Sources of pharmaceutical pollution in the New York City Watershed

An investigation was carried out in the New York City Watershed for the presence of selected pharmaceuticals. In four seasonal sampling events between August 2003 and May 2004, surface water was collected from eight reservoir keypoints and effluent was collected from four wastewater treatment plants. We evaluated the following twelve compounds: amoxicillin, atenolol, caffeine, carbamazepine, cephalexin, estrone, 17alpha-ethinylestradiol, 17beta-estradiol, ibuprofen, sulfamethoxazole, trimethoprim, and valproic acid. In the treated effluents, carbamazepine was detected most frequently (100%; concentration range: 22-551 ng/L), followed by atenolol (94%; ND - 14,200 ng/L), trimethoprim (83%; ND - 37,000 ng/L), ibuprofen (61%; ND - 14,600 ng/L), and caffeine (49%; ND - 37,200 ng/L), while estrone was detected once (56 ng/L). In the reservoir keypoint samples, only ibuprofen (2.5%; ND - 932 ng/L) and caffeine (2.9%; ND - 177 ng/L) were detected. The other analytes were not detected in any sample. It is expected that investigation of other wastewater treatment plants in the New York City Watershed would show that their effluents are also a potential source of pharmaceuticals, but that these pharmaceuticals are unlikely to be detected in the Watershed's surface waters.     

Pharmaceuticals and personal care products (PPCPs) in surface and treated waters of Louisiana,USA and Ontario,Canada

A newly developed analytical method was used to measure concentrations of nine pharmaceuticals and personal care products (PPCPs) in samples from two surface water bodies, a sewage treatment plant effluent and various stages of a drinking water treatment plant in Louisiana, USA, and from one surface water body, a drinking water treatment plant and a pilot plant in Ontario, Canada. The analytical method provides for simultaneous extraction and quantification of the following broad range of PPCPs and endocrine-disrupting chemicals: naproxen; ibuprofen; estrone; 17beta-estradiol; bisphenol A; clorophene; triclosan; fluoxetine; and clofibric acid. Naproxen was detected in Louisiana sewage treatment plant effluent at 81-106 ng/l and Louisiana and Ontario surface waters at 22-107 ng/l. Triclosan was detected in Louisiana sewage treatment plant effluent at 10-21 ng/l. Of the three surface waters sampled, clofibric acid was detected in Detroit River water at 103 ng/l, but not in Mississippi River or Lake Pontchartrain waters. None of the other target analytes were detected above their method detection limits. Based on results at various stages of treatment, conventional drinking-water treatment processes (coagulation, flocculation and sedimentation) plus continuous addition of powdered activated carbon at a dosage of 2 mg/l did not remove naproxen from Mississippi River waters. However, chlorination, ozonation and dual media filtration processes reduced the concentration of naproxen below detection in Mississippi River and Detroit River waters and reduced clofibric acid in Detroit River waters. Results of this study demonstrate that existing water treatment technologies can effectively remove certain PPCPs. In addition, our study demonstrates the importance of obtaining data on removal mechanisms and byproducts associated with PPCPs and other endocrine-disrupting chemicals in drinking water and sewage treatment processes.     

Selective degradation of ibuprofen and clofibric acid in two model river biofilm systems

A field survey indicated that the Elbe and Saale Rivers were contaminated with both clofibric acid and ibuprofen. In Elbe River water we could detect the metabolite hydroxy-ibuprofen. Analyses of the city of Saskatoon sewage effluent discharged to the South Saskatchewan river detected clofibric acid but neither ibuprofen nor any metabolite. Laboratory studies indicated that the pharmaceutical ibuprofen was readily degraded in a river biofilm reactor. Two metabolites were detected and identified as hydroxy- and carboxy-ibuprofen. Both metabolites were observed to degrade in the biofilm reactors. However, in human metabolism the metabolite carboxy-ibuprofen appears and degrades second whereas the opposite occurs in biofilm systems. In biofilms the pharmacologically inactive stereoisomere of ibuprofen is degraded predominantly. In contrast, clofibric acid was not biologically degraded during the experimental period of 21 days. Similar results were obtained using biofilms developed using waters from either the South Saskatchewan or Elbe River. In a sterile reactor no losses of ibuprofen were observed. These results suggested that abiotic losses and adsorption played only a minimal role in the fate of the pharmaceuticals in the river biofilm reactors.     

