Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants

Eight pharmaceuticals, two polycyclic musk fragrances and nine endocrine disrupting chemicals were analysed in several waste water treatment plants (WWTPs). A membrane bioreactor in pilot scale was operated at different solid retention times (SRTs) and the results obtained are compared to conventional activated sludge plants (CASP) operated at different SRTs. The SRT is an important design parameter and its impact on achievable treatment efficiencies was evaluated. Different behaviours were observed for the different investigated compounds. Some compounds as the antiepileptic drug carbamazepine were not removed in any of the sampled treatment facilities and effluent concentrations in the range of influent concentrations were measured. Other compounds as bisphenol-A, the analgesic ibuprofen or the lipid regulator bezafibrate were nearly completely removed (removal rates >90%). The operation of WWTPs with SRTs suitable for nitrogen removal (SRT>10 days at 10 degrees C) also increases the removal potential regarding selected micropollutants. No differences in treatment efficiencies were detected between the two treatment techniques. As in conventional WWTP also the removal potential of MBRs depends on the SRT. Ultrafiltration membranes do not allow any additional detention of the investigated substances due to size exclusion. However, MBRs achieve a high SRT within a compact reactor. Nonylphenolpolyehtoxylates were removed in higher extend in very low-loaded conventional WWTPs, due to variations of redox conditions, necessary for the degradation of those compounds.     

Biological degradation of pharmaceuticals in municipal wastewater treatment: proposing a classification scheme

A simple classification scheme is suggested to characterize the biological degradation of micropollutants such as pharmaceuticals, musk fragrances and estrogens during wastewater treatment. The scheme should be a basis for the discussion about potential removal efficiencies. Hence, the biological degradation of 25 pharmaceuticals, hormones and fragrances was studied in batch experiments at typical concentration levels using activated sewage sludge originating from nutrient-eliminating municipal wastewater treatment plants. Since pseudo first-order degradation kinetics was observed for all compounds down to ng L(-1) levels, the removal rates can be predicted for various reactor configurations. Therefore dilution of wastewater (e.g. by extraneous water) is expected to reduce the degree of biological removal. Wastewater segregation and treatment at the source are therefore to be favoured for elimination of persistent micropollutants over centralized end-of-pipe treatment. For reactor configurations typical for nutrient removal in municipal wastewater, the derived formula for predicting removal allows the identification of three groups of micropollutants according to their degradation constant k(biol): compounds with k(biol)<0.1 L g(SS)(-1)d(-1) are not removed to a significant extent (<20%), compounds with k(biol)>10 L g(SS)(-1)d(-1) transformed by >90% and in-between moderate removal is expected. Based on the degradation of a heterogeneous group of 35 compounds (including literature data), state of the art biological treatment schemes for municipal wastewater are not efficient in degrading pharmaceuticals: only 4 out of 35 compounds are degraded by more than 90% while 17 compounds are removed by less than 50%.     

Pathways and metabolites of microbial degradation of selected acidic pharmaceutical and their occurrence in municipal wastewater treated by a membrane bioreactor

Laboratory degradation tests with five acidic pharmaceuticals using activated sludge as inocculum under aerobic conditions were performed and microbial metabolites were analysed by liquid chromatography-mass spectrometry (LC-MS). Ketoprofen was partly mineralized as a sole source of carbon and energy and the metabolites determined by LC-MS suggest microbial ketoprofen degradation to proceed along the pathway known for biphenyls and related compounds. Bezafibrate, naproxen and ibuprofen were degraded only cometabolically whereas no transformation was obtained for diclofenac. Some biodegradation intermediates in these batch tests could be tentatively identified by means of LC-MS. The first step in microbial bezafibrate degradation appears to be the hydrolytic cleavage of the amide bond, generating well degradable 4-chlorobenzoic acid as one of the hydrolysis products. As previously found for mammals, ether cleavage and formation of desmethylnaproxen was the initial step in microbial degradation of naproxen. Two isomers of hydroxy-ibuprofen were detected as intermediates in the mineralization of ibuprofen. Laboratory studies suggest that naproxen and ibuprofen can be fully mineralized whereas more stable metabolites occur in microbial ketoprofen and bezafibrate transformation, that may deserve further attention. A LC-MS method for the trace analysis of these metabolites in water was developed and applied to municipal wastewater. Municipal wastewater treatment by a membrane bioreactor may gradually improve the removal of these pharmaceuticals.     

Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment

In this paper we report on the performances of full-scale conventional activated sludge (CAS) treatment and two pilot-scale membrane bioreactors (MBRs) in eliminating various pharmaceutically active compounds (PhACs) belonging to different therapeutic groups and with diverse physico-chemical properties. Both aqueous and solid phases were analysed for the presence of 31 pharmaceuticals included in the analytical method. The most ubiquitous contaminants in the sewage water were analgesics and anti-inflammatory drugs ibuprofen (14.6-31.3 μg/L) and acetaminophen (7.1-11.4 μg/L), antibiotic ofloxacin (0.89-31.7 μg/L), lipid regulators gemfibrozil (2.0-5.9 μg/L) and bezafibrate (1.9-29.8 μg/L), β-blocker atenolol (0.84-2.8 μg/L), hypoglycaemic agent glibenclamide (0.12-15.9 μg/L) and a diuretic hydrochlorothiazide (2.3-4.8 μg/L). Also, several pharmaceuticals such as ibuprofen, ketoprofen, diclofenac, ofloxacin and azithromycin were detected in sewage sludge at concentrations up to 741.1, 336.3, 380.7, 454.7 and 299.6 ng/g dry weight. Two pilot-scale MBRs exhibited enhanced elimination of several pharmaceutical residues poorly removed by the CAS treatment (e.g., mefenamic acid, indomethacin, diclofenac, propyphenazone, pravastatin, gemfibrozil), whereas in some cases more stable operation of one of the MBR reactors at prolonged SRT proved to be detrimental for the elimination of some compounds (e.g., β-blockers, ranitidine, famotidine, erythromycin). Moreover, the anti-epileptic drug carbamazepine and diuretic hydrochlorothiazide by-passed all three treatments investigated.Furthermore, sorption to sewage sludge in the MBRs as well as in the entire treatment line of a full-scale WWTP is discussed for the encountered analytes. Among the pharmaceuticals encountered in sewage sludge, sorption to sludge could be a relevant removal pathway only for several compounds (i.e., mefenamic acid, propranolol, and loratidine). Especially in the case of loratidine the experimentally determined sorption coefficients (K_ds) were in the range 2214-3321 L/kg (mean). The results obtained for the solid phase indicated that MBR wastewater treatment yielding higher biodegradation rate could reduce the load of pollutants in the sludge. Also, the overall output load in the aqueous and solid phase of the investigated WWTP was calculated, indicating that none of the residual pharmaceuticals initially detected in the sewage sludge were degraded during the anaerobic digestion. Out of the 26 pharmaceutical residues passing through the WWTP, 20 were ultimately detected in the treated sludge that is further applied on farmland.     

Fate of antibiotics in activated sludge followed by ultrafiltration (CAS-UF) and in a membrane bioreactor (MBR)

The fates of several macrolide, sulphonamide, and trimethoprim antibiotics contained in the raw sewage of the Tel-Aviv wastewater treatment plant (WWTP) were investigated after the sewage was treated using either a full-scale conventional activated sludge (CAS) system coupled with a subsequent ultrafiltration (UF) step or a pilot membrane bioreactor (MBR) system. Antibiotics removal in the MBR system, once it achieved stable operation, was 15-42% higher than that of the CAS system. This advantage was reduced to a maximum of 20% when a UF was added to the CAS. It was hypothesized that the contribution of membrane separation (in both systems) to antibiotics removal was due either to sorption to biomass (rather than improvement in biodegradation) or to enmeshment in the membrane biofilm (since UF membrane pores are significantly larger than the contaminant molecules). Batch experiments with MBR biomass showed a markedly high potential for sorption of the tested antibiotics onto the biomass. Moreover, methanol extraction of MBR biomass released significant amounts of sorbed antibiotics. This finding implies that more attention must be devoted to the management of excess sludge.     

