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.     

Assessing the removal of pharmaceuticals and personal care products in a full-scale activated sludge plant

Purpose

This study aimed to investigate the removal mechanisms of pharmaceutical active compounds (PhACs) and musks in a wastewater treatment plant (WWTP). Biological removal and adsorption in the activated sludge tank as well as the effect of UV radiation used for disinfection purposes were considered when performing a mass balance on the WWTP throughout a 2-week sampling campaign.

Methods

Solid-phase extraction (SPE) was carried out to analyse the PhACs in the influent and effluent samples. Ultrasonic solvent extraction was used before SPE for PhACs analysis in sludge samples. PhAC extracts were analysed by LC-MS. Solid-phase microextraction of liquid and sludge samples was used for the analysis of musks, which were detected by GC-MS. The fluxes of the most abundant compounds (13 PhACs and 5 musks) out of 79 compounds studied were used to perform the mass balance on the WWTP.

Results

Results show that incomplete removal of diclofenac, the compound that was found in the highest abundance, was observed via biodegradation and adsorption, and that UV photolysis was the main removal mechanism for this compound. The effect of adsorption to the secondary sludge was often negligible for the PhACs, with the exceptions of diclofenac, etofenamate, hydroxyzine and indapamide. However, the musks showed a high level of adsorption to the sludge. UV radiation had an important role in reducing the concentration of some of the target compounds (e.g. diclofenac, ibuprofen, clorazepate, indapamide, enalapril and atenolol) not removed in the activated sludge tank.

Conclusions

The main removal mechanism of PhACs and musks studied in the WWTP was most often biological (45%), followed by adsorption (33%) and by UV radiation (22%). In the majority of the cases, the WWTP achieved >75% removal of the most detected PhACs and musks, with the exception of diclofenac.     

中型污水处理厂中药物和个人护理品的分布与去除

为了解15种药物及个人护理用品(PPCPs)在中小型污水处理厂中的分布及其去除效果,采用液相色谱-串联质谱(LC-MS/MS)技术对3座A2/O工艺的污水处理厂水样进行分析研究。结果显示,除普萘洛尔、吉非罗平和吲哚美辛在3座中小型污水处理厂各个工艺单元中均未被检出外,其余12种目标化合物的检出频率在90%~100%之间。进水水样中PPCPs的平均检出浓度为2 285.4 ng/L,其中咖啡因(CF)的平均检出浓度最高为973.3 ng/L,酮洛芬(KP)的平均检出浓度次之为844.7 ng/L,两者之和占进水水样中PPCPs平均含量的79.5%,表明污水处理厂的主要污染物为CF和KP。3座污水处理厂对CF的去除效果最为显著,平均去除率为95.3%,对15种PPCPs总去除效率在39.3%~82.8%之间。     

污水处理中几种去除药物及个人护理用品方法的机理及效果比较

目前广泛分布在环境中的药物及个人护理品（pharmaceuticals and personal care products, PPCPs）在环境中的迁移、转化和处理已成为环境科学与工程研究的一个新的领域。污水处理厂排水是PPCPs进入环境中的主要途径。介绍了污水处理过程中传统活性污泥法、膜处理技术以及氧化处理等主要工艺对PPCPs的去除机理,并对去除效果进行了比较。以传统活性污泥法及在其改进后的膜处理技术为基础的大部分现有污水处理厂只能够去除一部分PPCPs,并且主要通过吸附（如对于吐纳麝香、佳乐麝香、萨利麝香等脂溶性较高的有机物）和生物降解作用（如对于布洛芬,17β-雌二醇,雌酮等易反应的有机物）。然而,吸附了PPCPs的污泥通过土壤施肥又将PPCPs带入土壤中,进而会渗滤到地下水,或随径流水进入地表水中。因此,PPCPs并没有从根本上得以去除。相比之下氧化处理工艺（如氯化、臭氧氧化、紫外辐射）或这些工艺的组合能够将大部分的PPCPs进行氧化,去除效果明显优于以上2种技术。然而,氧化后产物的种类和毒理性需要更深入的研究。     

