A tiered procedure for assessing the formation of biotransformation products of pharmaceuticals and biocides during activated sludge treatment

Upon partial degradation of polar organic micropollutants during activated sludge treatment, transformation products (TPs) may be formed that enter the aquatic environment in the treated effluent. However, TPs are rarely considered in prospective environmental risk assessments of wastewater-relevant compound classes such as pharmaceuticals and biocides. Here, we suggest and evaluate a tiered procedure, which includes a fast initial screening step based on high resolution tandem mass spectrometry (HR-MS/MS) and a subsequent confirmatory quantitative analysis, that should facilitate consideration of TPs formed during activated sludge treatment in the exposure assessment of micropollutants. At the first tier, potential biotransformation product structures of seven pharmaceuticals (atenolol, bezafibrate, ketoprofen, metoprolol, ranitidine, valsartan, and venlafaxine) and one biocide (carbendazim) were assembled using computer-based biotransformation pathway prediction and known human metabolites. These target structures were screened for in sludge-seeded batch reactors using HR-MS/MS. The 12 TPs found to form in the batch experiments were then searched for in the effluents of two full-scale, municipal wastewater treatment plants (WWTPs) to confirm the environmental representativeness of this first tier. At the second tier, experiments with the same sludge-seeded batch reactors were carried out to acquire kinetic data for major TPs that were then used as input parameters into a cascaded steady-state completely-stirred tank reactor (CSTR) model for predicting TP effluent concentrations. Predicted effluent concentrations of four parent compounds and their three major TPs were corroborated by comparison to 3-day average influent and secondary effluent mass flows from one municipal WWTP. CSTR model-predicted secondary effluent mass flows agreed within a factor of two with measured mass flows and confidence intervals of predicted and measured mass flows overlapped in all cases. The observed agreement suggests that the combination of batch-determined transformation kinetics with a simple WWTP model may be suitable for estimating aquatic exposure to TPs formed during activated sludge treatment. Overall, we recommend the tiered procedure as a realistic and cost-effective approach to include consideration of TPs of wastewater-relevant compounds into exposure assessment in the context of prospective chemical risk assessment.     

Impact of wastewater treatment plant discharge of lidocaine, tramadol, venlafaxine and their metabolites on the quality of surface waters and groundwater

The presence of the anesthetic lidocaine (LDC), the analgesic tramadol (TRA), the antidepressant venlafaxine (VEN) and the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) was investigated in wastewater treatment plant (WWTP) effluents, in surface waters and in groundwater. The analytes were detected in all effluent samples and in only 64% of the surface water samples. The mean concentrations of the analytes in effluent samples from WWTPs with wastewater from only households and hospitals were 107 (LDC), 757 (TRA), 122 (ODT), 160 (VEN) and 637 ng L(-1) (ODV), while the mean concentrations in effluents from WWTPs treating additionally wastewater from pharmaceutical industries as indirect dischargers were for some pharmaceuticals clearly higher. WWTP effluents were identified as important sources of the analyzed pharmaceuticals and their metabolites in surface waters. The concentrations of the compounds found in surface waters ranged from 相似文献   

Multivariate analyses of the effect of an urban wastewater treatment plant on spatial and temporal variation of water quality and nutrient distribution of a tropical mid-order river

