Persistent organic pollutants (POPs) in the conventional activated sludge treatment process: model predictions against experimental values

The FATE and treatibility estimator (FATE) model, developed by the United States Environmental Protection Agency was used for the prediction of the FATE of 26 persistent organic pollutants (POPs), i.e. 7 PCBs and 19 organochlorine compounds (OCs), during the conventional activated sludge treatment process applied in the waste water treatment plant (WWTP) of Thessaloniki, Greece. The removal rates predicted by the model for the primary and the secondary treatment stages were found to differ substantially from those experimentally measured. When the overall treatment was considered, the differences between measured and model predicted removals were within acceptable limits of confidence. Possible reasons that might cause deviations from experimental values were suggested to be the wastewater content in dissolved organic carbon (DOC), and/or the low concentrations of POPs in untreated wastewater.     

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.     

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.     

Characteristics of biotic and abiotic removals of dissolved organic carbon in wastewater effluents using soil batch reactors.

Biodegradable dissolved organic carbon (BDOC) analyses and abiotic adsorption of dissolved organic carbon (DOC) from different wastewater effluent were conducted to evaluate biotic and abiotic removal mechanisms as a function of the initial DOC concentration and source of DOC using soil batch reactors. To obtain high DOC concentrations, a laboratory-scale reverse osmosis unit was used. It was found that BDOC fraction was independent of the initial DOC concentration and was dependent on the source of wastewater and/or the types of wastewater treatment. The BDOC fractions varied from 9 to 73%. Trickling filter effluent (Tucson, Arizona) showed the highest BDOC, ranging from 65 to 73% biodegradable, while wastewater treated by the soil aquifer treatment (SAT) (NW-4) was found to be most refractory, with DOC removals of 9 to 14%. For nitrified/denitrified tertiary effluent (Mesa, Arizona) and secondary effluent (Scottsdale, Arizona), 36 to 42% removal of DOC was observed during the BDOC test. The amount of BDOC in the wastewater depended not on the concentration of DOC, but on the effectiveness of pretreatment. Abiotic adsorption capacity of wastewater effluent varied from 6 to 18%. Molecular weight distribution analyses showed that more than 50% of DOC in the Scottsdale concentrate had a molecular weight of less than 1000 Da, and no significant change in distribution profiles occurred after approximately 12% abiotic adsorption with both soils with acclimated microorganisms (SAT soil) and soils without acclimated microorganisms (non-SAT soils). Hence, preferential adsorption was not observed and the presence of acclimated microbes did not influence adsorption.     

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.     

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.     

Comparison of dissolved-organic-carbon residuals from air- and pure-oxygen-activated-sludge sequencing-batch reactors.

Literature shows that full-scale pure-oxygen activated sludge (O2-AS) wastewater treatment plants (WWTPs) generate effluents with higher dissolved-organic carbon (DOC) concentrations and larger high-molecular-weight fractions compared to air-activated-sludge (Air-AS) WWTP effluents. The purpose of this paper was to evaluate how gas supplied (air vs. pure oxygen) to sequencing-batch reactors affected DOC transformations. The main conclusions of this paper are (a) O2-AS effluent DOC is more refractory than air-AS effluent DOC; and (b) O2-AS systems may have higher five-day biochemical oxygen demand removals than air-AS systems; however, in terms of COD and DOC removal, air-AS systems are better than O2-AS systems. Analysis of a database from side-by-side O2- and air-AS pilot tests from literature supported these observations.     

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.     

Transformation of molecular weight distributions of dissolved organic carbon and UV-absorbing compounds at full-scale wastewater-treatment plants.

The molecular-weight distribution (MWD) of wastewater dissolved-organic carbon (DOC) was determined in samples from seven full-scale wastewater-treatment plants (WWTPs) that use different biological treatments (air activated sludge [air-AS], pure-oxygen AS [O2-AS], and trickling filters). The research objective was to determine how different biological treatments influenced the MWD of wastewater DOC. Primary sedimentation effluent DOC from most of the WWTPs exhibited a skewed distribution toward the low-molecular-weight fraction (MWF) (40 to 50%, < 0.5 K Daltons [KDa]). The Air-AS effluent DOC exhibited a centrally clustered distribution, with the majority of DOC in the intermediate MWF (0.5 to 3 KDa). The O2-AS effluent DOC exhibited a skewed distribution toward the high MWF (> 3 KDa). The removal of DOC by air- and O2-AS bacteria followed trends predicted by a macromolecule degradation model. Trickling-filter effluent DOC exhibited a skewed distribution toward the high MWF (50% DOC, > 3 KDa).     

