Aleksandra Jelic

Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment

During 8 sampling campaigns carried out over a period of two years, 72 samples, including influent and effluent wastewater, and sludge samples from three conventional wastewater treatment plants (WWTPs), were analyzed to assess the occurrence and fate of 43 pharmaceutical compounds. The selected pharmaceuticals belong to different therapeutic classes, i.e. non-steroidal anti-inflammatory drugs, lipid modifying agents (fibrates and statins), psychiatric drugs (benzodiazepine derivative drugs and antiepileptics), histamine H2-receptor antagonists, antibacterials for systemic use, beta blocking agents, beta-agonists, diuretics, angiotensin converting enzyme (ACE) inhibitors and anti-diabetics. The obtained results showed the presence of 32 target compounds in wastewater influent and 29 in effluent, in concentrations ranging from low ng/L to a few μg/L (e.g. NSAIDs). The analysis of sludge samples showed that 21 pharmaceuticals accumulated in sewage sludge from all three WWTPs in concentrations up to 100 ng/g. This indicates that even good removal rates obtained in aqueous phase (i.e. comparison of influent and effluent wastewater concentrations) do not imply degradation to the same extent. For this reason, the overall removal was estimated as a sum of all the losses of a parent compound produces by different mechanisms of chemical and physical transformation, biodegradation and sorption to solid matter. The target compounds showed very different removal rates and no logical pattern in behaviour even if they belong to the same therapeutic groups. What is clear is that the elimination of most of the substances is incomplete and improvements of the wastewater treatment and subsequent treatments of the produced sludge are required to prevent the introduction of these micro-pollutants in the environment.

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain.

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.

Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole-linear ion trap mass spectrometry

A simple and sensitive method for simultaneous analysis of 43 pharmaceutical compounds in sewage sludge and sediment samples was developed and validated. The target compounds were extracted using pressurized liquid extraction (PLE) and then purified and pre-concentrated by solid phase extraction (SPE) using a hydrophilic-lipophilic balanced polymer. PLE extraction was performed on temperature of 100 degrees C, with methanol/water mixture (1/2, v/v) as extraction solvent. The quantitative analysis was performed by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole-linear ion trap mass spectrometer (LC-QqLIT-MS). Data acquisition was carried out in selected reaction monitoring (SRM) mode, monitoring two SRM transitions to ensure an accurate identification of target compounds in the samples. Additional identification and confirmation of target compounds were performed using the Information Dependent Acquisition (IDA) function. The method was validated through the estimation of the linearity, sensitivity, repeatability, reproducibility and matrix effects. The internal standard approach was used for quantification because it efficiently corrected matrix effects. Despite the strong matrix interferences, the recoveries were generally higher of 50% in both matrixes and the detection and quantification limits were very low. Beside the very good sensitivity provided by LC-QqLIT-MS, an important characteristic of the method is that all the target compounds can be simultaneously extracted, treated and analysed. Hence, it can be used for routine analysis of pharmaceuticals providing large amount of data. The method was applied for the analysis of pharmaceuticals in river sediment and wastewater sludge from three treatment plants with different treatment properties (i.e. capacity, secondary treatment, quality of influent waters). The analysis showed a widespread occurrence of pharmaceuticals in the sludge matrices.

Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two wwtp effluents and their receiving bodies in the po valley, italy

This study describes an investigation on the occurrence of 27 pharmaceutical compounds, belonging to different classes, in the effluent from two wastewater treatment plants (WWTPs) and their receiving water bodies in the sensitive area of the Po Valley (northern Italy). These canals were monitored upstream and downstream of the effluent discharge points in order to evaluate the effluent impact on the quality of surface waters, commonly used for irrigation. An environmental risk assessment was also conducted by calculating the risk quotient, i.e. the ratio between measured concentration and predicted no effect concentration. Collected data show that, although average values of the selected compounds were in general higher in the effluent than in the surface waters, some compounds not detected in the WWTP effluent were detected in the receiving water (upstream as well as downstream), indicating that sources other than treated effluents are present as contaminations during extraction and analysis have to be excluded. The most critical compounds for the environment were found to be the antibiotics sulfamethoxazole, clarithromycin and azithromycin. The study shows that the potential toxicological effects of persistent micropollutants can be mitigated to some extent by a high dilution capacity, i.e. a high average flow rate in the receiving water body with respect to the effluent.

