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Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations. Many MPs, including per‐ and polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems. A β‐cyclodextrin polymer linked with tetrafluoroterephthalonitrile (TFN‐CDP) has high affinity for cationic and many neutral MPs from contaminated water because of anionic groups incorporated during the polymerization. But TFN‐CDP does not bind many anionic MPs strongly, including anionic PFASs. To address this shortcoming, we reduced the nitrile groups in TFN‐CDP to primary amines, which reverses its affinity towards charged MPs. TFN‐CDP exhibits adsorption distribution coefficients (log KD values) of 2–3 for cationic MPs and −0.5–1.5 for anionic MPs, whereas the reduced TFN‐CDP exhibits log KD values of −0.5–1.5 for cationic MPs and 2–4 for anionic MPs, with especially high affinity towards anionic PFASs. Kinetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80–98 % removal of all contaminants after 30 min and was superior to commercial granular activated carbon. These findings demonstrate the scope and tunability of CD‐based adsorbents derived from a single polymerization and the promise of novel adsorbents constructed from molecular receptors. [ABSTRACT FROM AUTHOR]

Global water resources contain a variety of micropollutants (MPs), including pharmaceuticals, personal care products, and pesticides. This study investigated the removal of MPs during drinking water production by means of biofiltration. The objective of this work was to investigate the influence of hydrodynamics on biofilm growth and development in a biofiltration process and the consequent effect on MP biotransformation rates. We operated three groups of biofiltration columns continuously for 381 days under three distinct hydrodynamic regimes (superficial velocity: 10, 20, 40 cm h −1 ) and fed them a mixture of 29 micropollutants at low concentrations. Total protein concentrations were used as a surrogate measurement for attached biomass and periodic tracer experiments were conducted to estimate dispersivity and assess changes in the depth of the biological zone in each biofilter. These data revealed significant differences in biofilm assembly among the biofilters; higher superficial velocities led to less concentrated surface biomass but a deeper biological zone and more total biomass. Eleven of the 29 MPs were biotransformed and nine of those could be evaluated to estimate biotransformation rates. The second-order rate constants for all nine MPs were not significantly different among the hydrodynamic regimes. However, a depth-based analysis of biotransformation rates revealed significantly greater second-order rate constants for 5 of the MPs at increasing biofilter depths, suggesting that sparse microbial communities found in deeper and more oligotrophic biofilters had a greater activity for the biotransformation of these MPs. The identification of several transformation products at similar relative distributions suggests that the greater activity was not the result of changing metabolic processes under more oligotrophic conditions. These results improve our fundamental understanding of biofilm assembly and functioning in biofiltration processes. [ABSTRACT FROM AUTHOR]

Biodiversities can differ substantially among different wastewater treatment plant (WWTP) communities. Whether differences in biodiversity translate into differences in the provision of particular ecosystem services, however, is under active debate. Theoretical considerations predict that WWTP communities with more biodiversity are more likely to contain strains that have positive effects on the rates of particular ecosystem functions, thus resulting in positive associations between those two variables. However, if WWTP communities were sufficiently biodiverse to nearly saturate the set of possible positive effects, then positive associations would not occur between biodiversity and the rates of particular ecosystem functions. To test these expectations, we measured the taxonomic biodiversity, functional biodiversity, and rates of 10 different micropollutant biotransformations for 10 full-scale WWTP communities. We have demonstrated that biodiversity is positively associated with the rates of specific, but not all, micropollutant biotransformations. Thus, one cannot assume whether or how biodiversity will associate with the rate of any particular micropollutant biotransformation. We have further demonstrated that the strongest positive association is between biodiversity and the collective rate of multiple micropollutant biotransformations. Thus, more biodiversity is likely required to maximize the collective rates of multiple micropollutant biotransformations than is required to maximize the rate of any individual micropollutant biotransformation. We finally provide evidence that the positive associations are stronger for rare micropollutant biotransformations than for common micropollutant biotransformations. Together, our results are consistent with the hypothesis that differences in biodiversity can indeed translate into differences in the provision of particular ecosystem services by full-scale WWTP communities. [ABSTRACT FROM AUTHOR]