Freshwater resources are increasingly scarce due to human activities, and the understanding of water quality variations at different spatial and temporal scales is necessary for adequate management. Here, we analyze the hypotheses that (1) the presence of a wastewater treatment plant (WWTP) and (2) a polluted tributary that drains downstream from the WWTP change the spatial patterns of physicochemical variables (pH, turbidity, dissolved oxygen, and electrical conductivity) and nutrient concentrations (reactive soluble phosphorus, total phosphorus, nitrogen series, total nitrogen, and total dissolved carbon) along a mid-order river in SE Brazil and that these effects depend on rainfall regime. Six study sites were sampled along almost 4 years to evaluate the impacts of human activities, including sites upstream (1–3) and downstream (5–6) from the WWTP. The impacts were observed presenting an increasing trend from the source (site 1) towards Água Quente stream (site 4, the polluted tributary), with signs of attenuation at site 5 (downstream from both WWTP and site 4) and the river mouth (site 6). Input of nutrients by rural and urban runoff was observed mainly at sites 2 and 3, respectively. At sites 4 and 5, the inputs of both untreated and treated wastewaters increased nutrient concentrations and changed physicochemical variables, with significant impacts to Monjolinho River. Seasonal variations in the measured values were also observed, in agreement with the pluviometric indexes of the region. Univariate analyses suggested no effect of the WWTP for most variables, with continued impacts at sites downstream, but non-parametric multivariate analysis indicated that these sites were recovering to chemical characteristics similar to upstream sites, apparently due to autodepuration. Therefore, multivariate methods that allow rigorous tests of multifactor hypotheses can greatly contribute to determine effects of both point and non-point sources in river systems, thus contributing to freshwater monitoring and management.     

Occurrence of pharmaceutical compounds in wastewater process streams in Dublin,Ireland

The aim of this work is to establish baseline levels of pharmaceuticals in three wastewater treatment plant (WWTP) streams in the greater Dublin region to assess the removal efficiency of the selected WWTPs and to investigate the existence of any seasonal variability. Twenty compounds including several classes of antibiotics, acidic and basic pharmaceuticals, and prescribed medications were selected for investigation using a combination of membrane filtration, solid phase extraction (SPE) cleanup, and liquid chromatography–electrospray ionization tandem mass spectrometry. Fourteen of the selected compounds were found in the samples. Increased effluent concentrations, compared to influent concentrations, for a number of compounds (carbamazepine, clotrimazole, propranolol, nimesulide, furosemide, mefenamic acid, diclofenac, metoprolol, and gemfibrozil) were observed. The detected concentrations were generally below toxicity levels and based on current knowledge are unlikely to pose any threat to aquatic species. Mefenamic acid concentrations detected in both Leixlip and Swords effluents may potentially exert ecotoxicological effects with maximum risk quotients (i.e., ratio of predicted exposure concentration to predicted no effect concentration) of 4.04 and 1.33, respectively.     

Use of pharmaceuticals and pesticides to constrain nutrient sources in coastal groundwater of northwestern Long Island, New York, USA

In developed, non-agricultural, unsewered areas, septic systems and fertilizer application to lawns and gardens represent two major sources of nitrogen to coastal groundwater, in addition to atmospheric input. This study was designed to distinguish between these two possible nitrogen sources by analyzing groundwater samples for pharmaceutical residuals, because fertilizers do not contain any of these pharmaceuticals, but domestic wastewater commonly does. In addition, several herbicides and insecticides used in lawn treatment were analyzed as indicators of nitrogen delivery to groundwater from fertilizers. Groundwater samples were taken through piezometres at shoreline sites in unsewered areas surrounding Northport Harbor and in sewered areas adjacent to Manhasset Bay (hereafter referred to as "Northport" and "Manhasset", respectively), both in northwestern Long Island, USA. Excessive nitrogen loading has led to reduced dissolved oxygen concentrations in Long Island Sound, and the groundwater contribution to the nitrogen budget is poorly constrained. The frequent detection of the anticonvulsant compound carbamazepine in groundwater samples of the Northport Harbor area (unsewered), together with the fact that few pesticides associated with lawn applications were detected, suggests that wastewater input and atmospheric input are the likely sources of nitrogen in the Northport groundwater. High concentrations of nitrogen were also detected in the Manhasset (sewered) groundwater. The low detection frequency and concentration of carbamazepine, however, suggest that the sewer system effectively intercepts nitrogen from wastewater there. The likely sources of nitrogen in the Manhasset groundwater are atmospheric deposition and lawn fertilizers, as this area is densely populated.     

