Treatment of micropollutants in wastewater: Balancing effectiveness, costs and implications.

In this contribution, we analyse scenarios of advanced wastewater treatment for the removal of micropollutants. By this we refer to current mainstream, broad spectrum processes including ozonation and sorption onto activated carbon. We argue that advanced treatment requires properly implemented tertiary (nutrient removal) treatment in order to be effective. We review the critical aspects of the main advanced treatment options, their advantages and disadvantages. We propose a quantification of the costs of implementing advanced treatment, as well as upgrading plants from secondary to tertiary treatment when needed, and we illustrate what drives the costs of advanced treatment for a set of standard configurations. We propose a cost function to represent the total costs (investment, operation and maintenance) of advanced treatment. We quantify the implications of advanced treatment in terms of greenhouse gas emissions. Based on the indicators of total toxic discharge, toxicity at the discharge points and toxicity across the stream network discussed in Pistocchi et al. (2022), we compare costs and effectiveness of different scenarios of advanced treatment. In principle the total toxic load and toxicity at the points of discharge could be reduced by about 75 % if advanced treatment processes were implemented virtually at all wastewater treatment plants, but this would entail costs of about 4 billion euro/year for the European Union as a whole. We consider a "compromise" scenario where advanced treatment is required at plants of 100 thousand population equivalents (PE) or larger, or at plants between 10 and 100 thousand PE if the dilution ratio at the discharge point is 10 or less. Under this scenario, the length of the stream network exposed to high toxicity would not increase significantly compared to the previous scenario, and the other indicators would not deteriorate significantly, while the costs would remain at about 1.5 billion Euro/year. Arguably, costs could be further reduced, without a worsening of water quality, if we replace a local risk assessment to generic criteria of plant capacity and dilution in order to determine if a WWTP requires advanced treatment.

Ozonation of 47 organic micropollutants in secondary treated municipal effluents: Direct and indirect kinetic reaction rates and modelling.

Micropollutants like pharmaceuticals, hormones and pesticides are still found in treated municipal wastewater. An effective way to degrade micropollutants is to use oxidants such as ozone or hydroxyl radicals. We designed an innovative experimental protocol combining batch experiments and a study of a full-scale WWTP to understand and predict the removal via ozonation of typical micropollutants present in secondary treated effluents. First, the direct and indirect ozonation of 47 organic micropollutants was scrutinized, then a model was developed and calibrated to simulate the ozone transfers and the oxidation of the selected micropollutants. The kinetic rate constants between micropollutants and ozone or hydroxyl radicals (OH●) were determined for 47 micropollutants found in secondary treated effluent. We classified the micropollutants into low- (kO3 between 1.50 and 4.47 × 102 L mol-1. s-1), medium- (kO3 between 1.31 × 103 and 4.92 × 103 L mol-1. s-1) and high-oxidizable groups (kO3 between 9.44 × 104 and 8.18 × 106 L mol-1. s-1) according to their reactivity with ozone, and identified the major degradation pathways for all 47 micropollutants. Micropolluants of the low- and medium-oxidizable groups were largely eliminated by the indirect pathway, at 96% and 84% on average, respectively. In contrast, micropollutants of high-oxidizable group were largely eliminated by the direct pathway, at 98% on average. The model successfully simulated the direct and indirect ozonation of the 47 micropollutants in batch experiments and confirmed the predominant pathways for each group. Finally, the model was applied to the full-scale ozonation process operated at an ozone dose ranging from 0.5 to 1.6 gO3. gDOC-1. The model was found to reliably simulate the ozonation-process removal efficiencies for 4 micropollutants (imidacloprid, fenofibric acid, metronidazole and ketoprofen).

Influence of water depth and season on the photodegradation of micropollutants in a free-water surface constructed wetland receiving treated wastewater.

