Evaluating an integrated nano zero-valent iron column system for emerging contaminants removal from different wastewater matrices - Identification of transformation products.

The presence of micropollutants in water bodies has become a growing concern due to their persistence, bioaccumulation and potential toxicological effects on aquatic life and humans. In this study, the performance of a column system consisting of zero-valent iron nanoparticles (nZVI) incorporated into a cationic resin and synthesized from green tea extract with the addition of persulfate for the elimination of selected pharmaceuticals and endocrine disruptors from wastewater is evaluated. Ibuprofen, naproxen, diclofenac and ketoprofen were the target pharmaceuticals from non-steroidal anti-inflammatory drugs group, while bisphenol A was the target endocrine disruptor. In this context, different real wastewater effluent matrices were investigated: anaerobic membrane bioreactor (AnMBR), upflow anaerobic sludge blanket reactor (UASB) after microfiltration, tertiary treated by conventional activated sludge system and saturated vertical constructed wetland followed by a sand filtration unit effluent (hybrid). The transformation products of diclofenac and bisphenol A were also identified. The experimental results indicated that the performance of the R-nFe/PS system towards the removal efficiency of the target compounds was enhanced in the order of effluents: tertiary > AnMBR ≈ hybrid > UASB. More than 70% removal was obtained for almost all target compounds when conventional tertiary effluent was used, while the maximum removal efficiency was about 50% in the case of filtered UASB. As far as we know, this is the first time that nZVI has been assessed in combination with persulfate for the removal of micropollutants in a continuous flow system receiving various types of real wastewater with different matrix characteristics.

Integrated selection of PHA-storing biomass and nitrogen removal via nitrite from sludge reject water: a mathematical model.

One of the most recent innovations to promote a circular economy during wastewater treatment is the production of biopolymers. It has recently been demonstrated that it is possible to integrate the production of biopolymers in the form of polyhydroxyalkanoates (PHA) with nitrogen removal via nitrite during the treatment of sludge reject water. In the present study, simulation of a new process for bioresource recovery was conducted by an appropriate modification of the Activated Sludge Model 3. The process consists of the integrated nitrogen removal via nitrite from sludge reject water and the selection of PHA-storing biomass by inducing a feast and famine regime under aerobic and anoxic conditions. According to the results, it is anticipated that simulation data matched very satisfactorily with the experimental data and confirmed the main experimental observation, showing that during the famine period the PHA depletion was almost complete due to the availability of nitrite as the electron acceptor. Simulation results indicate that the selection of the volumetric organic loading rate and of the relative duration of the aerobic feast/anoxic famine duration is critical in order to allow for the effective denitritation of the internally stored PHA during the famine phase.

Inhibition of free nitrous acid and free ammonia on polyphosphate accumulating organisms: Evidence of insufficient phosphorus removal through nitritation-denitritation.

The purpose of this study is to investigate the effect of Free Nitrous Acid (FNA) and Free Ammonia (FA) on enhanced biological phosphorus removal (EBPR) and in particular on the aerobic phosphorus uptake rate (PUR). To this end, a PAO-enriched biomass was developed at a lab-scale reactor in order to fuel a series of ex-situ batch experiments to test the effect of various nitrite or ammonium concentrations on the phosphorus uptake rate at different pH values. FNA was found to be a strong inhibitor of EBPR, in agreement with other studies with PUR being inhibited by 50 % under 1.5 µg HNO2-N L-1 and 100 % at 13 µg HNO2-N L-1. FA was also found to inhibit EBPR with PUR being inhibited by 50 % under 6.4 mg NH3-N L-1. The results of this study suggest that EBPR under high nitrogen loading alongside nitritation-denitritation may not be a viable option.

Fate of Emerging Contaminants in High-Rate Activated Sludge Systems.

