Christa S. McArdell

Elimination of Organic Micropollutants in a Municipal Wastewater Treatment Plant Upgraded with a Full-Scale Post-Ozonation Followed by Sand Filtration

The removal efficiency for 220 micropollutants was studied at the scale of a municipal wastewater treatment plant (WWTP) upgraded with post-ozonation followed by sand filtration. During post-ozonation, compounds with activated aromatic moieties, amine functions, or double bonds such as sulfamethoxazole, diclofenac, or carbamazepine with second-order rate constants for the reaction with ozone >10(4) M(-1) s(-1) at pH 7 (fast-reacting) were eliminated to concentrations below the detection limit for an ozone dose of 0.47 g O3 g(-1) dissolved organic carbon (DOC). Compounds more resistant to oxidation by ozone such as atenolol and benzotriazole were increasingly eliminated with increasing ozone doses, resulting in >85% removal for a medium ozone dose (approximately 0.6 g O3 g(-1) DOC). Only a few micropollutants such as some X-ray contrast media and triazine herbicides with second-order rate constants <10(2) M(-1) s(-1) (slowly reacting) persisted to a large extent. With a medium ozone dose, only 11 micropollutants of 55 detected in the secondary effluent were found at >100 ng L(-1). The combination of reaction kinetics and reactor hydraulics, based on laboratory-and full-scale data, enabled a quantification of the results by model calculations. This conceptual approach allows a direct upscaling from laboratory- to full-scale systems and can be applied to other similar systems. The carcinogenic by-products N-nitrosodimethylamine (NDMA) (< or =14 ng L(-1)) and bromate (<10 microg L(-1)) were produced during ozonation, however their concentrations were below or in the range of the drinking water standards. Furthermore, it could be demonstrated that biological sand filtration is an efficient additional barrier for the elimination of biodegradable compounds formed during ozonation such as NDMA. The energy requirement for the additional post-ozonation step is about 0.035 kWh m(-3), which corresponds to 12% of a typical medium-sized nutrient removal plant (5 g DOC m(-3)).

Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography- mass spectrometry

A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid-liquid extraction and liquid chromatography-mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level = 1 mg/kg) were as follows: sulfaguanidine (52%), sulfadiazine (47%), sulfathiazole (64%), sulfamethazine (89%), its metabolite N4-acetyl-sulfamethazine (88%), sulfamethoxazole (84%), sulfadimethoxine (51%), and trimethoprim (64%). Relative standard deviations of the recoveries were less than 5% within the same day and less than 20% between days. The limit of quantification was below 0.1 mg/kg liquid manure slurry for all compounds and calibration curves obtained from extracts of spiked samples were linear up to a level of 5 mg/kg liquid manure, except for trimethoprim (0.01-0.5 mg/kg). Analysis of six grab samples taken in Switzerland from manure pits on farms where medicinal feed had been applied revealed total sulfonamide concentrations of up to 20 mg/kg liquid manure.

Environmental toxicology and risk assessment of pharmaceuticals from hospital wastewater.

In this paper, we evaluated the ecotoxicological potential of the 100 pharmaceuticals expected to occur in highest quantities in the wastewater of a general hospital and a psychiatric center in Switzerland. We related the toxicity data to predicted concentrations in different wastewater streams to assess the overall risk potential for different scenarios, including conventional biological pretreatment in the hospital and urine source separation. The concentrations in wastewater were estimated with pharmaceutical usage information provided by the hospitals and literature data on human excretion into feces and urine. Environmental concentrations in the effluents of the exposure scenarios were predicted by estimating dilution in sewers and with literature data on elimination during wastewater treatment. Effect assessment was performed using quantitative structure-activity relationships because experimental ecotoxicity data were only available for less than 20% of the 100 pharmaceuticals with expected highest loads. As many pharmaceuticals are acids or bases, a correction for the speciation was implemented in the toxicity prediction model. The lists of Top-100 pharmaceuticals were distinctly different between the two hospital types with only 37 pharmaceuticals overlapping in both datasets. 31 Pharmaceuticals in the general hospital and 42 pharmaceuticals in the psychiatric center had a risk quotient above 0.01 and thus contributed to the mixture risk quotient. However, together they constituted only 14% (hospital) and 30% (psychiatry) of the load of pharmaceuticals. Hence, medical consumption data alone are insufficient predictors of environmental risk. The risk quotients were dominated by amiodarone, ritonavir, clotrimazole, and diclofenac. Only diclofenac is well researched in ecotoxicology, while amiodarone, ritonavir, and clotrimazole have no or very limited experimental fate or toxicity data available. The presented computational analysis thus helps setting priorities for further testing. Separate treatment of hospital wastewater would reduce the pharmaceutical load of wastewater treatment plants, and the risk from the newly identified priority pharmaceuticals. However, because high-risk pharmaceuticals are excreted mainly with feces, urine source separation is not a viable option for reducing the risk potential from hospital wastewater, while a sorption step could be beneficial.

