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.     

Micropollutant removal during biological wastewater treatment and a subsequent ozonation step

The design criteria for wastewater treatment plants (WWTP) and the sludge retention time, respectively, have a significant impact on micropollutant removal. The upgrade of an Austrian municipal WWTP to nitrogen removal (best available technology, BAT) resulted in increased elimination of most of the analyzed micropollutants. Substances, such as bisphenol-A, 17α-ethinylestradiol and the antibiotics erythromycin and roxithromycin were only removed after the upgrade of the WWTP. Nevertheless, the BAT was not sufficient to completely eliminate these compounds. Thus, a pilot scale ozonation plant was installed for additional treatment of the effluent. The application of 0.6 g O₃ g DOC⁻¹ increased the removal of most of the micropollutants, especially for compounds that were not degraded in the previous biological process, as for example carbamazepine and diclofenac. These results indicated that the ozonation of WWTP effluent is a promising technology to further decrease emissions of micropollutants from the treatment process.     

城镇污水处理厂用地、运行及建设费用研究

汇总收集了国内已建城镇污水处理厂的大量资料,分析探讨了污水处理厂厂区占地面积、运行及建设费用与处理规模之间的关系,为今后污水处理厂的设计规划、工艺选择、建设费用分析等提供参考依据。研究表明污水处理厂厂区占地面积与处理规模可用函数表示,且具有较高的相关性。城镇污水处理厂所选用的工艺和处理规模对其运行成本有较大的影响,分别对大中小规模的污水处理厂在不同工艺下的运行成本进行分析,得出大规模污水处理厂的工艺选择对其运行成本影响不大;中规模污水处理厂易采用氧化沟工艺;小规模的污水处理厂适合采用SBR工艺。建设费用与污水处理规模有密切关系,由于建设费用受多种因素影响,又以江浙地区为例,对其建设费用与污水处理规模之间关系进行具体分析,对以上结论给予一定的补充。     

Occurrence,elimination, and risk of anticoagulant rodenticides and drugs during wastewater treatment

Anticoagulants are biocides widely used as pest control agents in agriculture, urban infrastructures, and domestic applications for the control of rodents. Other anticoagulants such as warfarin and acenocoumarol are also used as drugs against thrombosis. After use, anticoagulants are discharged to sewage grids and enter wastewater treatment plants (WWTPs). Our hypothesis is that WWTP effluents can be a source of anticoagulants to receiving waters and that these can affect aquatic organisms and other nontarget species. Therefore, the objective of the present study was to determine the occurrence of 11 anticoagulants in WWTPs receiving urban and agricultural wastewaters. Warfarin was the most ubiquitous compound detected in influent waters and was partially eliminated during the activated sludge treatment, and low nanograms per liter concentration were found in the effluents. Other detected compounds were coumatetralyl, ferulenol, acenocoumarol, flocoumafen, brodifacoum, bromadiolone, and difenacoum at concentrations of 0.86–87.0 ng L^?1. Considering water volumes of each WWTP, daily emissions were estimated to be 0.02 to 21.8 g day^?1, and thus, WWTPs contribute to the loads of anticoagulants to receiving waters. However, low aquatic toxicity was observed using Daphnia magna as a model aquatic organism.     

Presence of carbamazepine,naproxen, and ibuprofen in wastewater from northern Tunisia

We investigated the occurrence of three pharmaceutical residues in four wastewater treatment plants (WWTPs) from northern Tunisia. The selected compounds were carbamazepine, naproxen, and ibuprofen; they are among the most commonly prescribed and widely used pharmaceutical agents worldwide. Samples (200?mL) were pre-concentrated using the solid phase extraction (SPE) enrichment procedure and the analysis of the pharmaceuticals was performed with high-performance liquid chromatography (HPLC-UV). The overall procedure provided limits of detection (LOD) lower than 0.5 µg.L^?1and recoveries of 78–97%. For the carbamazepine compound, the mean concentrations were 60.58, 93.19, and 132 µg.L^?1 for the Bizerte, Jendouba, and Tunis WWTPs, respectively. This pharmaceutical was not detected in the Beja WWTPs. Naproxen and ibuprofens were not detected in the Jendouba WWTP but were found in the three other WWTPs with concentrations ranging from 2.94 to 36.17 µg.L^?1 and from 8.02 to 43.22 µg.L^?1, respectively. From the obtained data, it seems that these WWTPs are not able to eliminate this kind of micro-pollutants.     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.     

