Removal and degradation characteristics of natural and synthetic estrogens by activated sludge in batch experiments

The removal and degradation characteristics of natural and synthetic estrogens by activated sludge were investigated by a series of batch experiments using the activated sludge samples of four actual wastewater treatment plants and synthetic wastewater spiked with estrogen. The rapid removal and degradation of 17β-estradiol (E2) and estrone (E1) were observed by the activated sludge samples of the oxidation ditch process which operated at higher solids retention time (SRT). On the other hand, E1 tended to remain both in the water phase and the sludge phase in the activated sludge samples of the conventional activated sludge process which operated at lower SRT. The anoxic condition was considered to be not favorable to the effective removal of estrogens as compared with the aerobic condition. The removal and degradation of EE2 showed the lag phase, which neither E2 nor E1 showed, but EE2 was finally removed and degraded completely after 24 h. The removal of estrogens in the water phase did not follow the first-order-rate reaction because a large part of the spiked estrogen was immediately removed from the water phase to the sludge phase by adsorption.     

Fate of natural estrogens in batch mixing experiments using municipal sewage and activated sludge

Since natural estrogens such as 17beta-estradiol (E2) and estrone (E1) are excreted daily by humans, E2 and E1, which are classified as inevitable endocrine-disrupting chemicals, are always present in sewage wastewater. For several years, the monitoring and removal of natural estrogens at sewage treatment plants have been examined by many investigators. However, little is known regarding the exact behavior of estrogens in actual sewage when in contact with activated sludge. In this study, the fate of E2 and E1 as a result of adsorption and decomposition in batch mixing experiments using municipal wastewater and activated sludge collected from an actual municipal sewage treatment plant was investigated. Estrogen concentrations were determined using an enzyme-linked immunosorbent assay (ELISA) kit. E2 and E1 in sewage were removed from the liquid phase in contact with activated sludge, and E2 and E1 adsorbed on the sludge were decomposed in 4h. Significant changes in the adsorption and decomposition of E2 and E1 on the sludge were not observed at low temperatures or when different sludge samples were used such as those acclimatized to low-loading and high-loading conditions. In contrast, the processes leading to the removal of estrogens, such as the adsorption and decomposition of estrogens in contact with activated sludge, were inactivated by sterilizing the sludge. Natural estrogens adsorb onto the activated sludge, and are therefore easy to be biodegraded. In a biological reaction process, therefore, the estrogens will be rapidly removed at the initial stage, when the sewage is satisfactorily mixed with the sludge.     

Effects of integrated fixed film activated sludge media on activated sludge settling in biological nutrient removal systems

Integrated fixed film activated sludge (IFAS) is an increasingly popular modification of conventional activated sludge, consisting of the addition of solid media to bioreactors to create hybrid attached/suspended growth systems. While the benefits of this technology for improvement of nitrification and other functions are well-demonstrated, little is known about its effects on biomass settleability. These effects were evaluated in parallel, independent wastewater treatment trains, with and without IFAS media, both at the pilot (at two solids residence times) and full scales. While all samples demonstrated good settleability, the Control (non-IFAS) systems consistently demonstrated small but significant (p < 0.05) improvements in settleability relative to the IFAS trains. Differences in biomass densities were identified as likely contributing factors, with Control suspended phase density > IFAS suspended phase density > IFAS attached phase (biofilm) density. Polyphosphate content (as non-soluble phosphorus) was well-correlated with density. This suggested that the attached phases had relatively low densities because of their lack of anaerobic/aerobic cycling and consequent low content of polyphosphate-accumulating organisms, and that differences in enhanced biological phosphorus removal performance between the IFAS and non-IFAS systems were likely related to the observed differences in density and settleability for the suspended phases. Decreases in solids retention times from 8 to 4 days resulted in improved settleability and increased density in all suspended phases, which was related to increased phosphorus content in the biomass, while no significant changes in density and phosphorus content were observed in attached phases.     

