Detection,occurrence and fate of 22 psychiatric pharmaceuticals in psychiatric hospital and municipal wastewater treatment plants in Beijing,China

The liquid chromatography–electrospray ionization-tandem mass spectrometer (LC–MS/MS) method coupled with an automated solid-phase extraction procedure has been developed to identify 22 psychiatric pharmaceuticals, including seven anxiolytic-sedative-hypnotics, six antidepressants, and nine anti-schizophrenia drugs, in wastewater samples from two psychiatric hospital wastewater treatment plants (P-WWTPs) and three municipal wastewater treatment plants (M-WWTPs) in Beijing, China. Analyte recoveries from spiking experiments in the WWTP influent and effluent at three concentrations ranged from 70% to 110%, excluding sulpiride, ziprasidone, and olanzapine. Method detection limits for five, eight, and nine analytes in the WWTP influent and effluent were 20–80, 1–16, and <1 ng L^?1, respectively. High psychiatric pharmaceutical concentrations (e.g., ～942 ng L^?1oxazepam, 5552–12,782 ng L^?1 clozapine, 2762–9832 ng L^?1sulpiride, and 2030–4967 ng L^?1quetiapine) were frequently observed in P-WWTP influent compared to M-WWTPs. Although P-WWTPs typically had higher removal rates, significantly higher concentrations of the target compounds were observed in the P-WWTP secondary effluent than in the M-WWTP influent (e.g., ～752 ng L^?1oxazepam, ～8183 ng L^?1 clozapine, ～10,833 ng L^?1sulpiride, and ～1168 ng L^?1quetiapine). Thus, the discharge control of psychiatric pharmaceuticals from psychiatric hospitals requires improvement.     

The occurrence of illicit and therapeutic pharmaceuticals in wastewater effluent and surface waters in Nebraska

The occurrence and estimated concentration of twenty illicit and therapeutic pharmaceuticals and metabolites in surface waters influenced by wastewater treatment plant (WWTP) discharge and in wastewater effluents in Nebraska were determined using Polar Organic Chemical Integrative Samplers (POCIS). Samplers were installed in rivers upstream and downstream of treated WWTP discharge at four sites and in a discharge canal at a fifth location. Based on differences in estimated concentrations determined from pharmaceuticals recovered from POCIS, WWTP effluent was found to be a significant source of pharmaceutical loading to the receiving waters. Effluents from WWTPs with trickling filters or trickling filters in parallel with activated sludge resulted in the highest observed in-stream pharmaceutical concentrations. Azithromycin, caffeine, 1,7-dimethylzanthine, carbamazepine, cotinine, DEET, diphenhydramine, and sulfamethazine were detected at all locations. Methamphetamine, an illicit pharmaceutical, was detected at all but one of the sampling locations, representing only the second report of methamphetamine detected in WWTP effluent and in streams impacted by WWTP effluent.     

Occurrence of pharmaceuticals in a municipal wastewater treatment plant: mass balance and removal processes

Occurrence and removal efficiencies of fifteen pharmaceuticals were investigated in a conventional municipal wastewater treatment plant in Michigan. Concentrations of these pharmaceuticals were determined in both wastewater and sludge phases by a high-performance liquid chromatograph coupled to a tandem mass spectrometer. Detailed mass balance analysis was conducted during the whole treatment process to evaluate the contributing processes for pharmaceutical removal. Among the pharmaceuticals studied, demeclocycline, sulfamerazine, erythromycin and tylosin were not detected in the wastewater treatment plant influent. Other target pharmaceuticals detected in wastewater were also found in the corresponding sludge phase. The removal efficiencies of chlortetracycline, tetracycline, sulfamerazine, acetaminophen and caffeine were >99%, while doxycycline, oxytetracycline, sulfadiazine and lincomycin exhibited relatively lower removal efficiencies (e.g., <50%). For sulfamethoxazole, the removal efficiency was approximately 90%. Carbamazepine manifested a net increase of mass, i.e. 41% more than the input from the influent. Based on the mass balance analysis, biotransformation is believed to be the predominant process responsible for the removal of pharmaceuticals (22% to 99%), whereas contribution of sorption to sludge was relatively insignificant (7%) for the investigated pharmaceuticals.     

