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

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

Occurrence and distribution of pharmaceuticals in wastewater from households, livestock farms, hospitals and pharmaceutical manufactures

Twenty-four pharmaceuticals were measured in wastewater from 12 municipal wastewater treatment plants (M-WWTPs), four livestock WWTPs (L-WWTPs), four hospital WWTPs (H-WWTPs) and four pharmaceutical manufacture WWTPs (P-WWTPs). The total concentration of pharmaceuticals in the influent samples was highest in the L-WWTPs followed by the P-WWTPs, H-WWTPs and M-WWTPs. The effluents had different patterns of pharmaceuticals than their corresponding influents because of the different fate of each compound in the WWTPs. Non-steroidal anti-inflammatory drugs (NSAIDs) were the most dominant in the influents from the M-WWTPs and P-WWTPs, while antibiotics were dominantly detected in the L-WWTP. In the H-WWTP influents, NSAIDs, caffeine and carbamazepine were dominant. In the P-WWTPs, the distribution of pharmaceuticals in the effluents varied with sampling sites and periods. The M-WWTP influents had the highest daily loads, while the effluents showed somewhat similar levels in all source types.     

Distribution and accumulation of endocrine-disrupting chemicals and pharmaceuticals in wastewater irrigated soils in Hebei, China

This study investigated the occurrence of 43 emerging contaminants including 9 endocrine-disrupting chemicals and 34 pharmaceuticals in three sites in Hebei Province, north China. Each site has a wastewater irrigated plot and a separate groundwater irrigated plot for comparison purpose. The results showed that the concentrations of the target compounds in the wastewater irrigated soils were in most cases higher than those in the groundwater irrigated soils. Among the 43 target compounds, nine compounds bisphenol-A, triclocarban, triclosan, 4-nonylphenol, salicylic acid, oxytetracycline, tetracycline, trimethoprim and primidone were detected at least once in the soils. Preliminary environmental risk assessment showed that triclocarban might pose high risks to terrestrial organisms while the other detected compounds posed minimal risks. Irrigation with wastewater could lead to presence or accumulation of some emerging contaminants to some extent in irrigated soils.     

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.     

Driving factors for coordinating urbanization with conservation of the ecological environment in China

Urbanization is a dominant component of social and economic development around the world, but this process creates tremendous pressure on the ecological environment. How to achieve coordination between urbanization and conservation of this environment has become a key issue, especially in developing countries. It is necessary to identify the driving factors that affect this coordination. To identify these factors, we chose 290 Chinese prefecture-level cities to analyze the driving factors behind urbanization using spatial regression analysis, and explored the spatial differences among regions in these factors. Our results show that industrial upgrading and technological progress were the main factors that promoted coordinated development, with industrialization having positive effects under government management, but with differences among regions in how the driving forces affected coordinated development. Using technological progress to promote industrial upgrading, creating new employment to absorb surplus rural labor, and providing workers with skills training so they can take advantage of new jobs can promote win–win solutions that coordinate urbanization with conservation of the ecological environment.     

Bromination of selected pharmaceuticals in water matrices

The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin > naproxen ? hydrochlorothiazide ≈ phenacetin ≈ metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK_a value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism.In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.     

Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 microg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur.     

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

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

Effects of the aquatic contaminant human pharmaceuticals and their mixtures on the proliferation and migratory responses of the bioindicator freshwater ciliate Tetrahymena

An increasing attention is paid to the potential harmful effects of aquatic contaminant pharmaceuticals exerted on both biosystems and humans. In the present work the effects of 14 pharmaceuticals including NSAIDs, antibiotics, β-blockers and a frequently used X-ray contrast media on the proliferation and migratory behavior of the freshwater ciliate Tetrahymena pyriformis was investigated. Moreover, the mixture toxicity of four selected pharmaceuticals (diclofenac, ibuprofen, metoprolol and propranolol) was evaluated in binary mixtures using full factorial experimental design. Our results showed that the sensitivity of Tetrahymena to NSAIDs and β-blockers (EC₅₀ ranged from 4.8 mg L⁻¹ to 308.1 mg L⁻¹) was comparable to that of algal or Daphnia bioassays. Based on these elevated EC₅₀ values acute toxic effects of these pharmaceuticals to T. pyriformis are unlikely. Antibiotics and the contrast agent sodium-diatrizoate had no proliferation inhibiting effect. Chemotactic response of Tetrahymena was more sensible than proliferation as significant chemorepellent action was observed in the environmentally realistic concentration range for acetylsalicylic acid, diclofenac, fenoprofen, paracetamol, metoprolol, propranolol, timolol and trimethoprim (Chemotaxis Index ranged from 63% to 88%).Mixture toxicity experiments resulted in a complex, concentration dependent interaction type pattern with antagonism being the predominant interaction type (59%) followed by additivity (37%) and synergism (4%). Hence the concept of concentration addition validated for NSAIDs in other organisms cannot be adopted for this ciliate.In summary authors suggest Tetrahymena as a sensible model of testing aquatic contaminants as well as underline the significance using more specific endpoints to understand the complex mechanisms investigated.     