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

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

Production of polyhydroxyalkanoates (PHA) by activated sludge treating municipal wastewater: effect of pH,sludge retention time (SRT), and acetate concentration in influent

In this paper, the production of biodegradable plastics polyhydroxyalkanoates (PHA) by activated sludge treating municipal wastewater was investigated. The effect of three operational factors, i.e. the acetate concentration in influent, pH, and sludge retention time (SRT) were studied. Sludge acclimatized with municipal wastewater supplemented with acetate could accumulate PHA up to 30% of sludge dry weight, while sludge acclimatized with only municipal wastewater achieved 20% of sludge dry weight. It was found that activated sludge with an SRT of 3 days possessed better PHA production capability than sludge with an SRT of 10 days. Sludge acclimatized under pH 7 and 8 conditions in sequencing batch reactors (SBRs) exhibited similar PHA production capability. However, in PHA production batch experiments, pH value influenced significantly the PHA accumulation behavior of activated sludge. When pH of batch experiments was controlled at 6 or 7, a very low PHA production was observed. The production of PHA was stimulated when pH was kept at 8 or 9.     

Comparison of control strategies for nitrogen removal in an activated sludge process in terms of operating costs: a simulation study

In this paper several control strategies for nitrogen removal are proposed and evaluated in a benchmark simulation model of an activated sludge process. The goal is to determine which control strategy delivers better performance with respect to plant operating costs. In the study, constant manipulated variables and various PI and feedforward control strategies are tested and compared with predictive control, which uses an ideal process model. The control strategies differ in the information used about the process (number of sensors and sensor location) and in the complexity of the control algorithms. To determine the set-points that yield optimal operating costs, an operational map is constructed for each control strategy. Results of the simulation show that with PI and feedforward controllers almost the same optimal operating costs can be achieved as with more advanced MPC algorithms under various plant operating conditions. More advanced control algorithms are advantageous only in cases where the plant is highly loaded and if stringent effluent fines are imposed by legislation.     

Biological hydrolysis and acidification of sludge under anaerobic conditions: the effect of sludge type and origin on the production and composition of volatile fatty acids

New wastewater treatment processes resulting in considerably reduced sludge production and more effective treatment are needed. This is due to the more stringent legislations controlling discharges of wastewater treatment plants (WWTPs) and existing problems such as high sludge production. In this study, the feasibility of implementing biological hydrolysis and acidification process on different types of municipal sludge was investigated by batch and semi-continuous experiments. The municipal sludge originated from six major treatment plants located in Denmark were used. The results showed that fermentation of primary sludge produced the highest amount of volatile fatty acids (VFAs) and generated significantly higher COD- and VFA-yields compared to the other sludge types regardless of which WWTP the sludge originated from. Fermentation of activated and primary sludge resulted in 1.9-5.6% and 8.1-12.6% COD-yields, soluble COD (SCOD)/total COD (TCOD), in batch experiments, respectively. The COD-yields for primary, activated and mixed sludge were 19.1%, 6.5% and 21.37%, respectively, in semi-continuous experiments operated at solids retention time (SRT) of 5d and temperature of 37 degrees C. The benefit of fermentation for full-scale application was roughly estimated based on the experiments performed in semi-continuous reactors. The results revealed that even though the VFA production of primary sludge was higher compared to activated sludge, substantial amounts of VFA could be produced by fermentation of activated sludge due to the substantially higher production of activated sludge in WWTPs.     

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in sewage treatment plants

In this study, the concentrations of PFOS and PFOA in the biological units of various full-scale municipal sewage treatment plants were measured. Samples of influent, primary effluent, aeration tank effluent, final effluent and grab samples of primary, activated, secondary and anaerobically digested sludge were collected by 5 sampling events over one year. The two sewage treatment plants (STPs) selected for this study include plant A receiving 95% domestic wastewater and plant B receiving 60% industrial wastewater and 40% domestic wastewater. PFOS and PFOA were observed at higher concentration in aqueous and sludge samples in plant B than that of plant A. Mass flow of PFOS increased significantly (mean 94.6%) in conventional activated sludge process (CAS) of plant B, while it remained consistent after the secondary treatment in plant A. Mass flow of PFOA increased 41.6% (mean) in CAS of plants A and B and 76.6% in membrane biological reactor (MBR), while it remained unchanged after the treatment of liquid treatment module (LTM). Our results suggest that mass flow of these two compounds remains consistent after treatment of activated sludge process operating at short sludge retention time (SRT). Seasonal variations of PFOS in concentrations of raw sewage were found in plant A, while PFOA did not have significant seasonal variation in both plants A and B.     