Removal of micropollutants (MPs) during activated sludge treatment can mainly be attributed to biotransformation and sorption to sludge floes, whereby the latter process is known to be of minor importance for polar organic micropollutants. In this work, we investigated the influence of pH on the biotransformation of MPs with cationic-neutral speciation in an activated sludge microbial community. We performed batch biotransformation, sorption control, and abiotic control experiments for 15 MPs with cationicneutral speciation, one control MP with neutral-anionic speciation, and two neutral MPs at pHs 6, 7, and 8. Biotransformation rate constants corrected for sorption and abiotic processes were estimated from measured concentration time series with Bayesian inference. We found that biotransformation is pH-dependent and correlates qualitatively with the neutral fraction of the ionizable MPs. However, a simple speciation model based on the assumption that only the neutral species is efficiently taken up and biotransformed by the cells tends to overpredict the effect of speciation. Therefore, additional mechanisms such as uptake of the ionic species and other more complex attenutation mechanisms are discussed. Finally, we observed that the sorption coefficients derived from our control experiments were small and showed no notable pH-dependence. From this we conclude that pH-dependent removal of polar, ionizable organic MPs in activated sludge systems is less likely an effect of pH-dependent sorption but rather of pH-dependent biotransformation. The latter has the potential to cause marked differences in the removal of polar, ionizable MPs at different operational pHs during activated sludge treatment. [ABSTRACT FROM AUTHOR]

Pollutants such as pesticides and their degradation products occur ubiquitously in natural aquatic environments at trace concentrations (μg L-1 and lower). Microbial biodegradation processes have long been known to contribute to the attenuation of pesticides in contaminated environments. However, challenges remain in developing engineered remediation strategies for pesticide-contaminated environments because the fundamental processes that regulate growth-linked biodegradation of pesticides in natural environments remain poorly understood. In this research, we developed a model framework to describe growthlinked biodegradation of pesticides at trace concentrations. We used experimental data reported in the literature or novel simulations to explore three fundamental kinetic processes in isolation. We then combine these kinetic processes into a unified model framework. The three kinetic processes described were: the growthlinked biodegradation of micropollutant at environmentally relevant concentrations; the effect of coincidental assimilable organic carbon substrates; and the effect of coincidental microbes that compete for assimilable organic carbon substrates. We used Monod kinetic models to describe substrate utilization and microbial growth rates for specific pesticide and degrader pairs. We then extended the model to include terms for utilization of assimilable organic carbon substrates by the specific degrader and coincidental microbes, growth on assimilable organic carbon substrates by the specific degrader and coincidental microbes, and endogenous metabolism. The proposed model framework enables interpretation and description of a range of experimental observations on micropollutant biodegradation. The model provides a useful tool to identify environmental conditions with respect to the occurrence of assimilable organic carbon and coincidental microbes that may result in enhanced or reduced micropollutant biodegradation. [ABSTRACT FROM AUTHOR]

Abstract: In western societies, clean and safe drinking water is often taken for granted, but there are threats to drinking water resources that should not be underestimated. Contamination of drinking water sources by anthropogenic chemicals is one threat that is particularly widespread in industrialized nations. Recently, a significant amount of attention has been given to the occurrence of micropollutants in the urban water cycle. Micropollutants are bioactive and/or persistent chemicals originating from diverse sources that are frequently detected in water resources in the pg/L to μg/L range. The aim of this review is to critically evaluate the viability of biological treatment processes as a means to remove micropollutants from drinking water resources. We first place the micropollutant problem in context by providing a comprehensive summary of the reported occurrence of micropollutants in raw water used directly for drinking water production and in finished drinking water. We then present a critical discussion on conventional and advanced drinking water treatment processes and their contribution to micropollutant removal. Finally, we propose biological treatment and bioaugmentation as a potential targeted, cost-effective, and sustainable alternative to existing processes while critically examining the technical limitations and scientific challenges that need to be addressed prior to implementation. This review will serve as a valuable source of data and literature for water utilities, water researchers, policy makers, and environmental consultants. Meanwhile this review will open the door to meaningful discussion on the feasibility and application of biological treatment and bioaugmentation in drinking water treatment processes to protect the public from exposure to micropollutants. [Copyright &y& Elsevier]

