Unraveling the evolution of dissolved organic matter in full-scale A/A/O wastewater treatment process using size exclusion chromatography with PARAFAC and nonnegative matrix factorization analysis.

Changes in spectral features and molecular weight (MW) of dissolved organic matter (DOM) along the A/A/O processes in eight full-scale wastewater treatment plants (WWTPs) were characterized using size exclusion chromatography with a diode array detector, a fluorescence detector and an organic carbon detector in tandem (SEC-DAD-FLD-OCD) as well as bulk water quality parameters. The parallel factor (PARAFAC) and the nonnegative matrix factorization (NMF) analyses have been effectively applied to the postprocessing of SEC-FLD fingerprints and SEC-OCD chromatograms, respectively. Individual SEC-FLD-PARAFAC or SEC-OCD-NMF components may span a broad range of MW, indicating that these SEC fractions within the same component were cognate and varied coherently across the dataset samples. The SEC-FLD-PARAFAC modeling and SEC-OCD-NMF analysis have clearly and concisely presented that the dramatic decreases of dissolved organic carbon, UV absorbance at 254 nm and protein-like fluorescence at Ex280/Em350 nm in the anaerobic process were primarily associated with the degradation of the large MW proteinaceous and polysaccharide-like biopolymers. It has also revealed that fluorescence of humic acid-like fractions increased significantly during the anaerobic process, but fluorescence of fulvic acid-like and humic substances' building blocks decreased slightly. Laboratory experiments further confirmed the presence of the humification process in anaerobic processes, and the formation of humic acid-like fluorophores may be associated with carbohydrate metabolism. The combination of SEC-FLD-PARAFAC and SEC-OCD-NMF helped to establish the links between changes in bulk water quality parameters and the evolution of SEC MW fractions, which provides a more in-depth insight into wastewater DOM treatability and enables the optimization of wastewater treatment processes.

Effects of pharmaceuticals on membrane bioreactor: Review on membrane fouling mechanisms and fouling control strategies.

Pharmaceuticals have become contaminants of emerging concern due to their toxicity towards aquatic life and pseudo persistent nature in the environment. Membrane bioreactor (MBR) is one such technology that has the potential to act as a barrier against the release of pharmaceuticals into the environment. Fouling is the deposition of the constituents of the mixed liquor on the membrane surface and it limit the world-wide applicability of MBRs. To remove foulant layer, aggressive chemicals and extra cost consideration in terms of energy are required. Extracellular polymeric substances (EPS) and soluble microbial products (SMP) are recognized as principal foulants. Presence of pharmaceuticals has been found to increase the fouling in MBRs. Fouling aggravates in proportion to the concentration of pharmaceuticals. Pharmaceuticals exert chemical stress in microbes, hence forcing them to secrete more EPS/SMP. Pharmaceuticals alter the composition of the foulants and affect microbial metabolism, thereby inflicting direct/indirect effects on fouling. Pharmaceuticals have been found to increase or decrease the size of sludge flocs, however the exact mechanism that govern the floc size change is yet to be understood. Different techniques such as coupling advanced oxidation processes with MBR, adding activated carbon, bioaugmenting MBR with quorum quenching strains have shown to reduce fouling in MBRs treating pharmaceutical wastewater. These fouling mitigation techniques work on reducing the EPS/SMP concentration, thereby alleviating fouling. The present review provides a comprehensive understanding of the effects induced by pharmaceuticals in the activated sludge characteristics and identifying the fouling mechanism. Furthermore, significant knowledge gaps and recent advances in fouling mitigation strategies are discussed. This review has also made an effort to highlight the positive aspect of the foulant layer in retaining pharmaceuticals and antibiotic resistance genes, thereby suggesting a possible delicate trade-off between the flux decline and enhanced removal of pharmaceuticals.

Effect of antibiotic mixtures on the characteristics of soluble microbial products and microbial communities in upflow anaerobic sludge blanket.