Pharmaceuticals in Drinking Water

Pharmaceuticals are a group of emerging contaminants that has received noticeable attention over the past decade. Continual development of the advanced instruments and improved analytical methodologies made possible detection of these microcontaminants in low levels in different environmental matrices. Traces of pharmaceuticals have also been found in groundwater and surface water that are used for drinking water supply. Therefore, concern has been raised over the potential risk to human health from exposure to the pharmaceutical residues via drinking water. Still, there is no evidence that any serious risk could arise from low concentrations of pharmaceuticals found in drinking water. Anyhow, there is much more to be understood about long-term, low-level exposure to a mixture of pharmaceuticals and their metabolites. In the following chapter, we give a brief overview of the technologies commonly applied for drinking water treatment, with reference to pharmaceutical removal, and we review available literature data on the occurrence of pharmaceuticals in finished drinking water.

Occurrence and Elimination of Pharmaceuticals During Conventional Wastewater Treatment

Pharmaceuticals have an important role in the treatment and prevention of disease in both humans and animals. Since they are designed either to be highly active or interact with receptors in humans and animals or to be toxic for many infectious organisms, they may also have unintended effects on animals and microorganisms in the environment. Therefore, the occurrence of pharmaceutical compounds in the environment and their potential effects on human and environ- mental health has become an active subject matter of actual research. There are several possible sources and routes for pharmaceuticals to reach the environment, but wastewater treatment plants have been identified as the main point of their collection and subsequent release into the environment, via both effluent wastewater and sludge. Conventional systems that use an activated sludge process are still widely employed for wastewater treatment, mostly because they produce effluents that meet required quality standards (suitable for disposal or recycling purposes), at reasonable operating and maintenance costs. However,

Tracing pharmaceuticals in a municipal plant for integrated wastewater and organic solid waste treatment

The occurrence and removal of 42 pharmaceuticals, belonging to different therapeutic groups (analgesics and anti-inflammatory drugs, anti-ulcer agent, psychiatric drugs, antiepileptic drug, antibiotics, ß-blockers, diuretics, lipid regulator and cholesterol lowering statin drugs and anti-histamines), were studied in the wastewater and sewage sludge trains of a full scale integrated treatment plant. The plant employs a biological nutrient removal (BNR) process for the treatment of municipal wastewater, and a single-stage mesophilic anaerobic co-digestion for the treatment of wasted activated sludge mixed with the organic fraction of municipal solid waste (OFMSW), followed by a short-cut nitrification-denitrification of the anaerobic supernatant in a sequential batch reactor. Influent and effluent wastewater, as well as thickened, digested and treated sludge were sampled and analyzed for the selected pharmaceuticals in order to study their presence and fate during the treatment. Twenty three compounds were detected in influent and effluent wastewater and eleven in sludge. Infiltration of groundwater in the sewer system led to a dilution of raw sewage, resulting in lower concentrations in wastewater (up to 0.7 μg/L in influent) and sludge (70 ng/g d.w.). Due to the dilution, overall risk quotient for the mixture of pharmaceuticals detected in effluent wastewater was less than one, indicating no direct risk for the aquatic environment. A wide range of removal efficiencies during the treatment was observed, i.e. <20% to 90%. The influent concentrations of the target pharmaceuticals, as polar compounds, were undoubtedly mostly affected by BNR process in the wastewater train, and less by anaerobic-co-digestion. Mass balance calculations showed that less than 2% of the total mass load of the studied pharmaceuticals was removed by sorption. Experimentally estimated distribution coefficients (<500 L/kg) also indicated that the selected pharmaceuticals preferably remain in the aqueous phase, and that biodegradation/transformation is the primary removal mechanism for these compounds during wastewater treatment.