Assessing the diurnal variability of pharmaceutical and personal care products in a full-scale activated sludge plant

An intensive sampling campaign has been carried out in a municipal wastewater treatment plant (WWTP) to assess the dynamics of the influent pharmaceutical active compounds (PhAC) and musks. The mass loadings of these compounds in wastewater influents displayed contrasting diurnal variations depending on the compound. The musks and some groups of PhACs tended to follow a similar diurnal trend as compared to macropollutants, while the majority of PhACs followed either the opposite trend or no repeatable trend. The total musk loading to the WWTP was 0.74 ± 0.25 g d⁻¹, whereas the total PhAC mass loading was 84.7 ± 63.8 g d⁻¹. Unlike the PhACs, the musks displayed a high repeatability from one sampling day to the next. The range of PhAC loadings in the influent to WWTPs can vary several orders of magnitude from one day or week to the next, representing a challenge in obtaining data for steady-state modelling purposes.     

Ecotoxicological risk assessment linked to the discharge by hospitals of bio-accumulative pharmaceuticals into aquatic media: The case of mitotane

The release of hospital wastewater into the urban sewer networks contributes to the general contamination of aquatic media by pharmaceutical residues. These residues include bio-accumulative pharmaceuticals that lead to increased risk for ecosystems because they can concentrate in organisms and food chains, and therefore reach toxic levels. In order to assess the ecotoxicological risks linked to this particular category of residues, we have developed a specific method, by combining a theoretical calculation of pollutant concentrations in organisms to estimate Body Residue (BR), and ecotoxicity biomarkers in fish cell lines, enabling the calculation of a Critical Body Residue (CBR). This method finally results in the calculation of a specific risk quotient (Qb = BR/CBR), characterizing the risk linked to this type of pollutant. This method was applied to mitotane, a bio-accumulative pharmaceutical typically found in hospital wastewater, in the framework of an exposure scenario corresponding to the discharge of all the hospital wastewaters into the Rhone River which flows through the city of Lyon, France. This approach leads to risk quotients (Qb and Qbg) much higher than those found with the classical approach, i.e. Q = PEC/PNEC (Predictive Environmental Concentration/Predictive Non Effect Concentration) = 0.0006. This difference in the appreciation of risk is important when using cytotoxicity as the criterion for measuring the toxicity of mitotane (Qb = 0.056) and it is even greater when the criterion used is genotoxicity (Qbg = 6.8). This study must be now consolidated by taking the biomagnification of the pharmaceuticals into consideration.     

华北农村水环境污染评价及源解析

近年来,国家相继发布多项重要文件要求整治农村人居环境、建设美丽乡村,但当前针对农村水环境问题研究相对较少,制约了农村环境治理工作开展。选取华北某镇农村河道坑塘,评价农村水环境污染水平、生态风险并进行污染溯源。结果表明,57处调查点位中有1处水体黑臭,但有多处调查点位水体溶解氧在2~3 mg∙L⁻¹、透明度在25~35 cm、氨氮在8~15 mg∙L⁻¹,接近黑臭阈值。仅有约9%的水体全部水质指标均能满足地表水V类要求 (检测指标为18项) ,超标指标主要为pH、COD_Mn、BOD、氨氮、总磷、总氮、粪大肠菌群等8项。底泥总磷、总氮标准指数分别处于中度、重度污染状态,营养盐综合指数属于重度污染状态。底泥存在不同程度的重金属富集,铜、锌、汞、镉、铬、铅、砷、镍等8项重金属的平均浓度是天津土壤背景值的0.45~2.73倍。汞的地累积指数平均值为0.64,为轻度污染;铜、锌、镉、铬、铅、砷、镍等其他7项重金属为清洁状态。汞的潜在生态风险指数约110,为较高生态危害;其他7项重金属生态风险指数均小于80,为轻微生态危害。综合Pearson相关性、主成分及PMF分析,研究区重金属最主要的污染来源是交通源和大气沉降,其次是工业源,最后是农业源。总体来看,研究区水体水质较差,沉积物有重金属轻度富集,其中汞是沉积物生态风险的主要贡献元素。     