城市污水二级出水中溶解性有机物特性分析

分别采用凝胶色谱、亲疏水性组分分离、荧光色谱等方法,研究了城市污水处理厂二级出水中溶解性有机物的分子量分布、亲疏水组分含量以及荧光光谱特性。结果表明,二级出水中疏水性组分较亲水性组分多,疏水性组分约占总有机物的64.3%,而亲水性组分占35.7%左右;二级出水及其不同亲/疏水组分中溶解性有机物分子量分布基本集中在4.5 kDa以下,其中弱疏水性组分和亲水性组分中主要为分子量小于1.5 kDa的有机物;二级出水溶解性有机物中含有腐殖酸类、富里酸类以及蛋白质类物质,其中含量以腐殖酸类为主。     

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.     

Activated sludge systems removal efficiency of veterinary pharmaceuticals from slaughterhouse wastewater

The knowledge on the efficiency of wastewater treatment plants (WWTPs) from animal food production industry for the removal of both hormones and antibiotics of veterinary application is still very limited. These compounds have already been reported in different environmental compartments at levels that could have potential impacts on the ecosystems. This work aimed to evaluate the role of activated sludge in the removal of commonly used veterinary drugs, enrofloxacin (ENR), tetracycline (TET), and ceftiofur, from wastewater during a conventional treatment process. For that, a series of laboratory-controlled experiments using activated sludge were carried out in batch reactors. Sludge reactors with 100 μg/L initial drug charge presented removal rates of 68 % for ENR and 77 % for TET from the aqueous phase. Results indicated that sorption to sludge and to the wastewater organic matter was responsible for a significant percentage of drugs removal. Nevertheless, these removal rates still result in considerable concentrations in the aqueous phase that will pass through the WWTP to the receiving environment. Measuring only the dissolved fraction of pharmaceuticals in the WWTP effluents may underestimate the loading and risks to the aquatic environment.     

Occurrence and removal of polycyclic aromatic hydrocarbons and their derivatives in an ecological wastewater treatment plant in South China and effluent impact to the receiving river

Ecological wastewater treatment plant (EWWTP), a kind of emerging wastewater treatment plant (WWTP) in recent years, combined microbiology with botany which is efficient for the removal of nitrogen and organic matter, as well as deodorization. The occurrence and removal of micro-organic pollutants in EWWTPs were still not well known. Polycyclic aromatic hydrocarbons (PAHs) and their typical derivatives (SPAHs) including the oxygenated PAHs (OPAHs), chlorinated PAHs (ClPAHs), and methyl PAHs (MPAHs) were investigated in an EWWTP in Guangdong Province, China. The concentrations of the Σ6 OPAHs (114–384 ng/L) were higher than the Σ16 PAHs (92–250 ng/L), and much higher than the Σ4 MPAHs (13–64 ng/L) and Σ9 ClPAHs (2–3 ng/L) in the EWWTP and the effluent receiving river. The total removal efficiencies of the PAHs, OPAHs, MPAHs, and ClPAHs in the EWWTP (43?±?14%, 41?±?7%, 55?±?16%, and 18?±?4%) were lower than the traditional WWTPs, probably due to the lower concentration of the sludge in the ecological treatment. The advanced treatment process (microfiltration and UV disinfection treatment) contributed much less (0–20%) to the whole removal efficiency than the ecological treatment (80–100%). The effluent from the EWWTP slightly reduced the PAHs and SPAHs concentrations in the receiving river. The high concentrations of the PAHs and SPAHs in the receiving river were similar to the influent of the EWWTP, indicating that some untreated wastewater was directly discharged to the river, especially in the upstream.