Two upflow anaerobic sludge blanket reactors (UASBs) were used to investigate the effects of three antibiotic mixtures (erythromycin, sulfamethoxazole, and tetracycline) on reactor performance, soluble microbial products (SMPs) composition and microbial community. One reactor (UASBantibiotics) was fed with antibiotic mixtures, whereas another reactor (UASBcontrol) was used as a control without the addition of antibiotic mixtures. Compared with those in UASBcontrol, UASBantibiotics show lower chemical oxygen demand removal efficiency and biogas content. A higher removal efficiency of antibiotic mixtures was obtained in first few stages in UASBantibiotics. The SMPs composition of effluent from the two reactors did not differ significantly, and the main components were protein-like substances, which produced higher fluorescence intensity in UASBantibiotics. Gas chromatography-mass spectrometry analysis revealed that the main compounds identified as SMPs (<580 Da) were alkanes, aromatics and esters, with only 20% similarity of SMPs between UASBantibiotics and UASBcontrol. Antibiotics had a significant effect on the microbial community structure. Notably, in UASBcontrol, hydrogenotrophic methanogens, key microorganisms in anaerobic digestion, had an obvious advantage at all stages compared with UASBantibiotics, whereas acetoclastic methanogen exhibited the opposite pattern. The above results demonstrated that antibiotic mixtures influenced the effluent quality during anaerobic treatment of synthetic wastewater, resulting in changes in the microbial community structure. This study clarified the effect of antibiotic mixtures on the operation of UASBs. It could contribute to identifying potential strategies for improving effluent quality in anaerobic treatment.

Investigation of critical sludge characteristics for membrane fouling in a submerged membrane bioreactor: Role of soluble microbial products and extracted extracellular polymeric substances.

Membrane bioreactors (MBRs) are considered a promising tool for resource recovery in wastewater treatment. Nevertheless, membrane fouling is an inevitable phenomenon that deteriorates the MBR performance. Although many studies have attempted to elucidate the effect of sludge characteristics on MBR fouling, they posed certain limitations. Most of the previous studies focused on the initial sludge or employ the results of short-term batch tests without long-term transmembrane pressure (TMP) profiles in the interpretation of fouling behaviors. This study was conducted considering these limitations to determine the sludge characteristics most closely related to long-term TMP profiles and to identify their role in fouling behaviors. In long-term TMP profiles, critical time (tc; time to TMP jump) and fouling rates (the increase in the TMP slope) were used as fouling indexes, which were used to correlate with average values of sludge characteristics before and after experiments. According to the results, the concentration of the total soluble microbial product (SMP) and extracted extracellular polymeric substance (eEPS) in sludge significantly increased by 1.9 times and up to 28 times after experiment. The increase in the SMP and eEPS caused early TMP jumps and resulted in low-fouling rates by increasing particle size. Owing to the increase in the SMP and eEPS concentration, the origin of fouling potential was shifted from suspended solids to colloids and soluble materials. Fouling resistance caused by soluble material increased by up to 11.38 times.

Removal of soluble microbial products and dyes using heavy metal wastes decorated on eggshell.

This work studied the potential of using eggshell (ES) (200-300 µm) waste as adsorbent for sequential removal of heavy metals, soluble microbial products, and dye wastes. In this study, among soluble microbial products, chicken egg white (CEW) proteins were selected as simulated contaminants. ES was applied to capture heavy metal ions (e.g., Cu2+ and Zn2+) and the formed eggshell metal (ES-M) complex was use to absorb soluble microbial products (e.g., soluble proteins), followed by subsequent removal of dyes from aqueous solutions using ES-M-CEW adsorbent. The experimental conditions for the adsorption of CEW proteins by ES-M include shaking rate, adsorption pH, isothermal and kinetic studies. The maximum protein adsorption by ES-Zn and ES-Cu were 175.67 and 153.65 mg/g, respectively. Optimal removal efficiencies of the ES-M-CEW particles for Acid Orange (AO7) and Toluidine blue (TBO) dyes were at pH 2 and 12, respectively, achieving performance of 75.38 and 114.18 mg/g, respectively. The removal of TBO dye by ES-M-CEW adsorbent was equilibrated at 5 min. The results showed that low cost and simple preparation of the modified ES particles are feasible for treating various wastewaters.

Long-Term Investigation into the Membrane Fouling Behavior in Anaerobic Membrane Bioreactors for Municipal Wastewater Treatment Operated at Two Different Temperatures.

In this study, the characteristics of activated sludge flocs were investigated and their effects on the evolution of membrane fouling were considered in the anaerobic membrane bioreactors (AnMBR), which were operated at 25 and 35 °C for municipal wastewater treatment. It was found that the membrane fouling rate of the AnMBR at 25 °C was more severe than that at 35 °C. The membrane fouling trends were not consistent with the change in the concentration of soluble microbial product (SMP). The larger amount of SMP in the AnMBR at 35 °C did not induce more severe membrane fouling than that in the AnMBR at 25 °C. However, the polysaccharide and protein concentration of extracellular polymeric substance (EPS) was higher in the AnMBR at 25 °C in comparison with that in the AnMBR at 35 °C, and the protein/polysaccharide ratio of the EPS in the AnMBR at 25 °C was higher in contrast to that in the AnMBR at 35 °C. Meanwhile, the fouling tendencies measured for the AnMBRs could be related to the characteristics of loosely bound EPS and tightly bound EPS. The analysis of the activated sludge flocs characteristics indicated that a smaller sludge particle size and more fine flocs were observed at the AnMBR with 25 °C. Therefore, the membrane fouling potential in the AnMBR could be explained by the characteristics of activated sludge flocs.

