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.     

Occurrence of steroid estrogens, endocrine-disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China

A scoping study was conducted to investigate the residues of nineteen pharmaceuticals and personal care products (PPCPs), including 4 natural and 3 synthetic steroid estrogens, 7 endocrine-disrupting phenols, and 5 acid pharmaceuticals in three urban streams and the Major Pearl River at Guangzhou, a megapolis in the Pearl River Delta, South China. Estrone was detected in >60% water samples with a maximum concentration of 65 ng L(-1). Endocrine-disrupting phenols (nonylphenol, bisphenol A, triclosan, 2-phenylphenol, methyparaben, and propylparaben) were found to be widely present at rather high concentrations in the urban riverine water of Guangzhou. Salicylic acid, clofibric acid and ibuprofen were detected in most water samples with maximum concentrations of 2098, 248 and 1417 ng L(-1) respectively, whereas naproxen was less frequently detected and also at lower concentration. Both the detection frequencies and median concentrations of the PPCPs appeared higher during the low-flow season than during the high-flow season. The seasonal difference in PPCPs occurrence was probably attributed to the dilution effect caused by the rainfall. PPCPs in the urban riverine water of Guangzhou originated mainly from random discharge and/or leakage of municipal wastewater. PPCPs contamination in the Major Pearl River may be of a potential environmental issue, especially during the low-flow season.     

Occurrence of endocrine disrupting compounds, pharmaceuticals, and personal care products in the Han River (Seoul, South Korea)

The occurrence of 31 selected endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in Korean surface waters was investigated. The area was selected since there is a lack of information in the Seoul area on the suspected contamination of rivers by micropollutants, although over 99% of drinking water is produced from surface waters in this area that has a population of approximately 15 million inhabitants. Samples were collected from upstream/downstream and effluent-dominated creeks along the Han River, Seoul (South Korea) and analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). Most target compounds were detected in both the Han River samples (63%) and the effluent-dominated creek samples (79%). Iopromide, atenolol, TCPP, TECP, musk ketone, naproxen, DEET, carbamazepine, caffeine, and benzophenone were frequently detected in both river and creek samples, although the mean concentrations in effluent-dominated creek samples (102 ng/L-3745 ng/L) were significantly higher than those in river samples (56 ng/L-1013 ng/L). However, the steroid hormones 17β-estradiol, 17α-ethynylestradiol, progesterone, and testosterone, were not detected (< 1 ng/L) in both the river and creek samples. Numerous target compounds (15) were found to be positively correlated (over 0.8) to the conventional water quality parameters (chemical oxygen demand, biochemical oxygen demand, dissolved organic carbon, and ultraviolet absorbance). Results of this study provide increasing evidence that certain EDCs and PPCPs commonly occur in the Han River as the result of wastewater outfalls.     

The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK

The presence and fate of 56 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) were investigated in the South Wales region of the UK. Two contrasting rivers: River Taff and River Ely were chosen for this investigation and were monitored for a period of 10 months. The impact of the factors affecting the levels of concentration of PPCPs and illicit drugs in surface water such as surrounding area, proximity to wastewater effluent and weather conditions, mainly rainfall was also investigated. Most PPCPs were frequently found in river water at concentrations reaching single microgL(-1) and their levels depended mainly on the extent of water dilution resulting from rainfall. Discharge of treated wastewater effluent into the river course was found to be the main cause of water contamination with PPCPs. The most frequently detected PPCPs represent the group of pharmaceuticals dispensed at the highest levels in the Welsh community. These were antibacterial drugs (trimethoprim, erythromycin-H(2)O and amoxicillin), anti-inflammatories/analgesics (paracetamol, tramadol, codeine, naproxen, ibuprofen and diclofenac) and antiepileptic drugs (carbamazepine and gabapentin). Only four PPCPs out of 56 (simvastatin, pravastatin, digoxin and digoxigenin) were not quantified over the course of the study. Several PPCPs were found to be both ubiquitous and persistent in the aqueous environment (e.g. erythromycin-H(2)O, codeine, carbamazepine, gabapentin and valsartan). The calculated average daily loads of PPCPs indicated that in total almost 6 kg of studied PPCPs are discharged daily into the studied rivers. The illicit drugs studied were found in rivers at low levels of ng L(-1). Average daily loads of amphetamine, cocaine and its main metabolite benzoylecgonine were as follows: 8, 1.2 and 39 gday(-1), respectively. Their frequent occurrence in surface water is primarily associated with their high illegal usage and is strongly associated with the discharge of insufficiently treated wastewater effluent.     