Critical flux and chemical cleaning-in-place during the long-term operation of a pilot-scale submerged membrane bioreactor for municipal wastewater treatment

The critical flux and chemical cleaning-in-place (CIP) in a long-term operation of a pilot-scale submerged membrane bioreactor for municipal wastewater treatment were investigated. Steady filtration under high flux (30 L/(m² h)) was successfully achieved due to effective membrane fouling control by sub-critical flux operation and chemical CIP with sodium hypochlorite (NaClO) in both trans-membrane pressure (TMP) controlling mode (cleaning with high concentration NaClO of 2000-3000 mg/L in terms of effective chorine was performed when TMP rose to 15 kPa) and time controlling mode (cleanings were performed weekly and monthly respectively with low concentration NaClO (500-1000 mg/L) and high concentration NaClO (3000 mg/L)). Microscopic analysis on membrane fibers before and after high concentration NaClO was also conducted. Images of scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed that NaClO CIP could effectively remove gel layer, the dominant fouling under sub-critical flux operation. Porosity measurements indicated that NaClO CIP could partially remove pore blockage fouling. The analyses from fourier transform infrared spectrometry (FTIR) with attenuated total reflectance accessory (ATR) and energy dispersive spectrometer (EDS) demonstrated that protein-like macromolecular organics and inorganics were the important components of the fouling layer. The analysis of effluent quality before and after NaClO CIP showed no obvious effect on effluent quality.     

Fate of aromatic hydrocarbons in Italian municipal wastewater systems: An overview of wastewater treatment using conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs)

We studied the occurrence, removal, and fate of 16 polycyclic aromatic hydrocarbons (PAHs) and 23 volatile organic compounds (VOCs) in Italian municipal wastewater treatment systems in terms of their common contents and forms, and their apparent and actual removal in both conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs). We studied five representative full-scale CASP treatment plants (design capacities of 12 000 to 700 000 population-equivalent), three of which included MBR systems (one full-scale and two pilot-scale) operating in parallel with the conventional systems. We studied the solid-liquid partitioning and fates of these substances using both conventional samples and a novel membrane-equipped automatic sampler. Among the VOCs, toluene, ethylbenzene, xylenes, styrene, 1,2,4-trimethylbenzene, and 4-chlorotoluene were ubiquitous, whereas naphthalene, acenaphthene, fluorene, and phenanthrene were the most common PAHs. Both PAHs and aromatic VOCs had removal efficiencies of 40-60% in the headworks, even in plants without primary sedimentation. Mainly due to volatilization, aromatic VOCs had comparable removal efficiencies in CASP and MBRs, even for different sludge ages. MBRs did not enhance the retention of PAHs sorbed to suspended particulates compared with CASPs. On the other hand, the specific daily accumulation of PAHs in the MBR’s activated sludge decreased logarithmically with increasing sludge age, indicating enhanced biodegradation of PAHs. The PAH and aromatic VOC contents in the final effluent are not a major driver for widespread municipal adoption of MBRs, but MBRs may enhance the biodegradation of PAHs and their removal from the environment.     

Degradation of pharmaceuticals in non-sterile urban wastewater by Trametes versicolor in a fluidized bed bioreactor

The constant detection of pharmaceuticals (PhACs) in the environment demonstrates the inefficiency of conventional wastewater treatment plants to completely remove them from wastewaters. So far, many studies have shown the feasibility of using white rot fungi to remove these contaminants. However, none of them have studied the degradation of several PhACs in real urban wastewater under non-sterile conditions, where mixtures of contaminants presents at low concentrations (ng L⁻¹ to μg L⁻¹) as well as other active microorganisms are present. In this work, a batch fluidized bed bioreactor was used to study, for the first time, the degradation of PhACs present in urban wastewaters at their pre-existent concentrations under non-sterile conditions. Glucose and ammonium tartrate were continuously supplied as carbon and nitrogen source, respectively, and pH was maintained at 4.5. Complete removal of 7 out of the 10 initially detected PhACs was achieved in non-sterile treatment, while only 2 were partially removed and 1 of the PhACs analyzed increased its concentration. In addition, Microtox test showed an important reduction of toxicity in the wastewater after the treatment.     

Musk fragrances, DEHP and heavy metals in a 20 years old sludge treatment reed bed system