Robust performance of a membrane bioreactor for removing antibiotic resistance genes exposed to antibiotics: Role of membrane foulants.

Antibiotic resistance genes (ARGs) are an emerging concern in wastewater treatment plants (WWTPs), as dissemination of ARGs can pose a serious risk to human health. Few studies, however, have quantified ARGs in membrane bioreactors (MBRs), although MBRs have been widely used for both municipal and industrial wastewater treatment. To reveal the capacity of MBRs for removal of ARGs and the response of membrane fouling after antibiotic exposure, five typical ARG subtypes (sulI, sulII, tetC, tetX and ereA) and int1 were quantified affiliated by systematic membrane foulants analysis in a laboratory-scale anoxic/aerobic membrane bioreactor (A/O-MBR). Sulfamethoxazole and tetracycline hydrochloride additions increased ARG abundances by 0.5-1.4 orders of magnitude in the activated sludge, while the ARG removal performance of the membrane module remained stable (or even increased with ARG absolute abundance in several cases), with the abundance of removed ARGs ranging from 0.6 to 5.6 orders of magnitude. Specifically, the distribution of ARGs in membrane foulants accounted for 13%-25% of the total absolute abundance of all tested MBR samples. Indeed, substantial fouling occurred after the antibiotic additions, with the mean concentrations of soluble microbial product (SMP) and extracellular polymeric substance (EPS) increasing by 340% and 220%, respectively, in a membrane fouling cycle; moreover, the contents of EPS and SMP in the membrane foulants were significantly correlated with the ARG absolute abundance of membrane foulants (p < 0.05), among which more significant correlations occurred between both the protein and polysaccharide of foulants than that with humic acid. The dense membrane fouling layer and the membrane itself constituted dual barriers that effectively avoided the leakage of ARGs from the membrane module. Our findings provide fundamental insights into the proliferation and removal of ARGs in MBR systems, and highlight the contribution of membrane fouling to ARG removals in terms of the potential of MBR as an effective strategy to reduce ARG levels in WWTP effluent.

The characteristic evolution of soluble microbial product and its effects on membrane fouling during the development of sponge membrane bioreactor coupled with fiber bundle anoxic bio-filter for treating saline wastewater.

Membrane fouling mitigation was observed during the development of novel sponge membrane bioreactor coupled with fiber bundle anoxic bio-filter (AF-MBMBR). Soluble microbial product (SMP) was found to be positively correlated with membrane fouling. To further clarify the mechanism of fouling mitigation, the effects of bio-carriers (sponge and fiber bundles) on characteristics and fouling potential of SMP were investigated. Characterization of SMP implied that as a consequence of employing bio-carriers, tyrosine and tryptophan in SMP significantly decreased, instead relative proportions of humic and fulvic acids increased. Meanwhile, batch filtration tests demonstrated that fouling potential of SMP was significantly alleviated, flux decline caused by filtrating SMP decreased from 84.5% to 60.1%. Further analysis on foulants and filtrate revealed that proteins performed high adhesion propensity on membrane while humic and fulvic acids mainly can pass through the membrane; this finding could well explain the mitigation of SMP fouling potential induced by bio-carriers.

Fouling analysis of membrane bioreactor treating antibiotic production wastewater at different hydraulic retention times.