Identification of relevant micropollutants in Austrian municipal wastewater and their behaviour during wastewater treatment

The European Union has defined environmental quality standards (EQSs) for surface waters for priority substances and several other pollutants. Furthermore national EQSs for several chemicals are valid in Austria. The study investigated the occurrence of these compounds in municipal wastewater treatment plant (WWTP) effluents. In a first screening of 15 WWTPs relevant substances were identified, which subsequently were monitored in 9 WWTPs over 1 year (every 2 months). Out of 77 substances or groups of substances (including more than 90 substances) 13 were identified as potentially relevant in respect to water pollution and subjected to the monitoring, whereas most other compounds were detected in concentrations far below the respective EQS for surface waters and therefore not further considered. The preselected 13 compounds for monitoring were cadmium (Cd), nickel (Ni), copper (Cu), selenium (Se), zinc (Zn), diuron, polybrominated diphenyl ethers (PBDEs), di(ethyl-hydroxyl)phthalate (DEHP), tributyltin compounds (TBT), nonylphenoles (NP), adsorbable organic halogens (AOX) and the complexing agents ethylenediaminetetraacetic acid (EDTA) as well as nitrilotriacetic acid (NTA). In the effluents of WWTPs the concentrations of the priority substances Cd, NP, TBT and diuron frequently exceeded the respective EQS, whereas the concentrations for DEHP and Ni were below the respective EQS. The effluent concentrations for AOX, EDTA, NTA, Cu, Se and Zn frequently are in the range or above the Austrian EQS for surface waters. Besides diuron and EDTA all compounds are removed at least partially during wastewater treatment and for most substances the removal via the excess sludge is the major removal pathway. For the 13 compounds which were monitored in WWTP effluents population equivalent specific discharges were calculated. Since for many compounds no or only few information is available, these population equivalent specific discharges can be used to assess emissions from municipal WWTPs to surface waters as well as to make a first assessment of the impact of a discharge on surface waters chemical status. Comparing discharges and river pollution on a load basis, the influence of diffuse sources becomes obvious and therefore should also be taken into consideration in river management.     

Comparison of the occurrence of antibiotics in four full-scale wastewater treatment plants with varying designs and operations

The occurrence of ciprofloxacin, sulfamethoxazole, tetracycline, and trimethoprim antibiotics in four full-scale wastewater treatment plants (WWTPs) that differ in design and operating conditions was determined. The WWTPs chosen utilized a variety of secondary removal processes, such as a two stage activated sludge process with a nitrification tank, extended aeration, rotating biological contactors, and pure oxygen activated sludge. Several of the WWTPs also employed an advanced treatment process, such as chlorination and UV radiation disinfection. The detected concentrations (microg/l) ranged from 0.20 to 1.4 for ciprofloxacin, 0.21 to 2.8 for sulfamethoxazole, 0.061 to 1.1 for tetracycline, and 0.21 to 7.9 for trimethoprim. The overall percent difference in the concentrations of the antibiotics in the effluent and influent of these antibiotics differed between plants and ranged from 33% to 97%. Based on these four full-scale WWTPs evaluated, the apparent removal of organic micropollutants in wastewater is dependent on a combination of biological and physico-chemical treatment processes and operating conditions of the treatment system.     

Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong

The study reported in this paper examined the concentrations of nineteen perfluorochemicals (PFCs), including perfluoroalkyl sulfonates, carboxylates, and sulfonamides in samples collected from Hong Kong wastewater treatment plants (WWTPs) and sediments. The study was the first to use an external isolator column to assist in the quantification of PFCs in environmental samples without having to make internal modifications to a liquid chromatography system. Perfluorooctanesulfonate was found to be the dominant PFC pollutant in Hong Kong, and the WWTP sludge was the major sink of PFCs discharged from the urban areas. Compared to discharge influenced by industrial activities, much less perfluorooctanoate was found in waste streams. The significantly lower level of perfluorodecanesulfonate in WWTP sludge reflects the important influence of consumer products on PFC distribution. The dominance of even-chain length perfluoroalkyl carboxylates in all of the WWTP sludge samples investigated further suggests the strong aerobic degradation of fluorotelomer alcohols in WWTPs.     

Polycyclic aromatic hydrocarbons in wastewater, WWTPs effluents and in the recipient waters of Beijing, China

In this study, surface water samples from the Wenyu River and the North Canal, effluent from major wastewater treatment plants (WWTPs) in Beijing, and wastewater from open sewers that discharge directly into the river system were collected and analyzed for 16 priority USEPA polycyclic aromatic hydrocarbons (PAHs). Concentrations of these 16 PAHs ranged from 193 to 1790 ng/L in river surface waters, 245 to 404 ng/L in WWTP effluents, and 431 to 2860 ng/L in the wastewater from the small sewers. The WWTP effluent was the main contributor of dissolved PAHs to the river, while wastewater from the small sewers contributed both dissolved and suspended particulate matter-associated PAH to the river as indicated by the high dissolved organic carbon and suspended particulate matter contents in the wastewater. Although the flow from each open sewer was small, a PAH discharge as high as 44 kg/year could occur into the river from these types of sewers. This amount was equivalent to about 22 % of the PAH loads discharged into the North Canal downstream from Beijing, whereas the remainder was mainly released by the major WWTPs in Beijing.     