Occurrence and risk assessment of acidic pharmaceuticals in the Yellow River, Hai River and Liao River of north China

Pharmaceuticals in the aquatic environment have received great attentions from the general and scientific community due to their potential impacts on ecological and human health. We investigated the occurrence of twelve acidic pharmaceuticals and herbicides (salicylic acid, clofibric acid, ibuprofen, gemfibrozil, fenoprofen, naproxen, ketoprofen, mefenamic acid, tolfenamic acid, diclofenac, meclofenamic acid and indomethacin) in surface waters of the Yellow River, Hai River and Liao River in north China during the wet and dry seasons and assessed the potential risks to aquatic organisms posed by these acidic compounds. Seven acidic compounds were detected in the rivers, including five non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, diclofenac, mefenamic acid and naproxen), and two blood lipid regulators (clofibric acid and gemfibrozil). The concentrations for acidic pharmaceuticals in the Yellow River and Liao River were in most cases higher in the dry season than in the wet season, but the concentrations of acidic compounds in the Hai River were generally higher in July than in November. High concentrations of these detected compounds in the Yellow River, Hai River and Liao River were found more frequently at those sites located in metropolitan areas, lower reaches or river confluences. Only diclofenac and ibuprofen were found to have medium to high risks in the three rivers based on the calculated risk quotients.     

Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) in stormwater canals and Bayou St. John in New Orleans, Louisiana, USA

Samples were collected from two stormwater canals and a recreational urban waterway known as Bayou St. John in New Orleans, Louisiana, USA and analyzed for a range of pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs). Concentrations of 7 PPCPs and EDCs were measured by a method that provides for simultaneous extraction and quantification of the following compounds: clofibric acid, naproxen, ibuprofen, fluoxetine, clorophene, triclosan, bisphenol A. The method also was used as an indicator of the occurrence of estrogenic compounds by targeting estrone and 17beta-estradiol. The two canals (Orleans and London) are used to drain a portion of the city's stormwater directly into the Mississippi River or Lake Pontchartrain. Bayou St. John is located between the two canals and supplied with water from Lake Pontchartrain. Results from the 6-month sampling period indicated the following concentration ranges for the two stormwater canals: naproxen (ND - 145 ng/l), ibuprofen (ND - 674 ng/l), triclosan (ND - 29 ng/l) and bisphenol A (1.9-158 ng/l). Concentrations of these target analytes increased with cumulative rainfall. For bayou waters, only naproxen (2.1-4.8 ng/l) and bisphenol A (0.9-44 ng/l) were detected. Estrone was detected but determined non-quantifiable for multiple sampling events at the 3 sites. None of the other target analytes (clofibric acid, fluoxetine, clorophene, and 17beta-estradiol) were detected above their method detection levels. Results of this study demonstrate the occurrence of PPCPs and EDCs in New Orleans stormwater canals and Bayou St. John. Results also demonstrate the use of this analytical technique as an indicator of non-point source sewage contamination in New Orleans stormwater canals.     