     

Improvement of DOC removal by multi-stage AOP-biological treatment

The single and multi-stages advanced oxidation process (AOP)-biological treatments were evaluated to apply for drinking water treatment, especially for the water containing less susceptible dissolved organic carbon (DOC) to ozone, comparing with the ozonation-biological treatment. Minaga reservoir water and the secondary effluent from a Municipal wastewater treatment plant were used as dissolved organic matter (DOM) solutions. DOC removals after 60 min AOP-biological treatment were 62% and 41% in the Minaga reservoir water and the secondary effluent, respectively, whereas those in the ozonation-biological treatment only 40% and 15% of DOC were removed, respectively. The result indicated that the single-stage AOP-biological treatment could improve DOC removal in comparison with the single-stage ozonation-biological treatment. This is because the AOP mineralized both biodegradable dissolved organic carbon (BDOC) produced in the early stage of oxidation and non-biodegradable dissolved organic carbon (NBDOC), whereas only BDOC was mineralized by further ozonation and NBDOC was not oxidized in the ozonation-biological treatment. The multi-stage treatment could not improve DOC removal in comparison with the single-stage treatment in the ozonation-biological treatment for the secondary effluent containing less susceptible DOC to ozone. However, the multi-stage AOP-biological treatment significantly reduced DOC and achieved 71% of DOC removal by 4 times repetition of 15 min oxidation, whereas DOC removal was 41% in the single-stage AOP-biological treatment for the same oxidation time. The improvement of DOC removal by the multi-stage AOP-biological treatment was due to BDOC removal as a radical scavenger by subsequent biological treatment in the early stage of oxidation and direct mineralization in the latter stage of oxidation.     

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.     

Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

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.

     

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.     

Efficacy and reliability of upgraded industrial treatment plant at Porto Marghera, near Venice, Italy, in removing nutrients and dangerous micropollutants from petrochemical wastewaters

Chemical and petrochemical wastewaters contain a host of contaminants that require different treatment strategies. Regulation of macropollutants and micropollutants in the final discharge from industrial wastewater treatment plants (WWTPs) have become increasingly stringent in recent decades, requiring many WWTPs to be upgraded. This article presents an analysis of a WWTP treating petrochemicals in Porto Marghera, Italy, that recently was upgraded following legislative changes. Because of strict legal limits for macropollutants and micropollutants and a lack of space necessary for a full-scale WWTP overhaul, the existing activated sludge tank was converted into a membrane biological reactor. The paper presents experimental data collected during a five-month investigation showing the removal rates achieved by the upgraded plant for macropollutants (particularly nitrogen compounds) and micropollutants (heavy metals and organic and inorganic toxic compounds).     

Occurrence and behaviour of pharmaceutical compounds in a Portuguese wastewater treatment plant: Removal efficiency through conventional treatment processes

Wastewater treatments can eliminate or remove a substantial amount of pharmaceutical active compounds (PhACs), but there may still be significant concentrations of them in effluents discharged into surface water bodies. Beirolas wastewater treatment plant (WWTP) is located in the Lisbon area and makes its effluent discharges into Tagus estuary (Portugal). The main objective of this study is to quantify a group of 32 PhACs in the different treatments used in this WWTP. Twelve sampling campaigns of wastewater belonging to the different treatments were made in 2013–2014 in order to study their removal efficiency. The wastewaters were analysed by solid phase extraction (SPE) and ultra-performance liquid chromatography coupled with tandem mass detection (UPLC–MS/MS). The anti-diabetics were the most frequently found in wastewater influent (WWI) and wastewater effluent (WWE) (208 and 1.7 μg/L, respectively), followed by analgesics/antipyretics (135 μg/L and < LOQ, respectively), psychostimulants (113 and 0.49 μg/L, respectively), non-steroidal anti-inflammatory drugs (33 and 2.6 μg/L, respectively), antibiotics (5.2 and 1.8 μg/L, respectively), antilipidemics (1.6 and 0.24 μg/L, respectively), anticonvulsants (1.5 and 0.63 μg/L, respectively) and beta blockers (1.3 and 0.51 μg/L, respectively). A snapshot of the ability of each treatment step to remove these target PhACs is provided, and it was found that global efficiency is strongly dependent on the efficiency of secondary treatment. Seasonal occurrence and removal efficiency was also monitored, and they did not show a significant seasonal trend.