Fate of selected pharmaceuticals in river waters

The aqueous environmental fate of two antibiotics, lincomycin and clarithromycin, and an antiepileptic drug, carbamazepine, was investigated by monitoring drugs decomposition and identifying intermediates in Po river water (North Italy). Initially, control experiments in the dark and under illumination were performed on river water spiked with drugs to simulate all possible transformation processes occurring in the aquatic system. Under illumination, these pharmaceuticals were degraded and transformed into numerous organic intermediate compounds. Several species were formed and characterised by analysing MS and MS ⁿ spectra and by comparison with parent molecule fragmentation pathways. River water was sampled at three sampling points in an urban area. The selected pharmaceuticals were detected in all samples. Eight transformation products identified in the laboratory simulation were found in natural river water from carbamazepine degradation, three from clarithromycin and two from lincomycin. Their transformation occurring in aquatic system mainly involved mono- and poly-hydroxylation followed by oxidation of the hydroxyl groups.     

Occurrence of endocrine disrupters and selected pharmaceuticals in Aisonas River (Greece) and environmental risk assessment using hazard indexes

Purpose

The presence of four phenolic endocrine disrupting compounds (EDCs: nonylphenol [NP], NP monoethoxylate[NP1EO], bisphenol A [BPA], triclosan, [TCS]) and four nonsteroidal anti-inflammatory drugs (NSAIDs: ibuprofen[IBF], ketoprofen [KFN], naproxen [NPX], diclofenac [DCF]) in a Greek river receiving treated municipal wastewater was investigated in this study.

Methods

Samples were taken from four different points of the river and from the outlet of a sewage treatment plant (STP) during six sampling campaigns, and they were analyzed using gas chromatography?Cmass spectrometry.

Results

According to the results, EDCs were detected in almost all samples, whereas NSAIDs were detected mainly in wastewater and in the part of the river that receives wastewater from the STP. Among the target compounds, the highest mean concentrations in the river were detected for NP (1,345?ng?L^?1) and DCF (432?ng?L^?1). Calculation of daily loads of the target compounds showed that STP seems to be the major source of NSAIDs to the river, whereas other sources contribute significantly to the occurrence of EDCs. The environmental risk due to the presence of target compounds in river water was estimated, calculating risk quotients for different aquatic organisms (algae, daphnids, and fish). Results denoted the possible threat for the aquatic environment due to the presence of NP and TCS in the river.     

微絮凝-直接过滤工艺在城市污水深度处理中的应用研究

微絮凝 -直接过滤工艺是一种将混凝反应、沉淀截留集中在同一滤柱内同步完成的高效水处理工艺。该工艺应用于城市污水的深度处理中 ,通过絮凝剂的加入 ,具有同步去除PO3 -4 P、SS和部分COD的功能。本文研究了该工艺对二级处理出水中PO3 -4 P、SS和COD的去除效果及其规律。研究表明 :采用聚合氯化铁 (PFC)作为絮凝剂 ,当Fe/P摩尔比为 2∶1时 ,水中PO3 -4 P的去除率达 98.8% ,浓度可降至 0 .1mg/L以下 ,同时SS、COD去除率也有明显提高。与传统的混凝、沉淀除磷工艺相比 ,该工艺具有操作简单、结构紧凑、占地面积小、污泥量少等优点 ,是一种更为经济和简单的处理单元 ,适用于现有城市污水处理厂的除磷和进一步提高水质的深度处理     

Occurrence, fate and assessment of polar metamizole (dipyrone) residues in hospital and municipal wastewater

