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。     

环境介质中药物和个人护理品的潜在风险研究进展

药物和个人护理品(PPCPs)在环境介质中的残留物作为一种新型污染物在环境介质中的转归,逐渐成为环境工作者和公众密切关注的焦点.这些物质特殊的物化特性及其被大量使用的现状,给生态环境和人类健康带来一定的潜在风险.由PPCPs使用所引发的风险问题正在成为当前学术界所面临的研究方向之一.欧洲和美国已经开始了对PPCPs的风险评估研究,中国研究者仅对某些药物的分析检测方法进行了初步探索,对PPCPs的潜在风险研究还呈空白.从PPCPs的物化特性及其对环境介质的影响入手,对其潜在风险进行了分析,并介绍了目前国外PPCPs风险研究进展,以期为中国开展PPCPs的风险评估提供参考.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

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.     

Benzyl-penicillin (Penicillin G) transformation in aqueous solution at low temperature under controlled laboratory conditions

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated. Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn-Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5°C, 12.5°C and 20°C). The testing period was extended from the OECD standard of 28-42d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5°C and considerably faster at 12.5°C and 20°C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5°C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20°C ambient temperatures).     

Systematic screening of common wastewater-marking pharmaceuticals in urban aquatic environments: implications for environmental risk control

In this report, we refer to pharmaceuticals that are widespread in the urban aquatic environment and that mainly originate from wastewater treatment plants or non-point source sewage as “wastewater-marking pharmaceuticals” (WWMPs). To some extent, they reflect the condition or trend of water contamination and also contribute to aquatic environmental risk assessment. The method reported here for screening typical WWMPs was proposed based on academic concerns about them and their concentrations present in the urban aquatic environment, as well as their properties of accumulation, persistence, eco-toxicity and related environmental risks caused by them. The screening system consisted of an initial screening system and a further screening system. In the former, pharmaceuticals were categorised into different evaluation levels, and in the latter, each pharmaceutical was given a normalised final evaluation score, which was the sum of every score for its properties of accumulation, persistence, eco-toxicity and environmental risk in the aquatic environment. The system was applied to 126 pharmaceuticals frequently detected in the aquatic environment. In the initial screening procedure, five pharmaceuticals were classified into the “high” category, 16 pharmaceuticals into the “medium” category, 15 pharmaceuticals into the “low” category and 90 pharmaceuticals into the “very low” category. Subsequently, further screening were conducted on 36 pharmaceuticals considered as being of “high”, “medium” and “low” categories in the former system. We identified 7 pharmaceuticals with final evaluation scores of 1–10, 10 pharmaceuticals with scores of 11–15, 15 pharmaceuticals with scores from 16 to 20 and 4 pharmaceuticals with scores above 21. The results showed that this screening system could contribute to the effective selection of target WWMPs, which would be important for spatial-temporal dynamics, transference and pollution control of pharmaceuticals in the urban aquatic environment. However, there remains a number of pharmaceutical parameters with measured data gaps, such as organic carbon adsorption coefficients and bioconcentration factors, which, if filled, would improve the accuracy of the screening system.     

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.     

A review of personal care products in the aquatic environment: environmental concentrations and toxicity

Considerable research has been conducted examining occurrence and effects of human use pharmaceuticals in the aquatic environment; however, relatively little research has been conducted examining personal care products although they are found more often and in higher concentrations than pharmaceuticals. Personal care products are continually released into the aquatic environment and are biologically active and persistent. This article examines the acute and chronic toxicity data available for personal care products and highlights areas of concern. Toxicity and environmental data were synergized to develop a preliminary hazard assessment in which only triclosan and triclocarban presented any hazard. However, numerous PCPs including triclosan, paraben preservatives, and UV filters have evidence suggesting endocrine effects in aquatic organisms and thus need to be investigated and incorporated in definitive risk assessments. Additional data pertaining to environmental concentrations of UV filters and parabens, in vivo toxicity data for parabens, and potential for bioaccumulation of PCPs needs to obtained to develop definitive aquatic risk assessments.     

The potential environmental risks of pharmaceuticals in Vietnamese aquatic systems: case study of antibiotics and synthetic hormones

Presently, many pharmaceuticals are listed as emerging contaminants since they are considered to be great potential threats to environmental ecosystems. These contaminants, thus, present significant research interest due to their extensive use and their physicochemical and toxicological properties. This review discusses a whole range of findings that address various aspects of the usage, occurrence, and potentially environmental risks of pharmaceuticals released from various anthropogenic sources, with emphasis on the aquatic systems in Vietnam. The published information and collected data on the usage and occurrence of antibiotics and synthetic hormone in effluents and aquatic systems of Vietnam is reported. This is followed by a potential ecological risk assessment of these pollutants. The extensive use of antibiotics and synthetic hormones in Vietnam could cause the discharge and accumulation of these contaminants in the aquatic systems and potentially poses serious risks for ecosystems. Vietnam is known to have extensively used antibiotics and synthetic hormones, so these contaminants are inevitably detected in aquatic systems. Thus, an appropriate monitoring program of these contaminants is urgently needed in order to mitigate their negative effects and protect the ecosystems.     

Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern

The monitoring of pharmaceuticals and personal care products (PPCPs) has focused on the distribution in rivers and small lakes, but data regarding their occurrence and effects in large lake systems, such as the Great Lakes, are sparse. Wastewater treatment processes have not been optimized to remove influent PPCPs and are a major source of PPCPs in the environment. Furthermore, PPCPs are not currently regulated in wastewater effluent. In this experiment we evaluated the concentration, and corresponding risk, of PPCPs from a wastewater effluent source at varying distances in Lake Michigan. Fifty-four PPCPs and hormones were assessed on six different dates over a two-year period from surface water and sediment samples up to 3.2 km from a wastewater treatment plant and at two sites within a harbor. Thirty-two PPCPs were detected in Lake Michigan and 30 were detected in the sediment, with numerous PPCPs being detected up to 3.2 km away from the shoreline. The most frequently detected PPCPs in Lake Michigan were metformin, caffeine, sulfamethoxazole, and triclosan. To determine the ecological risk, the maximum measured environmental concentrations were compared to the predicted no-effect concentration and 14 PPCPs were found to be of medium or high ecological risk. The environmental risk of PPCPs in large lake systems, such as the Great Lakes, has been questioned due to high dilution; however, the concentrations found in this study, and their corresponding risk quotient, indicate a significant threat by PPCPs to the health of the Great Lakes, particularly near shore organisms.     

The fate and risk of selected pharmaceutical and personal care products in wastewater treatment plants and a pilot-scale multistage constructed wetland system

The removal of 12 pharmaceuticals and personal care products (PPCPs) in two full-scale wastewater treatment plants (WWTPs) and a tertiary treatment system was studied. The ecological risks of effluents from both secondary and tertiary treatment systems as well as excess sludge were evaluated. Primary treatment and ultraviolet light disinfection showed limited ability to remove most selected PPCPs. The combination of an anaerobic process and triple-oxidation ditches can eliminate DEET better than the anaerobic/anoxic/oxic process. Adsorption to sludge played a key role in the removal of triclocarban. Multistage constructed wetlands as a tertiary treatment efficiently removed caffeine and ibuprofen from wastewater and could decrease the risk of partial selected PPCPs. Selected PPCPs residues in excess sludge generally produced higher risks to the ecological environment than effluents from WWTPs.     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca,Romania

Background, aim, and scope

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.

Materials and methods

The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide.

Results and discussion

The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400–2,000 g/day), carbamazepine (78–213 g/day), galaxolide (140–684 g/day), ibuprofen (84–108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP’s removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2–3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants).

Conclusions

The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters.

Recommendations and perspectives

Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.

     

Benzyl-penicillin (Penicillin G) transformation in aqueous solution at low temperature under controlled laboratory conditions

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated.Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn–Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5 °C, 12.5 °C and 20 °C). The testing period was extended from the OECD standard of 28–42 d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5 °C and considerably faster at 12.5 °C and 20 °C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5 °C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20 °C ambient temperatures).     

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).     

First report on the occurrence of pharmaceuticals and cocaine in the coastal waters of Santa Catarina,Brazil, and its related ecological risk assessment

Environmental Science and Pollution Research - The worldwide occurrence of pharmaceuticals and personal care products (PPCPs) in aquatic ecosystems is reason for public concern. These emerging...     

Occurrence and fate of PPCPs and correlations with water quality parameters in urban riverine waters of the Pearl River Delta, South China

The occurrence and fate of eight PPCPs was studied in river waters from upstream to downstream of the three rivers in the Pearl River Delta, China. The correlations of PPCP levels and water quality parameters were also investigated. The analytes of the highest concentrations were caffeine, acetaminophen, and ciprofloxacin. Carbamazepine and erythromycin-H₂O were detected at the lowest concentrations. The highest concentrations of PPCPs were found in the Shijing River, with 865 ng/L caffeine, 339 ng/L acetaminophen, and 304 ng/L ciprofloxacin. In general, the levels of PPCPs in the Zhujiang River were higher at sites where the metropolitan city Guangzhou is located and decreased from the epicenter along the river. Low levels of PPCPs were generally found in the Beijiang River. Positive correlations were found between PPCP levels, total nitrogen, ammonium nitrogen, and cumulative fluorescence excitation-emission matrix (EEM) volume. Among the four PPCPs evaluated (caffeine, acetaminophen, ciprofloxacin, and sulfamethoxazole), caffeine had the best correlations with the correlation coefficients ranging from 0.62 to 0.98. The prediction of PPCP concentrations at specified locations can be substantially simplified.     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca, Romania

Background, aim, and scope  

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.     

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.     

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.     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca,Romania

Background, aim, and scope

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.

Materials and methods

The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide.

Results and discussion

The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400–2,000 g/day), carbamazepine (78–213 g/day), galaxolide (140–684 g/day), ibuprofen (84–108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP’s removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2–3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants).

Conclusions

The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters.

Recommendations and perspectives

Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.