Occurrence and fate of antibiotics as trace contaminants in wastewaters, sewage sludges, and surface waters

Environmental analytical studies show that trace concentrations of antibacterial agents (antibiotics) occur in hospital and municipal wastewaters and in the aquatic environment. Fluoroquinolones and macrolides, two important human-use antibiotic classes, were studied in detail. The results are discussed regarding input sources and behavior in wastewater treatment and rivers. The fluoroquinolones ciprofloxacin and norfloxacin are substantially eliminated in wastewater treatment (80-90%) by sorption transfer to sewage sludge. In digested sludges the fluoroquinolones occur at mg/kg levels. Ciprofloxacin and norfloxacin are further removed in the Glatt river by 66 and 48%, respectively. The most abundant macrolide clarithromycin was detected at 57 to 330 ng/l concentrations in treated wastewater effluents. Different compositions of the macrolides (clarithromycin and erythromycin-H 2 O) determined in treated effluents of three wastewater treatment plants can be explained by distinct consumption patterns, in one case due to an international airport located in the catchment area. Residual levels of clarithromycin in the Glatt river were up to 75 ng/l with no apparent removal in the river. These results provide important information on environmental exposures, which can be incorporated into environmental risk assessments of the particular chemicals.

Hospital wastewater treatment by membrane bioreactor: performance and efficiency for organic micropollutant elimination.

A pilot-scale membrane bioreactor (MBR) was installed and operated for one year at a Swiss hospital. It was fed an influent directly from the hospitals sanitary collection system. To study the efficiency of micropollutant elimination in raw hospital wastewater that comprises a complex matrix with micropollutant concentrations ranging from low ng/L to low mg/L, an automated online SPE-HPLC-MS/MS analytical method was developed. Among the 68 target analytes were the following: 56 pharmaceuticals (antibiotics, antimycotics, antivirals, iodinated X-ray contrast media, antiinflamatory, cytostatics, diuretics, beta blockers, anesthetics, analgesics, antiepileptics, antidepressants, and others), 10 metabolites, and 2 corrosion inhibitors. The MBR influent contained the majority of those target analytes. The micropollutant elimination efficiency was assessed through continuous flow-proportional sampling of the MBR influent and continuous time-proportional sampling of the MBR effluent. An overall load elimination of all pharmaceuticals and metabolites in the MBR was 22%, as over 80% of the load was due to persistent iodinated contrast media. No inhibition by antibacterial agents or disinfectants from the hospital was observed in the MBR. The hospital wastewater was found to be a dynamic system in which conjugates of pharmaceuticals deconjugate and biological transformation products are formed, which in some cases are pharmaceuticals themselves.

