Sorption and biodegradation of sulfonamide antibiotics by activated sludge: experimental assessment using batch data obtained under aerobic conditions

This study investigated the adsorption, desorption, and biodegradation characteristics of sulfonamide antibiotics in the presence of activated sludge with and without being subjected to NaN₃ biocide. Batch experiments were conducted and the relative contributions of adsorption and biodegradation to the observed removal of sulfonamide antibiotics were determined. Three sulfonamide antibiotics including sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfamonomethoxine (SMM), which had been detected in the influent and the activated sludge of wastewater treatment plants (WWTP) in Taiwan, were selected for this study. Experimental results showed that the antibiotic compounds were removed via sorption and biodegradation by the activated sludge, though biodegradation was inhibited in the first 12 h possibly due to competitive inhibition of xenobiotic oxidation by readily biodegradable substances. The affinity of sulfonamides to sterilized sludge was in the order of SDM > SMM > SMX. The sulfonamides existed predominantly as anions at the study pH of 6.8, which resulted in a low level of adsorption to the activated sludge. The adsorption/desorption isotherms were of a linear form, as well described by the Freundlich isotherm with the n value approximating unity. The linear distribution coefficients (K_d) were determined from batch equilibrium experiments with values of 28.6 ± 1.9, 55.7 ± 2.2, and 110.0 ± 4.6 mL/g for SMX, SMM, and SDM, respectively. SMX, SMM, and SDM desorb reversibly from the activated sludge leaving behind on the solids 0.9%, 1.6%, and 5.2% of the original sorption dose of 100 μg/L. The sorbed antibiotics can be introduced into the environment if no further treatments were employed to remove them from the biomass.     

Fate of linear alkylbenzene sulfonate (LAS) in activated sludge plants

Monitoring data were collected in a pilot-scale municipal activated sludge plant to assess the fate of the C12-homologue of linear alkyl benzene sulfonate (LAS-C12). The pilot-plant was operated at influent LAS-C12 concentrations between 2 and 12 mg l(-1) and at sludge retention times of 10 and 27 days. Effluent and waste sludge concentrations varied between 5 and 10 microg l(-1) and between 37 and 69 microg g(-1) VSS, respectively. In the sludge samples only 2-8% was present as dissolved LAS-C12, whereas the remaining 92-98% was found to be adsorbed to the sludge. In spite of this high degree of sorption, more than 99% of the LAS-C12 load was removed by biodegradation, showing that not only the soluble fraction but also the adsorbed fraction of LAS-C12 is readily available for biodegradation. Sorption and biodegradation of LAS-C12 were also investigated separately. Sorption was an extremely fast and reversible process and could be described by a linear isotherm with a partition coefficient of 3.2 l g(-1) volatile suspended solids. From the results of biodegradation kinetic tests it was concluded that primary biodegradation of LAS-C12 cannot be described by a (growth) Monod model, but a secondary utilisation model should be used instead. The apparent affinity of the sludge to biodegrade LAS-C12 increased when the sludge was loaded with higher influent concentrations of LAS-C12.     

Evaluation and modeling of benzalkonium chloride inhibition and biodegradation in activated sludge

The inhibitory effect and biodegradation of benzalkonium chloride (BAC), a mixture of alkyl benzyl dimethyl ammonium chlorides with different alkyl chain lengths, was investigated at a concentration range from 5 to 20 mg/L and different biomass concentrations in an activated sludge system. A solution containing glucose and mineral salts was used as the wastewater in all the assays performed. The inhibition of respiratory enzymes was identified as the mode of action of BAC as a result of oxygen uptake rate analysis performed at BAC concentrations ranging between 5 and 70 mg/L. The glucose degradation in the activated sludge at different BAC and biomass concentrations was well-described with Monod kinetics with competitive inhibition. The half-saturation inhibition constant (K_I) which is equivalent to EC₅₀ of BAC for the activated sludge tested ranged between 0.12 and 3.60 mg/L. The high K_I values were recorded at low BAC-to-biomass ratios, i.e. less than 10 mg BAC/g VSS, at which BAC was almost totally adsorbed to biomass and not bioavailable. BAC degradation started as soon as glucose was totally consumed. Although BAC was almost totally adsorbed on the biomass, it was degraded completely. Therefore, BAC degradation was modeled using two-phase biodegradation kinetics developed in this study. This model involves rapid partitioning of BAC to biomass and consecutive degradation in both aqueous and solid phases. The aqueous phase BAC degradation rate was twenty times, on average, higher than the solid phase degradation rate. The specific aqueous (k_I1) and solid (k_I2) phase BAC utilization rate constants were 1.25 and 0.31 mg BAC/g VSS h, respectively. The findings of this study would help to understand the reason of extensive distribution of quaternary ammonium compounds in wastewater treatment plant effluents and in natural water systems although QACs are biodegradable, and develop strategies to avoid their release and accumulation in the environment.     