High-rate activated sludge (HRAS) systems are designed to shift the energy-intensive processes to energy-saving and sustainable technologies for wastewater treatment. The high food-to-microorganism (F/M) ratios and low solid retention times (SRTs) and hydraulic retention times (HRTs) applied in HRAS systems result in the maximization of organic matter diversion to the sludge which can produce large amounts of biogas during anaerobic digestion, thus moving toward energy-neutral (or positive) treatment processes. However, in addition to the energy optimization, the removal of emerging contaminants (ECs) is the new challenge in wastewater treatment. In the context of this study, the removal efficiencies and the fates of selected ECs (three endocrine disruptors (endocrine disrupting chemicals (EDCs))-nonylphenol, bisphenol A and triclosan, and four pharmaceuticals (PhACs)-ibuprofen, naproxen, diclofenac and ketoprofen) in HRAS systems have been studied. According to the results, EDCs occurred in raw wastewater and secondary sludge at higher concentrations compared to PhACs. In HRAS operating schemes, all compounds were poorly (<40%) to moderately (<60%) removed. Regarding removal mechanisms, biotransformation was found to be the dominant process for PhACs, while for EDCs sorption onto sludge is the most significant removal mechanism affecting their fates and their presence in excess sludge.

Analytical and mathematical assessment of emerging pollutants fate in a river system.

The fate of several emerging pollutants in a Greek river system was assessed through analytical measurements and mathematical modelling. Target compounds selected in this study consist of five endocrine disrupting chemicals and four non-steroidal anti-inflammatory drugs. Two sampling campaigns were implemented to assess target compounds concentrations along the river system during dry period. Furthermore a mathematical model was developed in order to simulate the spatial distribution of target compounds concentration. The mathematical model describes several abiotic and biotic processes (sorption, photodegradation, biodegradation, biotransformation) in order to account for the removal of target compounds. Following sensitivity analysis, the model was calibrated and validated against measured values. Environmental risk assessment was performed based on both analytical measurements and simulation results. Uncertainty analysis was also conducted by applying Monte Carlo technique. According to the results the simulation data matched very satisfactorily with the analytical measurements, thus confirming the main experimental observations showing that the primary removal mechanism for the photo-sensitive chemicals is photodegradation, the latter being mostly influenced by weather conditions and river general quality characteristics (e.g. chlorophyll, turbidity). Model results demonstrate a gradual increase of uncertainty from the upstream to the downstream of the river system for all target compounds.

Assessment of the environmental fate of endocrine disrupting chemicals in rivers.

Laboratory tests were conducted with five endocrine disruptors (bishenol A, triclosan. nonylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate) under different redox conditions (aerobic, anoxic, anaerobic and sulfate-reducing conditions) to assess abiotic and biotic degradation in a river water/sediment system. The river water sample was collected from Spercheios River while the sediment was collected from the banks of a tributary of the river at the point where the discharge point of a wastewater treatment plant is located. To describe quantitatively elimination kinetics of the target compounds, pseudo first-order kinetics were adopted. According to the results from the microcosms studies, it can be stated that the substances are eliminated from the aqueous phase with relatively high rates under aerobic conditions due to both sorption and biotransformation processes. However, when reduced oxygen conditions were established in the microcosms incubations, biotransformation decreased, indicating the almost complete cease of the EDCs microbial degradation, while substances' sorption onto sediments showed no significant differences. All compounds were found to be biodegradable under aerobic conditions, and the low to high order of the calculated dissipation rate constants was 0.064±0.004d-1 (TCS)→0.067±0.006d-1 (NP)→0.076±0.009d-1 (NP2EO)→0.081±0.007d-1 (NP1EO)→0.103±0.011d-1 (BPA). Finally, regarding the biotransformation experiments, the elimination of the compounds limited in the absence of oxygen as compared to aerobic.

A review on nitrous oxide (N2O) emissions during biological nutrient removal from municipal wastewater and sludge reject water.