(AO)_2SBR同步脱氮除磷的研究

以人工配水为研究对象,采用厌氧/好氧/缺氧/好氧交替运行的序批式反应器,研究了(AO)2SBR系统同步脱氮除磷的效果,并结合批式实验讨论了同步脱氮除磷的反应机理。研究结果表明,该系统以厌氧1.5 h、好氧1 h、缺氧3h、好氧0.5 h的方式运行,在DO=2.5 mg/L,SRT=15 d的条件下,具有良好的脱氮除磷效果,配水中的总氮、总磷、COD和总有机碳的去除率分别为96.26%、99.87%、90.46%和85.57%。批式实验表明,合成的内碳源越多,氨氮的硝化越充分,反硝化除磷越多。     

Characterizing the passage of personal care products through wastewater treatment processes.

Wastewater treatment facilities use secondary treatment to stabilize the effect of discharged effluent on receiving waters by oxidizing biodegradable organic matter and reducing suspended solids and nutrients. The process was never specifically intended to remove trace quantities of xenobiotics, such as endocrine-disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs). Nevertheless, European studies performed at bench-scale or at small facilities have demonstrated that a critical minimum solids retention time (SRT) can achieve good reduction of many EDCs and pharmaceuticals. The objective of this study was to expand these findings to the removal performance for 20 PPCPs commonly found in the influent to full-scale facilities operating in the United States. The participating plants use SRT conditions ranging from 0.5 to 30 days and include facility capacities ranging from 19 000 m3/d (5 mgd) to greater than 1 136 000 m3/d (300 mgd). Two pilot membrane bioreactors were also included in the study. The 20 PPCPs were categorized into nine bin combinations of occurrence frequency and treatment reduction performance. While most compounds were well removed, galaxolide (a musk fragrance) occurred frequently and was resistant to removal. A minimum critical SRT, defined as the minimum SRT, needed to consistently demonstrate greater than 80% removal (SRT80), was compound-dependent, with most compounds removed at 5 to 15 days and a small group requiring longer SRTs. From limited data, no additional removal could be attributed to the use of membrane bioreactors, media filters, or longer hydraulic retention times. Reverse osmosis was effective in removing any remaining compounds.     

西安市某污水处理厂A2/O工艺除磷效果分析

基于西安市污水处理厂出水一级A达标排放的要求,对西安市某污水处理厂A2/O工艺运行效果进行监测分析,结果表明,该污水处理厂出水总磷一级A达标率仅为31.61%,出水总磷浓度偏高成为该污水处理厂一级A达标的限制因素。通过对污水处理厂现场调研与水质沿程监测分析发现,该污水处理厂污泥水中含有大量SS和TP,此部分污泥水回流至系统前端导致生物池进水总磷浓度急剧升高,生物池超负荷运行导致出水总磷偏高。同时由于生物池碳源不足,厌氧池释磷作用微弱,影响了系统的除磷效果。针对以上问题,进行了初沉池运行方式调整、强化污泥处理、出水增设滤池等一系列改造措施。改造后系统除磷效果明显提高,出水TP降低至（0.39±0.08）mg·L-1,基本可以达到一级A排放标准。     

Fate of pharmaceuticals and personal care products in wastewater treatment plants - Conception of a database and first results

We created a database in order to quantitatively assess the occurrence and removal efficiency of pharmaceuticals and personal care products (PPCPs) in wastewater treatment plants (WWTPs). From 117 scientific publications, we compiled 6641 data covering 184 PPCPs. Data included the concentrations of PPCPs in WWTP influents and effluents, their removal efficiency and their loads to the aquatic environment. The first outputs of our database allowed to identify the most investigated PPCPs in WWTPs and the most persistent ones, and to obtain reliable and quantitative values on their concentrations, frequency of detection and removal efficiency in WWTPs. We were also able to compare various processes and pointed out activated sludge with nitrogen treatment and membrane bioreactor as the most efficient ones.     

Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater

This study aimed to provide the first and comprehensive data on the occurrence of 17 target pharmaceuticals and personal care products (PPCPs) in urban water environment in Singapore. Meanwhile, this study also verified the suitability of these PPCPs as specific markers of raw wastewater contamination in receiving water bodies in highly urbanized areas where both surface water and groundwater are not impacted by the discharge of treated wastewater effluents. Analytical results of wastewater showed that among 17 target PPCPs examined, only 5 PPCPs were detected in 100 % of raw wastewater samples, including acetaminophen (ACT), carbamazepine (CBZ), caffeine (CF), diethyltoluamide (DEET), and salicylic acid (SA). Similarly, these PPCPs were found in most surface water and groundwater. Interestingly, the three PPCPs (ACT, CBZ, and SA) were only detected in surface water and groundwater in the sampling sites close to relatively older sewer systems, while they were absent in background samples that were collected from the catchment with no known wastewater sources. This suggests that ACT, CBZ, and SA can be used as specific molecular markers of raw wastewater in surface water and groundwater. This study also confirmed that CF and DEET were not really associated with wastewater sources, thus cannot serve well as specific molecular markers of wastewater contamination in receiving water bodies. To the best knowledge of the authors, the use of ACT and SA as specific molecular markers of raw wastewater contamination in urban surface waters and groundwater was first reported. Further studies on the use of ACT, CBZ, and SA along with other chemical/microbial markers are recommended to identify and differentiate contamination sources of surface waters/groundwater.     

Endocrine disruptors compounds, pharmaceuticals and personal care products in urban wastewater: implications for agricultural reuse and their removal by adsorption process

In the last years, a lot of emerging contaminants, such as, endocrine disruptors compounds (EDCs), pharmaceuticals, and personal care products (PPCPs) have been detected in wastewater. Because of their toxicity and possible adverse effects on the environment and humans, their release from urban wastewater treatment plants (UWWTPs) effluents should be minimized, particularly when a wastewater reuse for crops irrigation is expected. Many processes have been investigated for advanced treatment of UWWTP effluents as well as for emerging contaminant degradation; among these, adsorption process was successfully used to remove EDCs and PPCPs from wastewater. This article shortly reviews EDCs and PPCPs removal from UWWTP effluents by adsorption process using conventional and non-conventional adsorbents. The fate of EDCs and PPCPs in UWWTPs and the implications for agricultural wastewater reuse has been addressed too. In spite of the adsorption process looking to be a valuable alternative to other advanced technologies for the removal of emerging contaminants from wastewater, some gaps still remain to evaluate the actual feasibility at full scale. However, according to a few studies available in scientific literature on the use of both powdered activated carbon and granular activated carbon at full scale, adsorption process by activated carbon is a promising, potentially effective, and economically feasible solution for producing safe wastewater for agricultural reuse.     

Removal and seasonal variability of selected analgesics/anti-inflammatory,anti-hypertensive/cardiovascular pharmaceuticals and UV filters in wastewater treatment plant

Seasonal removal efficiency of 16 pharmaceuticals and personal care products was monitored in a wastewater treatment plant in ?eské Budějovice, Czech Republic, over a period of 1 year (total amount of samples, n?=?272). The studied compounds included four UV filters, three analgesics/anti-inflammatory drugs and nine anti-hypertensive/cardiovascular drugs. In most cases, elimination of the substances was incomplete, and overall removal rates varied strongly from ?38 to 100 %. Therefore, it was difficult to establish a general trend for each therapeutic group. Based on the removal efficiencies (REs) over the year, three groups of target compounds were observed. A few compounds (benzophenon-1, valsartan, isradipine and furosemide) were not fully removed, but their REs were greater than 50 %. The second group of analytes, consisting of 2-phenylbenzimidazole-5-sulfonic acid, tramadol, sotalol, metoprolol, atenolol and diclofenac, showed a very low RE (lower than 50 %). The third group of compounds showed extremely variable RE (benzophenon-3 and benzophenon-4, codeine, verapamil, diltiazem and bisoprolol). There were significant seasonal trends in the observed REs, with reduced efficiencies in colder months.     