Free synthetic and natural estrogen hormones in influent and effluent of three municipal wastewater treatment plants.

Three municipal wastewater treatment plants (WWTPs) in southeastern Pennsylvania were sampled to determine the presence and concentrations of 12 natural and synthetic estrogen hormones in the wastewater influent and effluent. The target estrogens were 17alpha-estradiol, estrone, estriol, equilin, 17alpha-dihydroequilin, 17beta-estradiol, 17alpha-ethinyl estradiol, gestodene, norgestrel, levonorgestrel, medrogestone, and trimegestone. One WWTP uses a biofilm reactor (packed-bed trickling filter),and the other two use suspended-growth media (continuously stirred activated sludge reactor and sequential batch reactor). Estrone was detected in all the three plants; estriol and estradiol were detected at two WWTPs; and 17 alpha-dihydroequilin and 17 alpha-ethinyl estradiol were detected at one WWTP. The concentration of estrogens in the influent and effluent of the three treatment plants ranged from 1.2 to 259 ng/L and 0.5 to 49 ng/L, respectively. The percentage removal of estrogens from the aqueous phase ranged from 41 to 99%, except in the case of 17alpha-dihydroequilin; the removal of 17alpha-dihydroequilin was negligible. The suspended-growth media systems showed higher removal efficiencies for estrogens than the biofilm system. The analytical method uses a Varian C-18 solid-phase extraction (Varian Inc., Palo Alto, California), followed by a derivatization with bis(trimethylsilyl)trifluoroacetamide. The detection limits for the estrogen compounds ranged from 0.1 to 10 ng/L using a sample size of 1 L. The method recoveries ranged from 71 to 120%, and the relative standard deviation ranged from 6 to 14% for all the hormones.     

Perfluorooctane surfactants in waste waters, the major source of river pollution

Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) are persistent and widely distributed in the environment. Recently, the discharge of municipal waste water has been shown to be an important route of such perfluoroalkyl surfactants into the aquatic environment. The aim of this study was to assess the mass flow of PFOA and PFOS from typical waste water treatment plants (WWTPs) into surface waters. Samples were collected at different stages of treatment of four WWTPs in Northern Bavaria, Germany, and from the rivers receiving the treated waste waters (WW). The outflow of PFOA from the WWTPs to the rivers was 20-fold higher than the inflow to the plants; about a tenth was removed with the sludge. For PFOS, the increase from inlet to outlet was about 3-fold; almost half of it was retained in the sludge. Both surfactants were released into river water from the WWTP of a medium-sized city with domestic, industrial and commercial waste waters; in domestic waste waters the surfactants were found at much lower levels.     

Waste water treatment plants as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

To investigate waste water treatment plants (WWTPs) as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two WWTPs and two reference sites using high volume samplers. Contaminants were accumulated on glass fiber filters and PUF/XAD-2/PUF cartridges, extracted compound-dependent by MTBE/acetone, methanol, or hexane/acetone and detected by GC-MS or HPLC-MS/MS. Total (gas + particle phase) concentrations ranged from 97 to 1004 pg m⁻³ (neutral PFCs), <MQL to 13 pg m⁻³ (ionic PFCs), 5781 to 482,163 pg m⁻³ (musk fragrances) and <1 to 27 pg m⁻³ (PBDEs) and were usually higher at WWTPs than at corresponding reference sites, revealing that WWTPs can be regarded as sources of musk fragrances, PFCs and probably PBDEs to the atmosphere. Different concentrations at the two WWTPs indicated an influence of WWTP size or waste water origin on emitted contaminant amounts.     

Occurrence of estrogenic effects in sewage and industrial wastewaters in Beijing, China

Estrogenic potencies of the effluents or water samples from wastewater treatment plants (WWTPs), industries and hospitals and some receiving rivers in Beijing city were estimated by using a human estrogen receptor recombinant yeast assay. Estrogenic activity of industrial wastewaters was found to range from 0.1 to 13.3 ng EEQ/L and decreased to the range of 0.03-1.6 ng EEQ/L after treatment. Estrogenic activity in WWTP influent ranged from 0.3 to 1.7 ng EEQ/L and decreased to the range of 0.05-0.5 ng EEQ/L after treatment. In the receiving river waters, the estrogenic effect range was 0.1-4.7 ng EEQ/L. These data suggest that treated industrial effluents and WWTP effluents of concern are not the only source of estrogenic pollution in surface waters in Beijing city. EEQ levels in Beijing river water are likely attributable to untreated municipal and industrial wastewaters discharged directly into the river.     