The occurrence and fate of residues from the therapeutic use of the non-steroidal anti-inflammatory drug metamizole have been studied in investigations of sewage effluents from a military hospital, municipal sewers and a sewage treatment plant (STP) in Berlin, Germany. The loads of the metabolites aminoantipyrin (AA), 4-acetylaminoantipyrin (AAA) and 4-formyl-aminoantipyrin (FAA), rapidly formed after the application of metamizole, were predicted from pharmacokinetic data and based on the evaluation of extensive data sets of on the administration in hospitals and private households. In parallel, the actual concentrations were measured within three field trials. For the military hospital, the estimated average annual discharges of AA/AAA and FAA were 10.5 and 3.2 kg, respectively. For the STP, annual loads of 333 and 133 kg were determined for AA/AAA and FAA, respectively. During sewage treatment, an average decrease of 26% of the loads was measured for AA/AAA whereas no changes were observed for FAA. Generally, the prediction of the loads resulted in an overestimation of the residue levels compared to those measured in the respective sewers. Thus, modeling of predicted loads or concentrations alone will not be sufficient for a realistic assessment. Concerns for human or other mammals' health are not expected from the occurrence of metamizole residues in the aquatic system measured at concentrations up to 7 microg l(-1) in STP effluents. However, a rest of uncertainty remains as it was not possible to derive a no observed effect level for the induction of rare but potentially fatal toxicological side effects reported for metamizole.     

Determination of beta-adrenergic receptor blocking pharmaceuticals in United States wastewater effluent

Beta adrenergic receptor antagonists (beta-Blockers) are frequently prescribed medications in the United States and have been identified in European municipal wastewater effluent, however no studies to date have investigated these compounds in United States wastewater effluent. Municipal wastewater effluent was collected from treatment facilities in Mississippi, Texas, and New York to investigate the occurrence of metoprolol, nadolol, and propranolol. Propranolol was identified in all wastewater samples analyzed (n = 34) at concentrations < or = 1.9 microg/l. Metoprolol and nadolol were identified in > or = 71% of the samples with concentrations of metoprolol < or = 1.2 microg/l and nadolol < or = 0.36 microg/l. Time course studies at both Mississippi plants and the Texas plant indicate that concentrations of propranolol, metoprolol, and nadolol remain relatively constant at each sampling period. This study indicates that beta-Blockers are present in United States wastewater effluent in the ng/l to microg/l range.     

Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge

The presence of pharmaceuticals in aquatic environment has become a topic of concern because of their potential adverse effects on human health and wildlife species. A total of 45 dewatered sewage sludge samples were collected throughout China and analyzed for 30 commonly consumed pharmaceutical residues. Ofloxacin was found to be the dominant contaminant with concentrations up to 24 760 μg kg⁻¹, followed by oxytetracycline (5280 μg kg⁻¹), norfloxacin (5280 μg kg⁻¹) and ketoprofen (4458 μg kg⁻¹). The concentration of pharmaceutical residues varied greatly depending on the operation conditions of wastewater treatment plants and sampling locations. Poor agreement was found between the predicted (calculation based on the annual consumption and coefficient of sludge water partition) and detected concentrations of the pharmaceuticals indicating that the occurrence of pharmaceutical residues was affected by various factors such as loading rates, sewage properties and the chemical properties such as the contribution from polar groups. National wide fate and ecotoxicity study is required for the development of control strategies.     

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.     