The Sludge Treatment Reed Bed (STRB) technology is a cost-efficient and environmentally friendly technology to dewater and mineralize surplus sludge from conventional wastewater treatment systems. Primary and secondary liquid sludge is loaded onto the surface of the bed over several years, where it is dewatered, mineralized and turned into a biosolid with a high dry matter content for use as an organic fertilizer on agricultural land. We analysed the concentrations of five organic micropollutants (galaxolide, tonalide, cashmeran, celestolide and DEHP) and six heavy metals (Pb, Ni, Cu, Cd, Zn and Cr) in the accumulated sludge in a 20-year old STRB in Denmark in order to assess the degradation and fate of these contaminants in a STRB and the relation to sludge composition. The results showed that the deposited sludge was dewatered to reach a dry matter content of 29%, and that up to a third of the organic content of the sludge was mineralized. The concentrations of heavy metals generally increased with depth in the vertical sludge profile due to the dewatering and mineralization of organic matter, but in all cases the concentrations were below the European Union legal limits for agricultural land disposal. The concentrations of fragrances and DEHP ranged from 10 to 9000 ng g⁻¹ dry mass. The attenuation of hydrophobic micropollutants from the top to the bottom layer of the reed bed ranged from 40 to 98%, except for tonalide which increased significantly with sludge depth, and consequently showed an unusual depth distribution of the galaxolide/tonalide ratio. This unexpected pattern may reflect changes imposed by a long storage time and/or different composition of the fresh sludge in the past. The lack of a significant decreasing DEHP concentration with sludge age might indicate that this compound is very persistent in STRBs. In conclusion the STRB was a feasible technology for sludge treatment before its land disposal.     

Decay processes of nitrifying bacteria in biological wastewater treatment systems

A knowledge of the decay rates of autotrophic bacteria is important for reliably modeling nitrification in activated sludge plants. The introduction of nitrite to activated sludge models also requires the separate determination of the kinetics of ammonia- and nitrite-oxidizing bacteria. Batch experiments were carried out in order to study the effects of different oxidiation-reduction potential conditions and membrane separation on the separate decay of these bacteria. It was found that decay is negligible in both cases under anoxic conditions. No significant differences were detected between the membrane and conventional activated sludge. The aerobic decay of these two types of bacteria did not diverge significantly either. However, the measured loss of autotrophic activity was only partly explained by the endogenous respiration concept as incorporated in activated sludge model no. 3 (ASM3). In contrast to nitrite-oxidizing bacteria, ammonia-oxidizing bacteria needed 1-2 h after substrate addition to reach their maximum growth rate measured as a maximum OUR. This pattern could be successfully modeled using the ASM3 extended by enzyme kinetics. The significance of these findings on wastewater treatment is discussed on the basis of the extended ASM3.     

Removal of cosmetic ingredients and pharmaceuticals in sewage primary treatment

Two physico-chemical processes, coagulation-flocculation and flotation, have been assessed for enhancing the removal of some selected pharmaceutical and personal care products (PPCPs) present in sewage. Eight compounds, representative of three main groups of PPCPs according to their physico-chemical properties, have been selected: lipophilic compounds (the synthetic musks Galaxolide and Tonalide), neutral compounds (the tranquillizer Diazepam and the antiepileptic Carbamazepine) and acidic compounds (the anti-inflammatories Ibuprofen, Naproxen and Diclofenac). During the coagulation-flocculation assays, the main parameters considered were the selection of the additives, their doses and the temperature of operation (12 or 25 degrees C). Musks-which are highly lipophilic and Diclofenac-with significant sorption affinity-were removed around 50-70% at both temperatures independently of the dose and type of coagulant used. However, the rest of the compounds, which are more hydrophilic, were affected to a lesser degree (with maximum reductions below 25%). The exceptions to this behavior were Carbamazepine and Ibuprofen, which were not removed under any condition tested. During the flotation assays, the parameters studied were the initial content of fat in wastewaters and temperature. Again, musks were removed to a greater degree (35-60%), followed by Diazepam (40-50%) and Diclofenac (20-45%) and, to a lesser extent, Carbamazepine (20-35%), Ibuprofen (10-25%) and Naproxen (10-30%). The best results were always obtained at 25 degrees C, although in some cases the operation at 12 degrees C gave similar results. The removal of musks and neutral compounds was higher in wastewaters with a high fat content (around 150 mgl(-1)).     

Membrane bioreactors for municipal wastewater treatment - a viable option to reduce the amount of polar pollutants discharged into surface waters?