The fate of selected micropollutants in a single-house MBR

Membrane bioreactor (MBR) technology is an interesting option for single-house wastewater treatment or small communities. Because typically a very high effluent quality is achieved with respect to pathogens, suspended solids, organics and nitrogen, the permeate is well suited for reuse. Little is known about the fate of micropollutants in such small systems. The differences between centralized and decentralized biological wastewater treatment with respect to micropollutants are manifold: besides the operational parameters like hydraulic and sludge retention time, the main difference is in the load variation. While the influent load is expected to be more or less constant in large catchments, it varies strongly in small MBRs due to irregular consumption (e.g. of medication by individuals). Concentrations of micropollutants are higher by a factor 50-1000 than in centralized treatment. It is also unknown how reliable degradation of micropollutants is in case of irregular exposure. In this study, two experiments were conducted in a small MBR treating the wastewater of a three-person household. During normal operation of the treatment plant, 25 pharmaceuticals (antibiotics, antiphlogistics, lipid regulators, iodinated contrast media and hormones) that had not been used by members of the household were added in concentrations typical for municipal wastewater. The removal of most substances was in the same range as for centralized wastewater treatment. It was shown that biological transformation was the main elimination process while adsorption to the activated sludge was negligible for most substances due to the low sludge production at high sludge retention time. No appreciable lag for inducing biological degradation was observed. The high hydraulic and sludge residence time had a positive effect on the elimination of slowly degradable substances, but this was partly compensated by the lower biological activity. An experiment with antibiotics concentrations typical for decentralized treatment (between 500 and 1000 microg l(-1); sulfamethoxazole, sulfapyridine, trimethoprim, clarithromycin, roxithromycin) did not show an inhibitory effect on either nitrification or denitrification.

Elimination of Micropollutants during Post-Treatment of Hospital Wastewater with Powdered Activated Carbon, Ozone, and UV

A pilot-scale hospital wastewater treatment plant consisting of a primary clarifier, membrane bioreactor, and five post-treatment technologies including ozone (O3), O3/H2O2, powdered activated carbon (PAC), and low pressure UV light with and without TiO2 was operated to test the elimination efficiencies for 56 micropollutants. The extent of the elimination of the selected micropollutants (pharmaceuticals, metabolites and industrial chemicals) was successfully correlated to physical-chemical properties or molecular structure. By mass loading, 95% of all measured micropollutants in the biologically treated hospital wastewater feeding the post-treatments consisted of iodinated contrast media (ICM). The elimination of ICM by the tested post-treatment technologies was 50-65% when using 1.08 g O3/gDOC, 23 mg/L PAC, or a UV dose of 2400 J/m(2) (254 nm). For the total load of analyzed pharmaceuticals and metabolites excluding ICM the elimination by ozonation, PAC, and UV at the same conditions was 90%, 86%, and 33%, respectively. Thus, the majority of analyzed substances can be efficiently eliminated by ozonation (which also provides disinfection) or PAC (which provides micropollutants removal, not only transformation). Some micropollutants recalcitrant to those two post-treatments, such as the ICM diatrizoate, can be substantially removed only by high doses of UV (96% at 7200 J/m(2)). The tested combined treatments (O3/H2O2 and UV/TiO2) did not improve the elimination compared to the single treatments (O3 and UV).

Multiresidue analysis of 88 polar organic micropollutants in ground, surface and wastewater using online mixed-bed multilayer solid-phase extraction coupled to high performance liquid chromatography–tandem mass spectrometry

An automated multiresidue method consisting of an online solid-phase extraction step coupled to a high performance liquid chromatography-tandem mass spectrometer (online-SPE-HPLC-MS/MS method) was developed for the determination of 88 polar organic micropollutants with a broad range of physicochemical properties (logD(OW) (pH 7): -4.2 to 4.2). Based on theoretical considerations, a single mixed-bed multilayer cartridge containing four different extraction materials was composed for the automated enrichment of water samples. This allowed the simultaneous analysis of pesticides, biocides, pharmaceuticals, corrosion inhibitors, many of their transformation products, and the artificial sweetener sucralose in three matrices groundwater, surface water, and wastewater. Limits of quantification (LOQs) were in the environmentally relevant concentration range of 0.1-87 ng/L for groundwater and surface water, and 1.5-206 ng/L for wastewater. The majority of the compounds could be quantified below 10 ng/L in groundwater (82%) and surface water (80%) and below 100 ng/L in wastewater (80%). Relative recoveries were largely between 80 and 120%. Intraday and inter-day precision, expressed as relative standard deviation, were generally better than 10% and 20%, respectively. 50 isotope labeled internal standards were used for quantification and accordingly, relative recoveries as well as intraday and inter-day precision were better for compounds with corresponding internal standard. The applicability of this method was shown during a sampling campaign at a riverbank filtration site for drinking water production with travel times of up to 5 days. 36 substances of all compound classes investigated could be found in concentrations between 0.1 and 600 ng/L. The results revealed the persistence of carbamazepine and sucralose in the groundwater aquifer as well as degradation of the metamizole metabolite 4-acetamidoantipyrine.

