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.     

Factors impacting on pharmaceutical leaching following sewage application to land

Sewage effluent application to land is a treatment technology that requires appropriate consideration of various design factors. Soil type, level of sewage pre-treatment and irrigation rate were assessed for their influence on the success of soil treatment in removing pharmaceuticals remaining after conventional sewage treatment. A large scale experimental site was built to assess treatment performance in a realistic environment. Of the factors investigated, soil type had the biggest impact on treatment performance. In particular, carbamazepine was very efficiently removed (>99%) when irrigated onto a volcanic sandy loam soil. This was in contrast to irrigation onto a sandy soil where no carbamazepine removal occurred after irrigation. Differences were likely caused by the presence of allophane in the volcanic soil which is able to accumulate a high level of organic matter. Carbamazepine apparent adsorption distribution coefficients (K(d)) for both soils when irrigated with treated sewage effluent were determined as 25 L kg(-1) for the volcanic soil and 0.08 L kg(-1) for the sandy soil. Overall, a volcanic soil was reasonably efficient in removing carbamazepine while soil type was not a major factor for caffeine removal. Removal of caffeine, however, was more efficient when a partially treated rather than fully treated effluent was applied. Based on the investigated pharmaceuticals and given an appropriate design, effluent irrigation onto land, in conjunction with conventional sewage treatment may be considered a beneficial treatment for pharmaceutical removal.     

Pharmaceutical contamination in residential, industrial, and agricultural waste streams: risk to aqueous environments in Taiwan

This is a comprehensive study of the occurrence of antibiotics, hormones and other pharmaceuticals in water sites that have major potential for downstream environmental contamination. These include residential (hospitals, sewage treatment plants, and regional discharges), industrial (pharmaceutical production facilities), and agricultural (animal husbandries and aquacultures) waste streams. We assayed 23 Taiwanese water sites for 97 targeted compounds, of which a significant number were detected and quantified. The most frequently detected compounds were sulfamethoxazole, caffeine, acetaminophen, and ibuprofen, followed closely by cephalexin, ofloxacin, and diclofenac, which were detected in >91% of samples and found to have median (maximum) concentrations of 0.2 (5.8), 0.39 (24.0), 0.02 (100.4), 0.41 (14.5), 0.15 (31.4), 0.14 (13.6) and 0.083 (29.8) microg/L, respectively. Lincomycin and acetaminophen had high measured concentrations (>100 microg/L), and 35 other pharmaceuticals occurred at the microg/L level. These incidence and concentration results correlate well with published data for other worldwide locations, as well as with Taiwanese medication usage data, suggesting a human contamination source. Many pharmaceuticals also occurred at levels exceeding predicted no-effect concentrations (PNEC), warranting further investigation of their occurrence and fate in receiving waters, as well as the overall risks they pose for local ecosystems and human residents. The information provided here will also be useful for development of strategies for regulation and remediation.     

Pharmaceutical removal in tropical subsurface flow constructed wetlands at varying hydraulic loading rates

Determining the fate of emerging organic contaminants in an aquatic ecosystem is important for developing constructed wetlands (CWs) treatment technology. Experiments were carried out in subsurface flow CWs in Singapore to evaluate the fate and transport of eight pharmaceutical compounds. The CW system included three parallel horizontal subsurface flow CWs and three parallel unplanted beds fed continuously with synthetic wastewater at different hydraulic retention times (HRTs). The findings of the tests at 2-6 d HRTs showed that the pharmaceuticals could be categorized as (i) efficiently removed compounds with removal higher than 85% (ketoprofen and salicylic acid); (ii) moderately removed compounds with removal efficiencies between 50% and 85% (naproxen, ibuprofen and caffeine); and (iii) poorly removed compounds with efficiency rate lower than 50% (carbamazepine, diclofenac, and clofibric acid). Except for carbamazepine and salicylic acid, removal efficiencies of the selected pharmaceuticals showed significant (p<0.05) enhancement in planted beds as compared to the unplanted beds. Removal of caffeine, ketoprofen and clofibric acid were found to follow first order decay kinetics with decay constants higher in the planted beds than the unplanted beds. Correlations between pharmaceutical removal efficiencies and log K(ow) were not significant (p>0.05), implying that their removal is not well related to the compound's hydrophobicity.     

