Pilot-scale study of powdered activated carbon recirculation for micropollutant removal.

Adsorption onto powdered activated carbon (PAC) is a promising technique for the removal of organic micropollutants (OMPs) from treated wastewater. To enhance the adsorption efficiency, PAC is recycled back into the adsorption stage. This technique was examined in pilot scale in comparison to a reference without recirculation. Coagulation with Fe(3+) was carried out simultaneously to adsorption. Extensive OMP measurements showed that recirculation significantly increased OMP eliminations. Thus, significant PAC savings were feasible. The PAC concentration in the contact reactor proved to be an important operating parameter that can be surrogated by the easily measurable total suspended solids (TSS) concentration. OMP eliminations increased with increasing TSS concentrations. At 20 mg PAC L(-1) and 2.8 g TSS L(-1) in the contact reactor, well-adsorbable carbamazepine was eliminated by 97%, moderately adsorbable diclofenac was eliminated by 92% and poorly-adsorbable acesulfame was eliminated by 54% in comparison to 49%, 35% and 18%, respectively, without recirculation. The recirculation system represents an efficient technique, as the PAC's adsorption capacity is practically completely used. Small PAC dosages yield high OMP eliminations. Poorly-adsorbable gabapentin was eliminated to an unexpectedly high degree. A laboratory-scale biomass inhibition study showed that aerobic biodegradation removed gabapentin in addition to adsorption.

The benefits of powdered activated carbon recirculation for micropollutant removal in advanced wastewater treatment.

PAC adsorption is a widespread option for the removal of organic micropollutants (OMP) from secondary effluent. For an optimal exploitation of the adsorption capacity, PAC recirculation is nowadays a common practice, although the mechanistic interrelations of the complex recirculation process are not fully resolved. In this work, extensive multi-stage batch adsorption testing with repeated PAC and coagulant dosage was performed to evaluate the continuous-flow recirculation system. Partly loaded PAC showed a distinct amount of remaining capacity, as OMP and DOC removals considerably increased with each additional adsorption stage. At a low PAC dose of 10 mg PAC L(-1), removals of benzotriazole and carbamazepine were shown to rise from <40% in the first stage up to >80% in the 11th stage at 30 min adsorption time per stage. At a high PAC dose of 30 mg PAC L(-1), OMP and DOC removals were significantly higher and reached 98% (for benzotriazole and carbamazepine) after 11 stages. Coagulant dosage showed no influence on OMP removal, whereas a major part of DOC removal can be attributed to coagulation. Multi-stage adsorption is particularly beneficial for small PAC doses and significant PAC savings are feasible. A new model approach for predicting multi-stage OMP adsorption on the basis of a single-stage adsorption experiment was developed. It proved to predict OMP removals and PAC loadings accurately and thus contributes towards understanding the PAC recirculation process.

A hybrid process of biofiltration of secondary effluent followed by ozonation and short soil aquifer treatment for water reuse.

The Shafdan reclamation project facility (Tel Aviv, Israel) practices soil aquifer treatment (SAT) of secondary effluent with hydraulic retention times (HRTs) of a few months to a year for unrestricted agricultural irrigation. During the SAT, the high oxygen demand (>40 mg L(-1)) of the infiltrated effluent causes anoxic conditions and mobilization of dissolved manganese from the soil. An additional emerging problem is the occurrence of persistent trace organic compounds (TrOCs) in reclaimed water that should be removed prior to reuse. An innovative hybrid process based on biofiltration, ozonation and short SAT with ∼22 d HRT is proposed for treatment of the Shafdan secondary effluent to overcome limitations of the existing system and to reduce the SAT's physical footprint. Besides efficient removal of particulate matter to minimize clogging, coagulation/flocculation and filtration (5-6 m h(-1)) operated with the addition of hydrogen peroxide as an oxygen source efficiently removed dissolved organic carbon (DOC, to 17-22%), ammonium and nitrite. This resulted in reduced effluent oxygen demand during infiltration and oxidant (ozone) demand during ozonation by 23 mg L(-1) and 1.5 mg L(-1), respectively. Ozonation (1.0-1.2 mg O3 mg DOC(-1)) efficiently reduced concentrations of persistent TrOCs and supplied sufficient dissolved oxygen (>30 mg L(-1)) for fully oxic operation of the short SAT with negligible Mn(2+) mobilization (<50 µg L(-1)). Overall, the examined hybrid process provided DOC reduction of 88% to a value of 1.2 mg L(-1), similar to conventional SAT, while improving the removal of TrOCs and efficiently preventing manganese dissolution.