The mini mobile environmental monitoring unit: a novel bio-assessment tool

This paper introduces a new bio-assessment tool, the mini-mobile environmental monitoring unit (MMU). The MMU is a portable, lightweight, energy-efficient, miniaturized laboratory that provides a low-flow system for on-site exposure of aquatic animals to local receiving waters in a protected, controllable environment. Prototypes of the MMU were tested twice in week-long studies conducted during the summers of 2008 and 2009, and in a 12-day study in 2010. In 2008, fathead minnows and polar organic chemical integrative samplers (POCIS) were deployed downstream from the Hastings, Nebraska wastewater treatment plant (WWTP), a waterway known to contain estrogenic contaminants in biologically active concentrations. In 2009, minnows and POCIS were deployed downstream, upstream and within the Grand Island, Nebraska WWTP, a site where the estrogenic contaminants had been detected, but were found at levels below those necessary to directly impact fish. In 2010, an advanced prototype was tested at the Sauk Center, Minnesota WWTP to compare its performance with that of traditional fish exposure methods including caged fish and static-renewal laboratory testing of effluent. Results from the prototype illustrate the capabilities of the MMU and offer an inexpensive monitoring tool to integrate the effects of pollutant sources with temporally varying composition and concentration.     

Determination of micropollutants in combined sewer overflows and their removal in a wastewater treatment plant (Seoul,South Korea)

The present study investigated the occurrence of 29 selected micropollutants such as endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in surface waters and wastewaters in Seoul (South Korea) during both dry and wet weather conditions. The study area was selected based on the lack of available information regarding the suspected contamination of rivers/creeks by EDCs and PPCPs in the Seoul region and the presence of a wastewater treatment plant (WWTP), which serves approximately 4.1 million inhabitants and has a design capacity of 1,297?×?10³ m³/day. Many target compounds (83 %) were detected in samples collected from wastewater treatment influent/effluent, creek water, and combined sewer overflow (CSO). The total EDC/PPCP concentrations were as follows: WWTP influent (69,903 ng/L)?>?WWTP effluent (50,175 ng/L) >3 creek samples (16,035–44,446 ng/L) during dry weather, and WWTP influent (53,795 ng/L)?>?WWTP bypass (38,653 ng/L) >5 creek samples (15,260–29,113 ng/L) >2 CSO samples (11,109–11,498 ng/L) during wet weather. EDCs and PPCPs were found to be present at high daily loads (65.1 and 69.8 kg/day during dry and wet weather, respectively) in the WWTP effluent. Compound removal by the WWTP varied significantly by compound: caffeine, diclofenac, ibuprofen, naproxen, and propylparaben (>90 %), and acesulfame, DEET, iohexol, iopromide, and iopamidol (<5 %). These findings and literature information support the hypothesis that the efficiency of removal of EDCs and PPCPs is strongly dependent on both removal mechanism (e.g., biodegradation, adsorption to sludge, and oxidation by chlorine) and compound physicochemical properties (e.g., pK _a and hydrophobicity).     

Dynamics of steroid estrogen daily concentrations in hospital effluent and connected waste water treatment plant

Hospital effluent and connected waste water treatment plant (WWTP) influent and effluent were sampled daily to determine the levels and inter-day variations of three naturally occurring steroid estrogens: estrone, 17β-estradiol, estriol, and synthetic 17α-ethinylestradiol. After solid phase extraction, interferences were removed with a silica gel clean-up step and the samples analysed using gas chromatography with mass selective detection (GC-MSD). The determined inter-day concentrations in hospital effluent were between 8.6 to 31.3 ng L(-1) for estrone, 相似文献   

An overview of pharmaceuticals and personal care products contamination along the river Somes watershed, Romania

