Adsorption Of Organic Micropollutants Research Articles

Adsorption of organic micropollutants in water: A review of advances in modelling, mechanisms, adsorbents, and their characteristics

The presence of organic micropollutants (OMPs) in water resources poses significant environmental and health risks due to their bioaccumulative and toxic properties. Adsorption technologies offer a promising solution for removing OMPs from water, yet comprehensive information on their development and application is limited. This review examines recent advancements in OMP removal using adsorption technologies, focusing on isotherms, breakthroughs, and kinetics modelling in both batch and column adsorption systems. It explores the mechanisms and characteristics of various adsorbents, highlighting significant progress in synthesizing green, mineral, porous carbon, and nanomaterial adsorbents. These developments aim to enhance properties like surface area, pore structure, surface chemistry, and particle size to optimize OMP adsorption. Despite the existence of accurate models for OMP removal by porous carbons, there is a gap in models for other adsorbents and a research bias toward batch systems. This review underscores the need for more research, particularly in computational simulation, to develop and optimize suitable models for predicting the removal of different OMPs from water via adsorption technologies using novel adsorbents in continuous column adsorption systems, to enhance the practical application of adsorption technologies in drinking water purification.

Removal of Micropollutants in Water Reclamation by Membrane Filtration: Impact of Pretreatments and Adsorption.

Organic micropollutants (OMPs) present in water and wastewater are in the spotlight because of their potentially harmful effects even at low concentrations and the difficulties of their elimination in urban wastewater treatment plants (UWWTPs). This study explores the impact of some membrane filtration processes on the removal of a group of 11 OMPs with an eye on the effects of two pretreatments (i.e., coagulation and adsorption onto powdered activated carbon (PAC)) and the adsorption of OMPs onto the membranes on the overall removal. For this purpose, ultrafiltration (UF) and nanofiltration (NF) experiments were conducted with selected OMPs spiked in ultrapure water and secondary effluents from UWWTPs. It was observed that the adsorption of OMPs onto the membranes was influenced by the characteristics of the membranes, as well as the presence of effluent organic matter (EfOM). Since adsorption was the dominant mechanism for the rejection of OMPs by UF membranes, a study of the adsorption equilibrium of the micropollutants using UF membrane pieces as the adsorbent was conducted. The adsorption isotherms for the most hydrophobic OMPs fitted the Langmuir model. The efficiency of coagulation and powdered activated carbon (PAC) adsorption coupled with UF were also investigated. Both pretreatments alleviated membrane fouling and improved the rejection of organic and inorganic matter. The PAC pretreatment significantly improved the removal of OMPs in the combined PAC/UF process. The best options for achieving reclaimed water with satisfactory physicochemical quality, nearly devoid of OMPs and microorganisms, and suitable for diverse reuse purposes are either the NF treatment or the combination of PAC/UF.

Modelling competitive adsorption of organic micropollutants onto powdered activated carbon in continuous stirred tank reactors for advanced wastewater treatment

This work investigates the validation and application of a competitive model approach for full-scale wastewater treatment plants (WWTP) with external recirculation of partially loaded powdered activated carbon (PAC) for removal of organic micropollutants (OMP). It is based on the ideal adsorbed solution theory (IAST) for multisolute mixtures combined with calibration of fictive organic components and correction of single-solute model parameters for OMP by use of the tracer model (TRM). Adsorption kinetics are represented by a pseudo first order reaction (PFO) and compared to mass transfer calculated with the homogenous surface diffusion model (HSDM). Model validation with operational data from two different WWTPs showed a strong dependency of model results on the batch sample quality used for model calibration. In contrast, the kinetic approach is of less importance for predicting full-scale OMP removal with long PAC sludge retention times. Further model application demonstrated that external PAC recirculation significantly improves the OMP removal with regard to both adsorption capacity and compensation of competitive effects of Dissolved Organic Carbon (DOC).

Comparing different versions of the Yoon-Nelson model in describing organic micropollutant adsorption within fixed bed adsorbers.