Impacts of ozonation on the competition between organic micro-pollutants and effluent organic matter in powdered activated carbon adsorption.

This study investigates if ozonation of wastewater treatment plant (WWTP) effluent can reduce the negative impacts of effluent organic matter (EfOM) on the adsorption of organic micro-pollutants (OMP) onto powdered activated carbon (PAC). Pre-treatment of the water included membrane filtration for the removal of suspended/colloidal organics, ozonation with various specific ozone consumptions, and subsequent OMP spiking to comparable initial concentrations in all of the ozonated waters. This approach allowed for comparative PAC adsorption tests. Adsorption analyses show that the adsorbability of EfOM decreases with increasing specific ozone consumptions. This is also reflected by liquid chromatography with online carbon and UV254 detection (LC-OCD) which shows the ozone-induced disintegration of large EfOM into smaller fragments. Also, small organic neutrals are decreased while the small organic acids peak continuously increases with rising specific ozone consumptions. UV254 demonstrates that the aromaticity of all LC-OCD fractions continuously declines together with increasing specific O3 consumptions. This explains the varying EfOM adsorbabilities that occur due to ozonation. The ozone-induced decrease of EfOM adsorbability directly translates into reduced adsorption competition against the adsorption of OMP. With higher specific ozone consumptions, OMP removal and OMP loadings increase. The reduced adsorption competition is reflected in the outputs from equivalent background compound (EBC) modeling. In each of the ozonated waters, correlations between the OMP removals and the UV254 removal were found.

Lab-testing, predicting, and modeling multi-stage activated carbon adsorption of organic micro-pollutants from treated wastewater.

Multi-stage reuse of powdered activated carbon (PAC) is often applied in practice for a more efficient exploitation of the PAC capacity to remove organic micro-pollutants (OMP). However, the adsorption mechanisms in multi-stage PAC reuse are rarely investigated, as large-scale experiments do not allow for systematic tests. In this study, a laboratory method for the separation of PAC/water suspensions and the subsequent reuse of the PAC and the water was developed. The method was tested on wastewater treatment plant (WWTP) effluent in a setup with up to 7 PAC reuse stages. The tests show that the overall OMP removal from WWTP effluent can be increased when reusing PAC. The reason is that a repeated adsorption in multi-stage PAC reuse results in similar equilibrium concentrations as a single-stage adsorption. Thus, a single relationship between solid and liquid phase OMP concentrations appears valid throughout all stages. This also means that the adsorption efficiency of multi-stage PAC reuse setups can be estimated from the data of a single-stage setup. Furthermore, the overall OMP removals in multi-stage setups coincide with the overall UV254 removals, and for each respective OMP one relationship to UV254 removal is valid throughout all stages. The results were modeled by a simple modification of the equivalent background compound model (EBCM) which was also used to simulate the additional OMP removals in multi-stage setups with up to 50 reuse stages.

Rapid small-scale column testing of granular activated carbon for organic micro-pollutant removal in treated domestic wastewater.

This study investigates the applicability of the rapid small-scale column test (RSSCT) concept for testing of granular activated carbon (GAC) for organic micro-pollutants (OMPs) removal from wastewater treatment plant (WWTP) effluent. The chosen experimental setup was checked using pure water, WWTP effluent, different GAC products, and variable hydrodynamic conditions with different flow velocities and differently sized GAC, as well as different empty bed contact times (EBCTs). The setup results in satisfying reproducibility and robustness. RSSCTs in combination with WWTP effluent are effective when comparing the OMP removal potentials of different GAC products and are a useful tool for the estimation of larger filters. Due to the potentially high competition between OMPs and bulk organics, breakthrough curves are likely to have unfavorable shapes when treating WWTP effluent. This effect can be counteracted by extending the EBCT. With respect to the strong competition observed in GAC treatment of WWTP effluent, the small organic acid and neutral substances are retained longer in the RSSCT filters and are likely to cause the majority of the observed adsorption competition with OMPs.