城市绿地降低空气中含菌量的生态效应研究

按照大气生物监测的方法和要求，选择了上海市区的交通干通。公园和居住区的主要类型的绿地，对绿地降低气挟菌数量的生态效应进行了初步研究，结果表明，绿地结构，植物种类配置和粉尘污染是影响绿地降低气挟菌数量效应的主要因素。     

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.     

颗粒活性炭对水中典型医药类物质的吸附特性

通过静态与动态吸附实验考察了颗粒活性炭对水中4种典型医药类物质降固醇酸（CA）、卡马西平（CBZ）、萘普生（NAP）和双氯芬酸（DCF）的吸附特性。首先在比较木质炭（MAC）和椰壳炭（YAC）对药物吸附效果和表征测试基础上,优选YAC为实验活性炭。静态实验研究发现,当YAC投加量133 mg·L-1,温度25℃和转速150 r·min-1时,CA、CBZ、NAP和DCF的平衡吸附量分别为2.48、3.0、2.74和2.52 mg·g-1,YAC对4种药物的吸附强弱为：CBZ >NAP >DCF >CA;4种药物的吸附均符合假二级吸附动力学模型和Friendlich等温吸附模型,吸附速率受化学吸附、颗粒内扩散、表面吸附和液膜扩散等颗粒外扩散过程的控制;YAC对药物的吸附能力与其pKa、lgKow和水溶液中的存在状态等有关。通过YAC对超纯水溶液、污水厂过滤前后二级出水中4种目标物的去除率比较,发现污水中的离子强度是降低目标物去除率的主要因素,它减弱了目标物与活性炭的静电作用力,而溶解性有机物由于竞争椰壳炭上的吸附点位在一定程度上也降低了其去除率。YAC固定床动态吸附穿透实验表明,YAC对CBZ的吸附性能最强、CA最弱,动态与静态实验结果是一致的。     

Identification and dose dependency of ibuprofen biliary metabolites in rainbow trout

The biotransformation of the anti-inflammatory drug ibuprofen (IBF) was studied by exposing rainbow trout (Oncorhynchus mykiss) to IBF via intraperitoneal (i.p.) injection, and via water at four (0.17, 1.9, 13 and 145 μg L⁻¹) exposure levels for 4 d. Following exposure, the bile was collected and analyzed by LC–MS/MS methods. The identification of the formed metabolites in i.p. injected fish bile was based on the exact mass determinations by a time-of-flight mass analyzer (Q–TOF–MS) and on the studies of fragments and fragmentation patterns of precursor ions by ion trap mass analyzer (IT-MS). In addition to unmetabolized IBF, several phase I and phase II metabolites were found in the bile. The main metabolites were acyl glucuronides and taurine conjugates of IBF and of hydroxylated IBFs. The bioconcentration factors (BCF_bile), defined as the ratio of the sum of IBF and its metabolites in fish bile to the concentration of IBF in water, was determined following enzymatic deconjugation and was found to range from 14 000 to 49 000. The highest BCF_bile was found at the lowest exposure concentration (0.17 μg L⁻¹). The results show that rainbow trout has a high capacity for biotransformation of IBF, and the exposure of fish to sub μg L⁻¹ concentrations of IBF can be determined by the analyses of the biliary metabolites of the compound.     

Calibration of the Chemcatcher passive sampler for the monitoring of priority organic pollutants in water

An integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low-density polyethylene diffusion membrane was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polyaromatic hydrocarbons and organochlorine pesticides, in water. The effect of temperature and water turbulence on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water was studied in a flow-through system under controlled conditions. It was found that the absorption of test analytes from water to the sampler is related to their desorption to water. This allows for the in situ calibration of the uptake of pollutants using offload kinetics of performance reference compounds. The sampling kinetics are dependent on temperature, and for most of the tested analytes also on the flow velocity. Sampler-water partition coefficients did not significantly change with temperature.