Effects of pH and oxidation state of chromium on the behavior of chromium in the activated sludge process

The behavior of chromium (Cr) in the activated sludge process (ASP) was evaluated in laboratory-scale, fill-and-draw activated sludge experiments. Both pH and the oxidation state of chromium were confirmed as critical parameters in the ASP for evaluating the behavior of chromium. More than 55% of chromium was removed when trivalent chromium [Cr(III)] was introduced into the influent while less than 60% was removed when hexavalent chromium [Cr(VI)] was added over a pH range from 5 to 9. As pH was increased, the removal increased when Cr(III) was introduced but the reverse occurred with Cr(VI). Introduction of Cr(VI) into the influent resulted in less than 80% of chromium associated with solids; however, with Cr(III), more than 90% of chromium was bound with solids. These results suggest that the ASP is capable of controlling the transport of Cr(III) to the environment but such is not case for Cr(VI).Theoretical consideration based on thermodynamics predicted that no reduction of Cr(VI) into Cr(III) should occur and the only redox reaction should be the oxidation of Cr(III) into Cr(VI). However, no oxidation of Cr(III) into Cr(VI) was observed; some Cr(VI) was reduced into Cr(III). Kinetic constraints may have impeded the oxidation of Cr(III). Under the conditions of this study, Cr(III) may have been removed through adsorption rather than precipitation as Cr(OH)₃. Cr(VI) might be adsorbed on the bacterial surface through specific adsorption.     

Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide

This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide (AOP O(3)/H(2)O(2)). The rate constants of reactions of NDMA with ozone and hydroxyl radical ((*)OH) were determined to be 0.052+/-0.0016M(-1)s(-1) and (4.5+/-0.21)x10(8)M(-1)s(-1), respectively. The experiments performed with buffered deionized water varying solution pH and employing H(2)O(2) and HCO(3)(-) clearly showed that the reaction with (*)OH dominates the NDMA oxidation during ozonation. Conventional ozonation with up to 160 microM (=7.7 mgL(-1)) ozone led to less than 25% NDMA oxidation in natural waters. The AOP O(3)/H(2)O(2) required 160-320 microM ozone ([O(3)](0)/[H(2)O(2)](0)=2:1) to achieve 50-75% NDMA oxidation. However, multiple injections of ozone of the same overall dose somewhat improved the oxidant utilization efficiency by minimizing (*)OH scavenging contribution of oxidants. Methylamine (MA) was found to be a major amino product from NDMA oxidation initiated by (*)OH. The mechanism of NDMA oxidation to MA is discussed based on the results obtained in this study and the previous literature. Bromate formation may be the limiting factor for NDMA oxidation during ozonation and ozone-based AOPs in bromide-containing waters.     

Long-term formation of microbial products in a sequencing batch reactor

Activated sludge in a sequencing batch reactor (SBR) is subjected to alternating feast-and-famine conditions, which may result in the enhanced production of microbial products: extracellular polymeric substances (EPS), soluble microbial products (SMP), and internal storage products (X_STO). In this work, the long-term formation of these three microbial products by activated sludge in an SBR is investigated using an expanded unified model with a parallel experimental study. We also use the model to compare the impacts in an SBR to those in a continuous-flow activated sludge system. The model captures all experimental trends for all components with solids retention time (SRT) for global steady state and within a cycle. At an SRT of 20 days, the active microorganisms constitute about 28% of the mixed liquor volatile suspended solids (MLVSS); the remaining biomass is comprised of residual inert biomass (X_I) of 40%, EPS of 31%, and X_STO of ∼1%. The active biomass becomes a smaller fraction with the increasing SRT, while the inert biomass becomes increasingly dominant. For soluble components, effluent chemical oxygen demand (COD) is dominated by SMP, which varies to some degree in a cycle, peaking as external substrate becomes depleted. Within the SBR cycle, external substrate (S) declines strongly in the first part of the cycle, and SMP shows a small peak at the time of S depletion. X_STO is the only biomass component that varies significantly during the cycle. It peaks at the time that the input substrate (S) is depleted. Simulation for a continuous-flow activated sludge system and comparison with an SBR reveals that the constant “famine” conditions of the continuous system lead to lower EPS and X_STO, but higher MLVSS and X_I.     