Ozonation products of carbamazepine and their removal from secondary effluents by soil aquifer treatment--indications from column experiments.

Ozonation is known as an efficient treatment to reduce the concentration of many trace organic compounds from WWTP effluents, but the formation of unknown and possibly persistent and toxic transformation products has to be considered. In this paper tertiary treatment of wastewater by the combination of ozone and soil aquifer treatment was investigated with respect to the removal of the antiepileptic drug carbamazepine (CBZ, 10 µg/L) and its transformation products. Batch tests and pilot experiments confirmed efficient removal of carbamazepine from secondary effluent by ozone. With typical ozone consumption of 0.7 mg O3/mg DOC0, approx. 50% of the transformed CBZ was detected as its primary product 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM). Structure proposals and a formation pathway were elaborated for a total of 13 ozonation products of CBZ. In subsequent biological treatment BQM turned out to be more effectively biodegraded than CBZ. Its aldehyde group was quickly oxidized to a carboxylic acid (BaQM), which was removed in sand column experiments. Most of the minor ozonation products of CBZ persisted in sand column experiments with residence times of 5-6 days. Non-target screening of column effluent revealed no formation of persistent biotransformation products.

Tertiary treatment of Berlin WWTP effluents with ferrate (Fe(VI)).

New and higher standards in the EU water framework directive necessitate advanced treatment of secondary effluents for reduction of trace organic compounds (TrOCs) and nutrients before the discharge into receiving surface waters. Due to its dual function as oxidant and coagulant, ferrate is considered as a promising alternative for tertiary treatment. The oxidation of selected TrOCs and simultaneous flocculation of phosphates by ferrate was tested in batch experiments with secondary effluent from Berlin Ruhleben. The concentrations of carbamazepine (CBZ) and diclofenac were reduced by >90% with ferrate dosages of 6 mg/L as Fe. CBZ was transformed to 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one, which is known as the major product from the reaction of CBZ with ozone. In contrast to ozonation, no further transformation of this product was observed. The concentration of ibuprofen was not reduced by ferrate treatment. For efficient removal of 60-100 µg/L phosphate-P to values <20 µg/L, ferrate dosages of 3-4 mg/L as Fe were sufficient.

Evaluation of the prediction of trace organic compound removal during ozonation of secondary effluents using tracer substances and second order rate kinetics.

The application of the R(CT)-concept for predicting the removal of trace organic compounds (TrOCs) in organic rich WWTP effluents is often problematic due to the fast ozone depletion with instantaneous ozone demand in the range of typically applied ozone dosages. In this study, the determination of OH-radical and ozone exposure from second order rate kinetics with two internal tracer substances was evaluated as alternative approach for these waters. Results from batch and semi-batch experiments showed a linear correlation of OH-radical exposure with ozone consumption, characterized by its slope indicating the formation efficiency of OH-radicals and a lag ozone consumption without significant formation of OH-radicals. Evaluation of data from the project PILOTOX on ozonation of secondary effluent confirmed reasonable prediction of ozone resistant compound removal from relative residual concentration of an internal tracer substance. In contrast, predicting the reduction of TrOCs by direct reactions with ozone from internal tracers was not feasible. Similar removal efficiencies for fast reacting compounds with different rate constants from k(O3) = 10(4) M(-1) s(-1) to k(O3) = 10(6) M(-1) s(-1) were observed indicating a limitation of the reaction by mass transfer. This effect was observed at low ozone dosages in semi-batch and pilot experiments as well as in batch experiments, where mass transfer from gas to liquid phase is not limiting. It is assumed that consumption of low ozone dosages is faster than sample homogenization in the batch reactors used. Thus, prediction of compound removal by direct reaction with ozone always needs to consider reactor design and geometry.

Optimized removal of dissolved organic carbon and trace organic contaminants during combined ozonation and artificial groundwater recharge.