The Yoon-Nelson model serves as a widely used tool for describing the breakthrough behavior of organic micropollutants within fixed bed adsorbers. This study aims to augment its modeling efficacy through two proposed refinements found in the literature: a logarithmic transformation and the incorporation of steric hindrance effects. We systematically evaluated the original Yoon-Nelson model alongside the modified versions, using breakthrough data associated with micropollutant adsorption on solid materials. Three distinct cases were scrutinized: (1) caffeine adsorption on activated carbon; (2) tetracycline adsorption on hierarchical porous carbon; and (3) diclofenac adsorption on organoclay. While all three models demonstrated comparable performance with highly symmetric breakthrough data in case 1, their efficacy diverged significantly when confronted with strongly asymmetric breakthrough data in cases 2 and 3. The original Yoon-Nelson model and the logarithmically modified version fell short in accurately representing these intricate breakthrough curves. In contrast, the version incorporating steric hindrance effects showcased substantial accuracy, outperforming other models in capturing the complexities of asymmetric breakthrough data. This advancement markedly enhances the modeling accuracy and versatility of the Yoon-Nelson model, particularly in assessing the dynamic behavior of organic micropollutants within fixed bed adsorbers.

How aromatic dissolved organic matter differs in competitiveness against organic micropollutant adsorption

Activated carbon is employed for the adsorption of organic micropollutants (OMPs) from water, typically present in concentrations ranging from ng L−1 to μg L−1. However, the efficacy of OMP removal is considerably deteriorated due to competitive adsorption from background dissolved organic matter (DOM), present at substantially higher concentrations in mg L−1. Interpreting the characteristics of competitive DOM is crucial in predicting OMP adsorption efficiencies across diverse natural waters. Molecular weight (MW), aromaticity, and polarity influence DOM competitiveness. Although the aromaticity-related metrics, such as UV254, of low MW DOM were proposed to correlate with DOM competitiveness, the method suffers from limitations in understanding the interplay of polarity and aromaticity in determining DOM competitiveness. Here, we elucidate the intricate influence of aromaticity and polarity in low MW DOM competition, spanning from a fraction level to a compound level, by employing direct sample injection liquid chromatography coupled with ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry. Anion exchange resin pre-treatment eliminated 93% of UV254-active DOM, predominantly aromatic and polar DOM, and only minimally alleviated DOM competition. Molecular characterization revealed that nonpolar molecular formulas (constituting 26% PAC-adsorbable DOM) with medium aromaticity contributed more to the DOM competitiveness. Isomer-level analysis indicated that the competitiveness of highly aromatic LMW DOM compounds was strongly counterbalanced by increased polarity. Strong aromaticity-derived π-π interaction cannot facilitate the competitive adsorption of hydrophilic DOM compounds. Our results underscore the constraints of depending solely on aromaticity-based approaches as the exclusive interpretive measure for DOM competitiveness. In a broader context, this study demonstrates an effect-oriented DOM analysis, elucidating counterbalancing interactions of DOM molecular properties from fraction to compound level.

Fate of antibiotics and hormones during hydrothermal carbonization of poultry litter: degradation kinetics and toxicity assessment of filtrates and hydrochars

This study investigated degradation kinetics of five selected organic micropollutants (OMPs) present in poultry litter (namely: sulfadiazine, tetracycline, and doxycycline hyclate (antibiotics); estrone and 17-β-estradiol (hormones)) during hydrothermal carbonization (HTC) treatment as the temperature stepwise increased to 250 °C. All five pure OMPs were completely degraded before 250 °C was reached during the HTC process. Nevertheless, presence of poultry litter slowed down the degradation of OMPs. Through elemental mass balance calculation, it is noted that after 15 min (temperature less than 137 °C), 69–82% of organic carbon and 50–66% of organic nitrogen initially consisting part of the target antibiotics were fully mineralized. Both HTC filtrates and hydrochars obtained from poultry litter inhibited Escherichia coli and Bacillus subtilis growth. A combination of high salinity, high nutrients, dissolved organic carbon, and other ions in the filtrate as well as the adsorption of OMPs on hydrochars were probably the reason for the high toxicity.