Micropollutants such as pharmaceutical products and pesticides are still present in treated wastewater. Several of these compounds are photoactive, either by direct or indirect photodegradation. An innovative on-site experimental protocol was designed to investigate the contribution of photodegradation processes to eliminate micropolluants in constructed wetland (CW). The solar photodegradation of 23 organic micropollutants was studied using in situ photoreactors at different depths. A CW-photodegradation model was designed and calibrated to further scrutinize the contribution of direct and indirect photodegradation processes in the elimination of micropollutants. The results show that photodegradation is most effective in the first 10 cm of the water column. A classification of micropollutants in 3 groups was developed to characterize their photodegradation. A significant increase of the half-life by direct photodegradation was observed in winter compared to summer due to a lower light intensity in winter. On the opposite, for direct + indirect photodegradation, no significant difference was observed between seasons. The decrease in light intensity in winter was compensated by higher nitrates concentration which promoted the formation of hydroxyl radicals and increased indirect photodegradation. The CW-photodegradation model successfully simulated the measured concentrations for direct and indirect photodegradation for 23 micropolluants. Nonetheless, it overestimated the indirect photodegradation with hydroxyl radicals when using default parameter values derived for surface waters. Hence, the consumption of hydroxyl radicals was increased by a factor of 20 for treated water. This model highlighted the predominance of direct photodegradation in the elimination of all micropollutants, except sotalol for the winter campaign.

Understanding the contribution of biofilm in an integrated fixed-film-activated sludge system (IFAS) designed for nitrogen removal.

The objective of this study is to improve knowledge on the integrated fixed-film-activated sludge (IFAS) system designed for nitrogen removal. Biofilm growth and its contribution to nitrification were monitored under various operating conditions in a semi-industrial pilot-scale plant. Nitrification rates were observed in biofilms developed on free-floating media and in activated sludge operated under a low sludge retention time (4 days) and at an ammonia loading rate of 45-70 gNH4-N/kgMLVSS/d. Operational conditions, i.e. oxygen concentration, redox potential, suspended solids concentration, ammonium and nitrates, were monitored continuously in the reactors. High removal efficiencies were observed for carbon and ammonium at high-loading rate. The contribution of biofilm to nitrification was determined as 40-70% of total NOx-N production under the operating conditions tested. Optimal conditions to optimize process compacity were determined. The tested configuration responds especially well to winter and summer nitrification conditions. These results help provide a deeper understanding of how autotrophic biomass evolves through environmental and operational conditions in IFAS systems.

Lab-scale experimental strategy for determining micropollutant partition coefficient and biodegradation constants in activated sludge.

The nitrifying/denitrifying activated sludge process removes several micropollutants from wastewater by sorption onto sludge and/or biodegradation. The objective of this paper is to propose and evaluate a lab-scale experimental strategy for the determination of partition coefficient and biodegradation constant for micropollutant with an objective of modelling their removal. Four pharmaceutical compounds (ibuprofen, atenolol, diclofenac and fluoxetine) covering a wide hydrophobicity range (log Kow from 0.16 to 4.51) were chosen. Dissolved and particulate concentrations were monitored for 4 days, inside two reactors working under aerobic and anoxic conditions, and under different substrate feed conditions (biodegradable carbon and nitrogen). We determined the mechanisms responsible for the removal of the target compounds: (i) ibuprofen was biodegraded, mainly under aerobic conditions by cometabolism with biodegradable carbon, whereas anoxic conditions suppressed biodegradation; (ii) atenolol was biodegraded under both aerobic and anoxic conditions (with a higher biodegradation rate under aerobic conditions), and cometabolism with biodegradable carbon was the main mechanism; (iii) diclofenac and fluoxetine were removed by sorption only. Finally, the abilities of our strategy were evaluated by testing the suitability of the parameters for simulating effluent concentrations and removal efficiency at a full-scale plant.

Removal of xenobiotics from effluent discharge by adsorption on zeolite and expanded clay: an alternative to activated carbon?