Colloids as a sink for certain pharmaceuticals in the aquatic environment

Background, aim, and scope  

The occurrence and fate of pharmaceuticals in the aquatic environment is recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Existing data tend to focus on the concentrations of pharmaceuticals in the aqueous phase, with limited studies on their concentrations in particulate phase such as sediments. Furthermore, current water quality monitoring does not differentiate between soluble and colloidal phases in water samples, hindering our understanding of the bioavailability and bioaccumulation of pharmaceuticals in aquatic organisms. In this study, an investigation was conducted into the concentrations and phase association (soluble, colloidal, suspended particulate matter or SPM) of selected pharmaceuticals (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid) in river water, effluents from sewage treatment works (STW), and groundwater in the UK.     

The occurrence of antihistamines in sewage waters and in recipient rivers

Background, aim and scope  Each year, large quantities of pharmaceuticals are consumed worldwide for the treatment and prevention of human and animal diseases. Although the drugs and the metabolites observed in the wastewaters and in the environment are present at concentrations several orders of magnitude lower than the concentrations required to exert their effects in humans or animals, their long-term impact on the environment is commonly not known. In this study, the occurrence of six antihistamines, which are used for the relief of allergic reactions such as hay fever, was determined in sewage treatment plants wastewaters and in recipient river waters. Materials and methods  The occurrence of the antihistamines cetirizine, acrivastine, fexofenadine, loratadine, desloratadine and ebastine in sewage treatment plants wastewaters and in recipient river waters was studied. The analytical procedure consisted of solid-phase extraction of the water samples followed by liquid chromatography separation and detection by a triple-quadrupole mass spectrometer in the multiple reaction mode. Results  Cetirizine, acrivastine and fexofenadine were detected in both influent and effluent wastewater samples at concentration levels ranging from about 80 to 220 ng/L, while loratadine, desloratadine and ebastine could not be detected in any samples. During sewage treatment, the concentration of the antihistamines dropped by an average of 16–36%. Furthermore, elevated concentrations of antihistamines were observed in samples collected during the season of most intensive plant pollen production, i.e. in May. In the river water samples, the relative pattern of occurrence of cetirizine, acrivastine and fexofenadine was similar to that in the wastewater samples; although the concentration of the compounds was substantially lower (4–11 ng/L). The highest concentrations of the studied drugs were observed near the discharging point of the sewage treatment plant. Discussion  The highest concentrations of antihistamines in STP wastewaters correlate with the outbreak of allergic reaction caused by high amounts of plant pollens in the air. The analysis results of the river water samples show that the antihistamines are carried far away from the effluent discharge points. They may account for a part of the mix of pharmaceuticals and of pharmaceutical metabolites that occur downstream of STPs. Conclusions  Antihistamines are poorly degraded/eliminated under the biological treatment processes applied in the wastewater treatment plants and, consequently, they are continuously being discharged along with other drugs to the aquatic environment. Recommendations and perspectives  As a huge quantity and variety of drugs and their metabolites are continuously discharged to rivers and the sea, the compounds should be considered as contaminants that may possess risks to the aquatic ecosystem. Further studies are urgently needed on the environmental fate of the antihistamines and other pharmaceuticals in the aquatic environment. These studies should be concerned with the stability of the compounds, their transformation reactions and the identity of the transformation products, the distribution of drugs and their uptake and effects in organisms. On the basis of these studies, the possible environmental hazards of pharmaceuticals may be assessed.     

Modelling of pharmaceutical residues in Australian sewage by quantities of use and fugacity calculations

A conceptual model is presented for determining which currently prescribed pharmaceutical compounds are most likely to be found in sewage, and for estimating their concentrations, both in raw sewage and after successive stages of secondary sewage treatment. A ranking of the "top-50" pharmaceutical compounds (by total mass dispensed) in Australia over the 1998 calendar year was prepared. Information on the excretion ratios and some metabolites of the pharmaceuticals enabled prediction of the overall rates of excretion into Australian sewage. Mass-balance and fugacity modelling, applied to sewage generation and to a sewage treatment plant, allowed calculation of predicted concentrations of the compounds in raw, primary and secondary treated sewage effluents. Twenty nine of the modelled pharmaceutical residuals were predicted to be present in raw sewage influent at concentrations of 1 microgl(-1) or greater. Twenty of the compounds were predicted to remain in secondary effluent at concentrations of 1 microgl(-1) or greater.     