Reconnaissance of selected PPCP compounds in Costa Rican surface waters

Eighty-six water samples were collected in early 2009 from Costa Rican surface water and coastal locations for the analysis of 34 pharmaceutical and personal care product compounds (PPCPs). Sampling sites included areas receiving treated and untreated wastewaters, and urban and rural runoff. PPCPs were analyzed using a combination of solid phase extraction and liquid chromatography tandem mass spectrometry. The five most frequently detected compounds were doxycycline (77%), sulfadimethoxine (43%), salicylic acid (41%), triclosan (34%) and caffeine (29%). Caffeine had the maximum concentration of 1.1 mg L⁻¹, possibly due to coffee bean production facilities upstream. Other compounds found in high concentrations include: doxycycline (74 μg L⁻¹), ibuprofen (37 μg L⁻¹), gemfibrozil (17 μg L⁻¹), acetominophen (13 μg L⁻¹) and ketoprofen (10 μg L⁻¹). The wastewater effluent collected from an oxidation pond had similar detection and concentrations of compounds compared to other studies reported in the literature. Waters receiving runoff from a nearby hospital showed higher concentrations than other areas for many PPCPs. Both caffeine and carbamazepine were found in low frequency compared to other studies, likely due to enhanced degradation and low usage, respectively. Overall concentrations of PPCPs in surface waters of Costa Rica are inline with currently reported occurrence data from around the world, with the exception of doxycycline.     

Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking, and waste waters

Liquid chromatography/tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was used to measure the concentrations of 14 pharmaceuticals, 6 hormones, 2 antibiotics, 3 personal care products (PCPs), and 1 flame retardant in surface waters and wastewater treatment plant effluents in South Korea. Tris (2-chloroethyl) phosphate (TCEP), iopromide, naproxen, carbamazepine, and caffeine were quite frequently observed (>80%) in both surface waters and effluents. The analytes of greatest concentration were iopromide, TCEP, sulfamethoxazole, and carbamazepine. However, the primary estrogen hormones, 17alpha-ethynylestradiol and 17beta-estradiol, were rarely detected, while estrone was detected in both surface water and wastewater effluent. The elimination of these chemicals during drinking water and wastewater treatment processes at full- and pilot-scale also was investigated. Conventional drinking water treatment methods were relatively inefficient for contaminant removal, while efficient removal (approximately equal to 99%) was achieved by granular activated carbon (GAC). In wastewater treatment processes, membrane bioreactors (MBR) showed limited target compound removal, but were effective at eliminating hormones and some pharmaceuticals (e.g., acetaminophen, ibuprofen, and caffeine). Membrane filtration processes using reverse osmosis (RO) and nanofiltration (NF) showed excellent removal (>95%) for all target analytes.     

Predicted and measured concentrations for selected pharmaceuticals in UK rivers: implications for risk assessment

Predicted environmental concentrations for five commonly used pharmaceuticals were calculated using data from the UK Department of Health according to risk assessment guidelines proposed by the European Agency for the Evaluation of Medicinal Products. Surface waters from the South-East of England were analysed and results were compared with predicted concentrations and findings from other studies from the UK and Europe. It was found that the efficacy of these predictions varied and was hampered by a shortage of data for many of the drugs. Ibuprofen, paracetamol and salbutamol were detected and quantified in all locations sampled. Ibuprofen was consistently found at the highest concentrations (up to 3 microg l(-1)). Levels up and downstream of two wastewater treatment works were compared in order to investigate the link between sewage discharge and environmental concentrations of pharmaceuticals. Results from one site demonstrated a considerable increase in concentrations of ibuprofen, salbutamol and paracetamol downstream from the treatment works; however, no link was established for a second works.     

Determination of caffeine as a tracer of sewage effluent in natural waters by on-line solid-phase extraction and liquid chromatography with diode-array detection