The potential of a lab-scale membrane bioreactor (MBR) to remove polar pollutants from municipal wastewater was studied for industrial and household chemicals over a period of 22 months parallel to a conventional activated sludge (CAS) treatment. For half of the compounds, such as benzotriazole, 5-tolyltriazole (5-TTri), benzothiazole-2-sulfonate and 1,6-naphthalene disulfonate (1,6-NDSA), removal by MBR was significantly better than in CAS, while no improvement was recorded for the other half (1,5-NDSA, 1,3-NDSA, 4-TTri and naphthalene-1-sulfonate). The influence of operational conditions on trace pollutant removal by MBR was studied but no significant effects were found for variation of hydraulic retention time (7h-14h) and sludge retention time (26d-102d), suggesting that the lowest values selected have already been high enough for good removal. It is shown that the seemingly inconsistent results reported here and in previous studies regarding the comparison of trace pollutant removal in MBR and CAS are highly consistent. MBR is neither superior for well degradable compounds that are already extensively degraded in CAS treatment nor for recalcitrant compounds that are not amenable to biodegradation. For most compounds of intermediate removal in CAS treatment (15-80%), among them pharmaceuticals, personal care products and industrial chemicals, the MBR is clearly superior and reduces the effluent concentration by 20-50%. Despite of this clear benefit of MBR, the effect is not pronounced enough to serve as a sole argument for employing MBR in municipal wastewater treatment.     

Removal of trace organics by MBR treatment: the role of molecular properties

This study examined the relationship between specific molecular features of trace organic contaminants and their removal efficiencies by a laboratory scale membrane bioreactor (MBR). Removal efficiencies of 40 trace organic compounds were assessed under stable operating conditions. The reported results demonstrate an apparent correlation between chemical structures and the removal of trace organic contaminants by the laboratory scale MBR system. The removal of all 14 very hydrophobic (Log D > 3.2) trace organic compounds selected in this study was consistently high and was above 85%. The occurrence and types of electron withdrawing or donating functional groups appear to be important factors governing their removal by MBR treatment. In this study, all hydrophilic and moderately hydrophobic (Log D < 3.2) compounds possessing strong electron withdrawing functional groups showed removal efficiency of less than 20%. In contrast, high removal efficiencies were observed with most compounds bearing electron donating functional groups such as hydroxyl and primary amine groups. A qualitative framework for the assessment of trace organic removal by MBR treatment was proposed to provide further insights into the removal mechanisms.     

Fate of pharmaceuticals in contaminated urban wastewater effluent under ultrasonic irradiation

The application of sonolysis (US) for remediation of wastewater is an area of increasing interest. The aim of this study was to evaluate the ultrasonic (US) process on the degradation of pharmaceuticals (diclofenac (DCF), amoxicillin (AMX), carbamazepine (CBZ)) in single solutions and also in three mixtures spiked in urban wastewater effluent. Several operating conditions, such as power density (25-100 W L⁻¹), initial substrate concentrations (2.5-10 mg L⁻¹), initial solution pH (3-11), and air sparging were varied for the evaluation and understanding of the process. The degradation (as assessed by measuring UV absorbance), the generation of hydroxyl radicals (as assessed measuring H₂O₂ concentration), the mineralization (in terms of TOC and COD removal), and the aerobic biodegradability (as assessed by the BOD₅/COD ratio) were monitored during sonication. Ecotoxicity to Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum before and after treatment was also evaluated. It was found that the pharmaceuticals conversion is enhanced at increased applied power densities, acidic conditions and in the presence of dissolved air. The reaction rate increases with increasing initial concentration of single pharmaceuticals but it remains constant in the mixtures, indicating different kinetic regimes (i.e. first and zero order respectively). Mineralization is a slow process as reaction by-products are more stable than pharmaceuticals to total oxidation; nonetheless, they are also more readily biodegradable. The toxicity of the wastewater samples before and after contamination with pharmaceuticals both in mixtures and in single substance-containing solutions was observed more severely on P. subcapitata; a fact that raises concerns in regards to the discharge of such effluents. D. magna displayed less sensitivity compared to P. subcapitata because it belongs in a lower taxonomic species than D. magna. The germination index of L. sativum in the presence of the drugs' mixture was stimulated instead of inducing any toxicity effect and this might be attributed to the fact the sample, laden with very low drug concentrations was able to act as a provider of additional nutrient elements.     