Occurrence and removal of pharmaceuticals in wastewater treatment plants at the Spanish Mediterranean area of Valencia

A survey on the presence of pharmaceuticals in urban wastewater of a Spanish Mediterranean area (Castellon province) was carried out. The scope of the study included a wide variety of pharmaceuticals belonging to different therapeutical classes. For this purpose, 112 samples, including influent and effluent wastewater, from different conventional wastewater treatment plants were collected. Two monitoring programmes were carried out along several seasons. The first was in June 2008 and January 2009, and the second in April and October 2009. During the first monitoring, the occurrence of 20 analytes in 84 urban wastewater samples (influent and effluent) was studied. The selection of these pharmaceuticals was mainly based on consumption. From these, 17 compounds were detected in the samples, with analgesics and anti-inflammatories, cholesterol lowering statin drugs and lipid regulators being the most frequently detected groups. 4-Aminoantipyrine, bezafibrate, diclofenac, gemfibrozil, ketoprofen, naproxen and venlafaxine were the compounds most frequently found. In the highlight of these results, the number of analytes was increased up to around 50. A lot of antibiotic compounds were added to the target list as they were considered “priority pharmaceuticals” due to their more potential hazardous effects in the aquatic environment. Data obtained during the second monitoring programme (spring and autumn) corroborated the results from the first one (summer and winter). Analgesics and anti-inflammatories, lipid regulators together with quinolone and macrolide antibiotics were the most abundant pharmaceuticals. Similar median concentrations were found over the year and seasonal variation was not clearly observed. The removal efficiency of pharmaceuticals in the wastewater treatment plants was roughly evaluated. Our results indicated that elimination of most of the selected compounds occurred during the treatment process of influent wastewater, although it was incomplete.     

Synthetic musks in the aquatic environment and personal care products in Shanghai, China

The concentrations and distributions of six polycyclic musks and two nitro musks in Suzhou Creek, influent/effluent of a sewage treatment plant (STP), and household commodities were investigated and discussed in this study. The levels of 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexa-methylcyclopenta(g)-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN) in Suzhou Creek were 3-78 ng g(-1) (dry weight) and 2-31 ng g(-1) (dry weight) in sediments, while 20-93 ng l(-1) and 8-20 ng l(-1) in surface waters. The results indicated a low proportion of wastewater burden in this river. The concentrations of HHCB and AHTN in the effluent of the STP were 5- to 6-fold higher than those in Suzhou Creek. The amounts discharged into the aquatic environment from sewage in Shanghai are 1.26 t (HHCB) and 0.38 t (AHTN) in 2007, and the input into the STPs is estimated to be HHCB 0.2 g y(-1) and AHTN 0.06 g y(-1) per inhabitant, respectively. A broad concentration range of HHCB and AHTN could be observed in household commodities. The distributions are in accordance with the profiles of musks in aquatic environment, with HHCB and AHTN being the major components.     

Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels

Purpose

We analyzed and compared the distributions of 13 target pharmaceuticals in different water samples from the Hangzhou metropolitan area and Linan County, Southeast China.

Methods

Sampling was conducted in five hospitals, two wastewater treatment plants (WWTPs), and Qiantang River. Samples were concentrated by solid-phase extraction and PPCP concentrations were determined by UPLC-MS/MS.

Results and discussion

Trimethoprim, erythromycin A dihydrate, norfloxacin, ofloxacin, diclofenac sodium, and atenolol were the most frequently detected pharmaceuticals in hospital effluents. Most of the pharmaceutical concentrations in hospital effluents were higher than those in the WWTP influents. Although both WWTPs adopt the anaerobic?Caerobic?Canoxic treatment process, the removal rates for pharmaceuticals, such as trimethoprim and diclofenac sodium, were completely different. Meanwhile, erythromycin A dihydrate, ofloxacin, penicillin-G, cephalexin, cefazolin, ibuprofen, and diclofenac sodium were detected in Qiantang River.

Conclusions

These results indicate that hospitals are more concentrated sources of pharmaceuticals than WWTPs, and the WWTPs are not the only route of entry of pharmaceuticals into aquatic environments in these two regions.     