Membrane fouling, including foulants and factors, was investigated during hydraulic retention time (HRT) optimization of a membrane bioreactor (MBR) that treated wastewater from the production of antibiotics. The results showed that HRT played an important role in membrane fouling. Trans-membrane pressure (TMP), membrane flux, and resistance were stable at -6 kPa, 76 L m-2 h-1 bar-1, and 4.5 × 1012 m-1 when HRT was at 60, 48, and 36 h, respectively. Using Fourier transform infrared spectroscopy, foulants were identified as carbohydrates and proteins, which correlated with effluent organic matter and effluent chemical oxygen demand (COD) compounds. Therefore, membrane fouling trends would benefit from low supernatant COD (378 mg L-1) and a low membrane removal rate (26 %) at a HRT of 36 h. Serious membrane fouling at 72 and 24 h was related to soluble microbial products and extracellular polymeric substances in mixed liquor, respectively. Based on the TMP decrease and flux recovery after physical and chemical cleaning, irremovable fouling aggravation was related to extracellular polymeric substances' increase and soluble microbial products' decrease. According to changes in the specific oxygen uptake rate (SOUR) and mixed liquor suspended solids (MLSSs) during HRT optimization in this study, antibiotic production wastewater largely inhibited MLSS growth, which only increased from 4.5 to 5.0 g L-1 when HRT was decreased from 72 to 24 h, but did not limit sludge activity. The results of a principal component analysis highlighted both proteins and carbohydrates in extracellular polymeric substances as the primary foulants. Membrane fouling associated with the first principal component was positively related to extracellular polymeric substances and negatively related to soluble microbial products. Principal component 2 was primarily related to proteins in the influent. Additional membrane fouling factors included biomass characteristics, operational conditions, and feed characteristics.

Enrichment and characterization of microbial consortia degrading soluble microbial products discharged from anaerobic methanogenic bioreactors.

Soluble microbial products (SMP) produced in bioprocesses have been known as a main cause to decrease treatment efficiency, lower effluent quality, and promote membrane fouling in water reclamation plants. In this study, biological degradation of SMP using selectively enriched microbial consortia in a down-flow hanging sponge (DHS) reactor was introduced to remove SMP discharged from anaerobic methanogenic reactors. On average, 68.9-87.5% SMP removal was achieved by the enriched microbial consortia in the DHS reactor for >800 days. The influent SMP fed to the DHS reactor exhibited a bimodal molecular weight (MW) distribution with 14-20 kDa and <4 kDa. Between these two types of SMP, the small MW SMP were biodegraded in the upper part of the reactor, together with most of the large MW SMP. Using 16S rRNA gene pyrosequencing technology, the microbial community composition and structure were characterized and correlated with operational factors, such as hydraulic retention time, organic loading rate, and removal of soluble chemical oxygen demand at different depths of the reactor, by performing network and redundancy analyses. The results revealed that Saprospiraceae was strongly correlated to the increasing SMP loading condition, indicating positive co-occurrences with neighboring bacterial populations. Different microbial diversity along with the depth of the reactor implies that stratified microbial communities could participate in the process of SMP degradation. Taken together, these observations indicate that the spatial and temporal variability of the enriched microbial community in the DHS reactor could effectively treat SMP with respect to changes in the operational factors.

The effectiveness of coagulation for water reclamation from a wastewater treatment plant that has a long hydraulic and sludge retention times: A case study.

Coagulation is a feasible process to reclaim municipal wastewater, however, the role of coagulation in removing effluent organic matter (EfOM) from underutilized wastewater treatment plants (WWTPs) has not been fully explored. We identified the characteristics of the EfOM from a typical underutilized WWTP (i.e., the ratio of actual capacity to design capacity is 50%-70%), and investigated the performance of coagulation on suspended solids (SS) and dissolved organic matter (DOM) removal. The effluent could even satisfy the highest national standard of China (Class 1 A) for WWTP effluent, as evaluated by the traditional parameters such as SS and chemical oxygen demand (COD). However, the DOM in the EfOM we studied contained considerable biomass-associated products (BAPs), which were dominated by proteins with a molecular weight of approximately 150 kDa. In addition, protein also dominated the DOM after coagulation. Fulvic acid and humic-like acid organics were poorly removed by either AlCl3 or polyaluminum chloride (PAC) coagulation, even with a dosage as high as 24 mg Al L(-1). Biodegradability was very poor, as the ratio of biological oxygen demand (BOD5) to COD was less than 0.17. After coagulation the typical BAPs, protein and polysaccharide, remained as high as 1.6 mg L(-1) and 1.2 mg L(-1) respectively. In this study we found coagulation was ineffective for removal of recalcitrant BAPs.

Terminating pre-ozonation prior to biological activated carbon filtration results in increased formation of nitrogenous disinfection by-products upon subsequent chlorination.