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

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

Irrigation of treated wastewater in Braunschweig, Germany: an option to remove pharmaceuticals and musk fragrances

In this study the fate of pharmaceuticals and personal care products which are irrigated on arable land with treated municipal wastewater was investigated. In Braunschweig, Germany, wastewater has been irrigated continuously for more than 45 years. In the winter time only the effluent of the sewage treatment plant (STP) of Braunschweig is used for irrigation, while during summer digested sludge is mixed with the effluent. In the present case study six wells and four lysimeters located in one of the irrigated agricultural fields were monitored with regard to the occurrence of 52 pharmaceuticals and two personal care products (PPCPs; e.g. betablockers, antibiotics, antiphlogistics, carbamazepine, musk fragrances, iodinated contrast media (ICM) and estrogens). No differences in PPCP pollution of the groundwater were found due to irrigation of STP effluents with and without addition of digested sludge, because many polar compounds do not sorb to sludge and lipophilic compounds are not mobile in the soil-aquifer. Most of the selected PPCPs were never detected in any of the lysimeter or groundwater samples, although they were present in the treated wastewater irrigated onto the fields. In the groundwater and lysimeter samples primarily the ICM diatrizoate and iopamidol, the antiepileptic carbamazepine and the antibiotic sulfamethoxazole were detected up to several mugl(-1), while the acidic pharmaceuticals, musk fragrances, estrogens and betablockers were likely sorbed or transformed while passing the top soil layer. Potential estrogenic effects are likely to disappear after irrigation, since the most potent steroid estrogens were not measurable.     

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

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

Root uptake of atenolol,sulfamethoxazole and carbamazepine,and their transformation in three soils and four plants

Soils can be contaminated by pharmaceuticals. The aim of this study was to evaluate the impact of soil conditions (influencing sorption and persistence of pharmaceuticals in soils) and plant type on the root uptake of selected pharmaceuticals and their transformation in plant-soil systems. Four plants (lamb’s lettuce, spinach, arugula, radish) planted in 3 soils were irrigated for 20 days (26) with water contaminated by one of 3 pharmaceuticals (carbamazepine, atenolol, sulfamethoxazole) or their mixture. The concentrations of pharmaceuticals and their metabolites in soils and plant tissues were evaluated after the harvest. Sulfamethoxazole and atenolol dissipated rapidly from soils. The larger concentrations of both compounds and an atenolol metabolite were found in roots than in leaves. Sulfamethoxazole metabolites were below the limits of quantifications. Carbamazepine was stable in soils, easily uptaken, accumulated, and metabolized in plant leaves. The efficiency of radish and arugula (both family Brassicaceae) in metabolizing was very low contrary to the high and moderate efficiencies of lamb’s lettuce and spinach, respectively. Compounds’ transformations mostly masked the soil impact on their accumulation in plant tissues. The negative relationships were found between the carbamazepine sorption coefficients and its concentrations in roots of radish, lamb’s lettuce, and spinach.

     

Fate of selected pharmaceuticals in hospital and municipal wastewater effluent: occurrence,removal, and environmental risk assessment

The concentrations and distribution of β-blockers, lipid regulators, and psychiatric and cancer drugs in the influent and effluent of the municipal wastewater treatment plant (WWTP) and the effluent of 16 hospitals that discharge into the wastewater treatment plant mentioned in this study at two sampling dates in summer and winter were examined. The pharmaceutical contribution of hospitals to municipal wastewater was determined. The removal of target pharmaceuticals was evaluated in a WWTP consisting of conventional biological treatment using activated sludge. Additionally, the potential environmental risk for the aquatic receiving environments (salt lake) was assessed. Beta-blockers and psychiatric drugs were detected in high concentrations in the wastewater samples. Atenolol (919 ng/L) from β-blockers and carbamazepine (7008 ng/L) from psychiatric pharmaceuticals were detected at the highest concentrations in hospital wastewater. The total pharmaceutical concentration determined at the WWTP influent and effluent was between 335 and 737 ng/L in summer and between 174 and 226 ng/L in winter. The concentrations detected in hospital effluents are higher than the concentrations detected in WWTP. The total pharmaceutical contributions from hospitals to the WWTP in summer and winter were determined to be 2% and 4%, respectively. Total pharmaceutical removal in the WWTP ranged from 23 to 54%. According to the risk ratios, atenolol could pose a high risk (risk quotient > 10) for fish in summer and winter. There are different reasons for the increase in pharmaceutical consumption in recent years. One of these reasons is the COVID-19 pandemic, which has been going on for 2 years. In particular, hospitals were operated at full capacity during the pandemic, and the occurrence and concentration of pharmaceuticals used for the therapy of COVID-19 patients has increased in hospital effluent. Pandemic conditions have increased the tendency of people to use psychiatric drugs. It is thought that beta-blocker consumption has increased due to cardiovascular diseases caused by COVID-19. Therefore, the environmental risk of pharmaceuticals for aquatic organisms in hospital effluent should be monitored and evaluated.