The objective of this work was to identify relevant wastewater treatment plant (WWTP) parameters and underlying microbial processes that influence the biotransformation of a diverse set of micropollutants. To do this, we determined biotransformation rate constants for ten organic micropollutants in batch reactors seeded with activated sludge from ten diverse WWTPs. The estimated biotransformation rate constants for each compound ranged between one and four orders of magnitude among the ten WWTPs. The biotransformation rate constants were tested for statistical associations with various WWTP process parameters, amoA transcript abundance, and acetylene-inhibited monooxygenase activity. We determined that (i) ammonia removal associates with oxidative micropollutant biotransformation reaction rates; (ii) archaeal but not bacterial amoA transcripts associate with both ammonia removal and oxidative micropollutant biotransformation reaction rates; and (iii) the activity of acetylene-inhibited monooxygenases (including ammonia monooxygenase) associates with ammonia removal and the biotransformation rate of isoproturon, but does not associate with all oxidative micropollutant biotransformations. In combination, these results lead to the conclusion that ammonia removal and amoA transcript abundance can potentially be predictors of oxidative micropollutant biotransformation reactions, but that the biochemical mechanism is not necessarily linked to ammonia monooxygenase activity. [ABSTRACT FROM AUTHOR]

During wastewater treatment, many organic micropollutants undergo microbially mediated reactions resulting in the formation of transformation products (TPs). Little is known on the reaction pathways that govern these transformations or on the occurrence of microbial TPs in surface waters. Large sets of biotransformation data for organic micropollutants would be useful for assessing the exposure potential of these TPs and for enabling the development of structure-based biotransformation prediction tools. The objective of this work was to develop an efficient procedure to allow for high-throughput elucidation of TP structures for a broad and diverse set of xenobiotics undergoing microbially mediated transformation reactions. Six pharmaceuticals and six pesticides were spiked individually into batch reactors seeded with activated sludge. Samples from the reactors were separated with HPLC and analyzed by linear ion trap-orbitrap mass spectrometry. Candidate TPs were preliminarily identified with an innovative post-acquisition data processing method based on target and non-target screenings of the full-scan MS data. Structures were proposed following interpretation of MS spectra and MS/MS fragments. Previously unreported microbial TPs were identified for the pharmaceuticals bezafibrate, diazepam, levetiracetam, oseltamivir, and valsartan. A variety of previously reported and unreported TPs were identified for the pesticides. The results showed that the complementary use of the target and non-target screening methods allowed for a more comprehensive interpretation of the TPs generated than either would have provided individually. [ABSTRACT FROM AUTHOR]

Improved micropollutant (MP) biotransformation during biological wastewater treatment has been associated with high ammonia oxidation activities, suggesting co-metabolic biotransformation by ammonia oxidizing bacteria as an underlying mechanism. The goal of this study was to clarify the contribution of ammonia oxidizing bacteria to increased MP degradation in nitrifying activated sludge (NAS) communities using a series of inhibition experiments. To this end, we treated a NAS community with two different ammonia oxidation inhibitors, namely octyne (OCT), a mechanistic inhibitor that covalently binds to ammonia monooxygenases, and allylthiourea (ATU), a copper chelator that depletes copper ions from the active center of ammonia monooxygenases. We investigated the biotransformation of 79 structurally different MPs by the inhibitor-treated and untreated sludge communities. Fifty-five compounds exhibited over 20% removal in the untreated control after a 46 h-incubation. Of these, 31 compounds were significantly inhibited by either ATU and/or OCT. For 17 of the 31 MPs, the inhibition by ATU at 46 h was substantially higher than by OCT despite the full inhibition of ammonia oxidation by both inhibitors. This was particularly the case for almost all thioether and phenylurea compounds tested, suggesting that in nitrifying activated sludge communities, ATU does not exclusively act as an inhibitor of bacterial ammonia oxidation. Rather, ATU also inhibited enzymes contributing to MP biotransformation but not to bulk ammonia oxidation. Thus, inhibition studies with ATU tend to overestimate the contribution of ammonia-oxidizing bacteria to MP biotransformation in nitrifying activated sludge communities. Biolog tests revealed only minor effects of ATU on the heterotrophic respiration of common organic substrates by the sludge community, suggesting that ATU did not affect enzymes that were essential in energy conservation and central metabolism of heterotrophs. By comparing ATU- and OCT-treated samples, as well as before and after ammonia oxidation was recovered in OCT-treated samples, we were able to demonstrate that ammonia-oxidizing bacteria were highly involved in the biotransformation of four compounds: asulam, clomazone, monuron and trimethoprim. [ABSTRACT FROM AUTHOR]

