Hospitals and households as primary emission sources for risk-posing pharmaceuticals in municipal wastewater.

A wide range of pharmaceutical residues is known to occur in the environment. While they are released into surface waters mainly through centralized wastewater treatment plants (WWTPs), their primary emission sources are located upstream in the sewer network. Information on emissions from different types of primary emission sources is scarce. However, such information could help direct emission reduction measures more efficiently. In this study, we analysed the concentrations of selected active pharmaceutical ingredients (APIs) in wastewater samples taken from altogether ten sites, covering primary emission sources (hospitals and households), and conventional WWTPs. The concentrations in WWTP effluents were used to identify APIs causing risk in recipient waterbodies. Furthermore, the API loads from households and hospitals were compared to those reaching the WWTP in mixed influents. Our results confirm previously published observations of several pharmaceuticals exceeding their predicted no-effect concentrations in effluent wastewaters. Moreover, the concentrations of most of the analysed APIs are comparatively high in hospital wastewaters, resulting in elevated risk quotients. While the total API loads are relatively low from primary emission sources, owing to the low wastewater volume generated at those sites, per capita emissions were shown to be several times higher at hospital sites than at household sites for APIs such as metronidazole, trimethoprim, and ofloxacin. These findings indicate, that directing emission reduction measures to hospitals could be an effective way to decrease the loads of several risk-posing APIs into the environment, especially where hospital contribution to overall wastewater flow to WWTPs is high.

Occurrence of xenobiotics in gray water and removal in three biological treatment systems.

Eighteen selected xenobiotics related to personal care and household chemicals (UV-filters, fragrances, preservatives, biocides, surfactants) were measured in gray water from 32 houses and in effluents of three different biological treatment systems (aerobic, anaerobic, and combined anaerobic+aerobic). All selected xenobiotics were detected in gray water samples in the low microg L(-1) range. Generally, lower concentrations were measured after biological treatment and removal efficiencies were higher under aerobic conditions than under anaerobic conditions. However, most of the xenobiotics were still detected in biologically treated gray water. The most persistent compounds were the fragrance tonalide and the UV-filters 2-phenyl-5-benzimidazolesulfonic acid and ethylhexyl methoxycinnamate. Estimated estrogenic potential of the effluent ranged between 0.07 and 0.72 ng L(-1) of 17beta-estradiol equivalents. Depending on the application of the effluent and its environmental risk, physical-chemical processes might be required to increase the removal efficiency of these compounds from gray water.

Analysis of neutral and basic pharmaceuticals in sewage treatment plants and in recipient rivers using solid phase extraction and liquid chromatography-tandem mass spectrometry detection.

Analytical method was developed which allowed for the detection of four beta blockers (acebutolol, atenolol, metoprolol and sotalol), an antiepileptic drug (carbamazepine) and three fluoroquinolone antibiotics (ciprofloxacin, ofloxacin and norfloxacin) with a single pre-treatment and chromatographic method. The method included an isolation and concentration procedure using solid phase extraction, a separation step using high performance liquid chromatography and a detection procedure applying triple quadrupole mass spectrometry, which was working in the multiple reaction monitoring mode. The method was validated for ground, surface and sewage influent and effluent waters. Due to ion suppression in the electrospray source, the signals monitored for the analytes were less intense in sewage waters compared to ground and surface waters. The limits of quantification were as low as 1 ng L(-1) in ground water and 3.5 ng L(-1) in sewage influent. The method was successfully applied to the determination of the target compounds in raw and treated sewages of three treatment plants in Finland and in their recipient rivers. The results showed that many of the studied compounds pose a moderate to high persistency in sewage treatment as well as in the recipient rivers. The analytical protocol presented may be used for more in-depth studies on the occurrence and fate of these commonly used pharmaceuticals in the sewage treatment plants and in the aquatic environment.

Efficiency of the activated carbon filtration in the natural organic matter removal.

The removal and transformation of natural organic matter were monitored in the different stages of the drinking water treatment train. Several methods to measure the quantity and quality of organic matter were used. The full-scale treatment sequence consisted of coagulation, flocculation, clarification by flotation, disinfection with chlorine dioxide, activated carbon filtration and post-chlorination. High-performance size-exclusion chromatography separation was used to determine the changes in the humic substances content during the purification process; in addition, a UV absorbance at wavelength 254 nm and total organic carbon amount were measured. A special aim was to study the performance and the capacity of the activated carbon filtration in the natural organic matter removal. Four of the activated carbon filters were monitored over the period of 1 year. Depending on the regeneration of the activated carbon filters, filtration was effective to a degree but did not significantly remove the smallest molar mass organic matter fraction. Activated carbon filtration was most effective in the removal of intermediate molar mass compounds (range 1,000-4,000 g/mol). Regeneration of the carbon improved the removal capacity considerably, but efficiency was returned to a normal level after few months.

