Hansruedi Siegrist

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)).

Behavior of Metallic Silver Nanoparticles in a Pilot Wastewater Treatment Plant

We investigated the behavior of metallic silver nanoparticles (Ag-NP) in a pilot wastewater treatment plant (WWTP) fed with municipal wastewater. The treatment plant consisted of a nonaerated and an aerated tank and a secondary clarifier. The average hydraulic retention time including the secondary clarifier was 1 day and the sludge age was 14 days. Ag-NP were spiked into the nonaerated tank and samples were collected from the aerated tank and from the effluent. Ag concentrations determined by inductively coupled plasma-mass spectrometry (ICP-MS) were in good agreement with predictions based on mass balance considerations. Transmission electron microscopy (TEM) analyses confirmed that nanoscale Ag particles were sorbed to wastewater biosolids, both in the sludge and in the effluent. Freely dispersed nanoscale Ag particles were only observed in the effluent during the initial pulse spike. X-ray absorption spectroscopy (XAS) measurements indicated that most Ag in the sludge and in the effluent was present as Ag(2)S. Results from batch experiments suggested that Ag-NP transformation to Ag(2)S occured in the nonaerated tank within less than 2 h. Physical and chemical transformations of Ag-NP in WWTPs control the fate, the transport and also the toxicity and the bioavailability of Ag-NP and therefore must be considered in future risk assessments.

Biological treatment of ammonium-rich wastewater by partial nitritation and subsequent anaerobic ammonium oxidation (anammox) in a pilot plant

In wastewater treatment plants with anaerobic sludge digestion, 15-20% of the nitrogen load is recirculated to the main stream with the return liquors from dewatering. Separate treatment of this ammonium-rich digester supernatant would significantly reduce the nitrogen load of the activated sludge system. Some years ago, a novel biological process was discovered in which ammonium is converted to nitrogen gas under anoxic conditions with nitrite as the electron acceptor (anaerobic ammonium oxidation, anammox). Compared to conventional nitrification and denitrification, the aeration and carbon-source demand is reduced by over 50 and 100%, respectively. The combination of partial nitritation to produce nitrite in a first step and subsequent anaerobic ammonium oxidation in a second reactor was successfully tested on a pilot scale (3.6 m(3)) for over half a year. This report focuses on the feasibility of nitrogen removal from digester effluents from two different wastewater treatment plants (WWTPs) with the combined partial nitritation/anammox process. Nitritation was performed in a continuously stirred tank reactor (V=2.0 m(3)) without sludge retention. Some 58% of the ammonium in the supernatant was converted to nitrite. At 30 degrees C the maximum dilution rate D(x) was 0.85 d(-1), resulting in nitrite production of 0.35 kg NO(2)-N m(-3)(reactor) d(-1). The nitrate production was marginal. The anaerobic ammonium oxidation was carried out in a sequencing batch reactor (SBR, V=1.6 m(3)) with a nitrogen elimination rate of 2.4 kg N m(-3)(reactor) d(-1) during the nitrite-containing periods of the SBR cycle. Over 90% of the inlet nitrogen load to the anammox reactor was removed and the sludge production was negligible. The nitritation efficiency of the first reactor limited the overall maximum rate of nitrogen elimination.

Practical identifiability of ASM2d parameters-systematic selection and tuning of parameter subsets

In many applications, some parameters of the Activated Sludge Model No. 2d (ASM2d) need calibration. Since ASM2d usually is overparameterized with respect to the available data, the subset of calibration parameters is not unique. In practice, calibration of ASM2d (and other ASMs) is often addressed by ad hoc selecting and tuning procedures. In this paper, a more systematic approach based on parameter identifiability analysis of parameter subsets is applied. The approach consists of a preliminary prior parameter analysis and a subsequent iterative parameter subset selection and tuning procedure. The former includes the choice of suitable prior parameter values and uncertainties and a pre-selection of parameters which are reasonably estimated from the data available. The latter is based on three diagnostic measures which are simple to calculate and easy to interpret. It is demonstrated as to how these measures can be used to identify the most important model parameters and to analyze their interdependencies. In addition, it is shown how these measures facilitate the analysis of the influence of fixed parameter values on parameter estimates.