The biotransformation of some micropollutants has previously been observed to be positively associated with ammonia oxidation activities and the transcript abundance of the archaeal ammonia monooxygenase gene (amoA) in nitrifying activated sludge. Given the increasing interest in and potential importance of ammonia-oxidizing archaea (AOA), we investigated the capabilities of an AOA pure culture, Nitrososphaera gargensis, to biotransform ten micropollutants belonging to three structurally similar groups (i.e., phenylureas, tertiary amides, and tertiary amines). N. gargensis was able to biotransform two of the tertiary amines, mianserin (MIA) and ranitidine (RAN), exhibiting similar compound specificity as two ammonia-oxidizing bacteria (AOB) strains that were tested for comparison. The same MIA and RAN biotransformation reactions were carried out by both the AOA and AOB strains. The major transformation product (TP) of MIA, a-oxo MIA was likely formed via a two-step oxidation reaction. The first hydroxylation step is typically catalyzed by monooxygenases. Three RAN TP candidates were identified from nontarget analysis. Their tentative structures and possible biotransformation pathways were proposed. The biotransformation of MIA and RAN only occurred when ammonia oxidation was active, suggesting cometabolic transformations. Consistently, a comparative proteomic analysis revealed no significant differential expression of any protein-encoding gene in N. gargensis grown on ammonium with MIA or RAN compared with standard cultivation on ammonium only. Taken together, this study provides first important insights regarding the roles played by AOA in micropollutant biotransformation. [ABSTRACT FROM AUTHOR]

The removal of organic micropollutants (MPs) from water by means of adsorption is determined by the physicochemical properties of the adsorbent and the MPs. It is challenging to predict the removal of MPs by specific adsorbents due to the extreme diversity in physicochemical properties among MPs of interest. In this research, we established Quantitative Structure–Activity Relationships (QSARs) between the physicochemical properties of a diverse set of MPs and their distribution coefficients (K D) measured on coconut shell activated carbon (CCAC) and porous β-cyclodextrin polymer (P-CDP) adsorbents. We conducted batch experiments with a mixture of 200 MPs and used the data to calculate K D values for each MP on each adsorbent under conditions of infinite dilution (i.e., low adsorbate concentrations). We used computational software to calculate 3656 molecular descriptors for each MP. We then developed and applied a model-selection workflow to identify the most significant molecular descriptors for each adsorbent. The functional stability and predictive power of the resulting QSARs were confirmed with internal cross validation and external validation. The applicability domain of the QSARs was defined based on the most significant molecular descriptors selected into each QSAR. The QSARs are predictive tools for evaluating adsorption-based water treatment processes and provide new insights into CCAC and P-CDP adsorption mechanisms. Image 1 • Micropollutant adsorption measured on activated carbon and β-cyclodextrin polymers. • A novel model-selection workflow was developed and applied to build QSARs. • External validation confirmed the high predictive power of the developed QSARs. • QSARs enable prediction of adsorption affinity on both adsorbents. • QSARs provide new insights on adsorption mechanisms for both adsorbents. [ABSTRACT FROM AUTHOR]

