Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation

This work reports a systematic survey of over seventy individual pollutants in a Sewage Treatment Plant (STP) receiving urban wastewater. The compounds include mainly pharmaceuticals and personal care products, as well as some metabolites. The quantification in the ng/L range was performed by Liquid Chromatography-QTRAP-Mass Spectrometry and Gas Chromatography coupled to Mass Spectrometry. The results showed that paraxanthine, caffeine and acetaminophen were the main individual pollutants usually found in concentrations over 20 ppb. N-formyl-4-amino-antipiryne and galaxolide were also detected in the ppb level. A group of compounds including the beta-blockers atenolol, metoprolol and propanolol; the lipid regulators bezafibrate and fenofibric acid; the antibiotics erythromycin, sulfamethoxazole and trimethoprim, the antiinflammatories diclofenac, indomethacin, ketoprofen and mefenamic acid, the antiepileptic carbamazepine and the antiacid omeprazole exhibited removal efficiencies below 20% in the STP treatment. Ozonation with doses lower than 90 μM allowed the removal of many individual pollutants including some of those more refractory to biological treatment. A kinetic model allowed the determination of second order kinetic constants for the ozonation of bezafibrate, cotinine, diuron and metronidazole. The results show that the hydroxyl radical reaction was the major pathway for the oxidative transformation of these compounds.     

Occurrence and removal of pharmaceuticals and personal care products (PPCPs) in an advanced wastewater reclamation plant

The occurrence of nineteen pharmaceutically active compounds and personal care products was followed monthly for 12 months after various stages of treatment in an advanced wastewater reclamation plant in Gwinnett County, GA, U.S.A. Twenty-four hour composite samples were collected after primary clarification, activated sludge biological treatment, membrane filtration, granular media filtration, granular activated carbon (GAC) adsorption, and ozonation in the wastewater reclamation plant. Compounds were identified and quantified using high performance liquid chromatography/tandem mass spectrometry (LC-MS/MS) and gas chromatography/mass spectrometry (GC-MS) after solid-phase extraction. Standard addition methods were employed to compensate for matrix effects. Sixteen of the targeted compounds were detected in the primary effluent; sulfadimethoxine, doxycycline, and iopromide were not found. Caffeine and acetaminophen were found at the highest concentrations (∼10⁵ ng/L), followed by ibuprofen (∼10⁴ ng/L), sulfamethoxazole and DEET (∼10³ ng/L). Most of the other compounds were found at concentrations on the order of hundreds of ng/L. After activated sludge treatment and membrane filtration, the concentrations of caffeine, acetaminophen, ibuprofen, DEET, tetracycline, and 17α-ethynylestradiol (EE2) had decreased by more than 90%. Erythromycin and carbamazepine, which were resistant to biological treatment, were eliminated by 74 and 88%, on average, by GAC. Primidone, DEET, and caffeine were not amenable to adsorption by GAC. Ozonation oxidized most of the remaining compounds by >60%, except for primidone and DEET. Of the initial 16 compounds identified in the primary effluent, only sulfamethoxazole, primidone, caffeine and DEET were frequently detected in the final effluent, but at concentrations on the order of 10-100 ng/L. Removal of the different agents by the various treatment processes was related to the physical-chemical properties of the 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%.     

Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking, and waste waters

Liquid chromatography/tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was used to measure the concentrations of 14 pharmaceuticals, 6 hormones, 2 antibiotics, 3 personal care products (PCPs), and 1 flame retardant in surface waters and wastewater treatment plant effluents in South Korea. Tris (2-chloroethyl) phosphate (TCEP), iopromide, naproxen, carbamazepine, and caffeine were quite frequently observed (>80%) in both surface waters and effluents. The analytes of greatest concentration were iopromide, TCEP, sulfamethoxazole, and carbamazepine. However, the primary estrogen hormones, 17alpha-ethynylestradiol and 17beta-estradiol, were rarely detected, while estrone was detected in both surface water and wastewater effluent. The elimination of these chemicals during drinking water and wastewater treatment processes at full- and pilot-scale also was investigated. Conventional drinking water treatment methods were relatively inefficient for contaminant removal, while efficient removal (approximately equal to 99%) was achieved by granular activated carbon (GAC). In wastewater treatment processes, membrane bioreactors (MBR) showed limited target compound removal, but were effective at eliminating hormones and some pharmaceuticals (e.g., acetaminophen, ibuprofen, and caffeine). Membrane filtration processes using reverse osmosis (RO) and nanofiltration (NF) showed excellent removal (>95%) for all target analytes.     