Nickel sorption by acclimatized activated sludge culture

The sorption of Ni(2+) by acclimatized activated sludge treating Ni(2+) bearing wastewater was investigated using a once-through completely mixed tank reactor. The culture developed from sewage was acclimatized to 85.2 microM/l Ni(2+) influent concentration by stepwise increases, at a low dilution rate 0.11/h. Acclimation was found to enhance the sorptive capacity of the activated sludge. In fact, at all of the intermediate concentrations, percentage Ni(2+) adsorbed by the biomass and also the sorptive capacity of the activated sludge drastically increased with an increase in the influent Ni(2+) concentration. All influent Ni(2+) concentrations were found to significantly stimulate the observed biomass yield of the culture over that observed in the base line. Experimental findings obtained at two other dilution rates; namely, 0.25/h and 0.45/h revealed that dilution rate is a significant operational parameter affecting the Ni(2+) sorption characteristics of acclimatized activated sludge microorganisms. Considerable complexation of nickel and organic and inorganic ligands in the wastewater appeared to be responsible for a relatively lower Ni(2+) sorption capacity.     

Biodegradation of organonitriles by adapted activated sludge consortium with acetonitrile-degrading microorganisms

A microbial process for the degradation of three types of structurally distinct organonitriles (i.e., saturated and unsaturated aliphatic nitrile and aromatic nitrile) was studied. Microorganisms were enriched from the activated sludge of a pharmaceutical wastewater treatment plant and adapted through providing acetonitrile as the sole carbon and nitrogen source for their growth. The adapted mixed culture was then examined for their capability of degrading acetonitrile, acrylonitrile and benzonitrile under various operational conditions. The performance of biodegradation and the metabolic intermediate- and end-products in the process were monitored. The results show that an average removal rate of 0.083 g acetonitrile g(-1)-VSS h(-1), 0.0074 g acrylonitrile g(-1)-VSS h(-1) or 0.0029 g benzonitrile g(-1)-VSS h(-1) was achieved in the batch bioreactor under the common operational condition of 25 degrees C and pH 7. The biodegradation of acetonitrile and acrylonitrile showed a two-step pathway, with the generation of acetamide followed by acetic acid and ammonia for acetonitrile or acrylamide followed by acrylic acid and ammonia for acrylonitrile. However, the biodegradation of benzonitrile appeared to have only one step, with the direct production of benzoic acid and ammonia, but without benzamide being detected in the process. The results suggest that, depending on the substrates, the adapted mixed culture can develop very different degradation pathways, such as nitrile hydratase plus amidase for acetonitrile or acrylonitrile and nitrilase for benzonitrile. Therefore, the adapted mixed culture has a great potential and flexibility for actual applications in biodegradation of various organonitrile compounds.     

Fate of beta blockers and psycho-active drugs in conventional wastewater treatment

The removal of beta blockers and psycho-active drugs was investigated in a representative conventional German WWTP by long-term measurement campaigns along different biological treatment processes. The activated sludge treatment with an elevated SRT of 18 d was the only process which led to a significant removal of certain beta blockers and psycho-active drugs. The removal efficiency was below 60% for all compounds except for the natural opium alkaloids codeine and morphine being removed by more than 80%. Primary biological transformation and sorption onto sludge as the main removal mechanisms were examined in lab-scale batch experiments. Sorption onto activated sludge was found to be negligible (<3%). The biological transformation could be described by pseudo-first order kinetics and the transformation constants k_biol were used to predict the removal of beta blockers and psycho-active drugs in an activated sludge unit with a model. For most compounds the removal efficiencies measured on the full-scale WWTP were within the 95% confidence intervals predicted by the model. The results from full-scale measurements and modeling indicate that biological transformation in the nitrification tank together with parameters such as the sludge retention time and the temperature is crucial regarding the biological transformation of beta blockers and psycho-active drugs in conventional WWTPs.     