Previous research demonstrated that ozone dosed before biological activated carbon (BAC) filtration reduces the formation of disinfection by-products (DBPs) upon subsequent chlorination. The current work aimed to evaluate the impact of terminating this pre-ozonation on the ability of the BAC to remove the precursors of N-DBPs. More N-DBP precursors passed into the post-BAC water when the pre-ozonation was terminated, resulting in greater formation of N-DBPs when the water was subsequently chlorinated, compared to a parallel BAC filter when the pre-ozonation was run continuously. Moreover, the N-DBP formation potential was significantly increased in the effluent of the BAC filter after terminating pre-ozonation, compared with the influent of the BAC filter (i.e. the effluent from the sand filter). Therefore, while selectively switching pre-ozonation on/off may have cost and other operational benefits for water suppliers, these should be weighed against the increased formation of N-DBPs and potential associated health risks.

Characterization of the proton binding sites of extracellular polymeric substances in an anaerobic membrane bioreactor.

This paper focuses on the characterization of the chemical compositions and acidic constants of the extracellular polymeric substances (EPSs) in an anaerobic membrane bioreactor treating synthetic brewery wastewater by using chemical analysis, linear programming analysis (LPA) of titration data, and FT-IR analysis. The linear programming analysis of titration data revealed that the EPSs have proton binding sites with pKa values from pKa ≤ 6, between 6 and 7, and approximately 9.8. The strong acidic sites (pKa ≤ 6) and some weak acidic sites (7.5 < pKa < 9.0) were found to be readily removed by 0.45-µm membrane filtration. In addition, the FT-IR analysis confirmed the presence of proteins, carbohydrates, nucleic acids, and lipids in the EPS samples. Based on the FT-IR analysis and the main chemical functional groups at the bacterial cell surfaces, the identified proton binding sites were related to carboxyl, phosphate, and hydroxyl/amine groups with pKa values of 4.6 ± 0.7, 6.6 ± 0.01, and 9.7 ± 0.1, respectively, with the corresponding respective intensities of 0.31 ± 0.05, 0.96 ± 0.3, and 1.53 ± 0.3 mmole/g-EPS. The pKa values and intensities of the proton binding sites are the fundamental molecular properties of EPSs that affect the EPS charge, molecular interactions, and metal complexation characteristics. Determination of such properties can advance Derjaguin-Landau-Verwey-Overbeek (DLVO)-based concentration polarization modeling, facilitate the estimation of the osmotic pressure of the EPS concentration polarization layers, and lead to a deeper understanding of the role of metal complexation in membrane fouling.

Spectrometric characterization of the effluent dissolved organic matter from an anammox reactor shows correlation between the EEM signature and anammox growth.

Anaerobic ammonium oxidation (anammox) is a cost-effective process to treat high-strength nitrogenous wastewater. Even without organic carbon input, the effluent contains bioproducts from autotrophic and heterotrophic bacteria. In this work, excitation-emission matrix (EEM) fluorescence spectroscopy was used to characterize the effluent dissolved organic matter (EfOM) from an anammox reactor treating synthetic wastewater. Two dominant EEM components were identified as humic acid-like (component 1) and protein-like (component 2) substances with excitation/emission peaks at <240, 355, 420/464 nm and <240, 280, 330/346 nm, respectively. The presence of both compounds in the effluent was tracked during an activity recovery period (nitrogen load increased from 0.2 to 1.3 kg Nm(-3)d(-1)). The effluent concentration of both components increased during this period, indicating correlation between production and bacterial activity. The dynamics of these bioproducts during both substrate consumption and starvation phases was analyzed in batch experiments. Component 1 was only formed during substrate consumption in a rate proportional to ammonium removal and was considered an up-take associated product characteristic of anammox activity. The results show that the composition of the EfOM was qualitatively and quantitatively influenced by process performance. Monitoring the EfOM could, therefore, offer a useful approach to assess anammox process performance and must be further explored.

Scientific basis of dissolved organic carbon limitation for landfilling of municipal treatment sludge--is it attainable and justifiable?

This study evaluated the scientific and technical basis of the dissolved organic carbon (DOC) limitation imposed on municipal sludge for landfilling, mainly for assessing the attainability of the implemented numerical level. For this purpose, related conceptual framework was analyzed, covering related sewage characteristics, soluble microbial products generation, and substrate solubilization and leakage due to hydrolysis. Soluble COD footprint was experimentally established for a selected treatment plant, including all the key steps in the sequence of wastewater treatment and sludge handling. Observed results were compared with reported DOCs in other treatment configurations. None of the leakage tests performed or considered in the study could even come close to the prescribed limitation. All observed results reflected 10-20 fold higher DOC levels than the numerical limit of 800 mg/kg (80 mg/L), providing conclusive evidence that the DOC limitation imposed on municipal treatment sludge for landfilling is not attainable, and therefore not justifiable on the basis of currently available technology.