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.     

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 removal of estrogens and beta blockers by various processes in wastewater treatment plants

This study aims at evaluating occurrence and treatment efficiency of five estrogenic hormones and ten beta blockers in wastewater treatment plants (WWTP). The use of consistent sampling procedures, analytical techniques and data processing enabled to achieve an accurate comparison of the performances of the different treatment processes. First, the occurrence of molecules was evaluated in fourteen rural and urban WWTP located in France. Free and total estrogens were analyzed showing that more than 84% of estrogens in the dissolved phase of influent samples are in the free form. In effluent samples, comparable mean values but higher variation are underlined (RSD from 13 to 54% depending on the estrogen, compared to 11-21% for influents). Most of the target molecules are quantified in 30 influent and 31 effluent samples. Similar occurrence frequencies are obtained for influents from rural (6 WWTP) and urban areas (8 WWTP), except for betaxolol which is only quantified in urban wastewaters. Removal efficiencies of 8 biological treatments were studied: suspended growth biomass (activated sludge) and attached growth systems (biofilter, rotating biological contactor, reed-bed filter, trickling filter). Biological treatments are efficient to remove estrogens from the dissolved phase, with removal rate around 90%. For beta blockers, acebutolol and nadolol are efficiently removed (mean removal rate of 80%), whereas sotalol and propranolol are hardly impacted by biological treatments (removal rate below 20%). Finally, 9 tertiary treatment processes were evaluated. Ozonation, reverse osmosis and activated carbon filtration prove a high removal efficiency for beta blockers (above 80%). On the contrary, high speed chemical settler, sand filtration, silex filtration, microfiltration and UV present generally removal rates below 30% for all beta blockers. The polishing pond studied presents variable removal performances depending on the molecules (up to 75% for propranolol). The role of the hydraulic retention time on the removal efficiencies is confirmed.     

Biofiltration of wastewater treatment plant effluent: effective removal of pharmaceuticals and personal care products and reduction of toxicity

This study investigates biofiltration for the removal of dissolved organic carbon (DOC), pharmaceuticals and personal care products (PPCPs), and for the reduction of non-specific toxicity expressed as baseline toxicity equivalent concentration (baseline-TEQ). Two filtering media, sand and granular activated carbon, were tested. The influence of pre-ozonation and empty-bed contact time (EBCT, from 30 to 120 min) was determined. The experiments were performed at a pilot-scale with real WWTP effluent. A previous study showed that biological activity had developed on the filtering media and dissolved organic removal had reached a steady state before sampling commenced. The results show that biological activated carbon (BAC) has a good potential for the removal of DOC (35-60%), PPCPs (>90%) and baseline-TEQ (28-68%) even without pre-ozonation. On the contrary, the sand shows limited improvement of effluent quality. Varying the EBCT does not influence the performance of the BAC filters; however, dissolved oxygen concentration could be a limiting factor. The performances of the BAC filters were stable for over two years suggesting that the main mechanism of organic matter and PPCPs removal is biodegradation. It is concluded that BAC filtration without pre-ozonation could be implemented as a low cost advanced treatment option to improve WWTP effluent chemical quality.     

Occurrence and behavior of four of the most used sunscreen UV filters in a wastewater reclamation plant

Four UV filters, benzophenone-3 (BP-3), 4-methylbenzylidence camphor (4-MBC), ethylhexyl methoxycinnamate (EHMC), and octocrylene (OC), have been examined along the different units of a wastewater reclamation plant (WWRP) located in Tianjin, North China. The analytical procedure included solid-phase extraction and gas chromatographic/mass spectrometric analyses. All four UV filters were detected in the influent during the three sampling campaigns (February, July, and September), and the concentrations ranged from 34 to 2128 ng L(-1). The concentrations of the four UV filters were higher in hot weather (July and September) than in cool weather (February). The monthly average removal ranged from 7.6% to 21% for the selected UV filters during coagulation-flocculation (C-F) treatment. The ozonation treatment achieved the maximum removal (16-28%); on the contrary, the continuous microfiltration (CMF) achieved the lowest removal (3.6-8.2%). The total removal efficiencies along the plant varied from 28% to 43%. These results indicate that the UV filters are not completely removed during WWRP treatment and may be carried over into the environment during the reuse applications.     

Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden

The occurrence and removal rate of seven pharmaceuticals (ibuprofen, naproxen, diclofenac, fluoxetine, ofloxacin, norfloxacin, ciprofloxacin), two metabolites (norfluoxetine, clofibric acid), one degradation product (4-isobutylacetophenone) and 3 estrogens (17α-ethinylestradiol, 17β-estradiol, estrone) were studied in the inlet and outlet of a tertiary sewage treatment plant (STP) in Sweden as well as between different treatment steps in the STP which includes a conventional activated sludge step. Pharmaceuticals in raw household and raw hospital sewage streams leading to the STP were as well investigated. Hydraulic retention times (HRT) of each treatment step was considered for sampling and for the calculation of the removal rates. These rates were above 90%, except for diclofenac, clofibric acid, estrone and ofloxacin. However, only diclofenac and naproxen showed significant effluent loads (> 145 mg/d/1000 inh). Diclofenac was not eliminated during the treatment and in fact even higher concentrations were found at the effluent than in the inlet of the STP. 17α-Ethinylestradiol was not detected in any of the samples. Results indicate that a STP such as the one in Kristianstad, Sweden, with a tertiary treatment is sufficient to remove significantly most of the investigated pharmaceuticals. The chemical treatment improved the removal of several pharmaceuticals especially the antibiotics, which showed step removal rates between 55 and 70%. The expected concentration levels of the pharmaceuticals in the surface water (dilution 1 to 10) close to the outlet of the STP are below the no-observed effect-concentration (NOEC). However, despite that this would imply no important effects in the aquatic environment one cannot rule out negative consequences nearby the STP because most of the NOEC values are derived from acute toxicity data. This may underestimate the real impact of pharmaceuticals in the aquatic ecosystem.     

Groundwater quality impacts from the land application of treated municipal wastewater in a large karstic spring basin: Chemical and microbiological indicators

Geochemical and microbiological techniques were used to assess water-quality impacts from the land application of treated municipal wastewater in the karstic Wakulla Springs basin in northern Florida. Nitrate-N concentrations have increased from about 0.2 to as high as 1.1 mg/L (milligrams per liter) during the past 30 years in Wakulla Springs, a regional discharge point for groundwater (mean flow about 11.3 m³/s) from the Upper Floridan aquifer (UFA). A major source of nitrate to the UFA is the approximately 64 million L/d (liters per day) of treated municipal wastewater applied at a 774 ha (hectare) sprayfield farming operation. About 260 chemical and microbiological indicators were analyzed in water samples from the sprayfield effluent reservoir, wells upgradient from the sprayfield, and from 21 downgradient wells and springs to assess the movement of contaminants into the UFA. Concentrations of nitrate-N, boron, chloride, were elevated in water samples from the sprayfield effluent reservoir and in monitoring wells at the sprayfield boundary. Mixing of sprayfield effluent water was indicated by a systematic decrease in concentrations of these constituents with distance downgradient from the sprayfield, with about a 10-fold dilution at Wakulla Springs, about 15 km (kilometers) downgradient from the sprayfield. Groundwater with elevated chloride and boron concentrations in wells downgradient from the sprayfield and in Wakulla Springs had similar nitrate isotopic signatures, whereas the nitrate isotopic composition of water from other sites was consistent with inorganic fertilizers or denitrification. The sprayfield operation was highly effective in removing most studied organic wastewater and pharmaceutical compounds and microbial indicators. Carbamazepine (an anti-convulsant drug) was the only pharmaceutical compound detected in groundwater from two sprayfield monitoring wells (1-2 ppt). One other detection of carbamazepine was found in a distant well water sample where enteroviruses also were detected, indicating a likely influence from a nearby septic tank.     