Pilot scale experiments using an 8 g/h ozonation unit and a 1.4 m(2) slow sand filter have demonstrated that the combination of ozonation and artificial groundwater recharge is suitable for efficient reduction of bulk and trace organics. The biodegradation of dissolved organic carbon (DOC) in the slow sand filter was enhanced from 22% without pre-treatment to 34% by pre-ozonation. In addition, realistic surface water concentrations of most investigated trace organic compounds (TrOCs) including carbamazepine, sulfamethoxazole, phenazone and metoprolol were reduced below the limits of quantification. Only a few TrOCs, e.g. primidone and benzotriazole, were not efficiently removed in both treatment steps and could be detected regularly in the filter effluent. For these compounds, enhanced treatment, such as advanced oxidation processes, needs to be considered. Testing for genotoxicity and cytotoxicity did not reveal any systematic adverse effects for human health. The formation of the by-product bromate from bromide was below the limit of the German drinking water directive of 10 µg/L. No removal of bromate was observed in the aerobic slow sand filter. Additional experiments with sand columns showed that operating a preceding bank filtration step to reduce DOC can reduce oxidant demand by approximately 20%.

Energy analysis of conventional and source-separation systems for urban wastewater management using Life Cycle Assessment.

This study investigates the cumulative energy demand (CED) of different systems for the management of urban wastewater, following the methodology of Life Cycle Assessment. In a hypothetical case study for an urban area (5,000 inhabitants), all relevant processes for wastewater collection and treatment and the construction of infrastructure are described in a substance flow model. The conventional system requires 1,250 MJ/(pe*a), with the operation contributing 45%, the infrastructure 7%, and the system expansion (production of mineral fertilizer and electricity) 48% to the total CED. The separation systems have a CED of 930-1,182 MJ/(pe*a) depending on their configuration. Results of the impact assessment show that recovering energy from the organic matter of toilet wastewater and household biowaste in a digestion process can decrease the cumulative energy demand by 13-26%. Energetic benefits of mineral fertilizer substitution are relatively small compared to the energy recovered from organic matter. Decisive parameters for the energy analysis are the amount of biowaste which is co-digested with toilet wastewater and the energy demand of the vacuum plant.

Comparison of two treatments for the removal of selected organic micropollutants and bulk organic matter: conventional activated sludge followed by ultrafiltration versus membrane bioreactor.

The potential of membrane bioreactor (MBR) systems to remove organic micropollutants was investigated at different scales, operational conditions, and locations. The effluent quality of the MBR system was compared with that of a plant combining conventional activated sludge (CAS) followed by ultrafiltration (UF). The MBR and CAS-UF systems were operated and tested in parallel. An MBR pilot plant in Israel was operated for over a year at a mixed liquor suspended solids (MLSS) range of 2.8-10.6 g/L. The MBR achieved removal rates comparable to those of a CAS-UF plant at the Tel-Aviv wastewater treatment plant (WWTP) for macrolide antibiotics such as roxythromycin, clarithromycin, and erythromycin and slightly higher removal rates than the CAS-UF for sulfonamides. A laboratory scale MBR unit in Berlin - at an MLSS of 6-9 g/L - showed better removal rates for macrolide antibiotics, trimethoprim, and 5-tolyltriazole compared to the CAS process of the Ruhleben sewage treatment plant (STP) in Berlin when both were fed with identical quality raw wastewater. The Berlin CAS exhibited significantly better benzotriazole removal and slightly better sulfamethoxazole and 4-tolyltriazole removal than its MBR counterpart. Pilot MBR tests (MLSS of 12 g/L) in Aachen, Germany, showed that operating flux significantly affected the resulting membrane fouling rate, but the removal rates of dissolved organic matter and of bisphenol A were not affected.

Application of GaN-based ultraviolet-C light emitting diodes--UV LEDs--for water disinfection.