Xenobiotics such as pesticides and pharmaceuticals are an increasingly large problem in aquatic environments. A fixed-bed adsorption filter, used as tertiary stage of sewage treatment, could be a solution to decrease xenobiotics concentrations in wastewater treatment plants (WWTPs) effluent. The adsorption efficiency of two mineral adsorbent materials (expanded clay (EC) and zeolite (ZE)), both seen as a possible alternative to activated carbon (AC), was evaluated in batch tests. Experiments involving secondary treated domestic wastewater spiked with a cocktail of ten xenobiotics (eight pharmaceuticals and two pesticides) known to be poorly eliminated in conventional biological process were carried out. Removal efficiencies and partitions coefficients were calculated for two levels of initial xenobiotic concentration, i.e, concentrations lower to 10 µg/L and concentrations ranged from 100 to 1,000 µg/L. While AC was the most efficient adsorbent material, both alternative adsorbent materials showed good adsorption efficiencies for all ten xenobiotics (from 50 to 100 % depending on the xenobiotic/adsorbent material pair). For all the targeted xenobiotics, at lower concentrations, EC presented the best adsorption potential with higher partition coefficients, confirming the results in terms of removal efficiencies. Nevertheless, Zeolite presents virtually the same adsorption potential for both high and low xenobiotics concentrations to be treated. According to this first batch investigation, ZE and EC could be used as alternative absorbent materials to AC in WWTP.

Modelling of micropollutant removal in biological wastewater treatments: a review.

Modelling the fate of micropollutants through wastewater treatment plants is of present concern. Indeed, such a tool is useful to increase the removal of micropollutants and reduce their release to the environment. In this paper, 18 literature models describing micropollutant removal in activated sludge processes were reviewed. Investigated micropollutants were mainly volatile organic compounds, metals, surfactants, pesticides and pharmaceutical compounds. This work provides a detailed insight about the main mechanisms leading to the micropollutant removal (volatilisation, sorption, biodegradation, cometabolism), the associated mathematical equations and the parameter values found in the literature. A critical analysis was carried out to evaluate the conditions and the domain of validity for which each model was set-up. We also propose (i) an inventory of the experimental methodologies applied to determine the values of model parameters, (ii) a critical study of the main differences between models and (iii) suggestions for a standardisation of calibration methodologies. Finally, this review highlights the lack of explanation concerning the domain of validity of the models and proposes future developments to improve modelling of micropollutant removal in wastewater treatment plants.

A calibration protocol of a one-dimensional moving bed bioreactor (MBBR) dynamic model for nitrogen removal.

This work suggests a procedure to correctly calibrate the parameters of a one-dimensional MBBR dynamic model in nitrification treatment. The study deals with the MBBR configuration with two reactors in series, one for carbon treatment and the other for nitrogen treatment. Because of the influence of the first reactor on the second one, the approach needs a specific calibration strategy. Firstly, a comparison between measured values and simulated ones obtained with default parameters has been carried out. Simulated values of filtered COD, NH(4)-N and dissolved oxygen are underestimated and nitrates are overestimated compared with observed data. Thus, nitrifying rate and oxygen transfer into the biofilm are overvalued. Secondly, a sensitivity analysis was carried out for parameters and for COD fractionation. It revealed three classes of sensitive parameters: physical, diffusional and kinetic. Then a calibration protocol of the MBBR dynamic model was proposed. It was successfully tested on data recorded at a pilot-scale plant and a calibrated set of values was obtained for four parameters: the maximum biofilm thickness, the detachment rate, the maximum autotrophic growth rate and the oxygen transfer rate.

Occurrence and fate of relevant substances in wastewater treatment plants regarding Water Framework Directive and future legislations.

The next challenge of wastewater treatment is to reliably remove micropollutants at the microgram per litre range. During the present work more than 100 substances were analysed through on-site mass balances over 19 municipal wastewater treatment lines. The most relevant substances according to their occurrence in raw wastewater, in treated wastewater and in sludge were identified, and their fate in wastewater treatment processes was assessed. About half of priority substances of WFD were found at concentrations higher than 0.1 µg/L in wastewater. For 26 substances, potential non-compliance with Environmental Quality Standard of Water Framework Directive has been identified in treated wastewater, depending on river flow. Main concerns are for Cd, DEHP, diuron, alkylphenols, and chloroform. Emerging substances of particular concern are by-products, organic chemicals (e.g. triclosan, benzothiazole) and pharmaceuticals (e.g. ketoprofen, diclofenac, sulfamethoxazole, carbamazepine). About 80% of the load of micropollutants was removed by conventional activated sludge plants, but about two-thirds of removed substances were mainly transferred to sludge.