Molecular level investigation of interactions between pharmaceuticals and β-cyclodextrin (β-CD) functionalized adsorption sites for removal of pharmaceutical contaminants from water

This study describes a novel application of the use of molecular modeling tools for investigating the adsorption of organic micropollutants (OMPs) from water by nanocomposites. The partitioning of pharmaceuticals onto β-Cyclodextrin (β-CD) functionalized adsorbents was investigated at the molecular level to explore the atomistic interactions of pharmaceutical contaminants in water systems with β-CD and to provide insight into possible approaches for removal of pharmaceuticals from water. Molecular electrostatic surface potential mapping of β-CD derivatives was employed to examine the impact of substitution degree of β-CD and type of grafting agent on host-guest complexation. The stability of the complexes of selected pharmaceuticals and β-CD derivatives were assessed via molecular dynamics simulations to evaluate competitive adsorption between organic micropollutants (OMPs) and between OMPs and fulvic acid, a representative natural organic material (NOM) component found in water systems. Molecular electrostatic surface potential maps showed that grafting agents with aromatic and amine functional groups were found to provide attractive interactions for negatively charged OMPs. In addition, optimization of substitution degree of β-CD is necessary to enhance adsorption of target OMPs. Furthermore, it was found that aromatic ring bearing grafting agents can provide additional electrostatic attractions by π-π interactions with the aromatic ring of the OMPs. The impact of common water quality characteristics on adsorption was assessed and it was revealed that the effect of pH and calcium on adsorption depends on the ionizable functional groups present on the grafting agent. Molecular dynamics simulations showed that adsorption of target OMPs does not solely depend on hydrophobicity but is affected by electrostatic interactions. The simulations revealed that fulvic acid which is commonly present in environmental waters can be a competitor with ibuprofen for the β-CD cavity. Ultimately, this study showed that molecular level simulation can be effectively employed to investigate adsorption of OMPs by β-CD functionalized adsorbents and could be employed to enhance their design and subsequent environmental applications.

Selective Adsorption of Organic Micro-Pollutants by Smectite Clays Revealed from Atomistic Simulations.

In this study, atomistic simulations were carried out to study the difference in the adsorption process between two similar molecules, diazepam and oxazepam, on Na+-montmorillonite. Kinetic and XRD measurements showed a contrasting adsorption mechanism of these two molecules, differing only by the presence/absence of methyl and hydroxyl groups, with a larger adsorption amount and intercalation for the oxazepam. The structural characterization of these molecules was investigated through DFT calculations and showed the vicinity of hydroxyl and carbonyl groups for only the chair conformation of oxazepam compared to the boat conformation. Classical molecular dynamics simulations of diazepam and the two forms of oxazepam on the external surface of Na+-montmorillonite highlighted the better coordination of the oxazepam-chair conformation, compared to its boat counterpart and diazepam. This has been confirmed through DFT calculations, from which a coordination energy that is greater by 10 kcal·mol-1 is observed. This strongly suggests that the experimentally observed intercalation of oxazepam occurs only in the chair form because of the strong coordination with the Na+ cation present in the Na-Mt interlayer. Classical MD simulations of the intercalated oxazepam chair molecule in the Na-Mt interlayer allowed the evaluation of the interlayer spacing d001, which was in very good agreement with the experimental XRD measurement.

Fate of organic micropollutants during brackish water desalination for drinking water production in decentralized capacitive electrodialysis

Capacitive electrodialysis (CED) is an emerging and promising desalination technology for decentralized drinking water production. Brackish water, often used as a drinking water source, may contain organic micropollutants (OMPs), thus raising environmental and health concerns. This study investigated the transport of OMPs in a fully-functional decentralized CED system for drinking water production under realistic operational conditions. Eighteen environmentally-relevant OMPs (20 µg L−1) with different physicochemical properties (charge, size, hydrophobicity) were selected and added to the feed water. The removal of OMPs was significantly lower than that of salts (∼94%), mainly due to their lower electrical mobility and higher steric hindrance. The removal of negatively-charged OMPs reached 50% and was generally higher than that of positively-charged OMPs (31%), whereas non-charged OMPs were barely transported. Marginal adsorption of OMPs was found under moderate water recovery (50%), in contrast to significant adsorption of charged OMPs under high water recovery (80%). The five-month operation demonstrated that the CED system could reliably produce water with low salt ions and TOC concentrations, meeting the respective WHO requirements. The specific energy consumption of the CED stack under 80% water recovery was 0.54 kWh m−3, which is competitive to state-of-the-art RO, ED, and emerging MCDI in brackish water desalination. Under this condition, the total OPEX was 2.43 € m−3, of which the cost of membrane replacement contributed significantly. Although the CED system proved to be a robust, highly adaptive, and fully automated technology for decentralized drinking water production, it was not highly efficient in removing OMPs, especially non-charged OMPs.