Mechanisms of N2O production in biological wastewater treatment under nitrifying and denitrifying conditions

Nitrous oxide (N2O) is an important greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment, microbial processes such as autotrophic nitrification and heterotrophic denitrification have been identified as major sources; however, the underlying pathways remain unclear. In this study, the mechanisms of N2O production were investigated in a laboratory batch-scale system with activated sludge for treating municipal wastewater. This relatively complex mixed population system is well representative for full-scale activated sludge treatment under nitrifying and denitrifying conditions. Under aerobic conditions, the addition of nitrite resulted in strongly nitrite-dependent N2O production, mainly by nitrifier denitrification of ammonia-oxidizing bacteria (AOB). Furthermore, N2O is produced via hydroxylamine oxidation, as has been shown by the addition of hydroxylamine. In both sets of experiments, N2O production was highest at the beginning of the experiment, then decreased continuously and ceased when the substrate (nitrite, hydroxylamine) had been completely consumed. In ammonia oxidation experiments, N2O peaked at the beginning of the experiment when the nitrite concentration was lowest. This indicates that N2O production via hydroxylamine oxidation is favored at high ammonia and low nitrite concentrations, and in combination with a high metabolic activity of ammonia-oxidizing bacteria (at 2 to 3 mgO2/l); the contribution of nitrifier denitrification by AOB increased at higher nitrite and lower ammonia concentrations towards the end of the experiment. Under anoxic conditions, nitrate reducing experiments confirmed that N2O emission is low under optimal growth conditions for heterotrophic denitrifiers (e.g. no oxygen input and no limitation of readily biodegradable organic carbon). However, N2O and nitric oxide (NO) production rates increased significantly in the presence of nitrite or low dissolved oxygen concentrations.

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.

Fate of beta blockers and psycho-active drugs in conventional wastewater treatment.

The removal of beta blockers and psycho-active drugs was investigated in a representative conventional German WWTP by long-term measurement campaigns along different biological treatment processes. The activated sludge treatment with an elevated SRT of 18 d was the only process which led to a significant removal of certain beta blockers and psycho-active drugs. The removal efficiency was below 60% for all compounds except for the natural opium alkaloids codeine and morphine being removed by more than 80%. Primary biological transformation and sorption onto sludge as the main removal mechanisms were examined in lab-scale batch experiments. Sorption onto activated sludge was found to be negligible (<3%). The biological transformation could be described by pseudo-first order kinetics and the transformation constants k(biol) were used to predict the removal of beta blockers and psycho-active drugs in an activated sludge unit with a model. For most compounds the removal efficiencies measured on the full-scale WWTP were within the 95% confidence intervals predicted by the model. The results from full-scale measurements and modeling indicate that biological transformation in the nitrification tank together with parameters such as the sludge retention time and the temperature is crucial regarding the biological transformation of beta blockers and psycho-active drugs in conventional WWTPs.

Anammox brings WWTP closer to energy autarky due to increased biogas production and reduced aeration energy for N-removal

Fifty years ago when only BOD was removed at municipal WWTPs primary clarifiers were designed with 2-3 hours hydraulic retention time (HRT). This changed with the introduction of nitrogen removal in activated sludge treatment that needed more BOD for denitrification. The HRT of primary clarification was reduced to less than one hour for dry weather flow with the consequence that secondary sludge had to be separately thickened and biogas production was reduced. Only recently the ammonia rich digester liquid (15-20% of the inlet ammonia load) could be treated with the very economic autotrophic nitritation/anammox process requiring half of the aeration energy and no organic carbon source compared to nitrification and heterotrophic denitrification. With the introduction of this new innovative digester liquid treatment the situation reverts, allowing us to increase HRT of the primary clarifier to improve biogas production and reduce aeration energy for BOD removal and nitrification at similar overall N-removal.

