Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Occurrence of pharmaceuticals and hormones in drinking water treated from surface waters

The levels of a wide variety of pharmaceuticals and hormones, in source and potable-water supplies of French drinking water treatment plants, were assessed. In surface waters, 27 of the 51 target compounds were determined at least once. Paracetamol, salicylic acid and carbamazepine were quantified in more than 80% of samples. The highest concentration of 71 ng/L was observed for paracetamol. Twelve other substances were widely found in the surface waters studied, contaminating between 33 and 80% of the samples. These compounds include analgesics, psychotropic drugs, antibiotics and beta-blockers consistent with the French consumption, as well as natural hormones (oestrone, progesterone and androgens) and synthetic progestatives. In drinking water supplies, 25 compounds were also present, salicylic acid being the most frequently detected. Carbamazepine and the β-blocker atenolol found at lower levels (maximum 2 ng/L), are also present in more than 30% of the contaminated drinking waters. The pharmaceuticals exhibit different reactivity towards the treatments, while progestagens and androgens seem resistant to most of them. The effectiveness of the treatments is discussed, as well as the consequences of the presence of all these compounds on human health. This is the first time that such a long list of compounds (51) is proposed to assessment, and consequently this study provides the first data on pharmaceuticals and steroids occurrences in French drinking waters and represents a basis for the assessment of risks for humans. Moreover, at the international level, this is the first time that so many substances are quantified in drinking water, due to the very low detection limits, especially in the case of the hormones.     

Occurrence and behavior of pharmaceuticals in sewage treatment plants in eastern China

The occurrence and removal efficiency of seven pharmaceuticals (norfloxacin, trimethoprim, roxithromycin, sulfamethoxazole, ibuprofen, diclofenac and carbamazepine) were determined in three sewage treatment plants (STPs) with anaerobic/anoxic/oxic, anoxic/oxic and oxidation ditches processes in Xuzhou City, Eastern China. The results showed that seven pharmaceuticals were detected in the influent samples with concentrations ranging from 93 to 2540 ng·L⁻¹. The removal of these substances among the three different STPs varied from 36 to 84%, with the highest performance obtained by the wastewater treatment works with tertiary treatment (sand filtration). Most of the compounds were removed effectively during biologic treatment while sand filtration treatment also made a contribution to the total elimination of most pharmaceuticals. The efficiency comparison of the three sewage treatment processes showed that the STP which employed anaerobic/anoxic/oxic was more effective to remove pharmaceuticals than the oxidation ditches and anoxic/oxic.     

3种不同功效医药品活性成分对发光菌的毒性作用

因药物活性成分的环境残留引发的风险和健康问题成为公众关注的焦点。本文以海洋发光细菌为受试生物,研究了布洛芬、阿奇霉素、三氯生3种医药品的单一和联合毒性作用。结果表明,3种医药品对发光菌的EC_(50)值分别为:36.5×10~(-5)、30.26×10~(-5)和0.0155×10~(-5)mol·L~(-1);二元及多元混合体系对发光菌的EC_(50)值高于单一体系的毒性作用,进一步采用相加指数法(AI)、毒性单位法(TU)、混合毒性指数法(MTI)评价3种医药品多元体系的联合毒性的作用类型,取得了一致的评价结果。3种医药品的二元混合体系及多元混合体系的作用类型均属于拮抗作用,但拮抗作用的强弱不同,这与医药品不同药效官能团结构可影响其对微生物生理生化反应过程有关。研究3种医药品对发光菌急性毒性作用可为该类新型污染物的环境风险评价提供基础数据。     

Wassertechnische Strategien zur Reduzierung der Trinkwasserbelastung durch Arzneimittelwirkstoffe