Production and characterization of graphene oxide-engineered biochars and application for organic micro-pollutant adsorption from aqueous solutions.

In this study, conventional and Graphene Oxide-engineered biochars were produced and thoroughly characterized, in order to investigate their potential as adsorptive materials. Two types of biomass, Rice Husks (RH) and Sewage Sludge (SS), two Graphene Oxide (GO) doses, 0.1% and 1%, and two pyrolysis temperatures, 400°C and 600°C were investigated. The produced biochars were characterized in physicochemical terms and the effect of biomass, GO functionalization and pyrolysis temperature on biochar properties was studied. The produced samples were then applied as adsorbents for the removal of six organic micro-pollutants from water and treated secondary wastewater. Results showed that the main factors affecting biochar structure was biomass type and pyrolysis temperature, while GO functionalization caused significant changes on biochar surface by increasing the available C- and O- based functional groups. Biochars produced at 600°C showed higher C content and Specific Surface Area, presenting more stable graphitic structure, compared to biochars produced at 400°C. Micro-pollutant adsorption rates were in the range of 39.9%-98.3% and 9.4%-97.5% in table water and 28.3%-97.5% and 0.0%-97.5% in treated municipal wastewater, for the Rice Husk and Sewage Sludge biochars respectively. The best biochars, in terms of structural properties and adsorption efficiency were the GO-functionalized biochars, produced from Rice Husks at 600°C, while the most difficult pollutant to remove was 2.4-Dichlorophenol.

Bifunctional covalent triazine frameworks based on Ti-ON bonds for micropollutants removal: Effects of 3D extended structure and electron transport bridges

Adsorption-photocatalysis technology enables the enrichment of pollutants and the regeneration of materials, which is expected to control long-lasting organic micropollutants (OMPs) in water. In particular, taking the comprehensive advantages of composites to simultaneously improve the adsorption and photocatalytic performance is currently worth considering. Therefore, a kind of Ti/MDCTF composite with specific and strong chemical bonds (Ti-ON bonds) was synthesized by a facile approach. Compared with pristine MDCTF, 30 %-Ti/MDCTF showed an increased saturated adsorption capacity (440.56 μmol/g) and a 5.6-fold increase in photocatalytic degradation kinetic (0.315 h−1). It was comfirmed by homogenous surface diffusion model (HSDM) that the adsorption kinetics were controlled by the intra-particle diffusion. Additionally, 30 %-Ti/MDCTF exhibited a high photocatalytic regeneration efficiency (91.7 %) after 7 rounds of degradation cycles in the natural water matrix. Experimental results and theoretical analysis collaboratively showed that the porous 3D extended structure with expanded interlayer spacing promoted the mass transfer and adsorption of OMPs. Furthermore, the Ti-ON bonds acting as electron transport bridges could promote the generation of photogenerated electrons from CTF and directional movement of them to TiO2 for efficient utilization. These findings reinforce the understanding of the adsorption-promoted 3D structure and site-specific regulation of directed electron-feeding, providing a feasible and convenient solution for the removal of OMPs in water.

Inhibition caused by adsorption of organic micropollutants (MPs) on PES@CoFe2O4 polymeric ultrafiltration membranes and the enhanced MPs degradation by a continuous pH regulation