Molecular docking: A potential tool to aid ecotoxicity testing in environmental risk assessment of pharmaceuticals

A cocktail of human pharmaceuticals pollute aquatic environments and there is considerable scientific uncertainty about the effects that this may have on aquatic organisms. Human drug target proteins can be highly conserved in non target species suggesting that similar modes of action (MoA) may occur. The aim of this work was to explore whether molecular docking offers a potential tool to predict the effects of pharmaceutical compounds on non target organisms. Three highly prescribed drugs, diclofenac, ibuprofen and levonorgestrel which regularly pollute freshwater environments were used as examples. Their primary drug targets are cyclooxygenase 2 (COX2) and progesterone receptor (PR). Molecular docking experiments were performed using these drugs and their primary drug target homologues for Danio rerio, Salmo salar, Oncorhynchus mykiss, Xenopus tropicalis, Xenopus laevis and Daphnia pulex. The results show that fish and frog COX2 enzymes are likely to bind diclofenac and ibuprofen in the same way as humans but that D. pulex would not. Binding will probably lead to inhibition of COX function and reduced prostaglandin production. Levonorgestrel was found to bind in the same binding pocket of the progesterone receptor in frogs and fish as the human form. This suggests implications for the fecundity of fish and frogs which are exposed to levonorgestrel. Chronic ecotoxicological effects of these drugs reported in the literature support these findings. Molecular docking may provide a valuable tool for ecotoxicity tests by guiding selection of test species and incorporating the MoA of drugs for relevant chronic test end points in environmental risk assessments.     

Simultaneous removal of emerging contaminants and disinfection for municipal wastewater treatment plant effluent quality improvement: a systemic analysis of the literature

Environmental Science and Pollution Research - This work presents a bibliographic review of the literature regarding the simultaneous removal of contaminants of emerging concern (CECs) and...     

Fate of sex hormones in two pilot-scale municipal wastewater treatment plants: conventional treatment

The fate of seven sex hormones (estrone (E1), estradiol (E2), estriol (E3), ethinylestradiol (EE2), testosterone, androstenedione, and progesterone) was determined in two pilot-scale wastewater treatment plants operated under conventional loading conditions. The levels of hormones in both the liquid and the solid matrixes of the plants were determined. Each of the two 20-l/h pilot-scale plants consisted of a primary clarifier followed by a three-stage aeration tank and a final clarifier. The primary sludge and the waste activated sludge (WAS) were digested anaerobically in one pilot plant and aerobically in the other. The pilot plants were fed a complex synthetic wastewater spiked with the hormones. Levels of testosterone, androstenedione and progesterone were close to method detection limit (MDL) concentrations in the final and digester effluents (both liquid and solid phases) and were considered as completely removed. Average mass flux removals from the liquid streams (plant influent minus secondary clarifier effluent) for the natural estrogens were 82% for E1, 99% for E2, and 89% for (E1+E2). An average overall removal of only 42% was achieved for EE2. These values reflect removals averaged for the two pilot plants.     

城市污水处理厂中全氟化合物的存在及去除效果研究

建立了一种基于超高效液相色谱/串联质谱的方法,实现了对北京3个污水处理厂污水中12种全氟化合物(PFCs)的快速、灵敏地定量分析.结果表明,城市污水处理厂进水和出水中短链的全氟丁酸(PFBA)、全氟戊酸(PFPA)和全氟丁磺酸(PFBS)是主要污染物,其中出水中PFBs的质量浓度高达253 ng/L.污水生物处理后,出...     

城市污水二级出水中溶解性有机物特性分析

分别采用凝胶色谱、亲疏水性组分分离、荧光色谱等方法,研究了城市污水处理厂二级出水中溶解性有机物的分子量分布、亲疏水组分含量以及荧光光谱特性。结果表明,二级出水中疏水性组分较亲水性组分多,疏水性组分约占总有机物的64.3%,而亲水性组分占35.7%左右;二级出水及其不同亲/疏水组分中溶解性有机物分子量分布基本集中在4.5 kDa以下,其中弱疏水性组分和亲水性组分中主要为分子量小于1.5 kDa的有机物;二级出水溶解性有机物中含有腐殖酸类、富里酸类以及蛋白质类物质,其中含量以腐殖酸类为主。     

Acidic pharmaceuticals in domestic wastewater and receiving water from hyper-urbanization city of China (Shanghai): environmental release and ecological risk