Results The available research results concerning the application of innovative methods of wastewater and drinking water purification to eliminate pharmaceuticals are summarized in the present paper. An increase of the activated sludge (aerobic sludge) age to 8–10 days in treatment plants can improve the metabolization of less persistent pharmaceutical agents whereas expansion of the sojourn time beyond 10 days will not result in a remarked increase of degradation for most pharmaceutical substances. First results have shown that wastewater treatment plants with integrated membrane bioreactors (MBR) using micro- and ultrafiltration membranes do not provide significantly better results compared to the conventional wastewater treatment plants with respect to the removal of organic micropollutants (including pharmaceutical residues). The use of powdered carbon in biologically treated wastewater is able to reduce pharmaceutical residues up to 80?% in the run-off water. Pilot studies scrutinize the treatment of highly contaminated effluents via catalytic photooxidation. Regarding the suitability of the method to reduce the contamination of drinking and wastewater with pharmaceuticals yet only few data from laboratory scale testing are available. Activated carbon filtration is preferably used for drinking water treatment. Primarily against the background of disinfection, ozonation is widely used for drinking water treatment, but for wastewater treatment the method is still at the experimental stage and will hardly become of practical importance because of high costs. Sustainable wastewater separation is grounded on decentralized concepts by considering material cycles (recycling) at the place of origin. In the long term, separation measures can significantly contribute to declining drug concentrations in drinking water. Regarding the quarrying of drinking water by bank filtration water, river water or artificially enriched ground water, end-of-pipe techniques are vital. Most commonly, activated carbon or activated carbon combined with ozonization is applied and assures a high drinking water quality. Discussion The advantages and disadvantages of the different water treatment methods mainly concern the varying degrees of effectiveness with respect to the elimination of very persistent pharmaceutical agents, the generation of problematical metabolites and additional waste materials, hygienic problems, energy needs and the necessity to employ appropriate technical staff for operation. Although the biodegradation of very persistent drugs cannot be enhanced by an extension of the activated sludge age, this modification should be considered in sewage plants to reduce the contamination with less persistent medical agents. Compared with conventional wastewater treatment, membrane bioreactors provide the advantage of a better control of biological activities on the plant and a comparably small plant size but high investment and operation costs. Additionally, pharmaceuticals such as carbamazepin are only insufficiently removed from wastewater by membrane bioreactors. The regular use of powdered activated carbon in sewage treatment plants would also increase the costs of wastewater treatment and would additionally exclude the further use of sewage sludge in agriculture. Currently, in Germany the further use of sewage sludge is handled differently by the Federal States and discussed controversially. The implementation of ozonation as an additional treatment method in wastewater treatment plants is not realistic because of cost concerns. Additionally, the method produces analytically as yet not assessed metabolites with unknown (eco-)toxicological impacts. For this reason ozonation should currently not be applied unless the reaction products are removed subsequently by filtration through activated carbon. For industrial sewage photooxidation is in a state of testing but an application for municipal wastewater is, up to now, out of question. When river bank filtration is used for the supply of drinking water the use of activated carbon for purification should be essential. The lifetime of the filters is often defined by the filter capacities to eliminate radiocontrast media (e.?g., iopamidole, amidotrizoic acid). Many water supply companies already apply the ozonization prior to activated carbon filtration which supports the elimination of pharmaceuticals from the sewage. The unique developmental potential of the wastewater separation can be seen in the possibility to link up these methods with sustainable exploitation techniques and concepts (re-use of sanitized water, production of fertilizer, compost and biogas). Wastewater separation will not make ‘middle/end-of-pipe’ techniques dispensable but will make their handling more effective because concentrations of pharmaceutical agents are higher in separated effluents compared to those usually found in municipal wastewater, which in mixing sewage systems is even diluted by surface runoff. Conclusions Following today’s state of knowledge activated carbon filtration (eventually coupled with ozonization) is best suited to remove drug residues and other xenobiotics from raw water. Water works that do not apply the activated carbon filtration technique for cleanup of bank filtration water should consider an upgrade. The ozonization is primarily required for disinfection of the water. As no acute health hazard proceeds from drinking water contamination by pharmaceuticals at the present time, the upgrade of wastewater treatment plants by one of the aforementioned innovative methods is currently not required in view of drinking water quality. This offers the opportunity to develop sustainable approaches that already aim to reduce drug contaminations of wastewater and hence of ground-, surface- and drinking water. Recommendations and perspectives On a short- to mid-term perspective enriched sewage of hospitals, nursing homes and other medical facilities should be collected and treated separately. From a technical point of view the conditioning of separated hospital effluents (yellow- and greywater) via activated carbon or membrane filtration is possible but should be combined with disinfection. On a mid- and long-term scale sustainable sanitary concepts based on wastewater separation (black-, grey- and/or rainwater) associated with the recycling of mineral nutrients (nitrogen, phosphorous and potassium) should be realized for development, industry and trade areas, buildings with public lavatories, airports, motorway service areas, and large office and hotel buildings. Strategies focusing primarily on up-grading of municipal wastewater treatment plants are currently existing but the related technologies are largely in a test phase. This is why a particular technique should not be favored at the moment. The combination of various techniques (i.?e., ozonization combined with activated carbon filtration) is known to be very efficient for the removal of pharmaceutical residues from water, but the combination cannot be expected to become of importance in treatment of domestic wastewater because of high costs. Moreover, improvement of wastewater treatment technologies to remove pharmaceutical residues will not make the employment of end-of-pipe techniques in water works redundant and therefore will not lead to saving of expenses.     