In this work, catalytic membranes were fabricated by blending CoFe2O4 catalysts into polyethersulfone (PES) and then used to treat naproxen with the addition of peroxymonosulfate (PMS). It was found that the addition of PMS results in a decrease in pH, which increases the adsorption of naproxen. This often overlooked phenomenon is demonstrated here to have an important role since the adsorption of naproxen on the polymeric matrix and catalytic particles decreases the degradation efficiency of naproxen. To verify this hypothesis and rule out the decrease in pH after the addition of pH, two ways of controlling the pH of the naproxen solution were compared: adjusting pH before and after the addition of PMS, respectively. Our results indicate that in the batch experiment, adjusting the pH of naproxen solution after adding PMS led to a dramatic 23-fold increase in the kinetic constant of the naproxen oxidation (0.42/min, pH6) compared to when pH was adjusted before adding PMS (0.018/min, pH 6). This enhancement in the overall kinetics was attributed to the elimination of the inhibition caused by MPs adsorption at low pH. In a dead-end cell, the catalytic membranes with 2.0 % of CoFe2O4 achieved quantitative conversion of naproxen, bisphenol A, and atrazine, with values of 98 %, 97 %, and 74 %, respectively, demonstrating the efficacy of this approach to convert multitype of MPs in wastewater streams. In a reusability study, the naproxen removal of the catalytic membranes with 2.0 % of CoFe2O4 decreased by 81 % and 45 % after 5 rounds in the batch experiment and dead-end cell, respectively. However, with a chemical cleaning process between each round, the degradation efficiency can be effectively recovered, proving the negative effects of the adsorption of MPs or their intermediates during the SR-AOPs. Our work demonstrates that pH in SR-AOP-based catalytic membrane processes determined both the reaction rate and the adsorption of MPs or their intermediates on the membrane and its reactive sites. We envision that these results will be valuable in developing efficient catalytic membranes for the treatment of MPs in wastewater streams.

Characterization of the organic micropollutants behavior during electrochemical ammonia recovery

Nutrient recovery systems can be impacted due to the presence of organic micropollutants (OMPs). TAN (total ammonium nitrogen, sum of ammonium and ammonia) recovery from wastewater can be achieved by combining an electrochemical system with membrane stripping. Essential components of these processes are cation-exchange membranes and a hydrophobic gas-permeable membrane. These membranes are barriers between the OMPs source (wastewater) and recovered products. Despite reports about OMPs – ion exchange membrane interactions, there is limited knowledge about the transport of OMPs in ammonium recovery systems. This work gives a first detailed description of the transport mechanism of a broad group of OMPs with varying properties during electrochemical ammonium recovery supplied with a complex matrix (digested blackwater). Even after continuous exposure to OMPs and consequent system equilibration, OMP concentrations in the effluent were often lower than in the inflow stream. The highest removal and transport towards the concentrate were found for positively charged OMPs. The presence of organic matter contributed to the adsorption and transport of OMPs. Although OMPs were transported over the CEMs, the gas permeable hydrophobic membrane for ammonia recovery retained all OMPs.

Adsorption of organic micropollutants on yeast: Batch experiment and modeling

Yeast is ubiquitous and may act as a solid phase in natural aquatic systems, which may affect the distribution of organic micropollutants (OMs). Therefore, it is important to understand the adsorption of OMs on yeast. Therefore, in this study, a predictive model for the adsorption values of OMs on the yeast was developed. For that, an isotherm experiment was performed to estimate the adsorption affinity of OMs on yeast (i.e., Saccharomyces cerevisiae). Afterwards, quantitative structure-activity relationship (QSAR) modeling was performed for the purpose of developing a prediction model and explaining the adsorption mechanism. For the modeling, empirical and in silico linear free energy relationship (LFER) descriptors were applied. The isotherm results showed that yeast adsorbs a wide range of OMs, but the magnitude of Kd strongly depends on the types of OMs. The measured log Kd values of the tested OMs ranged from −1.91 to 1.1. Additionally, it was confirmed that the Kd measured in distilled water is comparable to that measured in real anaerobic or aerobic wastewater (R2 = 0.79). In QSAR modeling, the Kd value could be predicted by the LFER concept with an R2 of 0.867 by empirical descriptors and an R2 of 0.796 by in silico descriptors. The adsorption mechanisms of yeast for OMs were identified in individual correlations between log Kd and each descriptor: Dispersive interaction, hydrophobicity, hydrogen-bond donor, and cationic Coulombic interaction of OMs attract the adsorption, while the hydrogen-bond acceptor and anionic Coulombic interaction of OMs act as repulsive forces. The developed model can be used as an efficient method to estimate OM adsorption to yeast at a low level of concentration.