Roles of extracellular polymeric substances (EPS) in the migration and removal of sulfamethazine in activated sludge system

The occurrences, transformation of antibiotics in biological wastewater treatment plants have attracted increasing interests. However, roles of extracellular polymeric substances (EPS) of activated sludge on the fate of antibiotics are not clear. In this study, the roles of EPS in the migration and removal of one typical antibiotic, sulfamethazine (SMZ), in activated sludge process were investigated. The interaction between EPS and SMZ was explored through a combined use of fluorescence spectral analysis, laser light scattering and microcalorimetry techniques. Results show that SMZ interacted with the proteins in EPS mainly with a binding constant of 1.91 × 10⁵ L/mol. The binding process proceeded spontaneously, and the driving force was mainly from the hydrophobic interaction. After binding, the structure of EPS was expanded and became loose, which favored the mass transfer and pollution capture. The removal of SMZ was influenced by interaction with EPS. SMZ could be effectively adsorbed on EPS, which accounted for up to 61.8% of total SMZ adsorbed by sludge at the initial adsorption stage and declined to around 35.3% at the subsequent biodegradation stage. The enrichment of SMZ by EPS was beneficial for SMZ removal and acquisition by microbes at the subsequent biodegradation stage.     

Partitioning of phenanthrene into surfactant hemi-micelles on the bacterial cell surface and implications for surfactant-enhanced biodegradation

Recent studies have suggested that the ability of a surfactant to enhance the bioavailability of hydrophobic organic compounds (HOC) requires the formation of surfactant hemi-micelles on the bacterial cell surface and subsequent partitioning of HOC into the hemi-micelles. However, the studies did not provide direct evidence of HOC partitioning into surfactant hemi-micelles on the bacterial cell surface. In this study, direct evidence is provided to demonstrate that the nonionic surfactant Brij 30 forms hemi-micelles on the bacterial cell surface and that phenanthrene sorption at the bacterial surface is enhanced by the surfactant. These results are in agreement with the current theory describing surfactant-enhanced HOC bioavailability. This enhanced bioavailability is put into context with microbial kinetics and system partitioning processes, and it is demonstrated that the addition of surfactant can enhance, have no effect, or inhibit HOC biodegradation depending upon surfactant concentration and microbial growth rate. Understanding these non-linear relationships between surfactant-enhanced HOC bioavailability, biodegradation kinetics, and system partitioning will assist in the design and implementation of surfactant-enhanced bioremediation programs.     

Biodegradation of the endogenous residue of activated sludge

This study evaluated the potential biodegradability of the endogenous residue in activated sludge subjected to batch digestion under either non-aerated or alternating aerated and non-aerated conditions. Mixed liquor for the tests was generated in a 200 L pilot-scale aerobic membrane bioreactor (MBR) operated at a 5.2 days SRT. The MBR system was fed a soluble and completely biodegradable synthetic influent composed of sodium acetate as the sole carbon source. This influent, which contained no influent unbiodegradable organic or inorganic materials, allowed to generate sludge composed of essentially two fractions: a heterotrophic biomass X_H and an endogenous residue X_E, the nitrifying biomass being negligible (less than 2%). The endogenous decay rate and the active biomass fraction of the MBR sludge were determined in 21-day aerobic digestion batch tests by monitoring the VSS and OUR responses. Fractions of X_H and X_E: 68% and 32% were obtained, respectively, at a 5.2 days SRT. To assess the biodegradability of X_E, two batch digestion units operated at 35 °C were run for 90 days using thickened sludge from the MBR system. In the first unit, anaerobic conditions were maintained while in the second unit, alternating aerated and non-aerated conditions were applied. Data for both units showed apparent partial biodegradation of the endogenous residue. Modeling the batch tests indicated endogenous residue decay rates of 0.005 d⁻¹ and 0.012 d⁻¹ for the anaerobic unit and the alternating aerated and non-aerated conditions, respectively.     