On-site evaluation of the removal of 100 micro-pollutants through advanced wastewater treatment processes for reuse applications.

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet reuse applications and contribute to reach the good status of the water bodies. A hundred priority and relevant emerging substances were measured to evaluate at full-scale the removal efficiencies of seven advanced treatment lines (one membrane bioreactor process and six tertiary treatment lines) that were designed for reuse applications. To reliably compare the processes, specific procedures for micro-pollutants were applied for sampling, analysis and calculation of removal efficiencies. The membrane bioreactor process allowed to upgrade the removal efficiencies of about 20% of the substances measured, especially those that were partially degraded during conventional processes. Conventional tertiary processes like high rate clarification, sand filtration and polishing pond achieved significant removal for some micro-pollutants, especially for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient to complete the removal of polar pesticides and pharmaceuticals; metals and less polar substances were better retained by reverse osmosis.

Influent concentrations and removal performances of metals through municipal wastewater treatment processes.

This extensive study aimed at quantifying the concentrations and removal efficiency of 23 metals and metalloids in domestic wastewater passing through full-scale plants. Nine facilities were equipped with secondary biological treatment and three facilities were equipped with a tertiary treatment stage. The metals investigated were Li, B, Al, Ti, V, Cr, Fe, Ni, Co, Cu, Zn, As, Se, Rb, Mo, Ag, Cd, Sn, Sb, Ba, TI, Pb and U. Particulate and dissolved metals were measured using 24 h composite samples at each treatment stage. In influents, total concentrations of Cd, Sb, Co, Se, U, Ag, V were below a few microg/L, whereas at the other extremity Zn, B, Fe, Ti, Al were in the range of 0.1 to > 1 mg/L. It was demonstrated that secondary treatment stage (activated sludge, biodisc and membrane bioreactor) were efficient to remove most metals (removal rate > 70%), with the exception of B, Li, Rb, Mo, Co, As, Sb and V due to their low adsorption capacities. With the tested tertiary stages (polishing pond, rapid chemical settler, ozonation), a removal efficiency was obtained for Ti, Cr, Cd, Cu, Zn, Sn, Pb, Fe, Ag and Al, whereas a little removal (< 30%) was obtained for other metals.

Biochemical acidogenic potential in domestic wastewaters: effect of sampling and storage to characterize daily average composite samples.

To estimate the expectable enhanced biological phosphorus removal value of a wastewater, the concentration of volatile fatty acids (VFAs) and the biochemical acidogenic potential (BAP) are generally determined on grab samples of wastewater, as these variables are prone to rapid change after sampling. However, such sampling technique do not take into account the variations of these parameters during the day. This work has evaluated the changes of VFAs and BAP occurring during sampling and storage in an automatic sampler over 24 h. The consequences of waterfall oxygen input during sampling, and changes during storage (fermentation and sulfatereducing process) were studied. The results for two wastewaters showed that the sampling technique used for daily flow proportional composite samples provided a correct estimation of VFAs, and underestimated BAP by up to 25%. For hourly-average composite samples of wastewaters, significant modifications of the concentrations of these two parameters were recorded around the daily average values.

Limiting the emissions of micro-pollutants: what efficiency can we expect from wastewater treatment plants?

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet the environmental quality standards set by new regulations like the Water Framework Directive. The present work assessed the efficiency of different types of primary, secondary and tertiary processes for the removal of more than 100 priority substances and other relevant emerging pollutants through on-site mass balances over 19 municipal wastewater treatment lines. Secondary biological processes proved to be in average 30% more efficient than primary settling processes. The activated sludge (AS) process led to a significant reduction of pollution loads (more than 50% removal for 70% of the substances detected). Biofilm processes led to equivalent removal efficiencies compared to AS, except for some pharmaceuticals. The membrane bioreactor (MBR) process allowed to upgrade removal efficiencies of some substances only partially degraded during conventional AS processes. Preliminary tertiary processes like tertiary settling and sand filtration could achieve significant removal for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient (close to 100%) to complete the removal of polar pesticides and pharmaceuticals; less polar substances being better retained by reverse osmosis.