Oestrogens and oestrogenic activity in raw and treated water in Severn Trent Water

Sewage effluent discharged to surface water has been shown to contain human hormones, particularly oestrogens, and synthetic chemicals which may be able to disrupt the endocrine system. Since many surface waters which receive sewage effluent are subsequently used as drinking water sources, it is important to demonstrate that treated drinking water is not contaminated. Oestrogenic activity in rivers and drinking water in the region of Severn Trent Water was studied using a combination of bioassay, to integrate exposure over time, and advanced chemical analysis. There was little or no evidence of substances that were oestrogenic, even in waters receiving significant amounts of sewage effluent. Oestrogenic activity, as measured in the rainbow trout vitellogenin assay, was seen at the Tame/Trent confluence but this activity was relatively weak. There was no activity detected at raw water intakes and no hormones or substances that are oestrogenic were detected in the final drinking water.     

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.     

Vorkommen und Verhalten eines Arzneimittels (Clofibrinsäure) im Grundwasser

As to nowadays knowledge drugs in groundwater originate from anthropogenic input by urine and production residue. Clofibric acid, a blood lipid regulator is one of the human drugs already detected in groundwater and drinking water with concentrations of up to 7300 ng/l. Recent investigations indicate, that some drugs are insufficiently or not degraded by sewage treatment or by drinking water production. Groundwater contamination is likely to be due to leaky sewage systems, influent streams and bank infiltration. The distribution of clofibric acid beneath the sewage farms south of Berlin shows the high mobility of this contaminant. Nevertheless, results indicate that there is no correlation between the concentrations of clofibric acid and physico-chemical parameters, groundwater constituents nor sediment material. First results of a column experiment show that clofibric acid is transported with tracer velocity, although some variations in concentration of clofibric acid occur. Again, no correlation between clofibric acid and pH, oxygen content nor the concentration of groundwater constituents has been found whereas a possible dependence of the redox potential on clofibric acid was observed. During the column experiment no sorption processes could be identified, but there were hints for a degradation of clofibric acid.     

The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters

A 5-month monitoring program was undertaken in South Wales in the UK to determine the fate of 55 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) in two contrasting wastewater plants utilising two different wastewater treatment technologies: activated sludge and trickling filter beds. The impact of treated wastewater effluent on the quality of receiving waters was also assessed.PPCPs were found to be present at high loads reaching 10 kg day⁻¹ in the raw sewage. Concentrations of PPCPs in raw sewage were found to correlate with their usage/consumption patterns in Wales and their metabolism. The efficiency of the removal of PPCPs was found to be strongly dependent on the technology implemented in the wastewater treatment plant (WWTP). In general, the WWTP utilising trickling filter beds resulted in, on average, less than 70% removal of all 55 PPCPs studied, while the WWTP utilising activated sludge treatment gave a much higher removal efficiency of over 85%. The monitoring programme revealed that treated wastewater effluents were the main contributors to PPCPs concentrations (up to 3 kg of PPCPs day⁻¹) in the rivers studied. Bearing in mind that in the cases examined here the WWTP effluents were also major contributors to rivers' flows (dilution factor for the studied rivers did not exceed 23 times) the effect of WWTP effluent on the quality of river water is significant and cannot be underestimated.     