Unexpected removal of the most neutral cationic pharmaceutical in river waters

Contamination of surface waters by pharmaceuticals is now widespread. There are few data on their environmental behaviour, particularly for those which are cationic at typical surface water pH. As the external surfaces of bacterio-plankton cells are hydrophilic with a net negative charge, it was anticipated that bacterio-plankton in surface-waters would preferentially remove the most extensively-ionised cation at a given pH. To test this hypothesis, the persistence of four, widely-used, cationic pharmaceuticals, chloroquine, quinine, fluphenazine and levamisole, was assessed in batch microcosms, comprising water and bacterio-plankton, to which pharmaceuticals were added and incubated for 21 days. Results show that levamisole concentrations decreased by 19 % in microcosms containing bacterio-plankton, and by 13 % in a parallel microcosm containing tripeptide as a priming agent. In contrast to levamisole, concentrations of quinine, chloroquine and fluphenazine were unchanged over 21 days in microcosms containing bacterio-plankton. At the river-water pH, levamisole is 28 % cationic, while quinine is 91–98 % cationic, chloroquine 99 % cationic and fluphenazine 72–86 % cationic. Thus, the most neutral compound, levamisole, showed greatest removal, contradicting the expected bacterio-plankton preference for ionised molecules. However, levamisole was the most hydrophilic molecule, based on its octanol–water solubility coefficient (K _ow). Overall, the pattern of pharmaceutical behaviour within the incubations did not reflect the relative hydrophilicity of the pharmaceuticals predicted by the octanol–water distribution coefficient, D _ow, suggesting that improved predictive power, with respect to modelling bioaccumulation, may be needed to develop robust environmental risk assessments for cationic pharmaceuticals.     

南方典型水源地及水产养殖区抗生素的复合污染特征及生态风险

抗生素作为生长促进剂和疾病预防控制药物在水产养殖领域得到广泛应用,目前在许多环境水体中检测到不同类型的抗生素。环境中抗生素的残留问题也是目前环境研究的热点问题之一。本研究选择南方某市8个水源地和5个典型水产养殖区作为研究对象,采用固相萃取、高效液相色谱串联三重四级杆质谱联用仪方法,调查了32种常用抗生素在水体中的含量水平和空间分布特征,揭示了抗生素的来源,并对其生态风险进行了评价。水源地共检出12种抗生素,浓度范围为0.12～44.6 ng·L~(-1),以磺胺甲噁唑含量最高;水产养殖区检出14种抗生素,浓度范围为0.95～716 ng·L~(-1),以氯四环素检出浓度最高。整体上水产养殖区抗生素的浓度高于水源地。抗生素浓度与环境因子的冗余分析表明,水产养殖和生活污水排放是水体中抗生素的主要来源。对检出的13种抗生素进行生态风险评价,单一抗生素而言,环丙沙星、氧氟沙星、磺胺嘧啶、氯四环素和脱水红霉素的风险商值大于0.01而小于0.1,表现为低风险。总抗生素风险商值加和在大部分水源地大于0.01而小于0.1,表现为低风险;总抗生素风险商值加和在2个水产养殖区大于0.1,表现为中等风险,水产养殖区抗生素的长期生态风险应该引起关注。     

Humanpharmakawirkstoffe in der Umwelt: Einträge, Vorkommen und der Versuch einer Bestandsaufnahme

Background

The presence of a large spectrum of pharmaceutical agents has been reported for aquatic environments (surface—and groundwater) and other aquatic media (influents and effluents of sewage treatment plants) in Germany and beyond, including their occurrence in drinking water. Considering the large number of pharmaceuticals produced for human use and released into the environment, various authors (Sattelberger 1999, Hanisch et al. 2004, Castiglioni et al. 2006, IWW 2006, Stockholm County Council 2006) tried to compile ‘priority lists’ focusing on those substances with environmental relevance. The following agents are included in all lists: ciprofloxacine, clarythromycine (antibiotics), carbamazepine (anti-epileptic agent), bezafibrate (lipid reducer), clofibric acid (lipid reducer metabolite), ethinylestradiol (sex hormone) and cylophosfamide (cytostatic agent). The agents erythromycine and sulfamethoxazole (antibiotics), ibuprofen, indometacine, propyphenazone (analgesics), atenolol (beta-blocker) and ifosfamide (cytostatic agent) can be found in three of four priority lists.