The mass flows of selected pharmaceuticals and personal care products (PPCPs) were studied in the aqueous compartment of the river Somes in Romania. PPCPs were measured in wastewater treatment effluents and in the receiving river water. The analytical method for the determination of PPCPs in river water was based on solid phase extraction and GC-ITMS. Carbamazepine, pentoxyfylline, ibuprofen, diazepam, galaxolide, tonalide and triclosan were determined in wastewater effluents with individual concentrations ranging from 15 to 774 ng L(-1). Caffeine was measured at concentrations up to 42 560 ng L(-1). Due to the high contamination of WWTP effluents, the receiving river was also polluted. The most abundant PPCPs measured in the Somes were caffeine, galaxolide, carbamazepine and triclosan. They were present at all the 15 sampling sites along the Somes, the concentrations ranging from 10 to 400 ng L(-1). The concentrations in the effluents of the different wastewater treatment plants (WWTPs) varied considerably and the differences are due to different elimination efficiencies of the studied PPCPs during sewage treatment. Only one of 5 WWTPs studied, the WWTP in Cluj-Napoca, was working properly, and therefore technical measures have to be taken for upgrading the WWTPs and reducing the environmental load of micropollutants. This study is the first overview of PPCPs along on Romanian part of river Somes.     

Input of selected human pharmaceutical metabolites into the Norwegian aquatic environment

The occurrence of the metabolites of five human pharmaceuticals was investigated in treated wastewater, surface waters and sediments. Metabolites of carbamazepine (carbamazepine epoxide), diclofenac (4'- and 5-hydroxy diclofenac) and atorvastatin (o- and p-hydroxy atorvastatin) were typically detected in flow proportional 24 h composite samples of wastewater effluent collected from the Norwegian cities of Oslo and Troms? at higher concentrations than the parent pharmaceutical. The concentrations determined in discharged effluent were as high as 3700 ng L(-1) for 5-hydroxy diclofenac. The overall mean concentration of metabolites being typically higher in the primary treated effluent from the city of Troms? compared to the tertiary treatment performed on the Oslo effluent. Metabolites of carbamazepine (carbamazepine-10,11-epoxide), metoprolol (α-hydroxy metoprolol) and simvastatin (hydroxy simvastatin) were detected in surface water samples collected from Oslofjord at concentrations of up to 108 ng L(-1), whilst α-hydroxy metoprolol and simvastatin hydroxy carboxylic acid were also detected in sediments at low ng L(-1) concentrations. These screening data show that the metabolites of selected pharmaceuticals are being discharged into the Norwegian coastal environment and that certain metabolites occur in marine surface waters and sediments.     

Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works

The occurrence of twenty pharmaceutical compounds was quantitatively determined in effluents from two major Oslo city hospitals, Rikshospitalet and Ullev?l, along with influent, sludge and final effluent from the city's VEAS wastewater treatment works (WTW). Composite hospital effluents were collected over a twelve week period and were showed to contain paracetamol, metoprolol, diclofenac, ibuprofen, 17beta-Estradiol, estriol, estrone, oxytetracycline, tetracycline, doxycycline, chlorotetracycline, demeclocycline, trimethoprim, ciprofloxacin, sulfamethoxazole, cyclophosphamide and ifosfamide. Three pharmaceuticals were not detected above the limit of detection; cefuroxime, 17alpha-ethinylestradiol and meclocycline. Composite influent, sludge and effluent samples were collected from VEAS WTW over a seven week period. The influent into VEAS WTW contained all of the same selected substances detected in the hospital effluents, except for oxytetracycline, chlorotetracycline, demeclocycline, cyclophosphamide and ifosfamide. The percentage of pharmaceuticals entering the works from the hospitals was <10% for all of the selected compounds. VEAS sludge samples contained a different profile of substances reflecting their physico-chemical properties. Hydrophobic antibiotics, such as oxytetracycline, tetracycline and ciprofloxacin, were detected in all of the collected sludge samples. Their absence in the collected influent samples suggests that they enter the works bound to effluent particles, with the dissolved fraction observed in the hospital effluents partitioning onto particulate matter within the sewerage network. The final effluent from VEAS WTW contained reduced concentrations of many pharmaceuticals, including paracetamol, ibuprofen and sulfamethoxazole. For other compounds, such as metoprolol, diclofenac and trimethoprim, there were often higher concentrations in the effluent than the influent. These effluent concentrations represent median inputs varying from low g day(-1) (e.g. paracetamol and ibuprofen) to nearly 200 g day(-1) (e.g. metoprolol and trimethoprim) into Oslofjord. A simple risk assessment showed that the antibiotic ciprofloxacin may at times pose an acute risk to the Oslofjord aquatic environment.     