     

Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment

The presence of pharmaceutical compounds in surface waters is an emerging environmental issue. Sewage treatment plants (STPs) are recognized as being the main point discharge sources of these substances to the environment. A monitoring campaign of STP effluents was carried out in four European countries (Italy, France, Greece and Sweden). More than 20 individual pharmaceuticals belonging to different therapeutic classes were found. For six selected pharmaceuticals (carbamazepine, diclofenac, clofibric acid, ofloxacin, sulfamethoxazole and propranolol) present in the STP effluents, the persistence towards abiotic photodegradation was evaluated submitting them to solar experiments at 40° N latitude during spring and summer. Based on experimentally measured quantum yields for the direct photolysis in bi-distilled water, half-life times (t_1/2) at varying seasons and latitude were predicted for each substance. In salt- and organic-free (bi-distilled) water carbamazepine and clofibric acid are characterized by calculated half-life times of the order of 100 days at the highest latitudes (50° N) in winter, whereas under the same conditions sulphamethoxazole, diclofenac, ofloxacin and propranolol undergo fast degradation with t_1/2 respectively of 2.4, 5.0, 10.6 and 16.8 days. For almost all studied compounds, except propranolol the presence of nitrate ions in aqueous solutions results in a reduction of t_1/2. When present, humic acids act as inner filters towards carbamazepine and diclofenac, and as photosensitizers towards sulphamethoxazole, clofibric acid, oflaxocin and propranolol.     

Fate and mobility of pharmaceuticals in solid matrices

The sorption and mobility of six pharmaceuticals were investigated in two soil types with different organic carbon and clay content, and in bacterial biomass (aerobic and anaerobic). The pharmaceuticals examined were carbamazepine, propranolol, diclofenac sodium, clofibric acid, sulfamethoxazole and ofloxacin. The sorption experiments were performed according to the OECD test Guideline 106. The distribution coefficients determined by this batch equilibrium method varied with the pharmaceutical tested and the solid matrix type. Ofloxacin was particularly strongly adsorbed (except of the case of using anaerobic biomass for the solid matrix) while clofibric acid was found to be weakly adsorbed. The fate of pharmaceuticals in soil was also assessed using lysimeters. Important parameters that were studied were: the pharmaceutical loading rate and the hydraulic loading rate for adsorption and the rate and duration of a "rain" event for desorption. Major differences in the mobility of the six pharmaceuticals were observed and correlated with the adsorption/desorption properties of the compounds.     

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 selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Troms?/Norway and in seawater from Troms?-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.     

An exposure assessment for selected pharmaceuticals within a watershed in Southern Ontario

Recent studies from a number of countries have shown that measurable concentrations of both human and veterinary pharmaceuticals can be found in a variety of environmental matrices such as surface and ground water, soils, and sediments. Few data are available that characterize the sources, exposure and effects of pharmaceuticals in the environment and there is clearly a need to define these parameters within a Canadian context. We present in this paper the first report in southern Ontario, Canada on the geographic and temporal distribution of pharmaceuticals detected within seven tributaries receiving primarily agricultural inputs in a typical watershed. Of the 28 pharmaceuticals surveyed, 14 were detected in the streams sampled (n=125). Temporal trends in concentration for five frequently detected pharmaceuticals show pulses occurring between May and November of 2003 at similar but varying times over the seasons, depending on the pharmaceuticals, flow rate, and precipitation. Fluctuations in concentration of ions indicative of agricultural run off, such as nitrate and phosphate, were not found to be useful predictors of changes in pharmaceutical concentration (P>0.4), however a significant correlation between dissolved organic carbon and monensin and carbamazepine concentrations were observed (P<0.013). Exposure profiles illustrating concentration distributions for three of the more prevalent pharmaceuticals detected, including lincomycin, monensin and carbamazepine, showed a log normal distribution, useful for calculating centiles of environmental concentrations. While distributions of estimated total potency of pharmaceuticals detected in the surface waters suggested small risks of environmental effects of mixtures to daphnia, green algae, Lemna gibba, and fish, the significance of non-target effects and impacts due to chronic low level exposures to chemical mixtures remains unclear.     