Organic micropollutant removal in a full-scale surface flow constructed wetland fed with secondary effluent

The mass emission rate of 12 pollutants from a wastewater treatment plant (WWTP) secondary effluent into a small tributary of the River Besòs (northeastern Spain) was determined. The pollutants tested included pharmaceutical and personal care products (PPCPs) and herbicides. Furthermore, a 1-ha surface flow constructed wetland (SFCW) was evaluated for pollution removal. Whereas the low concentration values (ngL(-1)) of PPCP discharge into the tributary was comparable to inter- and intra-campaigns, herbicides and a veterinary drug (flunixin) exhibited a high variability in concentrations (microgL(-1)). Moreover, removal efficiencies were often higher than 90% for all compounds, with the exception of carbamazepine and clofibric acid (ca. 30-47%). As expected, a seasonal trend of pollutant removal in the wetland was observed for compounds with low biodegradation and moderate photodegradation rates (i.e. naproxen and diclofenac).     

Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry

An analytical method for phenolic endocrine disrupting chemicals and acidic pharmaceuticals in river water was developed using gas chromatography mass spectrometry (GC-MS) coupled with negative chemical ionization (NCI) technique, and used for the determination of these compounds in the Pearl Rivers (Liuxi, Zhujiang and Shijing Rivers). Derivatization using pentafluorobenzoyl chloride (PFBOCl) and pentafluorobenzyl bromide (PFBBr) before GC-MS analysis were applied and optimized for phenolic compounds and acidic compounds, respectively. The target compounds were analyzed for river waters from the upstream to downstream of the Pearl Rivers. Phenolic compounds 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), bisphenol-A (BPA), estrone (E1), estradiol (E2) and triclosan (TCS) were detected at trace or low levels in the water samples from Liuxi River and Zhujiang River. Diethylstilbestrol (DES) was not detected in the Pearl Rivers. The highest concentrations of the phenolic compounds were found in Shijing River, and they were 3150 ng/L for 4-t-OP, 11,300 ng/L for 4-NP, 1040 ng/L for BPA, 79 ng/L for E1, 7.7 ng/L for E2 and 355 ng/L for TCS, respectively. Only a few acidic pharmaceuticals were detected at low concentrations in water from Liuxi River and Zhujiang River, but the highest concentrations for the acidic pharmaceuticals were also found in Shijing River. The highest concentrations detected for clofibric acid, ibuprofen, gemfibrozil, naproxen, mefenamic acid and diclofenac were 17 ng/L, 685 ng/L, 19.8 ng/L, 125 ng/L, 24.6 ng/l and 150 ng/L, respectively. The results suggest Liuxi and Zhujiang Rivers are only slightly contaminated and can be used as drinking water sources, but Shijing River is heavily polluted by the wastewater from nearby towns.     

Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden

The occurrence and removal rate of seven pharmaceuticals (ibuprofen, naproxen, diclofenac, fluoxetine, ofloxacin, norfloxacin, ciprofloxacin), two metabolites (norfluoxetine, clofibric acid), one degradation product (4-isobutylacetophenone) and 3 estrogens (17α-ethinylestradiol, 17β-estradiol, estrone) were studied in the inlet and outlet of a tertiary sewage treatment plant (STP) in Sweden as well as between different treatment steps in the STP which includes a conventional activated sludge step. Pharmaceuticals in raw household and raw hospital sewage streams leading to the STP were as well investigated. Hydraulic retention times (HRT) of each treatment step was considered for sampling and for the calculation of the removal rates. These rates were above 90%, except for diclofenac, clofibric acid, estrone and ofloxacin. However, only diclofenac and naproxen showed significant effluent loads (> 145 mg/d/1000 inh). Diclofenac was not eliminated during the treatment and in fact even higher concentrations were found at the effluent than in the inlet of the STP. 17α-Ethinylestradiol was not detected in any of the samples. Results indicate that a STP such as the one in Kristianstad, Sweden, with a tertiary treatment is sufficient to remove significantly most of the investigated pharmaceuticals. The chemical treatment improved the removal of several pharmaceuticals especially the antibiotics, which showed step removal rates between 55 and 70%. The expected concentration levels of the pharmaceuticals in the surface water (dilution 1 to 10) close to the outlet of the STP are below the no-observed effect-concentration (NOEC). However, despite that this would imply no important effects in the aquatic environment one cannot rule out negative consequences nearby the STP because most of the NOEC values are derived from acute toxicity data. This may underestimate the real impact of pharmaceuticals in the aquatic ecosystem.     