Nitrous oxide (N2O) is an important pollutant which is emitted during the biological nutrient removal (BNR) processes of wastewater treatment. Since it has a greenhouse effect which is 265 times higher than carbon dioxide, even relatively small amounts can result in a significant carbon footprint. Biological nitrogen (N) removal conventionally occurs with nitrification/denitrification, yet also through advanced processes such as nitritation/denitritation and completely autotrophic N-removal. The microbial pathways leading to the N2O emission include hydroxylamine oxidation and nitrifier denitrification, both activated by ammonia oxidizing bacteria, and heterotrophic denitrification. In this work, a critical review of the existing literature on N2O emissions during BNR is presented focusing on the most contributing parameters. Various factors increasing the N2O emissions either per se or combined are identified: low dissolved oxygen, high nitrite accumulation, low chemical oxygen demand to nitrogen ratio, slow growth of denitrifying bacteria, uncontrolled pH and temperature. However, there is no common pattern in reporting the N2O generation amongst the cited studies, a fact that complicates its evaluation. When simulating N2O emissions, all microbial pathways along with the potential contribution of abiotic N2O production during wastewater treatment at different dissolved oxygen/nitrite levels should be considered. The undeniable validation of the robustness of such models calls for reliable quantification techniques which simultaneously describe dissolved and gaseous N2O dynamics. Thus, the choice of the N-removal process, the optimal selection of operational parameters and the establishment of validated dynamic models combining multiple N2O pathways are essential for studying the emissions mitigation.

Environmental fate of non-steroidal anti-inflammatory drugs in river water/sediment systems.

Laboratory tests were conducted with four non-steroidal anti-inflammatory drugs (naproxen, ibuprofen, diclofenac and ketoprofen) under different redox conditions (aerobic, anoxic, anaerobic and sulfate-reducing conditions) in order to assess abiotic and biotic degradation in a river water/sediment system. The river water was sampled from Sperchios River and the sediment was collected from the banks of a rural stream where the discharge point of a wastewater treatment plant is located. To quantitatively describe degradation kinetics of the selected compounds, pseudo first-order kinetics were adopted. According to the results, it can be stated that the concentration of the substances remained constant or decreased only marginally (p≥0.05) in the sterile experiments and this excludes abiotic processes such as hydrolysis or sorption as major removal mechanisms of the target compounds from the water phase and assign their removal to microbial action. Results showed that the removal rate of the compounds decreases as dissolved oxygen concentration in the river water/sediment system decreases. All compounds were found to be biodegradable under aerobic conditions at dissipation half-lives between 1.6 and 20.1days, while dissipation half-lives for naproxen and ketoprofen increase by a factor of 2 under all tested conditions in the absence of oxygen.

Chlorination of benzothiazoles and benzotriazoles and transformation products identification by LC-HR-MS/MS.

The fate of four benzotriazoles [1-H-benzotriazole (1-H-BTRi), tolyltriazole (TTRi), xylyltriazole (XTRi) and 1-hydroxy-benzotriazole (1-OH-BTRi)] and three benzothiazoles [benzothiazole (BTH), 2-hydroxy-benzothiazole (2-OH-BTH) and 2-amino-benzothiazole (2-amino-BTH)], during chlorination batch experiments was investigated. In the first step, their degradation under different experimental conditions (applied molar ratio of NaOCl and the target contaminant (m.r.), reaction's contact time, pH value of the reaction's solution and the influence of total suspended solids (TSS) presence) was investigated and their removal kinetics parameters (kobs and t1/2) were determined. In the second step, LC-QTOFMS/MS was used for the detection and identification of transformation products (TPs) formed during chlorination, through the application of suspect and non-target screening approaches. Four and five TPs of XTRi and 2-amino-BTH, respectively, were detected and tentatively identified, while 1-H-BTRi was proven to be formed by the chlorination of 1-OH-BTRi. Moreover, since the identified TPs were also detected in spiked wastewater samples, after lab-scale chlorination experiments, toxicity assessment was carried out by ECOSAR calculations for the environmental relevance of their occurrence. The proposed chlorinated TPs were proven to be more toxic than their parent compounds.

Biological groundwater treatment for chromium removal at low hexavalent chromium concentrations.