Fate of diclofenac in municipal wastewater treatment plant - a review.

Diclofenac (DCF) is a common anti-inflammatory pharmaceutical that is often detected in waste wasters, effluents and surface waters. Recently, DCF was included in the watch list of substances in EU that requires its environmental monitoring in the member states. DCF is also known to harmfully affect several environmental species already at concentrations of ≤ 1 µg/l. This review focuses on the occurrence and fate of DCF in conventional wastewater treatment processes. Research done in this area was gathered and analyzed in order to find out the possibilities to enhance DCF elimination during biological wastewater treatment. More precisely, human metabolism, concentrations in wastewater influents and effluents, elimination rates in the treatment train, roles of sorption and biotransformation mechanisms during the treatment as well as formation of transformation products are reported. Additionally, the effect of process configuration, i.e. conventional activated sludge (CAS), biological nutrient removal (BNR), membrane bioreactor (MBR) and attached-growth bioreactor, and process parameters, i.e. solids retention time (SRT) and hydraulic retention time (HRT) are presented. Generally, DCF is poorly biodegradable which often translates into low elimination rates during biological wastewater treatment. Only a minor portion is sorbed to sludge. MBR and attached-growth bioreactors may result in higher elimination of DCF over CAS or BNR. Long SRTs (>150 d) favor the DCF elimination due to sludge adaptation. Longer HRTs (>2-3d) could significantly increase the elimination of DCF during biological wastewater treatment. Bioaugmentation could be used to enhance DCF elimination, however, this requires more research on microbial communities that are able to degrade DCF. Also, further research is needed to gain more information about the deconjugation processes and biotic and abiotic transformation and the nature of transformation products.

Occurrence of pharmaceuticals in river water and their elimination in a pilot-scale drinking water treatment plant.

The occurrence of four beta blockers, one antiepileptic drug, one lipid regulator, four anti-inflammatories, and three fluoroquinolones was studied in a river receiving sewage effluents. All compounds but two of the fluoroquinolones were observed in the water above their limit of quantification concentrations. The highest concentrations (up to 107 ng L(-1)) of the compounds were measured during the winter months. The river water was passed to a pilot-scale drinking water treatment plant, and the elimination of the pharmaceuticals was followed during the treatment. The processes applied by the plant consisted of ferric salt coagulation, rapid sand filtration, ozonation, two-stage granular activated carbon filtration (GAC), and UV disinfection. Following the coagulation, sedimentation, and rapid sand filtration, the studied pharmaceuticals were found to be eliminated only by an average of 13%. An efficient elimination was found to take place during ozonation at an ozone dose of about 1 mg L(-1) (i.e., 0.2-0.4 mg of O3/ mg of TOC). Following this treatment, the concentrations of the pharmaceuticals dropped to below the quantification limits with the exception of ciprofloxacin. Atenolol, sotalol, and ciprofloxacin, the most hydrophilic of the studied pharmaceuticals, were not fully eliminated during the GAC filtrations. All in all, the treatment train was found to very effectively eliminate the pharmaceuticals from the rawwater. The only compound that was found to pass almost unaffected through all the treatment steps was ciprofloxacin.

Seasonal variation in the occurrence of pharmaceuticals in effluents from a sewage treatment plant and in the recipient water.

The occurrence of five pharmaceuticals (ibuprofen, naproxen, ketoprofen, diclofenac, and bezafibrate) in the influent and effluent water of a sewage treatment plant (STP) in the recipient river water and in a drinking water treatment plant (DWTP) located downstream from the STP was followed during three seasons: winter, spring, and summer. In the STP, the elimination of the pharmaceuticals decreased significantly (an average of 25% compared to spring and summer) in wintertime leading to increased concentrations of pharmaceuticals in the effluent water. The total concentration of all the studied pharmaceuticals in the effluent water was 3-5 times higher in wintertime (about 2500 ng L(-1)) than during the other seasons (about 500-900 ng L(-1)). Accordingly, the highest concentrations (up to 129 ng L(-1)) in the recipient river were measured in the wintertime. Pharmaceuticals were carried longer distances downstream from the STP when the river was covered by ice and snow. During a drastic increase in water flow rate (i.e., during snowmelting), a fast transportation of the pharmaceuticals was observed. The DWTP located downstream from the STP produced water that contained about 8 ng L(-1) of ibuprofen and ketoprofen in the winter sample, whereas in spring and summer the studied pharmaceuticals could not be detected in the drinking water. The results show that cold seasons in boreal areas can severely increase the environmental risk of pharmaceuticals and the risk for contamination of drinking water.