Toxicity Assessment of Treated Wastewater Using Cultured Human Cell Lines

Bioassay using cultured human cell lines was applied to an effluent of a wastewater treatment plant (WWTP) in Sapporo to assess their toxicity, and in order to investigate the fate of toxicity in the WWTP, bioassay of the water samples from several points in WWTP (influent, effluent, return flow from thickener, from dewatering process and from incineration process) was performed. We also applied bioassay to the mixture of the activated sludge from the investigated plant and artificial sewage. These results showed that the toxicity of the effluent was more intensive than the influent, and organic matter released from activated sludge bacteria during their decay process contributed to the increase of toxicity in the effluent.     

Occurrence and removal of titanium at full scale wastewater treatment plants: implications for TiO2 nanomaterials

Titanium dioxide nanoparticles increasingly will be used in commercial products and have a high likelihood of entering municipal sewage that flows to centralized wastewater treatment plants (WWTPs). Treated water (effluent) from WWTPs flows into rivers and lakes where nanoparticles may pose an ecological risk. To provide exposure data for risk assessment, titanium concentrations in raw sewage and treated effluent were determined for 10 representative WWTPs that use a range of unit processes. Raw sewage titanium concentrations ranged from 181 to 1233 μg L(-1) (median of 26 samples was 321 μg L(-1)). The WWTPs removed more than 96% of the influent titanium, and all WWTPs had effluent titanium concentrations of less than 25 μg L(-1). To characterize the morphology and presence of titanium oxide nanoparticles in the effluent, colloidal materials were isolated via rota-evaporation, dialysis and lyophilization. High resolution transmission electron microscopy and energy dispersive X-ray analysis indicated the presence of spherical titanium oxide nanoparticles (crystalline and amorphous) on the order of 4 to 30 nm in diameter in WWTP effluents. This research provides clear evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems and offers a methodological framework for collecting and analyzing titanium-based nanomaterials in complex wastewater matrices.     

POCIS sampling in combination with ELISA: screening of sulfonamide residues in surface and waste waters

Sulfonamide antibiotics coming from both human and veterinary medicine are among the most common emerging pollutants in freshwater. The present paper shows the successful application of passive sampling using POCIS in combination with an immunochemical ELISA technique and HPLC/MS/MS analysis to study the distribution of sulfonamides in streams around small towns in the Czech Republic, as well as around a major agglomeration of the city of Brno, including its waste water treatment plant (WWTP). Results indicated the presence of sulfonamides at most studied sites with concentrations ranging from <20 up to 736 ng of sulfamethoxazole equivalents per POCIS. Very high levels were detected in both the influent and effluent of the Brno WWTP with maxima > 8000 ng SMX per POCIS. All samplers collected down-stream of the studied towns and WWTPs clearly showed an increase in sulfonamide drug residues. Higher concentrations were determined in rivers at the city of Brno agglomeration. In agreement with other available studies, these findings indicate low efficiency of conventional WWTPs to eliminate polar pharmaceuticals such as sulfonamides. Good performance and correlation with the LC/MS results, as well as ease of use, indicate good potential for the immunochemical ELISA technique to become the screening tool for sulfonamide determination in surface waters including passive samplers.     