On-site evaluation of the efficiency of conventional and advanced secondary processes for the removal of 60 organic micropollutants.

The next challenge of wastewater treatment is to reliably remove micropollutants at the microgram per litre range in order to reduce the discharge for priority substances and to meet the environmental quality standards set by the European Water Framework Directive. The present work assessed the occurrence of 60 organic substances (priority substances and other relevant pollutants) in municipal wastewater and sludge. Their fate in the treatment processes and their removal efficiencies were quantified. Thorough on-site mass balances were carried out at 8 municipal wastewater treatment plants chosen among conventional and advanced secondary processes. It was found that 70% of the substances were quantified in raw wastewater and 50% in effluent, with a transfer without a limited degradation for most of them. Low loaded activated sludge (AS) process reduced the emission of more than half of micropollutants. At low sludge retention time (AS under high load), lower removal efficiencies were measured compared to low loaded AS. No influence of temperature of the biological reactor was shown. The membrane bioreactor process increased the removal efficiencies for one third of the substances that were partially removed with AS. Still, five substances were measured at concentrations exceeding the environmental quality standards at the outlet of the studied plants. In addition to efforts for source-reduction, complementary treatments need to be set-up.

Modelling a full scale membrane bioreactor using Activated Sludge Model No.1: challenges and solutions.

A full-scale membrane bioreactor (1,600 m(3) d(-1)) was monitored for modelling purposes during the summer of 2006. A complete calibration of the ASM1 model is presented, in which the key points were the wastewater characterisation, the oxygen transfer and the biomass kinetics. Total BOD tests were not able to correctly estimate the biodegradable fraction of the wastewater. Therefore the wastewater fractionation was identified by adjusting the simulated sludge production rate to the measured value. MLVSS and MLSS were accurately predicted during both calibration and validation periods (20 and 30 days). Because the membranes were immerged in the aeration tank, the coarse bubble and fine bubble diffusion systems coexisted in the same tank. This allowed five different aeration combinations, depending whether the 2 systems were operating separately or simultaneously, and at low speed or high speed. The aeration control maintained low DO concentrations, allowing simultaneous nitrification and denitrification. This made it difficult to calibrate the oxygen transfer. The nitrogen removal kinetics were determined using maximum nitrification rate tests and an 8-hour intensive sampling campaign. Despite the challenges encountered, a calibrated set of parameters was identified for ASM1 that gave very satisfactory results for the calibration period. Matching simulated and measured data became more difficult during the validation period, mainly because the dominant aeration configuration had changed. However, the merit of this study is to be the first effort to simulate a full-scale MBR plant.

Biodegradable organic matter in domestic wastewaters: comparison of selected fractionation techniques.

The first objective of this work was to evaluate the ability of the long-term BOD tests to provide the total biodegradable COD (BCOD) for domestic wastewaters. Results show that the method is repeatable (using two different volume samples, 97 and 164 mL) and that the fractions of BCOD determined were not statistically different from the one obtained by respirometry (at low S/X ratio). Respirometric tests were also repeatable. They were shown to be sensitive to the origin of the sludge. The results obtained are in the range of literature data. But they later indicated that long-term bioassays (>20 days) give higher biodegradable fractions than the other methods (BOD and respirometry). The second objective was to compare soluble fractions obtained with raw and pre-flocculated samples. Flocculated filtered COD is significantly lower than filtered COD, even if a pore size of 0.1 microm is used. The comparison to literature values shows that physicochemical RBCOD fractions are significantly higher than the ones obtained using bioassays. Comparison with the fractions used in calibrated models would help the choice of the more suitable method for modelling purposes.

Occurrence and removal of estrogens and beta blockers by various processes in wastewater treatment plants.