A survey of emerging contaminants in the estuarine receiving environment around Auckland, New Zealand

Increasing urbanisation in the future will put mounting stresses on the receiving environments around those urban centres due to increased sedimentation and contaminant runoff. Emerging contaminants (ECs) are an extensive array of chemicals and many are not under regulatory action. Within New Zealand likely future pressures from ECs will be in both urban centres and rural areas due to intensive agriculture, although at present there is a lack of information on the state of the environment in both sectors. This study was initiated to gauge the distribution of ECs in the urban environment by measuring concentrations of flame retardants, plasticisers, alkylphenols, herbicides and pesticides, steroid oestrogens, pharmaceuticals and heavy metals in sediment from 13 estuarine sites around Auckland, New Zealands biggest city. Total polybrominated diphenyl ether (PBDE) flame retardant concentrations ((7)ΣPBDE) ranged from 0.55 to 573 ng/g (dw). The phthalate plasticiser di(2-ethylhexyl)phthalate (DEHP) was measured at up to 11,500 ng/g from one site. Nonylphenol (NP) was found at up to 32,000 ng/g at one site adjacent to the citys major wastewater treatment plant (WWTP). However, median concentrations of NP were 153 ng/g, suggesting this site was not representative of the region. Nonylphenol mono- and di-ethoxylates (NPEO1,2) had highest concentrations (1600 ng/g) at a marina. Highest glyphosate concentrations (up to 950 ng/g) were observed at residential sites. Steroid oestrogens were detected at extremely low concentrations (maximum 2.2 ng/g), while all other pesticides or herbicides were not detected at any sites. Multi-residue analysis of 46 pharmaceuticals showed presence of 21 compounds at one or more sites, with average concentrations ranging from 0.16 to 7.66 ng/g. Generally, environmental concentrations of ECs were similar to those reported world-wide. However, comparisons for pharmaceuticals were problematic, due to very few studies on pharmaceutical concentrations in estuarine sediments, with most focussed on sewage and stream water phases.

Solid-phase treatment with the fungus Trametes versicolor substantially reduces pharmaceutical concentrations and toxicity from sewage sludge

For safe biosolid-land-applying, sludge should be contaminant-free. However, it may contain important amounts of micropollutants, not removed in the wastewater-treatment-processes. An alternative treatment with the fungus Trametes versicolor was applied in sterile solid-phase systems consisting of sludge and a lignocellulosic substrate. Fungal colonization and activity were demonstrated during the process, according to monitoring of ergosterol, laccase activity and the naproxen-degradation test (ND24). Fourteen out of 43 analyzed pharmaceuticals were found in the raw sludge. After treatment, phenazone, bezafibrate, fenofibrate, cimetidine, clarithromycin, sulfamethazine and atenolol were completely removed, while removals between 42% and 80% were obtained for the remaining pharmaceuticals. Toxicological analyses (Daphnia magna, Vibrio fischeri and seed germination) showed an important reduction in sludge toxicity after treatment. Results suggest that a solid-phase treatment with T. versicolor may reduce the ecotoxicological impact of micropollutants present in sewage sludge. This is the first report of a fungal-approach for elimination of emerging pollutants from biosolids.

Transformation products and reaction pathways of carbamazepine during photocatalytic and sonophotocatalytic treatment

This study examines the degradation of the antiepileptic carbamazepine (CBZ) by sonolysis, TiO2-based heterogeneous photocatalysis under UV-A and simulated solar irradiation, and by the combined use of UV-A and ultrasound irradiation (i.e. sonophotocatalysis) in demineralized water, ground water and effluent wastewater. The processes were compared with respect to substrate conversion rate and the extent of DOC reduction as a measure of mineralization. CBZ was degraded following a pseudo-first order kinetics. Sonophotocatalysis provided the highest rate of CBZ transformation over the time-course of the experiment while the degree of DOC removal in pure water was similar for all the studied treatments (around 40%), and always lower than CBZ conversion. This indicated that a considerable organic load remained in the treated solutions that could also be attributed to the presence of persistent oxidation products. UPLC-(+ESI)-QToF-MS was employed to determine major CBZ-related transformation products. Several recalcitrant hydroxy- and keto-derivatives of CBZ were tentatively identified. A Daphnia magna bioassay was used to evaluate the potential toxicity of the samples collected at different time points showing that the mixtures were highly toxic to D. magna.