In this study, we evaluated the performance of a novel tetrafluoroterephthalonitrile-crosslinked β-cyclodextrin polymer (TFN-CDP) as a solid-phase extraction (SPE) material for the recovery of up to 189 diverse organic micropollutants (MPs) from water. The optimized extraction procedure requires loading of water samples adjusted to a pH of 3 onto 500 mg of TFN-CDP packed into an SPE cartridge. Under these conditions, 88.7% of the MPs have average extraction efficiencies greater than 80%. The optimized recovery procedure requires elution with 15 mL of methanol amended with 15 mg of calcium chloride. Under these conditions, 58.4% of the MPs have average absolute recoveries between 80% and 120%. We compared the performance of the optimized SPE method for TFN-CDP with a previously optimized SPE method employing hydrophilic-lipophilic balance (HLB) adsorbents in nanopure water and in wastewater-impacted surface water. The data indicate that the optimized TFN-CDP method performs as well as or better than the optimized HLB-based SPE method. These findings represent an important step forward in the development of sustainable and inexpensive materials for the extraction and recovery of organic MPs from water. [ABSTRACT FROM AUTHOR]

The cost-effective and energy-efficient removal of organic micropollutants (MPs) from water and wastewater is challenging. The objective of this research was to evaluate the performance of porous β-cyclodextrin polymers (P-CDP) as adsorbents of MPs in aquatic matrixes. Adsorption kinetics and MP removal were measured in batch and flow-through experiments for a mixture of 83 MPs at environmentally relevant concentrations (1 µg L-1) and across gradients of pH, ionic strength, and natural organic matter (NOM) concentrations. Performance was benchmarked against a coconut-shell activated carbon (CCAC). Data reveal pseudo-second-order rate constants for most MPs ranging between 1.5 and 40 g mg-1 min-1 for CCAC and 30 and 40000 g mg-1 min-1 for P-CDP. The extent of MP removal demonstrates slower but more uniform uptake on CCAC and faster but more selective uptake on P-CDP. Increasing ionic strength and the presence of NOM had a negative effect on the adsorption of MPs to CCAC but had almost no effect on adsorption of MPs to P-CDP. P-CDP performed particularly well for positively charged MPs and neutral or negatively charged MPs with McGowan volumes greater than 1.7 (cm³ mol-1)/100. These data highlight advantages of P-CDP adsorbents relevant to MP removal during water and wastewater treatment. [ABSTRACT FROM AUTHOR]

The performance of adsorbents for the removal of organic micropollutants (MPs) from water can be influenced by the presence of water matrix constituents. The objective of this research was to evaluate the influence of water matrix constituents on the performance of coconut-shell activated carbon (CCAC), porous β-cyclodextrin polymer (CDP), and CDP coated on cellulose microcrystal (CDP@CMC) adsorbents. MP removals were measured in batch experiments for a mixture of 90 MP at 1 μg L−1 and MP breakthrough was measured in rapid small-scale column test (RSSCT) experiments for a mixture of 15 MP at 500 ng L−1. All experiments were performed first with nanopure water, and subsequently with six different water samples collected from two separate groundwater, surface water, and wastewater effluent sources. The results of batch and RSSCT experiments demonstrate more rapid adsorption kinetics and less adsorption inhibition in the presence of matrix constituents for CDP adsorbents relative to CCAC. Further, the treatment capacity of CDP@CMC in the RSSCT experiments was higher than that of CCAC, particularly in more complex water matrices. Statistical analyses were performed to investigate associations between adsorption inhibition among groups of MPs and the concentrations of specific water matrix constituents. For CCAC, adsorption inhibition was observed for all MPs and was primarily attributed to the presence of dissolved organic matter with molar weight less than 1000 Da. For CDP adsorbents, adsorption inhibition was primarily observed for cationic MPs and was attributed to the screening of the negative surface charge of CDP by inorganic ions in water samples with high ionic strength. These data further demonstrate the value of CDP as an alternative adsorbent to CCAC for the removal of MPs during water and wastewater treatment. Image 1 • Water samples from different sources characterized for water matrix constituents. • Micropollutant removal measured in laboratory-scale batch adsorption experiments. • Micropollutant breakthrough measured in rapid small-scale column test experiments. • β-cyclodextrin polymers exhibit less adsorption inhibition than activated carbon. • Inorganic ions and dissolved organic matter contribute to adsorption inhibition. [ABSTRACT FROM AUTHOR]