Origin and spatial–temporal distribution of faecal bacteria in a bay of Lake Geneva, Switzerland

The origin and distribution of microbial contamination in Lake Geneva's most polluted bay were assessed using faecal indicator bacteria (FIB). The lake is used as drinking water, for recreation and fishing. During 1 year, water samples were taken at 23 points in the bay and three contamination sources: a wastewater treatment plant (WWTP), a river and a storm water outlet. Analyses included Escherichia coli, enterococci (ENT), total coliforms (TC), and heterotrophic plate counts (HPC). E. coli input flux rates from the WWTP can reach 2.5 x 10(10) CFU/s; those from the river are one to three orders of magnitude lower. Different pathogenic Salmonella serotypes were identified in water from these sources. FIB levels in the bay are highly variable. Results demonstrate that (1) the WWTP outlet at 30 m depth impacts near-surface water quality during holomixis in winter; (2) when the lake is stratified, the effluent water is generally trapped below the thermocline; (3) during major floods, upwelling across the thermocline may occur; (4) the river permanently contributes to contamination, mainly near the river mouth and during floods, when the storm water outlet contributes additionally; (5) the lowest FIB levels in the near-surface water occur during low-flow periods in the bathing season.     

Occurrence and fate of steroid estrogens in the largest wastewater treatment plant in Beijing, China

Concern over steroid estrogens has increased rapidly in recent years due to their adverse health effects. Effluent discharge from wastewater treatment plants (WWTPs) is the main pollutant source for environmental water. To understand the pollutant level and fate of steroid estrogens in WWTPs, the occurrence of estrone (E1), 17-β-estradiol (E2), estriol (E3), and 17-β-ethinylestradiol (EE2) was investigated in the Gaobeidian WWTP in Beijing, China. Water samples from influent as well as effluent from second sedimentation tanks and advanced treatment processes were taken monthly during 2006 to 2007. In influent, steroid estrogen concentrations varied from 11.6 to 1.1?×?10(2)?ng/l, 3.7 to 1.4?×?10(2)?ng/l, no detection (nd) to 7.6×10(2)?ng/l and nd to 3.3?×?10(2)?ng/l for E1, E2, E3, and EE2, respectively. Compared with documented values, the higher steroid estrogen concentrations in the WWTP influent may be due to higher population density, higher birthrate, less dilution, and different sampling time. Results revealed that a municipal WWTP with an activated sludge system incorporating anaerobic, anoxic, and aerobic processes could eliminate natural and synthetic estrogens effectively. The mean elimination efficiencies were 83.2%, 96.4%, 98.8%, and 93.0% for E1, E2, E3, and EE2, respectively. The major removal mechanism for natural estrogens and synthetic estrogen EE2 were biodegradation and sorption on the basis of mass balance in water, suspension particles, and sludge. In the WWTP effluent, however, the highest concentrations of E1, E2, E3, and EE2 attained were 74.2, 3.9, 5.1, and 4.6?ng/l, respectively. This is concerning as residual steroid estrogens in WWTP effluent could lead to pollution of the receiving water. Advanced flocculation treatment was applied in the WWTP and transformed the residual estrogen conjugates to free species, which were reduced further by filtration with removal shifting from 32% to 57% for natural estrogen, although no EE2 was removed.     

The use of multiple tracers for tracking wastewater discharges in freshwater systems

The assessment of potential impacts of wastewater effluent discharges in freshwater systems requires an understanding of the likely degrees of dilution and potential zones of influence. In this study, four tracers commonly present in wastewater effluents were monitored to compare their relative effectiveness in determining areas in freshwater systems that are likely to be impacted by effluent discharges. The four tracers selected were the human pharmaceutical carbamazepine, anthropogenic gadolinium, fluorescent-dissolved organic matter (fDOM), and electrical conductivity (EC). The four tracers were monitored longitudinally in two distinct freshwater systems receiving wastewater effluents, where one site had a high level of effluent dilution (effluent <1 % of total flow) and the other site had a low level of effluent dilution (effluent ～50 % of total flow). At both sites, the selected tracers exhibited a similar pattern of response intensity downstream of discharge points relative to undiluted wastewater effluent, although a number of anomalies were noted between the tracers. Both EC and fDOM are non-specific to human influences, and both had a high background response, relative to the highly sensitive carbamazepine and anthropogenic gadolinium responses, although the ease of measuring EC and fDOM would make them more adaptable in highly variable systems. However, the greater sensitivity and selectivity of carbamazepine and gadolinium would make their combination with EC and fDOM as tracers of wastewater effluent discharges highly desirable to overcome potential limitations of individual tracers.     