A new liquid chromatographic (LC) method with automated on-line solid phase extraction was developed to determine caffeine at sub-microgram per litre concentrations in waters. The filtered sample was pre-concentrated in a pre-column, which was backwashed with acidic water at pH of 2.70. The concentrated caffeine was separated using a C18 column with a gradient of water-acetonitrile and detected by diode array detection (DAD) at 210 nm. Four different pre-columns: C18, PRP-1, PLRP-s and Env were evaluated for the on-line solid phase extraction of caffeine. The PLRP-s pre-column allowed the enrichment of up to 100 mL of environmental water sample with highest recovery. The procedure was validated by recovery experiments in water spiked at 0.5 1.0 and 4.0 microg/L. Average recoveries were between 92.1 +/- 5.2% and 97.8 +/- 2.6%. Detection limits as low as 0.1 microg/L from 50 ml of sample were achieved. The proposed method has the advantages of higher reliability and sensitivity, simpler sample preparation and shorter analysis time in comparison with off-line solid-phase extraction. The utility of the method was demonstrated at two field sites: Bolivar and Halls Head (Australia). At Bolivar, the treatment process included 6-week lagoon storage which is believed to have attenuated caffeine, and thus limited its use as an environmental tracer of reclaimed water. At the Halls Head site, where the storage period is shorter, caffeine was detected in both the treated sewage effluent and in groundwater near ponds where the reclaimed water is at similar concentrations. These results suggest that the environmental conditions under which caffeine is conservative require better definition.     

Comprehensive assessment of the design configuration of constructed wetlands for the removal of pharmaceuticals and personal care products from urban wastewaters

Seven mesocosm-scale constructed wetlands (CWs) of different configurations were operated outdoors for nine months to assess their ability to remove pharmaceuticals and personal care products (PPCPs) from urban wastewaters. CWs differed in some design parameters, namely the presence of plants, the species chosen (i.e., Typha angustifolia vs Phragmites australis), flow configuration (i.e., surface flow vs subsurface flow) and the presence of a gravel bed. A nearby conventional activated-sludge wastewater treatment plant (WWTP) fed with the same sewage was simultaneously monitored for comparison. The PPCPs ketoprofen, naproxen, ibuprofen, diclofenac, salicylic acid, carbamazepine, caffeine, galaxolide, tonalide and methyl dihydrojasmonate were monitored. The presence of plants favoured the removal of some PPCPs. The performance of the mesocosm studied was compound-dependant, soilless CWs showing the highest removal efficiency for ketoprofen, ibuprofen and carbamazepine, while free-water CWs with effluent leaving through the bottom of the tank performed well for the degradation of ketoprofen, salicylic acid, galaxolide and tonalide. Finally, subsurface horizontal flow CWs were efficient for the removal of caffeine. Significant linear correlations were observed between the removal of some PPCPs and temperature or redox potential. Hence, microbiological pathways appear to be the most probable degradation route for PPCPs in the CWs studied.     

An investigation into the acute and chronic toxicity of eleven pharmaceuticals (and their solvents) found in wastewater effluent on the cnidarian, Hydra attenuata

Pharmaceuticals previously identified in the effluent from the wastewater treatment plant (WWTP) in Montreal discharging into the St. Lawrence river, were tested for acute and chronic toxicity using the cnidarian Hydra attenuata. Acute toxicity was based on the established technique looking at morphological changes in the Hydra, while recently developed endpoints of feeding behaviour, attachment and growth (hydranth number) were used to measure chronic effects. The compounds under investigation (ibuprofen, naproxen, gemfibrozil, bezafibrate, carbamazepine, sulfamethoxazole, sulfapyridine, oxytetracycline, novobiocin, trimethoprim and caffeine) were tested individually in controlled laboratory exposures with LC(50) and EC(50) results calculated. All compounds tested had relatively high LC(50) values with gemfibrozil, ibuprofen and naproxen having the lowest at 22.36 mg/L and EC(50) values based on morphology of 1.18 to 2.62 mg/L (all concentrations are nominal). The EC(50) values based on feeding were similar to those based on morphology but with increased sensitivity for carbamazepine, bezafibrate and novobiocin. A trend of a reduction in feeding with deterioration in morphology was observed in the Hydra, with the exception of novobiocin, where a lower than expected EC(50) of 13.53 mg/L was found with no negative effect on morphology. Significant reductions in attachment and hydranth number were seen at concentrations of 1 and 5 mg/L for gemfibrozil and ibuprofen respectively. A toxicity threshold (TT) of 320 microg/L was calculated for ibuprofen, only a factor of 10(2) or 10 higher than the concentration found in the effluent in the present study (1.19 mug/L) and in other Canadian effluents studied (22 microg/L [Brun GL, Bernier M, Losier R, Doe K, Jackman P, Lee HB, Pharmaceutically active compounds in Atlantic Canadian sewage treatment plant effluents and receiving waters and potential for environmental effects as measured by acute and chronic aquatic toxicity. Environ Toxicol Chem 2006; 25(8): 2163-2176.] respectively. Using EU directive 93/67/EEC the pharmaceuticals under investigation can be classified as toxic (gemfibrozil, ibuprofen and naproxen), harmful (carbamazepine, bezafibrate, sulfapyridine, oxytetracycline and novobiocin) and non-toxic (sulfamethoxazole, trimethoprim and caffeine) and their potential toxicity for the aquatic environment is discussed.     