GaN-based ultraviolet-C (UV-C) light emitting diodes (LEDs) are of great interest for water disinfection. They offer significant advantages compared to conventional mercury lamps due to their compact form factor, low power requirements, high efficiency, non-toxicity, and overall robustness. However, despite the significant progress in the performance of semiconductor based UV LEDs that has been achieved in recent years, these devices still suffer from low emission power and relatively short lifetimes. Even the best UV LEDs exhibit external quantum efficiencies of only 1-2%. The objective of this study was to investigate the suitability of GaN-based UV LEDs for water disinfection. The investigation included the evaluation of the performance characteristics of UV LEDs at different operating conditions as well as the design of a UV LED module in view of the requirements for water treatment applications. Bioanalytical testing was conducted using Bacillus subtilis spores as test organism and UV LED modules with emission wavelengths of 269 nm and 282 nm. The results demonstrate the functionality of the developed UV LED disinfection modules. GaN-based UV LEDs effectively inactivated B. subtilis spores during static and flow-through tests applying varying water qualities. The 269 nm LEDs reached a higher level of inactivation than the 282 nm LEDs for the same applied fluence. The lower inactivation achieved by the 282 nm LEDs was compensated by their higher photon flux. First flow-through tests indicate a linear correlation between inactivation and fluence, demonstrating a well designed flow-through reactor. With improved light output and reduced costs, GaN-based UV LEDs can provide a promising alternative for decentralised and mobile water disinfection systems.

Treatment of membrane concentrates: phosphate removal and reduction of scaling potential.

The widespread application of nanofiltration (NF) and reverse osmosis (RO) membranes in wastewater reuse inevitably generates a concentrate stream. Due to high concentrations of phosphate and salts, disposal of membrane concentrates is a problem which seriously constrains the application of this technology, especially in inland applications. There is a need for technologies which facilitate an affordable and environmentally-safe disposal of membrane concentrates. The objectives of this study are to investigate appropriate treatment techniques to (1) increase the recovery of the membrane filtration thus minimising the volume of the concentrate stream, and (2) increase the concentrate quality to enable discharge into surface water bodies. The results show that both adsorption onto granular ferric hydroxide (GFH) and chemical precipitation are generally effective for phosphate removal from NF concentrates. Chemical precipitation by dosing of sodium hydroxide solution is rapid and removes more than 90% of phosphate and calcium ions. By the removal of calcium ions, chemical precipitation can significantly reduce the scaling potential of NF and RO concentrates. This may allow higher recoveries in the NF/RO process.

Evidencing generation of persistent ozonation products of antibiotics roxithromycin and trimethoprim.

The mechanism of product formation during ozonation of two widely used antimicrobial agents, macrolide roxithromycin and inhibitor of dihydrofolate reductase (DHFR) trimethoprim was studied in laboratory-scale experiments with two types of matrix: distilled water and secondary wastewater effluent The structures ofthe primary and secondary reaction intermediates were elucidated byquadrupole-time-of-flight (QqToF) instrument, showing that in spite of their high ozone affinity both roxithromycin and trimethoprim oxidation pathway involve to a great degree the *OH radical chain reactions. In total nine ozonation products were detected, whereas two products of roxithromycin exhibited high refractoriness to ozonation, especially in the case of distilled water. Furthermore, the intact tertiary amine moiety of roxithromycin in these products suggests that the antimicrobial activity of the parent compound will be preserved.

Sustainable wastewater management: life cycle assessment of conventional and source-separating urban sanitation systems.

Conventional and source-separating urban sanitation systems are compared with regard to their ecological sustainability using the methodology of Life Cycle Assessment. A substance flow model of all relevant processes in a settlement with 5,000 inhabitants is set up and evaluated with environmental indicators for resource demand and emissions to air, water, and soil. The comparison shows that source separation does not necessarily result in a system with less environmental impacts. If the conventional system is energetically optimized and equipped with extended nutrient removal, its impact is comparable to the source-separating systems. However, source separation has the potential to offer ecological benefits depending on the system configuration. Especially the input of toxic heavy metals to agriculture with sewage sludge can be substantially lowered if separately collected urine and faeces are used as organic fertilizer.

Reductive dehalogenation of iopromide by zero-valent iron.