Short-term variation in air quality associated with firework events: a case study

The effect of fireworks on air quality was assessed from the ambient concentrations of various air pollutants (SO2, NO2, PM10 and TSP) during Diwali festival in Hisar city (India), in November 1999. The extensive use of fireworks was found to be related to short-term variation in air quality. During the festival the concentration of SO2 was observed to be increased approximately 10-fold at few sites, whereas the concentrations of NO2, PM10 and TSP increased 2-3 times, compared to the data collected on a typical winter day in December 1999. The maximum NO2 concentration was observed a day after the festival. The diurnal pattern of the above pollutants showed a slight increase in the night. The levels of these pollutants observed during Diwali were found to be moderately high, which can be associated with serious health impacts.     

Solid-phase extraction followed by liquid chromatography-time-of-flight-mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study

The present work provides a multi-residue analytical method for determining a selection of 20 pharmaceuticals from diverse therapeutical classes in hospital effluent wastewater. The method is based on the simultaneous extraction of the target compounds by solid phase extraction (SPE), followed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis. Using TOF-MS, accurate mass measurements within 2 ppm error were obtained for most of the pharmaceuticals studied. Empirical formula information can be obtained by this method, allowing the unequivocal identification of the target compounds in the samples. Validation studies showed that LC-TOF-MS analysis is a valuable new tool for identification and quantification of pharmaceuticals in wastewater. Recoveries, using Oasis HLB cartridges at pH 7, were higher than 75% for all pharmaceuticals, except for ranitidine, 4-methylaminoantipyrine (4-MAA), cefotaxime and omeprazole, which needed specific pH conditions for their extraction. Linearity of response over two orders of magnitude was demonstrated (r > 0.99). Matrix effects resulting in suppression of the response were observed. For most of the compounds ion suppression was less than 39%, except for metronidazole, carbamazepine 10,11-epoxide, naproxen and erythromycin, where the signal suppression was 42%, 59%, 46% and 95%, respectively. A simple and effective approach to minimize or avoid matrix interferences was the 1 : 4 dilution of the SPE extracts. Method detection limits (MDLs) and quantification limits (MQLs) ranged between 4-115 ng l(-1) and 14-384 ng l(-1), respectively. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1.1-19.8% and 1.7-21.7% for intra- and inter-day, respectively. The developed analytical method was applied to the analysis of hospital effluent wastewater during a survey study. 18 of the 20 pharmaceuticals studied were detected at concentration levels of microg l(-1), reaching in some cases concentrations over 100 microg l(-1), and in the case of the analgesic and antipyretic dipyrone metabolite, higher than 1000 microg l(-1).     

Monitoring waste metal pollution at Ganga Estuary via the East Calcutta Wetland areas

East Calcutta Wetlands, a Ramsar site, receives a huge amount of the city’s composite industrial effluent (～600 million liters per day) throughout the year. The waste-element-contaminated water flows down through a major storm water flow (SWF) canal into the wetland for nearly 40 km farther eastward and is finally discharged into Kultigong river that flows through the eastern limit of the wetland and that in turn unites with river Ganga. Elemental load in water and bottom sediment at selected sites of the SWF canal was assessed by proton-induced X-ray emission and atomic absorption spectroscopy techniques. Gradual decrease in concentration levels of elements was observed in both water and bottom sediments of SWF canal up to its site of confluence at Kultigong, indicating natural remediation processes taking place along the canal up to the confluence at Ganga estuary. Any further conversion of this wetland area should be prevented to get the benefit from this no-cost natural cleanup process in connection to pollution prevention.