Sorption behavior of potential organic wastewater indicators with soils

Soil-aquifer treatment is a wastewater treatment and reclamation option to facilitate beneficial water reuse. The fate of wastewater originated micropollutants in the soil-aquifer system is important to understand. In the study the sorption behavior of potential wastewater indicators such as two antiepileptic drugs (carbamazepine, primidone), one sulfonamide (sulfamethoxazole), and one corrosion inhibitor (benzotriazole) were determined with three natural soils (Lufa 2.2, Euro Soil 5, and Wulpen sand) that differed in pH, organic carbon content and particle size distribution. As aqueous phase a 0.01 M CaCl₂ solution as well as the effluent of a municipal wastewater treatment plant was used. Affinities of all analytes to the soil increased from Wulpen sand, over Lufa 2.2 to Euro Soil 5, indicating that the organic carbon contents might be crucial for sorption. Isotherms were well described by the Freundlich model. Sorption was mainly close to linear (n = 0.93-1.07) for most target compounds and soils. Desorption gave rise to a small hysteresis only for Euro Soil 5 which was likely artificial, due to slow desorption kinetics beyond 24 h used in the experiment. All sorption studies confirmed that Carbamazepine, Benzotriazole and Primidone are appropriate to be used as wastewater indicator substances based on their low sorption affinity to soils, while the suitability of Sulfamethoxazole is limited due to the formation of non-extractable residues, especially at lower pH values.     

膜生物反应器在水处理中的应用与发展

介绍了国内外膜生物反应器的研究及应用进展，结合膜生物反应器的特点与分类，就其应用现状作了阐述，并指出膜生物反应器技术是一种高效废水处理工艺，具有广阔的应用前景。     

Diurnal variations in the occurrence and the fate of hormones and antibiotics in activated sludge wastewater treatment in Oslo, Norway

We present an assessment of the dynamics in the influent concentration of hormones (estrone, estriol) and antibiotics (trimethoprim, sulfamethoxazole, tetracycline, ciprofloxacin) in the liquid phase including the efficiency of biological municipal wastewater treatment. The concentration of estradiol, 17-α−ethinylestradiol, doxycycline, oxytetracycline, demeclocycline, chlortetracycline, cefuroxime, cyclophosphamide, and ifosfamide were below the limit of detection in all of the sewage samples collected within this study. Two different types of diurnal variation pattern were identified in the influent mass loads of selected antibiotics and hormones that effectively correlate with daily drug administration patterns and with the expected maximum human hormone release, respectively. The occurrence of natural hormones and antimicrobials, administered every 12 hours, shows a daily trend of decreasing contaminant mass load, having the maximum values in the morning hours. The occurrence of antibiotics, typically administered every 8 hours, indicates a daily peak value in samples collected under the highest hydraulic loading. The efficiency of biological removal of both hormones and antibiotics is shown to be limited. Compared to the values obtained in the influent samples, increased concentrations are observed in the biologically treated effluent for trimethoprim, sulfamethoxazole and ciprofloxacin, mainly as a result of deconjugation processes. Ciprofloxacin is shown as the predominant antimicrobial compound in the effluent, and it is present at quantities approximately 10 fold greater than the total mass of the other of the compounds due to poor removal efficiency and alternating solid-liquid partitioning behaviour. Our results suggest that, to increase the micro-pollutant removal and the chemical dosing efficiency in enhanced tertiary treatment, significant benefits can be derived from the optimisation of reactor design and the development of control schemes that accounts for diurnal secondary effluent micro-pollutant and hydraulic loading patterns.     

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.     

Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: Laboratory photolysis, biodegradation, and sorption experiments

We selected eight pharmaceuticals with relatively high potential ecological risk and high consumption—namely, acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid, and propranolol—and conducted laboratory experiments to examine the persistence and partitioning of these compounds in the aquatic environment. In the results of batch sunlight photolysis experiments, three out of eight pharmaceuticals—propranolol, indomethacin, and ifenprodil—were relatively easily photodegraded (i.e., half-life < 24 h), whereas the other five pharmaceuticals were relatively stable against sunlight. The results of batch biodegradation experiments using river water suggested relatively slow biodegradation (i.e., half-life > 24 h) for all eight pharmaceuticals, but the rate constant was dependent on sampling site and time. Batch sorption experiments were also conducted to determine the sorption coefficients to river sediments and a model soil sample. The determined coefficients (K_d values) were much higher for three amines (atenolol, ifenprodil, and propranolol) than for neutral compounds or carboxylic acids; the K_d values of the amines were comparable to those of a four-ring polycyclic aromatic hydrocarbon (PAH) pyrene. The coefficients were also higher for sediment/soil with higher organic content, and the organic carbon-based sorption coefficient (log K_oc) showed a poor linear correlation with the octanol-water distribution coefficient (log D_ow) at neutral pH. These results suggest other sorption mechanisms—such as electrochemical affinity, in addition to hydrophobic interaction—play an important role in sorption to sediment/soil at neutral pH.