Results

Pharmaceuticals mainly enter the aquatic environment via effluent water, coming from wastewater treatment plants (including hospital and household sewerage), untreated discharges (e.g, secondary transfer of active agents into ground- and surface waters via sewage sludge application in agriculture and via landfill leachate) and leakages in the municipal sewer network.

Discussion

Potential activities towards a reduced release of pharmaceuticals into the environment should consider primarily the origin of the exposure to allow a separation of drug containing flows already at the source. Following the latter it would be possible to minimize the contamination of spring-, ground- and surface waters which serve as raw water resources for drinking water supply. However, considering the actual water pollution with pharmaceuticals and other substances, ‘end-of pipe’ techniques in the sewage and drinking water treatment are absolutely essential.

Conclusions

Sustainability criteria (e.g. protection of drinking water resources, habitats and biocoenoses, recycling and economizing use of resources) and economic aspects of modern sewage disposal concepts require a useful choice and combination of technical measures as components of centralized and decentralized sewage and drinking water treatment methods. It is though not realistic to cover and eliminate all pharmaceutical agents of environmental relevance equally effective even if a catalogue of potential technical treatment methods is elaborated thoroughly. Therefore, a concentration of efforts on selected drug agents, at least following initially some of the priority lists, is recommended.

Recommendations and Perspectives

The contamination of the water cycle with pharmaceuticals is nevertheless not exclusively to be solved via the application of technical methods. The BMBF (Federal Ministry for Education and Research) funded project start (Management Strategies for Pharmaceuticals in Drinking Water, www.start-project.de) therefore tries by implementation of a transdisciplinary approach to integrate technical-, behavioral-, and agent-orientated management strategies towards a more comprehensive and sustainable problem solution.     

Mycoremediation of diclofenac using Mucor hiemalis

Diclofenac (DCF) is a pharmaceutical drug widely found in the aquatic environment, where it represents a persistent, anthropogenic hazard to all biota. Owing to the reported inefficiency of water treatment strategies to remove pharmaceuticals, the present study aimed to investigate the ability of the aquatic fungus Mucor hiemalis to take up and accumulate DCF. Cultures of M. hiemalis were exposed to varying concentrations of DCF (10, 25 and 50 µg/L) over a period of 144 h. In the presence of M. hiemalis, DCF concentrations in the media decreased by 95% within 24 h. This early removal was most likely due to extracellular metabolism of DCF, as low proportions of the pharmaceutical were found in the mycelium of the fungus, thereby excluding bioaccumulation as the main mode of removal. However, adsorption of DCF onto the surface of the M. hiemalis pellets cannot be excluded. Our study provides the first report of DCF remediation using M. hiemalis and is the first successful step towards a feasible and inexpensive bioremediation technique for DCF.     

Persistence of oxyfluorfen in soil and detection of its residues in rice crop

Oxyfluorfen is a post-emergence herbicide used for control of annual and perennial broad-leaf weeds and sedges in rice. There is increasing concern about persistence of pesticide residues in soils, agricultural products and sub-sequent contamination of ground water through runoff, leaching and drift. Thus, persistence of oxyfluorfen was evaluated under field conditions in a rice cropping system. Oxyfluorfen was sprayed at 240 and 500 g ai ha^?1 application rates to the rice crop as post-emergence herbicide. Paddy grains, straw and soil samples were collected at harvest and analyzed for oxyfluorfen residues by HPLC. Straw samples contained 0.01 and 0.03 µg g^?1 oxyfluorfen residues at 240 and 500 g ha^?1 concentrations, respectively. In the soil, 0.028 and 0.03 µg g^?1 of oxyfluorfen residues were detected when applied at 240 and 500 g ai ha^?1, respectively. However, in rice grains, 0.018 and 0.106 µg g^?1 of oxyfluorfen residues were found in 240 and 500 g ai ha^?1 treated plots. In light of the potential adverse effects of oxyfluorfen, it is important to determine herbicide levels in these crops.     