Investigating the environmental transport of human pharmaceuticals to streams in the United Kingdom

The occurrence of 12 selected pharmaceutical compounds and pharmaceutical compound metabolites in sewage treatment works (STW) effluents and surface waters was investigated. The substances selected for the monitoring programme were identified by a risk ranking procedure to identify those substances with the greatest potential to pose a risk to the aquatic environment. STW final effluent and surface water samples were collected from Corby, Great Billing, East Hyde, Harpenden and Ryemeads STWs. Ten of the 12 pharmaceutical compounds were detected in the STW effluent samples: propranolol (100%, median = 76 ng/l), diclofenac (86%, median = 424 ng/l), ibuprofen (84%, median = 3086 ng/l), mefenamic acid (81%, median = 133 ng/l), dextropropoxyphene (74%, median = 195 ng/l), trimethoprim (65%, 70 ng/l), erythromycin (44%, < 10 ng/l), acetyl-sulfamethoxazole (33%, median =< 50 ng/l), sulfamethoxazole (9%, median =< 50 ng/l), tamoxifen (4%, median =< 10 ng/l). In the corresponding receiving streams, fewer compounds and lower concentrations were found: propranolol (87%, median = 29 ng/l), ibuprofen (69%, median = 826 ng/l), mefenamic acid (60%, median = 62 ng/l), dextropropoxyphene (53%, median = 58 ng/l), diclofenac (47%, median =< 20 ng/l), erythromycin (38%, median =< 10 ng/l), trimethoprim (38%, median =< 10 ng/l), acetyl sulfamethoxazole (38%, median =< 50 ng/l). Four human pharmaceutical compounds were detected in samples upstream of the STWs sampled: ibuprofen (57%, median = 181 ng/l), trimethoprim (36%, median < 10 ng/l), erythromycin (17%, median =< 10 ng/l), propranolol (14%, median =< 10 ng/l), suggesting that longer range stream transport of some compounds is possible. The particular STW that was sampled and the month that it was sampled significantly influenced the measured concentrations of several, but not all, substances. There was no significant relationship between usage data and the overall frequency with which different substances were detected. There was however, some evidence to suggest that usage data are positively associated with concentrations of pharmaceuticals in effluent and, particularly, with concentrations measured in surface waters below STWs. These results suggest that most sewage treatment works in England and Wales are likely to be routinely discharging small quantities of pharmaceuticals into UK rivers. None of the pharmaceuticals were found at concentrations that were high enough to cause acute toxic impacts to aquatic organisms. However, insufficient data were available to be able to comment on whether the concentrations measured have the potential to result in more subtle long-term effects on aquatic organisms (e.g. effects on growth, ability to reproduce).     