Occurrence of phthalates in aquatic environment and their removal during wastewater treatment processes: a review

Phthalates are plasticizers and are concerned environmental endocrine-disrupting compounds. Due to their extensive usage in plastic manufacturing and personal care products as well as the potential to leach out from these products, phthalates have been detected in various aquatic environments including drinking water, groundwater, surface water, and wastewater. The primary source of their environmental occurrence is the discharge of phthalate-laden wastewater and sludge. This review focuses on recent knowledge on the occurrence of phthalate in different aquatic environments and their fate in conventional and advanced wastewater treatment processes. This review also summarizes recent advances in biological removal and degradation mechanisms of phthalates, identifies knowledge gaps, and suggests future research directions.     

焦化厂A/O出水中的有机污染物分析

采用色谱－质谱（GC／MS）联用仪分析和鉴定了上海宝钢焦化厂A／O生化阶段出水的有机污染物组成,共检出各类有机污染物70多种。结合焦化废水专用混凝剂的混凝处理实验结果,指出了各类有机污染物的去除情况。     

Occurrence of pharmaceutical and personal care products in Cau River,Vietnam

Environmental Science and Pollution Research - This study evaluated the occurrence of PPCPs in Cau River (Vietnam). Surface water and sediment samples were collected to determine PPCP...     

水解/AMBBR/好氧工艺和传统A/O工艺处理低碳源污水的对比研究

为提高低碳氮比污水中易生物降解有机物的含量,实验设计了水解(H)/移动床生物膜反应器(AMBBR)/好氧(O)工艺,并与传统A/O工艺对比,考察其作为低碳源污水脱氮工艺的可行性。通过小试对比低温下(10.9~13℃)两工艺中污泥的反硝化性能,并进行了实验室规模的中试运行。小试结果显示,AMBBR两相污泥对硝酸盐的去除率比单纯反硝化污泥高出19.4%。中试结果表明,相同的运行条件下,两工艺对COD和NH3-N的去除效率相当,但H/AMBBR/O工艺对总氮的去除效率均优于传统A/O工艺;在各自最优工况下,前者平均总氮去除率较后者高出22.39%,且前者通过剩余污泥的回流水解实现了部分污泥减量化,尤其是对于温暖地区,该工艺能够有效改善低碳源污水脱氮性能。     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

Occurrence and behaviour of pharmaceutical compounds in a Portuguese wastewater treatment plant: Removal efficiency through conventional treatment processes

Wastewater treatments can eliminate or remove a substantial amount of pharmaceutical active compounds (PhACs), but there may still be significant concentrations of them in effluents discharged into surface water bodies. Beirolas wastewater treatment plant (WWTP) is located in the Lisbon area and makes its effluent discharges into Tagus estuary (Portugal). The main objective of this study is to quantify a group of 32 PhACs in the different treatments used in this WWTP. Twelve sampling campaigns of wastewater belonging to the different treatments were made in 2013–2014 in order to study their removal efficiency. The wastewaters were analysed by solid phase extraction (SPE) and ultra-performance liquid chromatography coupled with tandem mass detection (UPLC–MS/MS). The anti-diabetics were the most frequently found in wastewater influent (WWI) and wastewater effluent (WWE) (208 and 1.7 μg/L, respectively), followed by analgesics/antipyretics (135 μg/L and < LOQ, respectively), psychostimulants (113 and 0.49 μg/L, respectively), non-steroidal anti-inflammatory drugs (33 and 2.6 μg/L, respectively), antibiotics (5.2 and 1.8 μg/L, respectively), antilipidemics (1.6 and 0.24 μg/L, respectively), anticonvulsants (1.5 and 0.63 μg/L, respectively) and beta blockers (1.3 and 0.51 μg/L, respectively). A snapshot of the ability of each treatment step to remove these target PhACs is provided, and it was found that global efficiency is strongly dependent on the efficiency of secondary treatment. Seasonal occurrence and removal efficiency was also monitored, and they did not show a significant seasonal trend.