The objective of this work is to develop and evaluate biological groundwater treatment systems that will achieve hexavalent chromium reduction and total chromium removal from groundwater at hexavalent chromium (Cr(VI)) groundwater concentrations in the 0-200 µg/L range. Three lab-scale units operated, as sequencing batch reactors (SBR) under aerobic, anaerobic and anaerobic-aerobic conditions. All systems received groundwater with a Cr(VI) content of 200 µg/L. In order to support biological growth, groundwater was supplemented with milk, liquid cheese whey or a mixture of sugar and milk to achieve a COD concentration of 200 mg/L. The results demonstrate that a fully anaerobic system or an anaerobic-aerobic system dosed with simple or complex external organic carbon sources can lead to practically complete Cr(VI) reduction to Cr(III). The temperature dependency of maximum Cr(VI) removal rates can be described by the Arrhenius relationship. Total chromium removal in the biological treatment systems was not complete because a significant portion of Cr(III) remained in solution. An integrated system comprising of an anaerobic SBR followed by a sand filter achieved more than 95% total chromium removal thus resulting in average effluent total and dissolved chromium concentrations of 7 µg/L and 3 µg/L, respectively.

Degradation of emerging contaminants from water under natural sunlight: The effect of season, pH, humic acids and nitrate and identification of photodegradation by-products.

Both photodegradation and hydrolysis of non-steroidal anti-inflammatory drugs (NSAIDs) and endocrine disrupting chemicals (EDCs) were investigated in order to evaluate their photochemical fate in aquatic environment and to assess the effect of season and specific characteristics of water (pH, humic acids and nitrate concentration) on the removal of target EDCs and NSAIDs through photodegradation. An additional objective was the identification of the photodegradation by-products of specific NSAIDs and their dependence on irradiation time. Selected compounds' transformation was investigated under natural sunlight radiation while control experiments were conducted in the dark. As expected, most of compounds' degradation rate decreased with decreasing light intensity between two different experimental periods. Most of the tested compounds exhibited different rates of degradation during direct and indirect photolysis. The degradation rate of the selected compounds increased in the presence of NO3(-) and the photodegradation rate was higher for some compounds in alkaline than in acidic solution. The effect of humic acids' presence in the water depends on the absorbance spectrum of the compound and the produced photosensitizers. More specifically, humic acids act as inner filter toward most of the selected NSAIDs and as photosensitizers toward most of the EDCs. The results of the irradiation experiments in the presence of both humic acids and NO3(-), indicate that the direct photolysis is much more efficient than indirect photochemical processes. Finally, several degradation by-products of ketoprofen and diclofenac were identified in the samples, exposed to sunlight. The dependence of these by-products on radiation time is also demonstrated.

Removal of endocrine disruptors and non-steroidal anti-inflammatory drugs through wastewater chlorination: the effect of pH, total suspended solids and humic acids and identification of degradation by-products.

Endocrine disrupting chemicals (EDCs) and non-steroidal anti-inflammatory drugs (NSAIDs) are two groups of emerging pollutants the significance of which rests on their persistent detection in the aquatic environment and their possible adverse effects. Wastewater treatment plants are one of the major ways for transporting such chemicals in the aquatic environment. Chlorination is usually the last stage of treatment before wastewater being disposed to the aquatic environment. This work focuses on the evaluation of the effect of chlorine dose and specific wastewater characteristics (pH, total suspended solids and humic acids) on the removal of target EDCs and NSAIDs through chlorination. Another objective of this study is the identification of chlorination by-products of specific EDCs and NSAIDs and their dependence on contact time. Based on the results it is concluded that the effect of chlorine dose and humic acids concentration on the degradation of target compounds during chlorination is minimal. On the contrary, pH is a critical parameter which highly affects process performance. Moreover, it is concluded that not only the free available chlorine species, but also the properties of EDCs and NSAIDs under different pH conditions can affect chlorination process performance. The effect of TSS on the degradation of the target compounds during chlorination is more profound for chemicals with high Kow values and therefore higher affinity to partition to the particulate phase (i.e. nonylphenols, triclosan). Several degradation by-products were identified through chlorination of nonylphenol, bisphenol A and diclofenac. The dependence of these by-products on chlorination contact time is also demonstrated.

The role of activated carbon and disinfection on the removal of endocrine disrupting chemicals and non-steroidal anti-inflammatory drugs from wastewater.