Removal of organic micropollutants from municipal wastewater by powdered activated carbon - activated sludge treatment

In Powdered Activated Carbon (PAC)-Activated Sludge (AS) Treatment, PAC is directly dosed into the AS tank. In this study, batch and pilot plant experiments were carried out to investigate the efficacy of PAC-AS treatment concerning the removal of organic micropollutants (OMPs). Batch and pilot plant experiments showed comparable removal efficiency of nine OMPs: a mean removal of 80 % could be achieved at a specific PAC dose of 2.5 mg PAC/mg DOC; during a PAC cut-off experiment, the removal performance leveled off in the first 6 h without PAC dosage. A further investigation involving an intermittent dosage of PAC demonstrated that OMPs were removed stably when PAC was dosed every 6 h, which implies the possibility of reduced investment and maintenance costs of a dosing unit.DOC was removed by 18 ± 4 % when the PAC doses ranged from 1.9 to 2.3 mg PAC/mg DOC in this study. A more detailed characterization of the organic matter was performed by means of size exclusion chromatography coupled with organic carbon detection (SEC-OCD). The high molecular weight fraction (F1) and hydrophobic organic compounds (DOCh) were most adsorbed by PAC, revealed by batch and pilot plant experiments. It indicates a higher competition potential of these two fractions against OMP adsorption compared to other DOC fractions in the PAC-AS system.

A quick test method for predicting the adsorption of organic micropollutants on activated carbon

Controlling the contamination of water cycles with organic micropollutants (OMPs) has been targeted in many regions. Adsorption with activated carbon is an effective technology to remove OMPs from different water matrices. To efficiently design or operate the adsorption process, the adsorption of OMPs should be properly assessed, usually with time-consuming batch adsorption tests and sophisticated analyses. In this study, a quick adsorption test method has been developed by loading powdered activated carbon (PAC) into a syringe filter which can be used subsequently to filtrate the water sample in short time (<60 s). Treated wastewater was applied to compare the quick test method and conventional batch test regarding the adsorption of 14 frequently detected OMPs, the abatement of UV254, and changes in fractions of dissolved organic matter (DOM). Similar adsorption patterns of individual OMPs, total OMPs, and DOM fractions was found with two methods. UV254 can predict the removal of total OMPs and most individual OMPs in both methods. Both the abatement of UV254 or the removal of OMPs determined in the quick test led to a highly accurate prediction of OMP adsorption in the conventional adsorption tests. The novel quick test method thus could help operators and researchers quickly monitor the adsorption capacity of PAC products.

Removal of organic micropollutants from wastewater effluent: Selective adsorption by a fixed-bed granular zeolite filter followed by in-situ ozone-based regeneration

Organic micropollutants (OMPs) that occur in the aquatic environment are an emerging concern. Adsorption by granular zeolites and regenerating exhausted zeolites by gaseous ozone is an innovative and advanced treatment technology for removing OMPs from wastewater treatment plant (WWTP) effluent. In this study, WWTP effluent spiked with eleven OMPs at 4–5 µg/L was treated by this combined technology, which included five steps in each cycle. The five steps comprised 1) selective adsorption of OMPs from WWTP effluent for five days by a zeolite granules fixed-bed column, 2) pre-backwash of the column, 3) drying of the column, 4) in-situ regeneration of the column with gaseous ozone 5) post-backwash of the column. The removal efficiency of eight OMPs (sotalol, metoprolol, propranolol, trimethoprim, clarithromycin, carbamazepine, methyl-benzotriazole, and benzotriazole) reached between 70 % and 100 % in six cycles. The adsorption of sulfamethoxazole and diclofenac was less favourable. In each cycle, less than 8 % of dissolved organic carbon (DOC) was removed from the WWTP effluent. The effect of the natural organic matter (NOM) on the adsorption of OMPs was negligible. Ozone consumption during regeneration was reduced by around 70 % by increasing pre-backwash duration from 30 min to 1 h. Ozonation directly with ozone gas can effectively regenerate the zeolite granules in the column under low ozone consumption.