Fate and removal of typical pharmaceutical and personal care products in a wastewater treatment plant from Beijing: a mass balance study

The fate and removal of pharmaceuticals and personal care products (PPCPs) in wastewater treatment plants (WWTPs) has received great attention during the last decade. Numerous data concerning concentrations in the water phase can be found in the literature, however corresponding data from sludge as well as associated mass balance calculations are very limited. In the present study, the adsorbed and dissolved concentrations of 9 PPCPs were investigated in each unit of a WWTP in Beijing, China. Based on the calculation of mass balance, the relative mass distribution and removal efficiency of each target compound was obtained at each process. The amount of PPCPs entering into the WWTP ranged from 12 g·d^–1 to 3848 g·d^–1. Five target compounds (caffeine, chloramphenicol, bezafibrate, clofibric acid, and N,N-diethyl-meta-toluamide) were effectively removed, with rates of 57%–100%. Negative removal efficiencies were obtained for sulpiride, metoprolol, nalidixic acid, and carbamazepine, ranging from -19% to -79%. PPCPs mainly existed in dissolved form (≥92%) in both the raw influent and the final effluent. The sludge cake carried a much lower amount of PPCPs (17 g·d^–1) compared with the discharged effluent (402 g·d^–1). In A²/O treatment tanks, the anaerobic and anoxic tanks showed good performance for PPCPs removal, and the amount of adsorbed PPCPs was increased. The results reveal that both the dissolved and the adsorbed phases should be considered when assessing the removal capacity of each A²/O tank.     

Rückstände ausgewählter Humanarzneimittel in Oberflächenwasserkörpern im Einzugsgebiet Halle (Saale)

A method for the determination of 16 selected pharmaceuticals in surface water using LC-MS/MS has been developed Methods from literature were adapted within the scope of this study. The limit of quantification of 13 out of 16 analytes is below 10 ng/l. The analysis of samples from the Saale river and lakes around Halle demonstrated that Carbamacepin (Median 207 ng/l) and Diclofenac (Median 196 ng/l) are detectable at various sampling stations along the river. The wastewater path was identified as the most relevant source for pharmaceutical residues entering the environment. Besides, the results reveal increased levels of several substances in some smaller anabranches and brooks.     

Arzneimittel in der aquatischen Umwelt

The German Environmental Advisory Council evaluated German water protection policies in its last environmental report (2004) concluded that despite some great successes in this area there is still considerable need for action. Specifically, diffuse nutrient and chemical substances inputs remain an unsolved problem. The contamination of surface and groundwater with pharmaceuticals has been identified as an environmental risk increasing in pertinence. Pharmaceuticals and their metabolites are being detected in the whole aquatic environment, which they enter through sewage, soil contamination by agriculture, and waste storage facilities. Different pharmaceuticals have been tested for acute toxicity on various aquatic organisms, but almost nothing is known about chronic toxicity of these contaminants. This knowledge, however, is essential for estimating the ecotoxicological potential of pharmaceutical residues. In the opinion of the Environmental Council different strategies are necessary, to reduce the contamination of the environment with pharmaceuticals. Farmers should refrain from using pharmaceuticals for prophylactic purposes or from using hormonally or antibiotically active substances in livestock feed additives, so as to reduce inputs of veterinary drugs. As regards human medications, packaging should better correspond to appropriate dosage amounts, and environmentally responsible disposal measures should be followed. Still under discussion are a programme for the risk evaluation of existing pharmaceuticals and a ban on the use of sewage sludge in agriculture. In the future, improvement of sewage treatment facilities, for instances through membrane technologies, will offer further potential to reduce inputs of hazardous substances.     

Titanium dioxide photocatalysis for pharmaceutical wastewater treatment

Heterogeneous photocatalysis using the semiconductor titanium dioxide (TiO₂) has proven to be a promising treatment technology for water purification. The effectiveness of this oxidation technology for the destruction of pharmaceuticals has also been demonstrated in numerous studies. This review highlights recent research on TiO₂ photocatalytic treatment applied to the removal of selected pharmaceuticals. The discussions are tailored based on the therapeutic drug classes as the kinetics and mechanistic aspects are compound dependent. These classes of pharmaceuticals were chosen because of their environmental prevalence and potential adverse effects. Optimal operational conditions and degradation pathways vary with different pharmaceutical compounds. The main conclusion is that the use of TiO₂ photocatalysis can be considered a state-of-the-art pharmaceutical wastewater treatment methodology. Further studies are, however, required to optimize the operating conditions for maximum degradation of multiple pharmaceuticals in wastewater under realistic conditions and on an industrial scale.     

