practical treatment. In this study, the effects of wavelength and water quality were investigated to achieve higher degradation efficiency. The effects of wavelength were examined by comparing three UV lamps: a 222-nm Kr Cl Excimer UV lamp, a 254-nm LP mercury UV lamp, and a 230- to 270-nm filtered medium pressure (FMP) mercury UV lamp. The 222-nm lamp and FMP lamp achieved 4 times and 2.8 times higher degradation efficiency, respectively, than the conventional 254-nm LP lamp. Effects on water quality were also simulated by using absorption spectrum data of nitrate solutions and process water from a drinking-water treatment plant. In the simulation, the 222-nm lamp was affected by UV-absorbing compounds in the water, whereas the FMP lamp showed more stable degradation efficiency. Appropriate use of these three types of lamps could enhance the efficiency of degradation of NDMA.     

The arrival and discharge of conjugated estrogens from a range of different sewage treatment plants in the UK

The occurrence of free and conjugated estrogens was examined in a survey of eleven sewage treatment plants (STPs) and their discharge water in the United Kingdom using grab sampling. The STPs included trickling filter with and without tertiary treatment, and activated sludge with tertiary treatment. For three activated sludge plants both influent and effluent samples were compared. For a further 8 STPs only the effluent was examined. The estrone-3-sulphate, estradiol-3-sulphate and estriol-3-sulphate concentrations (up to 20 ng L⁻¹) were typically 5-fold that of the respective free estrogen concentration in the effluents. This represents a substantial additional ‘potential’ estrogen load arriving in the receiving waters. Estrone-3-glucuronide was found at 9 ng L⁻¹, estradiol-3-glucuronide at 7 ng L⁻¹, and estriol-3-glucuronide at 32 ng L⁻¹ in sewage influent. Except on one occasion, no glucuronide conjugates could be found in the effluent. The results suggest in most cases glucuronide conjugates will be completely transformed in sewage treatment whilst sulphate conjugates will only be partially removed.     

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.     

Gene expression profiles in the testis associated with testis-ova in adult Japanese medaka (Oryziaslatipes) exposed to 17α-ethinylestradiol

The occurrence of oocytes in the testis (testis-ova) of several fish species is often associated with exposure of estrogenic chemicals. However, induction mechanisms of the testis-ova remain to be elucidated. To develop marker genes for detecting testis-ova in the testis, adult male medaka were exposed to nominal concentration of 100 ng L⁻¹ of 17α-ethinylestradiol (EE2) for 3-5 weeks, and 800 ng estradiol benzoate (EB) for 3 weeks (experiment I), and a measured concentration of 20 ng L⁻¹ EE2 for 1-6 weeks (experiment II). Histological analysis was performed for the testis, and microarray analyses were performed for the testis, liver and brain. Microarray analysis in the estrogen-exposed medaka liver showed vitellogenin and choriogenin as estrogen responsive genes. Testis-ova were induced in the testis after 4 weeks of exposure to 100 ng L⁻¹ EE2, 3 weeks of exposure to 800 ng EB, and 6 weeks of exposure to 20 ng L⁻¹ EE2. Microarray analysis of estrogen-exposed testes revealed up-regulation of genes related to zona pellucida (ZP) and the oocytes marker gene, 42Sp50. Using quantitative RT-PCR we confirmed that Zpc5 gene can be used as a marker for the detection of testis-ova in male medaka.     

Distribution of bisphenol-A, triclosan and n-nonylphenol in human adipose tissue, liver and brain

In this study, an analytical method was optimized for the determination of bisphenol-A (BPA), triclosan (TCS) and 4-n-nonylphenol (4n-NP), environmental contaminants with potential endocrine disruptive activities, in human tissues. The method consisted of a liquid extraction step, derivatization with pentafluorobenzoylchloride followed by a clean-up on acidified silica and detection with gas chromatography coupled with mass spectrometry (GC-ECNI/MS). Recoveries ranged between 92% and 102% with a precision below 5%. Limits of quantification ranged between 0.3-0.4 ng g⁻¹, 0.045-0.06 ng g⁻¹ and 0.003-0.004 ng g⁻¹ for BPA, TCS and 4n-NP in different tissues, respectively. The method was applied for the determination of BPA, TCS and 4n-NP in paired adipose tissue, liver and brain samples from 11 individuals. BPA could be detected in almost all tissues, with the highest concentrations found in adipose tissue (mean 3.78 ng g⁻¹), followed by liver (1.48 ng g⁻¹) and brain (0.91 ng g⁻¹). TCS showed the highest concentrations in liver (3.14 ng g⁻¹), followed by adipose tissue (0.61 ng g⁻¹), while it could be detected in only one brain sample. Levels of 4n-NP were much lower, mostly undetected, and therefore 4n-NP is considered of minor importance for human exposure. Despite the measurable concentrations in adipose tissue, these compounds seem to have a low bioaccumulation potential. The reported concentrations of free BPA in the various tissues are slight disagreement with pharmacokinetic models in humans and rats and therefore the possibility of external contamination with BPA during sample collection/storage cannot be ruled out.     