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water

A photocatalytic reactor membrane pilot system, employing UV/TiO₂ photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m³). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H₂O₂ mode (UV/H₂O₂) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H₂O₂ mode for the conditions tested.     

Identifying model pollutants to investigate biodegradation of hazardous XOCs in WWTPs

Xenobiotic organic compounds (XOCs) in wastewater treatment plant (WWTP) effluents might cause toxic effects in ecosystems. Several investigations have emphasized biodegradation as an important removal mechanism to reduce pollution with XOCs from WWTP effluents. The aim of the study was to design a screening tool to identify and select hazardous model pollutants for the further investigation of biodegradation in WWTPs. The screening tool consists of three criteria: The XOC is present in WWTP effluents, the XOC constitutes an intolerable risk in drinking water or the environment, and the XOC is expected to be biodegradable in WWTPs. The screening tool was tested on bisphenol A (BPA), carbamazepine (CBZ), di(2ethylhexyl)-phthalate (DEHP), 17beta-estradiol (E2), estrone (E1), 17alpha-ethinyloetradiol (EE2), ibuprofen, naproxen, nonylphenol (NP), and octylphenol (OP). BPA, DEHP, E2, E1, EE2, and NP passed all criteria in the screening tool and were selected as model pollutants. OP did not pass the filter and was rejected as model pollutant. CBZ, ibuprofen, and naproxen were not finally evaluated due to insufficient data.     

Natural attenuation and characterization of contaminants composition in landfill leachate under different disposing ages

Chemical Oxygen Demand (COD) composition in landfill leachate would vary as the disposal time extended. Leachates with different ages were collected from Laogang Refuse Landfill of Shanghai, the largest landfill in China with a placement scale of 7600 t refuse per day. To characterize COD composition in leachate, samples were size-fractioned into suspended fractions (> 0.45 μm), colloid fraction (0.45 μm < fraction < 1 K Da MW) and dissolved fractions (< 1 KDa MW) based on the molecular weight distribution. The fractions < 0.45 μm (including colloid fraction and dissolved fractions) in leachate were further divided into 6 fractions, i.e. hydrophobic bases (Ho-base), hydrophobic acids (Ho-acid), hydrophobic neutral (Ho-neutral), hydrophilic bases (Hi-base), hydrophilic acids (Hi-acid) and hydrophilic neutral (Hi-neutral). It was found that the ratio of TOC/TC in leachate decreased over time, indicating that the percentage of organic matters in leachate decreased as the disposal time extended. It was also observed that the hydrophobic fraction accounted to about 50% of the total matters presented in the fraction < 0.45 μm of all leachate samples. The main components in < 0.45  μm fraction were the Ho-acid, Hi-acid and Hi-base fractions. The percentage of Ho-acid in leachate decreased from 60.8% (2 a) to 43.2% (12 a). In addition, leachate with different ages was categorized into 3 phases according to the results of Principle component analysis (PCA). TOC/COD ranges of leachate in periods I, II and III were 40-54.6%, 16.9-41.3% and 10-38.9%, respectively, indicating that the COD contribution of non-carbon reduction substances increased over time in leachate. Hence, the corresponding landfill leachate treatment process should be modified according to the leachate characterization. The results obtained in this study might provide the important information for modeling, design, and operation of landfill leachate treatment systems.