Medikamentenentsorgung in privaten Haushalten: Ein Faktor bei der Gewässerbelastung mit Arzneimittelwirkstoffen?

Background

Residues of pharmaceuticals are meanwhile detected widely in the aquatic environment. Waste water treatment plants are the main route of entry: after intake the agents or their metabolites are excreted predominantly via urine into the sewage. Largely unknown is, however, if the improper disposal of unused medicines via domestic sanitary devices (toilet or sink) contributes to the measured concentrations in the environment. Aim of this investigation was to clarify to what extent consumers in Germany dispose of unused medicines directly via domestic sewage. In July and August 2006 a representative survey of the population with 2.000 interviewees was performed for this purpose.

Results

The analysis of the survey shows that the disposal of unused medicines via domestic sewage takes place on relevant scales: approx. 16% of the population dispose at least occasionally of unused or expired tablets in the toilet whereas 43% proceed alike with liquid drugs (toilet or sink).

Discussion

A possible reason for this disposal behaviour is the widely inconsistent waste disposal communication by the municipalities and the federal states. The resulting uncertainty about the correct way to dispose of unused medicines gains in importance in the context of the high recycling willingness of the (German) population: appropriate disposal options for drug residues (tablets or liquids) arising from waste separation are often not realised.

Conclusions

Quantitative assessments on the basis of the collected data demonstrate that the established frequency of direct disposal of unused medicines via domestic sewage can partly contribute significantly to the occurrence of pharmaceuticals in the aquatic environment. Crucial parameters are here the excretion rate of the active pharmaceutical ingredient considered and the actual amount of medication waste.

Recommendations

Based on the inquiry results, measures that lead to a more adequate handling of pharmaceutical waste disposal are demanded. The establishment of a consistent and binding disposal standard for unused medicines via return in pharmacies is recommended. This measure needs to be accompanied by a simplification of the established take back systems which partly cause high time and effort for pharmacies.     

Bewertung der Umweltrelevanz von Arzneistoffen

Aim The aim of this work was to investigate, which human and veterinary pharmaceuticals are of high ecological relevance due to the input into the environment as well as with regard to the effects and behaviour in the environment. Furthermore, the state of knowledge concerning the ecologically relevant substances and the need of research was evaluated. Methods A two-step approach considering the criteria quantity of sold pharmaceuticals, concentrations, effects and fate in the environment was developed to identify the pharmaceuticals of potential ecological relevance. In a second step the identified individual substances and groups of substances were considered in more detail concerning metabolism, environmental behaviour and ecological effects. Results In a first step 29 out of approximate 2,700 licensed human pharmaceuticals and seven substances as well as three substance groups used in veterinary medicine were identified as potentially ecologically relevant. The detailed assessment in a second step lead to the conclusion, that of the human pharmaceuticals 9 substances as well as two substance groups concerning the environmental behaviour and seven substances concerning the effects are of high environmental relevance. Concerning the environmental behaviour six out of seven veterinary pharmaceuticals as well as three substance groups and only three substances concerning the ecological effects were classified as relevant for the environment. Discussion By means of the presented method it was possible to limit the scope of a wide spectrum of pharmaceuticals, so that a detailed assessment of only relevant active agents was possible. Nevertheless, it is a precondition that investigations concerning the occurrence, fate and effects of the individual compounds in the environment have been already carried out and published in the literature. Conclusions The method is suitable for a comprehensive assessment of the ecological relevance of pharmaceuticals, but for a lot of human and veterinary pharmaceuticals the data available in the literature are insufficient. Recommendations For a final extensive assessment of the environmental relevance for some of the human and veterinary pharmaceuticals more studies are necessary. Especially data concerning the environmental behaviour in water and soils, data from long-term-studies for the assessment of ecological effects and data concerning metabolites and mixtures of pharmaceutical compounds are lacking.     