The occurrence, behavior, and release of five acidic pharmaceuticals, including ibuprofen (IBP), naproxen (NPX), ketoprofen (KEP), diclofenac (DFC), and clofibric acid (CA), have been investigated along the different units in a tertiary-level domestic wastewater treatment plant (WWTP) in hyper-urbanization city of China (Shanghai). IBP was the most abundant chemicals among the measured in raw wastewater. The loads of the acidic pharmaceuticals in the WWTP influent ranged from 7.5 to 414 mg/day/1,000 inh, which were lower than those reported in the developed countries suggesting a less per capita consumption of pharmaceuticals in Shanghai. IBP obtained by highest removal (87 %); NPX and KEP were also significantly removed (69–76 %). However, DFC and CA were only moderately removed by 37–53 %, respectively. Biodegradation seemed to play a key role in the elimination of the studied pharmaceuticals except for DFC and CA. An annual release of acidic pharmaceuticals was estimated at 1,499 and 61.7 kg/year through wastewater and sludge, respectively, from Shanghai. Highest pharmaceuticals concentrations were detected in the effluent discharge point of the WWTP, indicating that WWTP effluent is the main source of the acidic pharmaceuticals to its receiving river. Preliminary results indicated that only DFC in river had a high risk to aquatic organisms. Nevertheless, the joint toxicity effects of these chemicals are needed to further investigate.     

Mass flows and removal of antibiotics in two municipal wastewater treatment plants

The mass flows and removal of 20 antibiotics of seven classes in two wastewater treatment plants (WWTPs) of Hong Kong were investigated in different seasons of a whole year, using bihourly 24 h flow proportional composite samples. Antibiotics were detected at concentrations of 3.2-1718, 1.3-1176 and 1.1-233 ng L⁻¹ in influents, secondary and disinfection effluents. Total daily discharges of all the detected antibiotics from effluents of Shatin and Stanley WWTPs were 470-710 and 3.0-5.2 g d⁻¹, respectively. Ampicillin, cefalexin, sulfamethoxazole, sulfadiazine, sulfamethazine, chlortetracycline and vancomycin were effectively (52-100%) eliminated by activated sludge process while ampicillin and cefalexin were effectively (91-99%) eliminated by disinfection. Bihourly variation analysis showed that concentrations of the major antibiotics in influents varied more significantly in Stanley WWTP which served small communities.     

Analysis of organic nitrogen removal in municipal wastewater by reverse osmosis

The results of a pilot study that was conducted to determine the total nitrogen removal by the reverse osmosis process are presented. The organic nitrogen removal rates are compared with removals observed from three full-scale reverse osmosis facilities and four pilot studies. The results of this analysis suggest that organic nitrogen removal is variable and that reverse osmosis may not consistently produce total nitrogen levels less than 1.0 mg/L without additional treatment. Three hypotheses to explain the variability in organic nitrogen removal in the different data sets are presented.     

Carbamazepine and diclofenac: removal in wastewater treatment plants and occurrence in water bodies

In the aquatic environment, pharmaceuticals have been widely found. Among them, carbamazepine and diclofenac were detected at the highest frequency. To evaluate the worldwide environmental impacts of both drugs, their global consumption volumes are estimated, based on the dose per capita. The metabolites of these pharmaceuticals are also of environmental concerns, especially trans-10,11-dihydro-10,11- dihydroxycarbamazepine (CBZ-diol) which probably has a similar concentration in water bodies to that of its parent drug. The removal efficiencies and mechanisms of both drugs in the wastewater treatment plants (WWTPs) are discussed with the actual state of knowledge. The occurrences of both drugs are examined in various water bodies including WWTP effluents, surface waters, groundwater and drinking water. Their chemical, physical and pharmacological properties are also addressed in context, which can largely influence their environmental behaviors. The ecotoxicological studies of both drugs imply that they do not easily cause acute toxic effects at their environmental concentrations. However their chronic effects need cautious attention.