Occurrence of selected pharmaceuticals in an agricultural landscape, western Lake Erie basin

The occurrence of 18 commonly used pharmaceuticals was investigated in an agricultural area, which is primarily affected by runoff from agricultural fields and septic systems, on the coastline of Maumee Bay, within the western Lake Erie basin. Selected pharmaceuticals were detected in surface water, except clofibric acid and fluoxethine. The most frequently detected compounds were caffeine (88%), carbamazepine (57%) and paraxanthine (56%). Caffeine, carbamazepine, ibuprofen and paraxanthine were detected with maximum concentrations of 4.2, 1.2, 2.8 and 1.8 μg L⁻¹, respectively. However, no compound was detected in any sediment samples. In a field receiving biosolids application, pharmaceuticals were detected in the field tile drainage following biosolids application but not in soil. The occurrence of pharmaceuticals in surface water can be linked to the use of septic systems.     

Drugs and personal care products as ubiquitous pollutants: occurrence and distribution of clofibric acid,caffeine and DEET in the North Sea

An analytical method is presented, which allows the simultaneous extraction of neutral and acidic compounds from 20-L seawater samples at ambient pH (approximately 8.3). It is based on a solid-phase extraction by means of a polystyrene-divinylbenzene sorbent and gas chromatographic-mass spectrometric detection, and provides detection limits in the lower pg/L range. The method was applied to the screening of samples from different North Sea areas for clofibric acid, diclofenac, ibuprofen, ketoprofen, propyphenazone, caffeine and N,N-diethyl-3-toluamide (DEET). Whereas clofibric acid, caffeine and DEET showed to be present throughout the North Sea in concentrations of up to 1.3, 16 and 1.1 ng/L, respectively, propyphenazone could only be detected after further clean-up. Diclofenac and ibuprofen were found in the estuary of the river Elbe (6.2 and 0.6 ng/L, respectively) but in none of the marine samples. Ketoprofen was below the detection limit in all samples.     

Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment

In this paper we report on the performances of full-scale conventional activated sludge (CAS) treatment and two pilot-scale membrane bioreactors (MBRs) in eliminating various pharmaceutically active compounds (PhACs) belonging to different therapeutic groups and with diverse physico-chemical properties. Both aqueous and solid phases were analysed for the presence of 31 pharmaceuticals included in the analytical method. The most ubiquitous contaminants in the sewage water were analgesics and anti-inflammatory drugs ibuprofen (14.6-31.3 μg/L) and acetaminophen (7.1-11.4 μg/L), antibiotic ofloxacin (0.89-31.7 μg/L), lipid regulators gemfibrozil (2.0-5.9 μg/L) and bezafibrate (1.9-29.8 μg/L), β-blocker atenolol (0.84-2.8 μg/L), hypoglycaemic agent glibenclamide (0.12-15.9 μg/L) and a diuretic hydrochlorothiazide (2.3-4.8 μg/L). Also, several pharmaceuticals such as ibuprofen, ketoprofen, diclofenac, ofloxacin and azithromycin were detected in sewage sludge at concentrations up to 741.1, 336.3, 380.7, 454.7 and 299.6 ng/g dry weight. Two pilot-scale MBRs exhibited enhanced elimination of several pharmaceutical residues poorly removed by the CAS treatment (e.g., mefenamic acid, indomethacin, diclofenac, propyphenazone, pravastatin, gemfibrozil), whereas in some cases more stable operation of one of the MBR reactors at prolonged SRT proved to be detrimental for the elimination of some compounds (e.g., β-blockers, ranitidine, famotidine, erythromycin). Moreover, the anti-epileptic drug carbamazepine and diuretic hydrochlorothiazide by-passed all three treatments investigated.Furthermore, sorption to sewage sludge in the MBRs as well as in the entire treatment line of a full-scale WWTP is discussed for the encountered analytes. Among the pharmaceuticals encountered in sewage sludge, sorption to sludge could be a relevant removal pathway only for several compounds (i.e., mefenamic acid, propranolol, and loratidine). Especially in the case of loratidine the experimentally determined sorption coefficients (K_ds) were in the range 2214-3321 L/kg (mean). The results obtained for the solid phase indicated that MBR wastewater treatment yielding higher biodegradation rate could reduce the load of pollutants in the sludge. Also, the overall output load in the aqueous and solid phase of the investigated WWTP was calculated, indicating that none of the residual pharmaceuticals initially detected in the sewage sludge were degraded during the anaerobic digestion. Out of the 26 pharmaceutical residues passing through the WWTP, 20 were ultimately detected in the treated sludge that is further applied on farmland.     