This study aims at evaluating occurrence and treatment efficiency of five estrogenic hormones and ten beta blockers in wastewater treatment plants (WWTP). The use of consistent sampling procedures, analytical techniques and data processing enabled to achieve an accurate comparison of the performances of the different treatment processes. First, the occurrence of molecules was evaluated in fourteen rural and urban WWTP located in France. Free and total estrogens were analyzed showing that more than 84% of estrogens in the dissolved phase of influent samples are in the free form. In effluent samples, comparable mean values but higher variation are underlined (RSD from 13 to 54% depending on the estrogen, compared to 11-21% for influents). Most of the target molecules are quantified in 30 influent and 31 effluent samples. Similar occurrence frequencies are obtained for influents from rural (6 WWTP) and urban areas (8 WWTP), except for betaxolol which is only quantified in urban wastewaters. Removal efficiencies of 8 biological treatments were studied: suspended growth biomass (activated sludge) and attached growth systems (biofilter, rotating biological contactor, reed-bed filter, trickling filter). Biological treatments are efficient to remove estrogens from the dissolved phase, with removal rate around 90%. For beta blockers, acebutolol and nadolol are efficiently removed (mean removal rate of 80%), whereas sotalol and propranolol are hardly impacted by biological treatments (removal rate below 20%). Finally, 9 tertiary treatment processes were evaluated. Ozonation, reverse osmosis and activated carbon filtration prove a high removal efficiency for beta blockers (above 80%). On the contrary, high speed chemical settler, sand filtration, silex filtration, microfiltration and UV present generally removal rates below 30% for all beta blockers. The polishing pond studied presents variable removal performances depending on the molecules (up to 75% for propranolol). The role of the hydraulic retention time on the removal efficiencies is confirmed.

Fate of pharmaceuticals and personal care products in wastewater treatment plants--conception of a database and first results.

We created a database in order to quantitatively assess the occurrence and removal efficiency of pharmaceuticals and personal care products (PPCPs) in wastewater treatment plants (WWTPs). From 117 scientific publications, we compiled 6641 data covering 184 PPCPs. Data included the concentrations of PPCPs in WWTP influents and effluents, their removal efficiency and their loads to the aquatic environment. The first outputs of our database allowed to identify the most investigated PPCPs in WWTPs and the most persistent ones, and to obtain reliable and quantitative values on their concentrations, frequency of detection and removal efficiency in WWTPs. We were also able to compare various processes and pointed out activated sludge with nitrogen treatment and membrane bioreactor as the most efficient ones.

Semi-quantitative analysis of a specific database on priority and emerging substances in wastewater and sludge.

The Water Framework Directive (WFD) has drawn attention to a series of metals and organic compounds because of their demonstrated or potential harmfulness for aquatic environments. The aim of our work was to build and to process a "practical" database focused on the role of wastewater treatment plants for the removal of the 37 priority compounds that have to be reduced or stopped by 2015, and of 34 additional relevant contaminants. About 11,000 concentration values in raw and treated wastewater and sludge, from more than 100 peer-reviewed articles and six French national screening programs, were integrated. A systematic approach showed the global low quality of data for most of the compounds, with missing information about the treatment process, sampling and analysis, leading to 10% of the data available for removal efficiency calculations. A semi-quantitative analysis allowed the identification of 20 priority and 10 additional relevant substances more frequently quantified at significant concentrations in raw wastewater and treated wastewater. Conventional activated sludge was able to remove more than 70% of half of the studied compounds, leaving only 10% of them with less than 50% removal. Physical-chemical treatments appeared to be about 30% less efficient than biological treatments. In addition, very few data are available concerning some compounds and some processes, especially sludge treatment and tertiary wastewater treatment processes. Therefore, complementary on-site measurements and modeling are required to propose adapted solutions for the treatment of priority and emerging substances in wastewater treatment plants.

Removal efficiency of pharmaceuticals and personal care products with varying wastewater treatment processes and operating conditions - conception of a database and first results.

We created a database in order to quantitatively assess the occurrence and removal efficiency of PPCPs in WWTPs. From 113 scientific publications, we compiled 5887 data on the concentrations and loads of PPCPs in WWTP influents and effluents, and on their removal efficiency. The first outputs of our database include: (1) a list of the most frequently studied molecules, their frequency of detection, their mean concentration and removal in liquid influent and effluent; (2) a comparison of the removal efficiency for different WWTP processes; (3) a study of the influence of the operating conditions (sludge and hydraulic retention times).