Enhanced desorption of fluoxetine from polyethylene terephthalate microplastics in gastric fluid and sea water

There are concerns that microplastics act as a vector of pharmaceuticals in the aquatic environment. Most studies have focussed on pharmaceutical adsorption and have not investigated desorption in the various matrices that microplastics enter. Therefore we studied the desorption of the antidepressant drug fluoxetine from polyethylene terephthalate (PET) microplastics in river water, sea water, and simulated gastric and intestinal fluids. We found that most desorption occurred rapidly, within a few hours of exposure. Fluoxetine desorption fitted well to the Freundlich isotherm with r² values ranging from 0.97 to 0.99. Desorption decreased in the following order: gastric fluid at 20 °C and 37 °C; sea water at 20 °C; intestinal fluid at 20 °C and 37 °C; then river water at 20 °C. The little difference in desorption in gastrointestinal fluids at 20 °C and 37 °C suggests a similar exposure risk to cold- and warm-blooded organisms following PET microplastic ingestion. Total desorption following sequential incubation 2 h in gastric fluid then 4 h in intestinal fluid to mimic gastrointestinal digestion was 37% at 20 °C and 41% at 37 °C. Interestingly, higher desorption of 18–23% occurred in sea water compared to river water, of 4–11%. Under a worst-case scenario, more than 44 mg kg⁻¹ body weight d⁻¹ or more than 52 mg kg⁻¹ body weight d⁻¹ of PET microplastics from river water or sea water, respectively, need to be consumed to exceed the mammalian acceptable daily intake for fluoxetine. Further studies are needed on microplastic ingestion and the bioavailability of adsorbed pharmaceuticals to a range of exposed aquatic organisms.

     

Application of permanganate in the oxidation of micropollutants: a mini review

As a green oxidant, permanganate has received considerable attention for the removal of micropollutants in drinking water treatment. To provide a better understanding of the oxidation of organic micropollutants with permanganate, the oxidation kinetics of 32 micropollutants were compiled. The pollutants include algal toxins, endocrine disrupting chemicals (EDCs), and pharmaceuticals. The oxidation kinetics of micropollutants by permanganate were found to be first order with respect to both contaminant and permanganate concentrations from which second-order rate constants (k″) were obtained. Permanganate oxidized the heterocyclic aromatics with vinyl moiety (i.e., microcystins, carbamazepine, and dichlorvos) by the addition of double bonds. For the polycyclic aromatic hydrocarbons (PAHs) with alkyl groups, permanganate attacked the benzylic C-H through abstraction of hydrogen. The mechanism for the oxidation of phenolic EDCs by permanganate was a single electron transfer and aromatic ring cleavage. The presence of background matrices could enhance the oxidation of some phenolic EDCs by permanganate, including phenol, chlorinated phenols, bisphenol A, and trichlosan. The toxicity of dichlorvos solution increased after permanganate oxidation, and the estrogenic activity of bisphnol A/estrone increased significantly at the beginning of permanganate oxidation. Therefore, the toxicity of degradation products or intermediates should be determined in the permanganate oxidation processes to better evaluate the applicability of permanganate. The influence of background ions on the permanganate oxidation process is far from clear and should be elucidated in the future studies to better predict the performance of permanganate oxidation of micropollutants. Moreover, methods should be employed to catalyze the permanganate oxidation process to achieve better removal of micropollutants.     

污水再生处理工艺中卡马西平的去除过程模拟及其生态风险评价

卡马西平在污水和水环境中广泛存在,且对水生生态系统安全构成风险,因此成为目前研究较多的药品之一。以北京清河再生水厂为例,研究"超滤—臭氧氧化—氯消毒"处理工艺中卡马西平的去除特性,并针对臭氧氧化和氯消毒工艺建立模拟卡马西平去除过程的机理模型。同时,利用美国环境保护署ECOTOX数据库,获取卡马西平对北京市水生生物物种的毒性数据,并基于毒性数据建立物种敏感度分布(species sensitivity distribution,SSD)模型,评价再生水厂出水补给地表水体时卡马西平产生的生态风险。臭氧氧化和氯消毒模型对卡马西平、总有机碳、氨氮等指标的模拟误差总体低于20%,模型的灵敏参数均可以被较好地识别,且其不确定性显著下降。对比7种SSD模型发现,对数正态分布和对数Logistic分布模型较好地拟合了北京市6个物种的卡马西平毒性数据,二者预测得到的总体生态风险期望值分别为7.4%和8.5%。