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.     

Biological removal of pharmaceuticals and personal care products during laboratory soil aquifer treatment simulation with different primary substrate concentrations

Pharmaceuticals and personal care products (PPCPs) have been detected in bodies of water worldwide, yet their effects on the environment are not fully understood. Recent toxicity studies suggest that mixtures of PPCPs at low concentrations may be detrimental to exposed organisms, highlighting the need to remove PPCPs from wastewater treatment plant effluent before it is discharged to the environment. In this study, the utility of biofilm-based PPCP removal as a means to prevent environmental PPCP contamination was investigated. The removal of 14 PPCPs, each at an initial concentration of 10 μg/L, was studied in laboratory sand columns inoculated with wastewater treatment plant effluent. The examined PPCPs included biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, sodium diclofenac, gabapentin, gemfibrozil, 5-fluorouracil, ibuprofen, ketoprofen, naproxen, triclosan, and valproic acid. Ten of the PPCPs were removed by greater than 95% during column passage, while the four other compounds proved more recalcitrant. The effect of the concentration (either 50 or 1000 μg/L) of an easily degradable primary substrate (acetate) supplied along with the mixture of PPCPs was examined. Most of the tested PPCPs were removed consistently by the biofilms regardless of the concentration of acetate, although the extent of removal for three compounds showed dependence on acetate concentration, and two behaved with no reproducible pattern over time. Biofilm protein measurements indicated that the mixture of PPCPs supplied to columns suppressed biofilm growth, suggesting toxicity of the PPCPs to the biofilm communities. This laboratory-scale experiment suggests that biofilm-based water treatment strategies, such as soil aquifer treatment and slow sand filtration, may be well-suited for the removal of many PPCPs from impacted water.     

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.     

Pharmaceutical and personal care products in tile drainage following land application of municipal biosolids

Land application of municipal biosolids (sewage) is a common farming practice in many parts of the world. There is potential for transport of pharmaceuticals and personal care products (PPCPs) from agricultural fields to adjacent surface waters via tile drainage systems. In this study, liquid municipal biosolids (LMB) (total solids=11,933 mg L(-1)), supplemented with selected PPCPs and the fluorescent dye tracer rhodamine WT (RWT), were applied to tile drained fields using two land application approaches. Objectives included evaluating the relative benefits of land application practices with respect to reducing PPCP loadings to tile drains, evaluating PPCP persistence in tile water, and determining whether rhodamine WT can be used to estimate PPCP mass loads in tile. The PPCPs examined included an antibacterial agent used in personal care products (triclosan), a metabolite of nicotine (cotinine), and a variety of drugs including two sulfonamide antimicrobials (sulfapyridine, sulfamethoxazole), a beta-blocker (atenolol), an anti-epileptic (carbamazepine), an antidepressant (fluoxetine), analgesic/anti-inflammatories (acetaminophen, naproxen, ibuprofen), and a lipid-regulator (gemfibrozil). Maximum observed PPCP concentrations in the spiked LMB were about 10(3) ng g(-1) dry weight. PPCPs were shown to move rapidly via soil macropores to tile drains within minutes of the land application. Maximum observed PPCP concentrations in tile effluent associated with the LMB application-induced tile flow event were approximately 10(1) to 10(3) ng L(-1). PPCP mass loads, for the application-induced tile-hydrograph event, were significantly (p<0.1) higher for surface spreading over non-tilled soil (incorporation tillage occurring 20 h post-application), relative to aerating soil immediately prior to surface spreading using an AerWay slurry deposition system. PPCP concentrations that were detected above the limit of quantitation (LOQ) in tile water during several precipitation-induced tile flow events that occurred post-application, included: triclosan (max. approximately 1.5 x 10(2) ng L(-1)), carbamazepine (max. approximately 7 x 10(1) ng L(-1)), atenolol (max approximately 4 x 10(1) ng L(-1)), and cotinine (max approximately 2 x 10(1) ng L(-1)). In spite of their presence in biosolids, the other PPCPs were not observed above LOQ concentrations during these events. PPCP concentrations were predicted from RWT concentrations over a 40 day study period. Tile mass loads as a percent of PPCP mass applied to soil ranged from 4.2%+/-SD of 9.2% to 7.1%+/-10.9% for the AerWay system and surface spreading plus incorporation treatments, respectively.     