Kinetic assessment and modeling of an ozonation step for full-scale municipal wastewater treatment: Micropollutant oxidation, by-product formation and disinfection

The kinetics of oxidation and disinfection processes during ozonation in a full-scale reactor treating secondary wastewater effluent were investigated for seven ozone doses ranging from 0.21 to 1.24 g O(3) g(-1) dissolved organic carbon (DOC). Substances reacting fast with ozone, such as diclofenac or carbamazepine (k(P, O3) > 10(4) M(-1) s(-1)), were eliminated within the gas bubble column, except for the lowest ozone dose of 0.21 g O(3) g(-1) DOC. For this low dose, this could be attributed to short-circuiting within the reactor. Substances with lower ozone reactivity (k(P, O3) < 10(4) M(-1) s(-1)) were only fully eliminated for higher ozone doses. The predictions of micropollutant oxidation based on coupling reactor hydraulics with ozone chemistry and reaction kinetics were up to a factor of 2.5 higher than full-scale measurements. Monte Carlo simulations showed that the observed differences were higher than model uncertainties. The overestimation of micropollutant oxidation was attributed to a protection of micropollutants from ozone attack by the interaction with aquatic colloids. Laboratory-scale batch experiments using wastewater from the same full-scale treatment plant could predict the oxidation of slowly-reacting micropollutants on the full-scale level within a factor of 1.5. The Rct value, the experimentally determined ratio of the concentrations of hydroxyl radicals and ozone, was identified as a major contribution to this difference. An increase in the formation of bromate, a potential human carcinogen, was observed with increasing ozone doses. The final concentration for the highest ozone dose of 1.24 g O(3) g(-1) DOC was 7.5 μg L(-1), which is below the drinking water standard of 10 μg L(-1). N-Nitrosodimethylamine (NDMA) formation of up to 15 ng L(-1) was observed in the first compartment of the reactor, followed by a slight elimination during sand filtration. Assimilable organic carbon (AOC) increased up to 740 μg AOC L(-1), with no clear trend when correlated to the ozone dose, and decreased by up to 50% during post-sand filtration. The disinfection capacity of the ozone reactor was assessed to be 1-4.5 log units in terms of total cell counts (TCC) and 0.5 to 2.5 log units for Escherichia coli (E. coli). Regrowth of up to 2.5 log units during sand filtration was observed for TCC while no regrowth occurred for E. coli. E. coli inactivation could not be accurately predicted by the model approach, most likely due to shielding of E. coli by flocs.

Behaviour of NTA and EDTA in biological wastewater treatment

The behaviour and diurnal load variations of nitrilotriacetate (NTA) and ethylenediaminetetraacetate (EDTA) were investigated in winter and in summer in the sewage treatment plant Zu¨rich-Glatt. The results are discussed using the activated sludge model of the IAWPRC task group extended by the degradation kinetics of NTA and by its adsorption behaviour onto activated sludge. The plant had a sludge age of 3.6 d in winter and 4.8 d in summer and was in winter only partly nitrifying. In the investigated lane, the average daily loads of NTA and EDTA in the primary effluent were during the two investigated periods 13 ± 7kg NTA d−1 (0.5 ± 0.3g NTA person−1 d−1) and 1.3 ± 0.6kg EDTA d−1 (0.05 ± 0.02g EDTA person−1 d−1), respectively. The influent concentration varied from 300 to 1500 μg NTA 1−1 and from 30 to 150 μg EDTA 1−1. In both seasons NTA was biologically degraded up to 97%, while no elimination was observed for EDTA. During the measurements in the winter period, an additional 17 kg of NTA (120% of a daily load) were added to the effluent of the primary clarifier. During 4–5 h the biological NTA degradation was saturated and four times more than the daily average of NTA was degraded. Due to the increased NTA concentration (up to 2000 μg 1−1 in the effluent of the secondary clarifier) zinc and lead were remobilized from the activated sludge, and their effluent concentration in the secondary clarifier increased by 200 and 50%, respectively. The concentration of copper did not increase during the NTA shock loading.