Occurrence of acidic pharmaceuticals in raw and treated sewages and in receiving waters

The occurrence of five acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, diclofenac and bezafibrate, in seven different sewage treatment plants (STP) and three receiving waters were determined. The analytical procedure included solid phase extraction, liquid chromatographic separation and detection by a triple-quadrupole mass spectrometer. The studied pharmaceuticals were found in all the STPs. The pattern of the occurrence of individual compounds was the same in every STP and matched the consumption figures reported in the literature. Ibuprofen is the most used pharmaceutical in Finland and was accordingly found to be the most abundant compound in the raw sewage. In the treatment processes, the highest removal rate was observed for ibuprofen and the lowest for diclofenac, 92%+/-8% and 26%+/-17%, respectively. Due to the incomplete removal in the STPs, the pharmaceuticals were found in rivers at the discharge points of the STP effluents. Downstream from the discharge points, the concentrations decreased significantly mainly due to dilution in the river water. The risk to the aquatic environment was estimated by a ratio of measured environmental concentration (MEC) and predicted no-effect concentration (PNEC). At the concentrations the compounds were found in the surface waters, they should not pose risk for the aquatic environment. However, at dry seasons and/or during malfunctions of STPs, ibuprofen could be associated with a risk in small river systems.     

Host-specific 16S rRNA gene markers of Bacteroidales for source tracking of fecal pollution in the subtropical coastal seawater of Hong Kong

This study investigated the diversity of Bacteroidales communities in the feces of eight host species in Hong Kong (subtropical Asia), including human (in the form of sewage), cow, pig, horse, cat, dog, rabbit and rat. The analysis of terminal restriction fragment length polymorphism (TRFLP) in the 16S rRNA genes revealed significant differences in Bacteroidales communities among all host species, with the exception of dog and cat. Manual examination of TRFLP profiles resulted in six terminal restriction fragments (TRFs) that were potentially specific to the sewage (one TRF), cow (three TRFs) or pig (two TRFs) samples. All six TRFs were (1) present in 100% of the samples of the respective target host, (2) absent in other hosts or present only in low frequency and low intensity, and (3) verified for sizes using in silico digestion of DNA sequences in clone libraries. The six TRFs could reliably indicate the source of fecal contaminations in natural seawater amended with sewage, cow or pig fecal samples. In field tests conducted for two polluted and one unpolluted coastal site, the sewage-specific TRF was detected in all seawater samples of the sites known to be impacted by raw and treated sewage. However, only two of three cow-specific TRFs were detected for the two polluted sites, which also received fecal input from feral cows. No pig-specific TRF was detected, although one of the coastal sites was chronically polluted by pig farm run-offs. Nevertheless, the total absence of the six potentially host-specific TRFs in the seawater of an unpolluted site demonstrated the specificity of the TRFs as gene markers in indicating actual pollution.     

Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment

We measured six acidic analgesics or anti-inflammatories (aspirin, ibuprofen, naproxen, ketoprofen, fenoprofen, mefenamic acid), two phenolic antiseptics (thymol, triclosan), four amide pharmaceuticals (propyphenazone, crotamiton, carbamazepine, diethyltoluamide), three phenolic endocrine disrupting chemicals (nonylphenol, octylphenol, bisphenol A), and three natural estrogens (17beta-estradiol, estrone, estriol) in 24-h composite samples of influents and secondary effluents collected seasonally from five municipal sewage treatment plants in Tokyo. Aspirin was most abundant in the influent, with an average concentration of 7300 ng/L (n = 16), followed by crotamiton (921 ng/L), ibuprofen (669 ng/L), triclosan (511 ng/L), and diethyltoluamide (503 ng/L). These concentrations were 1 order of magnitude lower than those reported in the USA and Europe. This can be ascribed to lower consumption of the pharmaceuticals in Japan. Aspirin, ibuprofen, and thymol were removed efficiently during primary + secondary treatment (> 90% efficiency). On the other hand, amide-type pharmaceuticals, ketoprofen, and naproxen showed poor removal (< 50% efficiency), which is probably due to their lower hydrophobicity (logKow < 3). Because of the persistence of crotamiton during secondary treatment, crotamiton was most abundant among the target pharmaceuticals in the effluent. This is the first paper to report ubiquitous occurrence of crotamiton, a scabicide, in sewage. Because crotamiton is used worldwide and it is persistent during secondary treatment, it is a promising molecular marker of sewage and secondary effluent.     

Dissolved silver in European estuarine and coastal waters

Silver is one of the most toxic elements for the marine microbial and invertebrate community. However, little is known about the distribution and behaviour of dissolved silver in marine systems. This paper reports data on dissolved and sediment-associated silver in European estuaries and coastal waters which have been impacted to different extents by past and present anthropogenic inputs. This is the first extended dataset for dissolved silver in European marine waters. Lowest dissolved silver concentrations were observed in the Gullmar Fjord, Sweden (8.9 ± 2.9 pM; x ± 1σ), the Tamar Estuary, UK (9.7 ± 6.2 pM), the Fal Estuary, UK (20.6 ± 8.3 pM), and the Adriatic Sea (21.2 ± 6.8 pM). Enhanced silver concentrations were observed in Atlantic coastal waters receiving untreated sewage effluent from the city of A Cor?na, Spain (243 ± 195 pM), and in the mine-impacted Restronguet Creek, UK (91 ± 71 pM). Anthropogenic wastewater inputs were a source of dissolved silver in the regions studied, with the exception of the Gullmar Fjord. Remobilisation of dissolved silver from historically contaminated sediments, resulting from acid mine drainage or sewage inputs, provided an additional source of dissolved silver to the estuaries. The ranges in the log particle-water partition coefficient (K_d) values of 5-6 were similar for the Tamar and Mero estuaries and agreed with reported values for other estuaries. These high K_d values indicate the particle reactive nature of silver with oxic sediments. In contrast, low K_d values (1.4-2.7) were observed in the Fal system, which may have been due to enhanced benthic inputs of dissolved silver coupled to limited scavenging of silver on to sediments rich in Fe oxide.     

The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment

This paper presents the results of a survey of the wastewater effluent and surface waters of the lower river Tyne, UK. Samples were analysed by reversed-phase high-performance liquid chromatography-electrospray tandem mass spectrometry following solid phase extraction, for the presence of 13 pharmaceuticals selected from the priority lists of the UK Environment Agency and the Oslo and Paris Commission (OSPAR). The pharmaceutical compounds measured were acetyl-sulfamethoxazole, clofibric acid, clotrimazole, dextropropoxyphene, diclofenac, erythromycin, ibuprofen, mefenamic acid, paracetamol, propranolol, sulfamethoxazole, tamoxifen and trimethoprim. Of the wastewater treatment works (WTW) samples (n=9) analysed, all compounds except sulfamethoxazole and acetyl-sulfamethoxazole were detected at concentrations ranging from 11 to 69,570 ng l(-1) (in raw effluent). In the surface water samples (n=18), clotrimazole, dextropropoxyphene, erythromycin, ibuprofen, propranolol, tamoxifen and trimethoprim were detected at concentrations ranging from 4 to 2370 ng l(-1). Results of this study show that various pharmaceutical compounds are effectively reduced during their passage through a tertiary wastewater treatment works, whilst others are sufficiently persistent to occur in estuarine systems.