Prediction of micropollutant elimination during ozonation of a hospital wastewater effluent

Determining optimal ozone doses for organic micropollutant elimination during wastewater ozonation is challenged by the presence of a large number of structurally diverse micropollutants for varying wastewater matrice compositions. A chemical kinetics approach based on ozone and hydroxyl radical (·OH) rate constant and measurements of ozone and ·OH exposures is proposed to predict the micropollutant elimination efficiency. To further test and validate the chemical kinetics approach, the elimination efficiency of 25 micropollutants present in a hospital wastewater effluent from a pilot-scale membrane bioreactor (MBR) were determined at pH 7.0 and 8.5 in bench-scale experiments with ozone alone and ozone combined with H2O2 as a function of DOC-normalized specific ozone doses (gO3/gDOC). Furthermore, ozone and ·OH exposures, ·OH yields, and ·OH consumption rates were determined. Consistent eliminations as a function of gO3/gDOC were observed for micropollutants with similar ozone and ·OH rate constants. They could be classified into five groups having characteristic elimination patterns. By increasing the pH from 7.0 to 8.5, the elimination levels increased for the amine-containing micropollutants due to the increased apparent second-order ozone rate constants while decreased for most micropollutants due to the diminished ozone or ·OH exposures. Increased ·OH quenching by effluent organic matter and carbonate with increasing pH was responsible for the lower ·OH exposures. Upon H2O2 addition, the elimination levels of the micropollutants slightly increased at pH 7 (<8%) while decreased considerably at pH 8.5 (up to 31%). The elimination efficiencies of the selected micropollutants could be predicted based on their ozone and ·OH rate constants (predicted or taken from literature) and the determined ozone and ·OH exposures. Reasonable agreements between the measured and predicted elimination levels were found, demonstrating that the proposed chemical kinetics method can be used for a generalized prediction of micropollutant elimination during wastewater ozonation. Out of 67 analyzed micropollutants, 56 were present in the tested hospital wastewater effluent. Two-thirds of the present micropollutants were found to be ozone-reactive and efficiently eliminated at low ozone doses (e.g., >80% for gO3/gDOC = 0.5).

Water reuse: >90% water yield in MBR/RO through concentrate recycling and CO2 addition as scaling control.

Over 1.5 years continuous piloting of a municipal wastewater plant upgraded with a double membrane system (ca. 0.6 m(3) d(-1) of product water produced) have demonstrated the feasibility of achieving high water quality with a water yield of 90% by combining a membrane bioreactor (MBR) with a submerged ultrafiltration membrane followed by a reverse osmosis membrane (RO). The novelty of the proposed treatment scheme consists of the appropriate conditioning of MBR effluent prior to the RO and in recycling the RO concentrates back to the biological unit. All the 15 pharmaceuticals measured in the influent municipal sewage were retained below 100 ng L(-1), a proposed quality parameter, and mostly below detection limits of 10 ng L(-1). The mass balance of the micropollutants shows that these are either degraded or discharged with the excess concentrate, while only minor quantities were found in the excess sludge. The micropollutant load in the concentrate can be significantly reduced by ozonation. A low treated water salinity (<10 mM inorganic salts; 280 ± 70 μS cm(-1)) also confirms that the resulting product has a high water quality. Solids precipitation and inorganic scaling are effectively mitigated by lowering the pH in the RO feed water with CO(2) conditioning, while the concentrate from the RO is recycled to the biological unit where CO(2) is stripped by aeration. This causes precipitation to occur in the bioreactor bulk, where it is much less of a process issue. SiO(2) is the sole exception. Equilibrium modeling of precipitation reactions confirms the effectiveness of this scaling-mitigation approach for CaCO(3) precipitation, calcium phosphate and sulfate minerals.