Adsorption-desorption of organic micropollutants by powdered activated carbon and coagulant in drinking water treatment

The addition of powdered activated carbon (PAC) and a coagulant during the coagulation-flocculation process is an easy and common option for tackling pollution peaks from organic micropollutants (OMPs) in the production of drinking water. However, the adsorption-desorption mechanisms during this process have not been thoroughly explored. Thus, this research aims to study the mechanisms involved and the impact of the operating conditions when PAC and coagulant are simultaneous used. A commercial PAC with a BET-specific surface area of 961 m2/g, and ferric chloride (FeCl3) were added simultaneously to three different waters spiked with 15 OMPs (pesticides and pharmaceuticals). Different parameters such as PAC and coagulant dosage, pH, contact time and the nature/content of the natural organic matter (NOM) were examined. Results showed that using coagulant + PAC reduced OMP adsorption efficiency, whereas increasing PAC dosage and extending contact time enhanced OMP removal efficiency. Furthermore, a high concentration of NOM affected micropollutant adsorption by competing for adsorption sites. This study highlights for the first time an unexpected phenomenon that significantly affects overall efficiency: i.e. OMPs adsorbed during the slow mixing step that desorbed during the sedimentation step. Desorption sometimes reduced by >30 % the overall efficiency of OMP removal. The parameters that affected efficiency loss were pH, contact time, NOM concentration, and PAC and FeCl3 dosage. Some operational adaptations could be considered regarding these parameters to avoid or reduce desorption, making the process more cost-effective.

Induced aging, structural change, and adsorption behavior modifications of microplastics by microalgae.

The effects of microalgal biofouling on microplastic (MP) may differ from bacterial biofouling. In this study, the influence of microalgae on MP surface alteration, structural change, and adsorption of organic micropollutants was evaluated. Virgin polyethylene (PE), polyvinyl chloride (PVC), and polyamide (PA) were each immersed in algal photobioreactor and river freshwater for 30days to simulate algal and river microbe biofouling respectively. Consequently, their physicochemical changes and adsorption potential of a mixture of six bisphenol analogues (BPA, BPS, BPE, BPB, BPF, BPAF) and two parabens (propyl-paraben, benzyl-paraben) were investigated. Owing to the algal bioactive compounds, major microalgae-induced biofouling and more MP aging than the river microbe aging were observed through fractures, pits, cracks, and algal attachments. Intrusion of algal organic matter and scission of polymeric functional groups were revealed during microalgal immersion and the potential MP aging pathways were proposed. Algal biofouling considerably altered the intrinsic properties of the MPs, consequently the adsorption capacity of PE and PVC was enhanced by 3.04-6.72 and 2.14-8.72 times, respectively. Adsorption process onto algal-aged MPs was pH-dependent, endothermic, non-spontaneous, and favored by hydrogen bonds. Meanwhile, the amide group in PA structure was conducive to organic micropollutant adsorption, which was likely reduced by algal aging and the erosion of the N-H stretching. Moreover, higher adsorption capacities of organic micropollutants were shown by the algal-biofilm PE and PVC than virgin and river microbial biofilm MPs. This study discloses that, biofouling and aging of MPs by microalgae through their bioactive components would engender more incidences on MP properties, organic micropollutants adsorption with associated environmental and health hazards.

Development and application of a predictive model for advanced wastewater treatment by adsorption onto powdered activated carbon

This work presents a mathematical method to describe adsorptive removal of organic micropollutants (OMPs) and dissolved organic carbon (DOC) from wastewater treatment plant effluent using powdered activated carbon (PAC). The developed model is based on the tracer model (TRM) as a modification of the ideal adsorbed solution theory (IAST) and uses the fictive component approach for organic matter fractionation. It enables the simulation of multisolute adsorption of OMPs considering competitive adsorption behavior of organic background compounds (OBC). Adsorption equilibrium data for DOC and seven different OMPs as well as kinetic data for DOC were derived from batch experiments performed with secondary clarifier effluent of two municipal wastewater treatment plants (WWTP 1 and WWTP 2). Two conventional PAC products were investigated as well as one biogenic PAC (BioPAC). Verification and validation of the fitting results based on operational data of WWTP 1 showed promising prediction of DOC and OMP removal efficiency. However, when applied to a static simulation of a full-scale PAC adsorption stage, the model overpredicts the removal efficiency of sulfamethoxazole and candesartan. For benzotriazole, carbamazepine or hydrochlorothiazide, predicted removal falls below operational removal. The model can be used to predict removals of good adsorbable OMPs but fails to accurately predict the removals of OMPs with variable or low PAC affinity. The model was further used for a dynamic simulation of DOC and diclofenac effluent concentrations of a full-scale PAC adsorption stage with varying operating conditions and influent concentrations. Results show that the hydraulic retention time (HRT) in the contact reactor is a decisive operational parameter for OMP removal efficiency besides the PAC dose.