Endocrine disrupting chemicals and non-steroidal anti-inflammatory drugs are two important groups of emerging pollutants due to their toxicological and chemical characteristics and their persistent detection in the aquatic environment. Wastewater treatment plants are a significant pathway for their transfer to the water courses. It is well evidenced that these chemicals are only partially removed through biological treatment of wastewater and therefore being detected in secondary effluents. This work focuses on the evaluation of the efficiency of two well-established disinfection technologies (chlorination and UV irradiation) along with UV/H2O2 and powdered activated carbon (PAC) to remove these chemicals from biologically treated wastewater. Based on the results it is shown that appreciable removal efficiencies due to chlorination should be expected for most of the target compounds, whereas this was not the case for ibuprofen and ketoprofen. With the exemption of diclofenac and ketoprofen direct UV irradiation did not efficiently removed target compounds for UV doses usually applied for disinfection purposes. The application of advanced UV treatment through the addition of H2O2 although resulted in increased removal of the target compounds is not sufficient at moderate UV and H2O2 doses to achieve satisfactory removal efficiencies. PAC use resulted in sufficient removal of target compounds although high PAC doses were required for some chemicals. Comparison of Freundlich isotherms of this study with those of other studies, derived employing water samples, suggested that the water matrix along with the target compounds concentration range can significantly affect the outcome of the experiments.

A hypothesis on Microthrix parvicella proliferation in biological nutrient removal activated sludge systems with selector tanks.

The objective of this study was to evaluate the ability of Microthrix parvicella for long-chain fatty acids uptake under anaerobic, anoxic, and aerobic conditions as well as its ability to utilize volatile fatty acids and long-chain fatty acids under anoxic and aerobic conditions. According to the results, a hypothesis on the competition between floc-forming microorganisms and M. parvicella for long-chain fatty acids uptake under aerobic, anoxic, and anaerobic conditions was formulated. According to this hypothesis, M. parvicella exhibits similar long-chain fatty acids uptake capacity with floc-forming microorganisms even at relatively high floc loading values that are very often imposed at selector tanks. Following this hypothesis, the failure of selector tanks to provide for an effective M. parvicella control is evidenced. Based on the experimental results, the ability of M. parvicella to utilize long-chain fatty acids with rates comparable to those of floc formers, even in anoxic conditions, in conjunction with its lower acetate utilization rates, provides a good explanation regarding its preference to slowly biodegradable organic carbon compounds.

Investigation of long-term operation and biomass activity in a membrane bioreactor system.

The aim of this work was to evaluate the long-term performance of a Membrane Bioreactor (MBR) that operated continuously for 2.5 years and to assess membrane fouling and biomass activity under various operating conditions. Furthermore, a method for the characterisation of influent wastewater was developed based on its separation into various fractions. The MBR system operated at the solids retention times (SRT) of 10, 15, 20 and 33 days. The increase of SRT resulted in a decrease of the fouling rate associated with the reduction of extracellular polymeric substances. Moreover, the SRT increase resulted in a significant reduction of the Oxygen Uptake Rate (OUR) due to the lower availability of substrate and in a notable decrease of the maximum OUR since high SRT allowed the development of slower growing microorganisms. Biomass consisted of small flocs due to extensive deflocculation caused by intense aeration. Finally, the method developed for wastewater characterisation is straightforward and less time consuming than the usual method that is employed.

Comparison of bioluminescence and nitrification inhibition methods for assessing toxicity to municipal activated sludge.

The aim of this study was to compare two alternative toxicity assessment methods to determine wastewater toxicity and predict treatment plant process upsets. The toxicity of two synthetic organic compounds (triclosan and 4-n-nonylphenol), which are commonly detected in municipal wastewater, and municipal and industrial wastewaters with different heavy metals content were evaluated by the nitrification inhibition assay and bioluminescence toxicity test. Comparison between both assays confirmed that Vibrio fischeri is generally more sensitive than autotrophic bacteria, and, if not calibrated, the bioluminescence method tends to overestimate toxic effects on activated sludge biomass. The nitrification inhibition assay appears to predict plant process upsets more accurately. Both methods showed a significant toxicity decrease through treatment that could be partially attributed to the significant heavy metals removal obtained by primary and secondary treatment. A good correlation for the two assays was obtained, as indicated by a high correlation coefficient (r2 = 0.80).