Pharmaceutical and personal care products (PPCPs) in urban receiving waters

The transport pathways of pharmaceutical and personal care products (PPCP) discharges within the urban water cycle include both combined and separate sewer systems with only the former receiving treatment. The dry-weather flow dilution patterns for selected PPCPs following discharge from a sewage treatment works (STW) to a North London stream indicate a persistent downstream increase in concentration. The dilution ratio analysis also indicates that the STW's final effluent only contributes a dilution of the endogenous concentrations already present in the river flow which reflects a progressive PPCP load with increasing urbanization; "worst-case" scenarios being probably related to wet-weather conditions. Maximum PPCP concentrations fall above the reported PEC levels and the analysis highlights the deficiencies of conventional acute toxicity for the evaluation of long-term effects of episodic urban discharges. Groundwater analysis points to sewer exfiltration which is limited in terms of PPCP impact to 25-50 cm depths.     

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.     

Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.     

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。     

Sorption and degradation of pharmaceuticals and personal care products (PPCPs) in soils

Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t _1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t _1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f _oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.     

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.     

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。     

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.     

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.     

Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identification

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ _1/2) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ_1/2 was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI^?-QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.     

Effects of soil moisture depletion on vegetable crop uptake of pharmaceuticals and personal care products (PPCPs)

Agricultural crops have a long history of being irrigated with recycled wastewater (RW). However, its use on vegetable crops has been of concern due to the potential prevalence of microcontaminants, such as pharmaceuticals and personal care products (PPCPs) in the latter, which represents a possible health hazard to consumers. We investigated the uptake of three PPCPs (atenolol, diclofenac, and ofloxacin), at three different concentrations in irrigation water (0.5, 5, and 25 μg L^?1) in relation to three varying volumetric soil moisture depletion levels of 14 % (?4.26 kPa), 10 % (?8.66 kPa), and 7 % (?18.37 kPa) by various vegetable crop species. Experiments were conducted in a split-split block completely randomized design. PPCPs were extracted using a developed method of accelerated solvent extraction and solid phase extraction and analyzed via liquid chromatography mass spectrometry (LCMS). Results indicate that all treated crops were capable of PPCP uptake at nanogram per gram concentrations independent of the applied soil moisture depletion levels and PPCP concentrations. Ofloxacin was the chemical with the highest uptake amounts, followed by atenolol and then diclofenac. Although the results were not statistically significant, higher concentrations of PPCPs were detected in plants maintained under higher soil moisture levels of 14 % (?4.26 kPa).     

Effects of pharmaceuticals and personal care products on marine organisms: from single-species studies to an ecosystem-based approach

Pharmaceuticals and personal care products (PPCPs) are contaminants of emerging concern that are increasing in use and have demonstrated negative effects on aquatic organisms. There is a growing body of literature reporting the effects of PPCPs on freshwater organisms, but studies on the effects of PPCPs to marine and estuarine organisms are limited. Among effect studies, the vast majority examines subcellular or cellular effects, with far fewer studies examining organismal- and community-level effects. We reviewed the current published literature on marine and estuarine algae, invertebrates, fish, and mammals exposed to PPCPs, in order to expand upon current reviews. This paper builds on previous reviews of PPCP contamination in marine environments, filling prior literature gaps and adding consideration of ecosystem function and level of knowledge across marine habitat types. Finally, we reviewed and compiled data gaps suggested by current researchers and reviewers and propose a multi-level model to expand the focus of current PPCP research beyond laboratory studies. This model includes examination of direct ecological effects including food web and disease dynamics, biodiversity, community composition, and other ecosystem-level indicators of contaminant-driven change.     

Removal of selected endocrine disrupting chemicals and personal care products in surface waters and secondary wastewater by ozonation

This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).     

Occurrences of pharmaceutical and personal care products as micropollutants in rivers from Romania

The occurrence of pharmaceutical and personal care products (PPCPs) was investigated in the Somes River. The aim of this study was to obtain a first overview about the contamination of Somes River (Transylvania) with PPCPs. The samples were preconcentrated by Solid Phase Extraction (SPE) procedures and analysed by GC/MS. A number of 15 compounds including pharmaceutics, metabolites, intermediates and musk fragrances were detected in concentration ranging from 30 ng/l to 10 μg/l. The detected pharmaceuticals are included in following therapeutic groups: analgesics, antiepileptics, psychiatric, stimulants, anticoagulants, antineoplastic and disinfectants.     

污染防治微生物制剂在城市河流污染控制中的应用及其生物安全

简要论述了污染防治微生物制剂的概念和在城市河流污染控制中的应用,并介绍了国外对微生物制剂的风险评估和对污染防治微生物制剂的管理方式,提出了国内应优先开发本土的天然的污染防治微生物制剂的建议,尽快发展中国环境微生物技术.     

Simultaneous quantification of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) in Mississippi river water, in New Orleans, Louisiana, USA

An effective analytical method for simultaneously determining 16 polycyclic aromatic hydrocarbons (PAHs), 28 polychlorinated biphenyl (PCBs), and 12 pharmaceuticals and personal care products (PPCPs) has been developed to measure their concentrations in the Mississippi river waters in New Orleans, Louisiana, USA. The method involves the simultaneous extraction of the selected PAHs, PCBs, and PPCPs, from the aqueous phase by solid phase extraction using two-layer disks consisting of C(18) and SDB-XC, and collection of suspended solid in water samples by 0.2-0.6 microm filter in a single step. Target compounds adsorbed on the extraction disks were eluted with methanol, acetone, and dichloromethane. The suspended particles retained by the filter were sonically extracted using the same solvents. GC/MS was used for quantification of PAHs and PCBs directly and of PPCPs after derivatization. The analytical method was used in a 6-month field study of the Mississippi river water for contamination by PAHs, PCBs, and PPCPs and the following concentrations (ng/l) have been obtained: clofibric acid (3.2-26.7), ibuprofen (0-34.0), acetaminophen (24.7-65.2), caffeine (0-38.0), naproxen (0-135.2), triclosan (8.8-26.3), bisphenol A (0-147.2), carbamazepine (42.9-113.7), estrone (0-4.7), 17beta-estradiol (0-4.5), total PAHs (62.9-144.7), and total PCBs (22.2-163.4).     

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.     

Assessment of heavy metal pollution from a Fe-smelting plant in urban river sediments using environmental magnetic and geochemical methods

Environmental magnetic proxies provide a rapid means of assessing the degree of industrial heavy metal pollution in soils and sediments. To test the efficiency of magnetic methods for detecting contaminates from a Fe-smelting plant in Loudi City, Hunan Province (China) we investigated river sediments from Lianshui River. Both magnetic and non-magnetic (microscopic, chemical and statistical) methods were used to characterize these sediments. Anthropogenic heavy metals coexist with coarse-grained magnetic spherules. It can be demonstrated that the Pollution Load Index of industrial heavy metals (Fe, V, Cr, Mo, Zn, Pb, Cd, Cu) and the logarithm of saturation isothermal remanent magnetization, a proxy for magnetic concentration, are significantly correlated. The distribution heavy metal pollution in the Lianshui River is controlled by surface water transport and deposition. Our findings demonstrate that magnetic methods have a useful and practical application for detecting and mapping pollution in and around modern industrial cities.     

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...