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.     

Levels of organochlorine pesticides and polychlorinated biphenyls in the critically endangered Iberian lynx and other sympatric carnivores in Spain

Accumulation of organochlorine compounds is well studied in aquatic food chains whereas little information is available from terrestrial food chains. This study presents data of organochlorine levels in tissue and plasma samples of 15 critically endangered Iberian lynx (Lynx pardinus) and other 55 wild carnivores belonging to five species from three natural areas of Spain (Doñana National Park, Sierra Morena and Lozoya River) and explores their relationship with species diet. The Iberian lynx, with a diet based on the consumption of rabbit, had lower PCB levels (geometric means, plasma: <0.01 ng mL⁻¹, liver: 0.4 ng g⁻¹ wet weight, fat: 87 ng g⁻¹ lipid weight) than other carnivores with more anthropic and opportunistic foraging behavior, such as the red fox (Vulpes vulpes; plasma: 1.11 ng mL⁻¹, liver: 459 ng g⁻¹, fat: 1984 ng g⁻¹), or with diets including reptiles at higher proportion, such as the Egyptian mongoose (Herpestes ichneumon; plasma: 7.15 ng mL⁻¹, liver: 216 ng g⁻¹, fat: 540 ng g⁻¹), or the common genet (Genetta genetta; liver: 466 ng g⁻¹, fat: 3854 ng g⁻¹). Chlorinated pesticides showed interspecific variations similar to PCBs. Organochlorine levels have declined since the 80s in carnivores from Doñana National Park, but PCB levels are still of concern in Eurasian otters (Lutra lutra; liver: 3873-5426 ng g⁻¹) from the industrialized region of Madrid.     

Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain)

A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 μg L⁻¹. Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 μg L⁻¹ median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 μg L⁻¹, so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L⁻¹ range. Pharmaceuticals and UV filters are typically below the 10 ng L⁻¹ level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L⁻¹ drinking water European Union limit.     

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.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Removal and formation of chlorinated triclosan derivatives in wastewater treatment plants using chlorine and UV disinfection

Triclosan, a common antimicrobial agent, may react during the disinfection of wastewater with free chlorine to form three chlorinated triclosan derivatives (CTDs). This is of concern because the CTDs may be photochemically transformed to tri- and tetra-chlorinated dibenzo-p-dioxins when discharged into natural waters. In this study, wastewater influent, secondary (pre-disinfection) effluent, and final (post-disinfection) effluent samples were collected on two occasions each from two activated sludge wastewater treatment plants, one using chlorine disinfection and one using UV disinfection. Concentrations of triclosan and three CTDs were determined using ultra performance liquid chromatography-triple quadrupole mass spectrometry with isotope dilution methodology. Triclosan and the CTDs were detected in every influent sample at levels ranging from 453 to 4530 and 2 to 98 ng L⁻¹, respectively, though both were efficiently removed from the liquid phase during activated sludge treatment. Triclosan concentrations in the pre-disinfection effluent ranged from 36 to 212 ng L⁻¹, while CTD concentrations were below the limit of quantification (1 ng L⁻¹) for most samples. In the treatment plant that used chlorine disinfection, triclosan concentrations decreased while CTDs were formed during chlorination, as evidenced by CTD levels as high as 22 ng L⁻¹ in the final effluent. No CTDs were detected in the final effluent of the treatment plant that used UV disinfection. The total CTD concentration in the final effluent of the chlorinating treatment plant reached nearly one third of the triclosan concentration, demonstrating that the chlorine disinfection step played a substantial role in the fate of triclosan in this system.