Molecularly imprinted polymer microspheres enhanced biodegradation of bisphenol A by acclimated activated sludge

The impacts of bisphenol A− imprinted polymeric microspheres (MIPMs) on the biodegradation of bisphenlol A by acclimated activated sludge were studied. Due to the selective adsorption of MIPMs to bisphenol A (BPA) and its analogues, addition of MIPMs to activated sludge increased levels of BPA and its metabolites, which were also the substrates of biodegradation. Higher substrates (BPA and its metabolites) level promoted biodegradation efficiencies of activated sludge via accelerating removal speed of BPA and its metabolites, increasing degradation rate and decreasing half-lives of biodegradation. The enhancement of MIPMs in degradation efficiencies was more significant in environmental water containing low-level of pollutants, and water containing interferences such as heavy metals and humic acid. Furthermore, MIPMs were more suitable than non-selective sorbents such as active carbon to be used as enhancer for BPA biodegradation. MIPMs combined with activated sludge are simple, effective, environmental-friendly processes to biodegrade low-level pollutants in environmental water.     

Aerobic batch degradation of 17-beta estradiol (E2) by activated sludge: effects of spiking E2 concentrations, MLVSS and temperatures

Aerobic batch degradation of 17beta estradiol (E2) spiked into the activated sludge liquor from a sewage treatment plant was studied; and the likely impacts of E2's initial concentrations (C0), microbial population densities (MLVSS) and temperatures (TEMPT) were examined for a variety of combinations of these three factors: C0 = 10, 30 and 50 microgl(-1); MLVSS = 1750, 875 and 435 mgl(-1); and TEMPT = 5, 20 and 35 degrees C. The results, together with those obtained through two control runs performed using a killed sludge sample, demonstrated clearly that E2 was eliminated from the aqueous phase readily under appropriate MLVSS and temperature levels, with the role of sorption by biomass being less significant. By fitting observed concentration data with a first-order rate expression, the degradation rate constants (k) under all experimental conditions were estimated. The magnitude of k changed markedly in the range of 0.23-4.79 h(-1), following a general order that the higher the MLVSS was, the higher the rate constant, and that the higher the temperature, the higher the rate constant. An obvious increasing trend of the biomass-modified average rate constant (k') with increases in the temperature was also presented: the k' values at 5, 20 and 35 degrees C were 0.79, 1.77 and 3.29l MLVSS g(-1)h(-1), respectively. Furthermore, based upon the estimated k values, the temperature coefficients (theta) over the ranges of 5-20 and 20-35 degrees C were determined. In similarity with the magnitude of theta reported for ordinary BOD-based organic matrices in domestic wastewater, the theta values of E2 varied in the range of 1.026-1.09, suggesting that the temperature impacts on the degradation rates of E2 and BOD constituents are probably similar.     

Evaluation of matrices for the sorption and biodegradation of phenanthrene

Permeable reactive barriers (PRBs), a new cost effective technology for the remediation of contaminated groundwater, have rarely been considered for PAH contamination. We evaluated three candidate matrices (activated carbon (AC), pouzzolana coated (PzF) or not (Pz) with heavy fuel oil) for phenanthrene (PHE) sorption capacity and the biodegradation of adsorbed PHE. Adsorption-desorption batch experiments showed higher sorption capacity of AC than PzF (60 fold) and Pz (1,500 fold). Sorption isotherms were not linear for all matrices as described by a Freundlich model. Phenanthrene desorption from AC and PzF within 48 h was limited (1-3%). Mineralization of (14)C-PHE by a PAH-degrading bacterial strain increased in the presence of AC and Pz (+16 and +12%). Among the three matrices, AC may be a good candidate for PRBs due to high adsorption, low desorption and increased PHE degradation.     

Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: Laboratory photolysis, biodegradation, and sorption experiments

We selected eight pharmaceuticals with relatively high potential ecological risk and high consumption—namely, acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid, and propranolol—and conducted laboratory experiments to examine the persistence and partitioning of these compounds in the aquatic environment. In the results of batch sunlight photolysis experiments, three out of eight pharmaceuticals—propranolol, indomethacin, and ifenprodil—were relatively easily photodegraded (i.e., half-life < 24 h), whereas the other five pharmaceuticals were relatively stable against sunlight. The results of batch biodegradation experiments using river water suggested relatively slow biodegradation (i.e., half-life > 24 h) for all eight pharmaceuticals, but the rate constant was dependent on sampling site and time. Batch sorption experiments were also conducted to determine the sorption coefficients to river sediments and a model soil sample. The determined coefficients (K_d values) were much higher for three amines (atenolol, ifenprodil, and propranolol) than for neutral compounds or carboxylic acids; the K_d values of the amines were comparable to those of a four-ring polycyclic aromatic hydrocarbon (PAH) pyrene. The coefficients were also higher for sediment/soil with higher organic content, and the organic carbon-based sorption coefficient (log K_oc) showed a poor linear correlation with the octanol-water distribution coefficient (log D_ow) at neutral pH. These results suggest other sorption mechanisms—such as electrochemical affinity, in addition to hydrophobic interaction—play an important role in sorption to sediment/soil at neutral pH.     

Fate of antibiotics in activated sludge followed by ultrafiltration (CAS-UF) and in a membrane bioreactor (MBR)

The fates of several macrolide, sulphonamide, and trimethoprim antibiotics contained in the raw sewage of the Tel-Aviv wastewater treatment plant (WWTP) were investigated after the sewage was treated using either a full-scale conventional activated sludge (CAS) system coupled with a subsequent ultrafiltration (UF) step or a pilot membrane bioreactor (MBR) system. Antibiotics removal in the MBR system, once it achieved stable operation, was 15-42% higher than that of the CAS system. This advantage was reduced to a maximum of 20% when a UF was added to the CAS. It was hypothesized that the contribution of membrane separation (in both systems) to antibiotics removal was due either to sorption to biomass (rather than improvement in biodegradation) or to enmeshment in the membrane biofilm (since UF membrane pores are significantly larger than the contaminant molecules). Batch experiments with MBR biomass showed a markedly high potential for sorption of the tested antibiotics onto the biomass. Moreover, methanol extraction of MBR biomass released significant amounts of sorbed antibiotics. This finding implies that more attention must be devoted to the management of excess sludge.     

Biodegradation of the endogenous residue of activated sludge in a membrane bioreactor with continuous or on-off aeration

The goal of this study was to determine the effect of a long sludge retention time on the biodegradation of the endogenous residue in membrane digestion units receiving a daily feed of sludge and operated under either aerobic or intermittently aerated (22 h off-2 h on) conditions. The mixed liquor for these experiments was generated in a 10.4 day sludge retention time membrane bioreactor fed with a synthetic and completely biodegradable influent with acetate as the sole carbon source. It had uniform characteristics and consisted of only two components, heterotrophic biomass X_H and endogenous residue X_E. Membrane digestion unit experiments were conducted for 80 days without any sludge wastage except for some sampling. The dynamic behaviour of generation and consumption of filtered organic digestion products was characterized in the membrane digestion unit systems using three pore filter sizes. Results from this investigation indicated that the colloidal matter with size between 0.04 μm and 0.45 μm was shown to contain a recalcitrant fraction possibly composed of polysaccharides bound to proteins which accumulated in the membrane digestion unit under both conditions. Modelling the membrane digestion unit results by considering a first-order decay of the endogenous residue allowed to determine values of the endogenous residue decay rate of 0.0065 and 0.0072 d⁻¹ under fully aerobic and intermittently aerated conditions, respectively. The effect of temperature on the endogenous decay rate was assessed for the intermittently aerated conditions in batch tests using thickened sludge from tests gave an endogenous decay rate constant of 0.0075 d⁻¹ at 20 °C and an Arrhenius temperature correction factor of 1.033.     