Healthcare facility effluents as point sources of select pharmaceuticals to municipal wastewater

Effluents from four healthcare facilities were characterized for the concentration of 16 common active pharmaceutical ingredients. The sampled facilities included a hospital, nursing care, assisted living, and independent living facility located within a single municipal wastewater system in Texas. Eleven of the 16 monitored pharmaceuticals were detected in at least 1 healthcare facility effluent and 2 measured antibiotics (sulfamethoxazole and trimethoprim) were detected in all 4 facility effluents. Active pharmaceutical ingredient concentrations ranged from non-detectable levels for several corticosteroids in all facility effluents to 180 microg/L sulfamethoxazole in the nursing care wastewater effluent. The mass of active pharmaceutical ingredients discharged to the municipality's wastewater conveyance system was determined by combining individual facility concentration data and daily wastewater flow. The estimated daily mass loading of all 16 pharmaceuticals ranged from 0.16 g/day to 23 g/day in the assisted living facility and nursing wastewater effluents, respectively. The combined active pharmaceutical ingredient mass loading for all four facilities was 42.6 g/day. These findings provide source characterization data for 16 common pharmaceuticals in healthcare facility wastewater and provide a basis for risk assessment of pharmaceuticals present in healthcare facility wastewaters.     

Evaluating pharmaceuticals and caffeine as indicators of fecal contamination in drinking water sources of the Greater Montreal region

We surveyed four different river systems in the Greater Montreal region, upstream and downstream of entry points of contamination, from April 2007 to January 2009. The studied compounds belong to three different groups: PPCPs (caffeine, carbamazepine, naproxen, gemfibrozil, and trimethoprim), hormones (progesterone, estrone, and estradiol), and triazine herbicides and their metabolites (atrazine, deethylatrazine, deisopropylatrazine, simazine, and cyanazine). In the system A, B, and C having low flow rate and high TOC, we observed the highest detection frequencies and mass flows of PPCPs compared to the other compounds, reflecting discharge of urban contaminations through WWTPs and CSOs. However, in River D, having high flow rate and low TOC, comparable frequency of detection of triazine and their by-products and PPCPs, reflecting cumulative loads of these compounds from the Great Lakes as well as persistency against natural attenuation processes. Considering large differences in the removal efficiencies of caffeine and carbamazepine, a high ratio of caffeine/carbamazepine might be an indicative of a greater proportion of raw sewage versus treated wastewater in surface waters. In addition, caffeine appeared to be a promising indicator of recent urban fecal contaminations, as shown by the significant correlation with FC (R² = 0.45), while carbamazepine is a good indicator of cumulative persistence compounds.     

Pilot survey monitoring pharmaceuticals and related compounds in a sewage treatment plant located on the Mediterranean coast

A one-year monitoring study was performed to evaluate the occurrence, persistence and fate of a group of 14 organic compounds in a sewage treatment plant (STP) located in the south of Spain. These results are part of a more extensive study, financed by the Spanish Ministry of Research with the aim to evaluate the traceability of new pollutants on the Mediterranean coast and to determine the removal efficiency of sewage treatment plants (STP) for these pollutants. The compounds which have been analyzed include pharmaceuticals of various therapeutic categories (ibuprofen, acetaminophen, dipyrone, diclofenac, carbamazepine and codeine), pesticides (chlorfenvinfos and permethrin), caffeine, triclosan, bisphenol A and three of their more relevant metabolites (1,7-dimethylxanthine, carbamazepine 10,11-epoxide and 2,7/2,8-dichlorodibenzo-p-dioxin). An SPE/GC-MS multi-residue analytical method was developed and validated to facilitate simultaneous determination of these compounds in both influent and effluent wastewater. The method provided mean recoveries higher than 75%, with the exception of 2,7/2,8-dichlorodibenzo-p-dioxin, dipyrone and permethrin which exhibited recoveries lower than 22%. The overall variability of the method was below 14%. The method detection limit (LOD) was between 1 and 100 ng l(-1) and precision, which was calculated as relative standard deviation (RSD), ranged from 1.8% to 11.2%. The application of the proposed method has allowed the identification of all the target compounds at mean concentrations which ranged from 0.12 to 134 microg l(-1) in the influent and from 0.09 to 18.0 microg l(-1) in the effluent. The removal efficiencies of the STP for these compounds varied from 20% (carbamazepine) to 99% (acetaminophen), but in all cases resulted insufficient in order to avoid their presence in treated water and subsequently in the environment.