Europe-wide survey of estrogenicity in wastewater treatment plant effluents: the need for the effect-based monitoring

A pan-European monitoring campaign of the wastewater treatment plant (WWTP) effluents was conducted to obtain a concise picture on a broad range of pollutants including estrogenic compounds. Snapshot samples from 75 WWTP effluents were collected and analysed for concentrations of 150 polar organic and 20 inorganic compounds as well as estrogenicity using the MVLN reporter gene assay. The effect-based assessment determined estrogenicity in 27 of 75 samples tested with the concentrations ranging from 0.53 to 17.9 ng/L of 17-beta-estradiol equivalents (EEQ). Approximately one third of municipal WWTP effluents contained EEQ greater than 0.5 ng/L EEQ, which confirmed the importance of cities as the major contamination source. Beside municipal WWTPs, some treated industrial wastewaters also exhibited detectable EEQ, indicating the importance to investigate phytoestrogens released from plant processing factories. No steroid estrogens were detected in any of the samples by instrumental methods above their limits of quantification of 10 ng/L, and none of the other analysed classes of chemicals showed correlation with detected EEQs. The study demonstrates the need of effect-based monitoring to assess certain classes of contaminants such as estrogens, which are known to occur at low concentrations being of serious toxicological concern for aquatic biota.     

Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography-mass spectrometry and fluorescence detection

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.     

Dioxin-like compounds in Australian sewage sludge--review and national survey

An Australian survey of dioxin-like compounds in sewage sludge was conducted in two parts (a) a national survey, and (b) a time-study. All sewage sludge samples analysed as part of these studies had low overall concentrations of dioxin-like compounds. Out of 37 samples, all except one, were within the reported concentration range of soil within the Australian environment. The mean concentration of dioxin-like compounds in the Australian sewage sludge survey of 2006 was found to be 5.6 (s.d. 4.5) ng WHO(05) TEQkg(-1) (n=14) and were within the range of 1.2-15.3 ng WHO(05) TEQ kg(-1). All the Australian sewage sludge samples cited in these studies were below the Victorian EPA "investigation limit" of 50 ng WHO(98) TEQ kg(-1), and well below the European proposed guidelines of 100 ng I-TEQ kg(-1). The burden of dioxin-like compounds in Australian sewage sludge is low and its land application as biosolids is not likely to pose a problem. A general positive relationship was found between population of the town producing the waste and both dioxin-like PCDD/Fs and dioxin-like PCBs. The one exception to this trend was sludge from a town that had a history of smelting and had a relatively high burden of dioxin-like compounds. Sludge from one rural WWTP also had a higher burden of dioxin-like compounds. The treatment plant services a geographically isolated town with a low population and no known emitters of dioxin-like compounds. However, this sample also had a relatively high burden of dioxin-like PCBs, which could be the source of the dioxin-like PCDD/Fs found in this sludge. The time study analyzing sludges from three WWTP from the same city between the years 2002 and 2006 found no apparent difference between WWTPs, but a statistically significant decline of 1.49 ng WHO(05) TEQ kg(-1) per year. Also, a comprehensive review of the scientific literature, presents typical levels and sources of dioxin-like compounds in international sewage sludges.     

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.     

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

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

Occurrence and ecological hazard assessment of selected veterinary medicines in livestock wastewater treatment plants

The occurrence of some veterinary medicines in the livestock wastewater plants (WWTPs) was investigated. This investigation represented the occurrence of veterinary medicines to treat in the livestock WWTPs or be discharged into the water system in Korea since the sampling sites were widely distributed across the nation and samples were collected from the 11 livestock WWTPs. Nine antibiotics, two analgesics, and two disinfectants occurred in the livestock wastewater plants (WWTPs). From 11 livestock WWTP influents, chlortetracycline, oxytetracycline, acetylsalicylic acid, and disinfectants frequently occurred with the high concentrations. Meanwhile, sulfamethoxazole, erythromycin-H₂O, and trimethoprim did not occur during sampling periods. The values for log Kow of each chemical showed a high correlation with the number of hydrogen bonding acceptors and were important parameters to estimate and understand the biodegradability and toxicity of a compound in the environment. The biodegradability of each compound was proportional to the hydrophilicity of each compound and the toxicity was proportional to the number of hydrogen bonding acceptors of each compound. The expected introductory concentration (EIC), predicted exposure concentration (PEC), and hazard quotient showed that the livestock WWTP effluents were hazardous to ecosystems.