Iodinated X-ray contrast media (ICM), as derivatives of 2, 4, 6-triiodo benzoic acid, are applied in high doses to humans and are excreted unchanged via urine within 24 h. Common as well as advanced wastewater treatment is not able to remove the iodinated compounds leading to an environmental pollution. A specific treatment of contaminated urine or hospital wastewater could minimise the emission. For that reason the deiodination of iopromide, the most commonly used ICM, was investigated using zero-valent iron. Initial experiments carried out in stirred batch reactors with an initial pH of 2 using iron powder and iopromide dissolved in ultra pure water showed that iopromide can be deiodinated by zero-valent iron. Even in contaminated urine collected in a hospital a deiodination of ICM was possible. Further experiments at different constant pH values, temperatures and stirring speeds were performed. The kinetic studies at constant pH showed that the deiodination can be described by pseudo-first order for equal iopromide and iron concentrations. In general, the reaction depends strongly on the pH, the temperature and the stirring speed. The observed rate constant K(obs) has an optimum at pH 3 and rises with increasing temperature and stirring speed.

Impact of temperature on biodegradation of bulk and trace organics during soil passage in an indirect reuse system.

Investigations on the behavior of bulk organics and trace organic compounds in a temperature controlled soil column system are reported. Objective of the research was to assess the importance of temperature for the degradation of bulk and trace organics. The analysis of the bulk organic behavior showed a fast mineralization of easily degradable organic carbon in the first few centimetres of the columns, which does not seem to be temperature-dependent. Along the further infiltration path an influence of the different temperatures on the bioactivity was clearly visible. However, a significant increase of mineralization potential of bulk organic compounds with increasing temperature was shown. The monitoring of the single organic pollutants Iopromide, Sulfamethoxazole and naphthalenedisulfonic acids showed that temperature has an influence on the degradation behavior of the monitored compounds. In most cases higher temperatures increased the mineralization potential.

An integrated wastewater reuse concept combining natural reclamation techniques, membrane filtration and metal oxide adsorption.

In a Sino-German research project, a sustainable water reclamation concept was developed for different applications of municipal water reuse at the Olympic Green 2008 in Beijing, China. Results from pilot-scale experiments in Beijing and Berlin show that selective nutrient removal by adsorption onto granular ferric hydroxide (GFH) after a membrane bioreactor (MBR) can maintain a total phosphorus concentration of <0.03 microg L(-1) P, thus preventing eutrophication of artificial lakes. Operation time of GFH adsorption columns can be extended by regeneration using sodium hydroxide solution. A subsequent ultrafiltration (UF) membrane after bank filtration creates an additional barrier for pathogens and allows for further urban reuse applications such as toilet flushing. Short term bank / bio-filtration prior to UF is shown to effectively remove biopolymers and reduce membrane fouling.

Ozonation and reductive deiodination of iopromide to reduce the environmental burden of iodinated X-ray contrast media.

The potential of ozonation for the removal of iodinated X-ray contrast media (ICM) with focus on the oxidation products was examined. Iopromide used as model compound was dissolved in tap water, respectively in the effluent of a membrane bioreactor and was ozonated. Ozone (10 mg/L) was continuously introduced into a semi-batch reactor (35 L/h). After 30 minutes the ozone concentration was increased to 30 mg/L. In all experiments the iopromide concentration decreased very fast, whereas the decrease of the amount of organic bound iodine (AOI) was much lower. The concentration of iodate, the inorganic oxidation product increases with time, depending on the AOI decrease. The data clearly show that the ozonation of iopromide using a common applied ozone dosage leads to the formation of numerous iodinated transformation products, which are detectable by LC-ESI-MS. As an alternative treatment, especially for the treatment of urine or hospital waste water, the source for the contamination, it was tested if iopromide can be deiodinated by zero-valent iron. First experiments done in stirred batch reactors using iopromide dissolved in ultra pure water and urine with an initial pH of 2 showed that iopromide can be deiodinated completely by zero-valent iron. Even in contaminated urine collected in a hospital a deiodination of ICM was possible. Kinetic studies at constant pH showed that the deiodination can be described by pseudo-first order for equal iopromide and iron concentrations. The observed rate constant kobs increased with decreasing pH with a maximum at pH 3 with 4.76x10(-4) s(-1). The concentration of iopromide can be decreased by ozonation and by the reductive dehalogenation. In case of ozonation iodinated organic compounds are the main reaction products, whereas the reductive dehalogenation leads to transformation products which are not iodinated and are thus most probable biodegradable.