Stereoselective biodegradation of amphetamine and methamphetamine in river microcosms

Here presented for the first time is the enantioselective biodegradation of amphetamine and methamphetamine in river microcosm bioreactors. The aim of this investigation was to test the hypothesis that mechanisms governing the fate of amphetamine and methamphetamine in the environment are mostly stereoselective and biological in nature. Several bioreactors were studied over the duration of 15 days (i) in both biotic and abiotic conditions, (ii) in the dark or exposed to light and (iii) in the presence or absence of suspended particulate matter. Bioreactor samples were analysed using SPE-chiral-LC-(QTOF)MS methodology. This investigation has elucidated the fundamental mechanism for degradation of amphetamine and methamphetamine as being predominantly biological in origin. Furthermore, stereoselectivity and changes in enantiomeric fraction (EF) were only observed under biotic conditions. Neither amphetamine nor methamphetamine appeared to demonstrate adsorption to suspended particulate matter. Our experiments also demonstrated that amphetamine and methamphetamine were photo-stable. Illicit drugs are present in the environment at low concentrations but due to their pseudo-persistence and non-racemic behaviour, with two enantiomers revealing significantly different potency (and potentially different toxicity towards aquatic organisms) the risk posed by illicit drugs in the environment should not be under- or over-estimated. The above results demonstrate the need for re-evaluation of the procedures utilised in environmental risk assessment, which currently do not recognise the importance of the phenomenon of chirality in pharmacologically active compounds.     

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

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

Comparison of batch sorption tests, pilot studies, and modeling for estimating GAC bed life

Saint Paul Regional Water Services (SPRWS) in Saint Paul, MN experiences annual taste and odor episodes during the warm summer months. These episodes are attributed primarily to geosmin that is produced by cyanobacteria growing in the chain of lakes used to convey and store the source water pumped from the Mississippi River. Batch experiments, pilot-scale experiments, and model simulations were performed to determine the geosmin removal performance and bed life of a granular activated carbon (GAC) filter-sorber. Using batch adsorption isotherm parameters, the estimated bed life for the GAC filter-sorber ranged from 920 to 1241 days when challenged with a constant concentration of 100 ng/L of geosmin. The estimated bed life obtained using the AdDesignS model and the actual pilot-plant loading history was 594 days. Based on the pilot-scale GAC column data, the actual bed life (>714 days) was much longer than the simulated values because bed life was extended by biological degradation of geosmin. The continuous feeding of high concentrations of geosmin (100-400 ng/L) in the pilot-scale experiments enriched for a robust geosmin-degrading culture that was sustained when the geosmin feed was turned off for 40 days. It is unclear, however, whether a geosmin-degrading culture can be established in a full-scale filter that experiences taste and odor episodes for only 1 or 2 months per year. The results of this research indicate that care must be exercised in the design and interpretation of pilot-scale experiments and model simulations for predicting taste and odor removal in full-scale GAC filter-sorbers. Adsorption and the potential for biological degradation must be considered to estimate GAC bed life for the conditions of intermittent geosmin loading typically experienced by full-scale systems.     

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168 h to achieve the equilibrium, much longer than 4 h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04 mmol g⁻¹ for PFOS and 2.92 mmol g⁻¹ for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.     

A three-compartment model for micropollutants sorption in sludge: Methodological approach and insights

In sludge resulting from wastewater treatment, organic micropollutants sorb to particles and to dissolved/colloidal matter (DCM). Both interactions may influence their physical and biological fate throughout the wastewater treatment processes. To our knowledge, sludge has never been considered as a three-compartment matrix, in which micropollutants coexist in three states: freely dissolved, sorbed-to-particles and sorbed-to-DCM. A methodology is proposed to concomitantly determine equilibrium constants of sorption to particles (K_part) and to DCM (K_DCM). Polycyclic Aromatic Hydrocarbons (PAHs) were chosen as model compounds for the experiments. The logarithm of estimated equilibrium constants ranged from 3.1 to 4.3 and their usual correlation to PAH hydrophobicity was verified. Moreover, PAH affinities for particles and for DCM could be compared. Affinity for particles was found to be stronger, probably due to their physical and chemical characteristics. This work provided a useful tool to assess the freely dissolved, sorbed-to-particles and sorbed-to-DCM concentrations of contaminants, which are necessary to accurately predict their fate. Besides, guidelines to investigate the link between sorption and the fundamental concept of bioavailability were proposed.