Surfactant-coated aluminum hydroxide for the rapid removal and biodegradation of hydrophobic organic pollutants in water

The removal of hydrophobic organic pollutants in water to surfactant-coated aluminum hydroxide [surfactant-Al(OH)₃] was investigated. Anionic surfactants such as sodium dodecyl sulfate (SDS), sodium bis(2-ethylhexyl)sulfosuccinate (AOT), and sodium oleate were sorbed on positively charged aluminum hydroxide at pH 7 and formed hydrophobic aggregates that can incorporate hydrophobic organic pollutants in water. Because of the hydrophobic interaction and decrease in the positive charge, surfactant-Al(OH)₃ was coagulated into precipitates that can readily be separated from water. Hydrophobic organic pollutants such as alkylphenols, polycyclic aromatic hydrocarbons, estrogens, chlorinated antifungals, and pesticides were well collected to the precipitates and thus efficiently removed from water. The collection of hydrophobic organic pollutants was correlated to their aqueous-octanol distribution coefficient. The decomposition of hydrophobic organic pollutants was examined using a bacterial agent (Bacillus subtilis). Hydrophobic organic compounds collected to AOT-Al(OH)₃ or sodium oleate-Al(OH)₃ were insufficiently decomposed. On the other hand, nonylphenol, octylphenol, and pendimethalin collected to SDS-Al(OH)₃ were decomposed within 1 week. The decomposition was accelerated by the collection to SDS-Al(OH)₃.     

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.     

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 and removal of antibiotics, hormones and several other pharmaceuticals in wastewater treatment plants of the largest industrial city of Korea

Occurrence and removal efficiencies of 20 pharmaceuticals and personal care products (PPCPs) including antibiotics, hormones, and several other miscellaneous pharmaceuticals (analgesics, antiepileptics, antilipidemics, antihypertensives, antiseptics, and stimulants) were investigated in five wastewater treatment plants (WWTPs) of Ulsan, the largest industrial city of Korea. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by High-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The results showed that acetaminophen, atenolol and lincomycin were the main individual pollutants usually found in concentrations over 10 μg/L in the sewage influent. In the WWTPs, the concentrations of analgesic acetaminophen, stimulant caffeine, hormones estriol and estradiol decreased by over 99%. On the contrary, the antibiotic sulfamethazine, the antihypertensive metoprolol, and the antiepileptic carbamazepine exhibited removal efficiencies below 30%. Particularly, removal of antibiotics was observed to vary between − 11.2 and 69%. In the primary treatment (physico-chemical processes), the removal of pharmaceuticals was insignificant (up to 28%) and removal of majority of the pharmaceuticals occurred during the secondary treatment (biological processes). The compounds lincomycin, carbamazepine, atenolol, metoprolol, and triclosan showed better removal in WWTPs employing modified activated sludge process with co-existence of anoxic-oxic condition. Further investigation into the design and operational aspects of the biological processes is warranted for the efficient removal of PPCPs, particularly antibiotics, to secure healthy water resource in the receiving downstream, thereby ensuring a sustainable water cycle management.     

Spatial and temporal variations in the occurrence of cocaine and benzoylecgonine in waste- and surface water from Belgium and removal during wastewater treatment

Estimates of cocaine consumption are currently resulting from population surveys, consumer interviews and crime statistics. A new approach (“sewage epidemiology”) based on the analysis of cocaine (COC) and its metabolite, benzoylecgonine (BE), in water samples was applied to 10 river sites and 30 wastewater treatment plants (WWTPs) in Belgium. Each river site was sampled twice, during the summer of 2007 and the winter of 2007-2008, while each WWTP was sampled on a Sunday and a Wednesday, during the summer-autumn of 2007 and the winter of 2007-2008. This sampling strategy allowed for the evaluation of spatial and seasonal variations in the occurrence of COC and BE in waste- and surface water. WWTP Brussel-Noord was sampled for 19 consecutive days to evaluate daily and weekly variations in the presence of COC and BE in wastewater. For 7 WWTPs, influent and effluent water samples were collected to investigate the removal of COC and BE during the wastewater treatment process. Analysis of water samples was performed using solid-phase extraction and liquid chromatography coupled to tandem mass spectrometry. Measured concentrations were further converted into an amount of used cocaine, called cocaine equivalents, as previously described in the literature. Results showed no significant difference in cocaine use between the investigated seasons. A constant cocaine consumption was observed during the week (Monday-Friday) with peaks during the weekend for WWTP Brussel-Noord. The COC/BE ratio in water samples was significantly higher during winter, most probably due to a slower hydrolysis of cocaine in low-temperature water. COC and BE were removed in the investigated WWTPs with a removal efficiency of >93%.     