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.     

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).     

Seasonal variations of several pharmaceutical residues in surface water and sewage treatment plants of Han River, Korea

We collected influent and effluent samples from four sewage treatment plants (STPs) as well as surface water samples in Han River of Seoul, Korea, in three sampling events representing different flow conditions, i.e., April, June, and August, 2005, and analyzed for eleven pharmaceuticals including acetaminophen, caffeine, carbamazepine, cimetidine, diltiazem, trimethoprim, and five sulfonamide antibiotics, using LC-MS-ESI. Pharmaceuticals of high annual production amount were detected in higher level in STP influents. Levels of pharmaceutical residues in the influents were the highest for acetaminophen (average 27,089 ng/L), followed by caffeine (23,664 ng/L), cimetidine (8045 ng/L), and sulfamethoxazole (523 ng/L). Levels of acetaminophen and caffeine in STP effluents were very low compared to the influent concentrations. However cimetidine was detected in relatively high levels even in STP effluent samples. In effluent samples, cimetidine showed the highest level (5380 ng/L), followed by caffeine (278 ng/L), sulfamethoxazole (193 ng/L), and carbamazepine (111 ng/L). The concentration of cimetidine was also the highest in surface water samples (average 281 ng/L), which is the highest level reported from surface water worldwide to our knowledge. Caffeine (268.7 ng/L), acetaminophen (34.8 ng/L), and sulfamethoxazole (26.9 ng/L) were also detected in relatively high levels. Levels of pharmaceuticals detected in surface water samples upstream STPs were generally very low compared to the downstream samples, suggesting that the STPs potentially be a major source of the test pharmaceuticals into Han River. The hazard quotients (HQs) were calculated for the test pharmaceuticals based on their occurrences in surface water, and no pharmaceutical resulted in HQ greater than one, suggesting that their potential environmental impact may be low.     

Distribution of estrogens, 17beta-estradiol and estrone, in Canadian municipal wastewater treatment plants

The distribution of female hormones, 17beta-estradiol and estrone, was determined in effluents of 18 selected municipal treatment plants across Canada. Replicate 24-h composite samples were collected from the influent and final effluent of each treatment plant, and the removal efficiency compared to the operational characteristics of the plants. In conventional activated sludge and lagoon treatment systems, the mean concentrations of 17beta-estradiol and estrone in influent were 15.6 ng/l (range 2.4-26 ng/l) and 49 ng/l (19-78 ng/l). In final effluents, the mean concentrations of both 17beta-estradiol and estrone were reduced to 1.8 ng/l (0.2-14.7 ng/l) and 17 ng/l (1-96 ng/l), respectively. 17beta-estradiol was removed effectively, >75% and as high as 98%, in most of the conventional mechanical treatment systems with secondary treatment. The removal of estrone was much more complex with removal varying from 98% to situations where the concentrations in the effluent were elevated above that detected in the influent. The estrogenicity, measured using a transfected estrogen receptor in yeast (YES) assay, was also variable, ranging from high removal to elevations of estrogenicity in final effluent. Although the apparent removals were not statistically correlated with either hydraulic (HRT) or solid (SRT) retention times, plants or lagoons with high SRT were very effective at reducing the levels of hormones. Well-operated plants that achieved nitrification also tended to have higher removal of hormones than those that did not nitrify. Laboratory aerobic reactor experiments confirmed the rapid removal of 17beta-estradiol, estrone, and estrogenicity when exposed to sewage slurries.