Persistent organic pollutants (POPs) in the sewage treatment plant of Thessaloniki, northern Greece: occurrence and removal

The occurrence and the removal of persistent organic pollutants (POPs) during the conventional activated sludge treatment process were investigated in the wastewater treatment plant of the city of Thessaloniki, northern Greece. POPs of interest were seven polychlorinated biphenyls (PCBs) and 19 organochlorine pesticides. Target compounds were determined at six different points across the treatment system. Most abundant compounds in raw wastewater at all treatment stages were PCB-52, PCB-110, PCB-180 and Heptachlor-exo-epoxide. Quintozene occurred frequently but in relatively low concentrations. Hexachlorocyclohexanes, DDT and its metabolites (DDE, DDD) and Aldrin, Dieldrin, Endrin, Isodrin ("Drins") were found at medium or low frequencies and in concentrations close to their detection limits. Removal percentages throughout the whole treatment process ranged from 65% to 91% for individual POP species. Significant linear relationship was observed between removal efficiency and log Kow for PCBs suggesting that compounds with a strong hydrophobic character are principally removed through sorption to sludge particles and transfer to the sludge processing systems. Total PCBs' concentrations in sewage sludge ranged between 185 and 765 ng g(-1) dw being below the EU limit for use of sludge in agriculture.     

Influence of electrostatic interactions on the rejection with NF and assessment of the removal efficiency during NF/GAC treatment of pharmaceutically active compounds in surface water

The removal efficiency of several pharmaceutically active compounds from two different surface water types was investigated. Two different nanofiltration (NF) membranes (Trisep TS-80 and Desal HL) were first studied at low feed water recoveries (10%). In a second phase, the combination of an NF unit at higher feed water recovery (80%) with subsequent granular activated carbon (GAC) filtration of the permeate was investigated. Results indicate that removal of the selected pharmaceuticals with NF is mainly influenced by charge effects: negatively charged solutes are better removed, compared with uncharged solutes, which are, in turn, better removed compared with positively charged solutes. This latter trend is mainly due to charge attractions between the negatively charged membrane surface and positively charged solutes. Increasing feed concentrations of positively charged pharmaceuticals lead to increasing rejection values, due to membrane charge-shielding effects. The removal efficiency of pharmaceuticals with the combination NF/GAC is extremely high. This is mainly due to an increased adsorption capacity of the activated carbon since the largest part of the natural organic matter (NOM) is removed in the NF step. This NOM normally competes with pharmaceuticals for adsorption sites on the carbon.     

Chemical coupling of photocatalysis with flocculation and adsorption in the removal of organic matter

An experimental investigation was made to study the effects of chemical coupling of flocculation and adsorption with photocatalysis in treating persistent organic pollutants in wastewater. The photocatalysis alone showed initial reverse reaction when titanium oxide (TiO(2)) was used in catalysis. The effect of the pretreatment of adsorption with powdered activated carbon (PAC) on photocatalysis was studied. The results showed that PAC adsorption followed by photocatalysis was not effective in alleviating reverse reaction. On the other hand, when PAC and TiO(2) were added simultaneously, the reverse reaction was eliminated. Further, the organic removal was also improved by simultaneous PAC and TiO(2) additions. When flocculation with ferric chloride (FeCl(3)) was used as pretreatment, the organic removal efficiency was superior. The initial reverse reaction was also eliminated/minimized. However, inadequate doses of FeCl(3) (less than 30 mgl(-1)) resulted in initial reverse reaction and inferior DOC removal.     

Occurrence, fate and removal of synthetic oral contraceptives (SOCs) in the natural environment: a review

Synthetic oral contraceptives (SOCs) are a group of compounds with progestagenic and/or androgenic activities, with some also possessing estrogenic activities. Recent research has documented that some of these emerging contaminants have adverse effects on aquatic organisms at very low concentrations. To facilitate the evaluation of their latent risks, published works on their occurrence and fate in the environment are reviewed. Androgenic/progestagenic relative potencies or relative binding affinity of these SOCs as well as their physicochemical properties and toxicity are summarized. Appropriate analytical methods are outlined for various environmental sample types, including methods of sample preparation and limit of detection/quantification (LOD/LOQ). Finally results on their occurrence and fate in wastewater treatment plants (WWTPs) and other environments are critically examined.