The goals of this study were to improve our understanding of the types of per- and polyfluoroalkyl substances (PFASs) that occur in wastewater from electronics fabrication facilities (fabs) and to ...assess the relative concentrations of PFAS species. We collected wastewater samples from three fabs in the United States, analyzed the samples by means of high-resolution mass spectrometry, and implemented complementary target and nontarget analyses. Twelve of 25 target PFASs were quantified in at least one sample, and five perfluorocarboxylates and perfluorobutane sulfonate (PFBS) were quantified in all samples. PFBS was quantified at the highest concentration among the samples (8040 ng L–1) and we expect that its presence is related to the use of photoacid generators during photolithography. The sum concentrations of the target PFASs in the diluted discharge samples from each fab were 623, 394, and 376 ng L–1. Nontarget analysis revealed the presence of 41 homologous series of PFASs comprising 133 homologues. We proposed structures for 15 homologous series of nontarget PFASs, six of which are reported here for the first time. Using an approach for semiquantification of nontarget PFASs, we estimated that the sum concentrations of target and nontarget PFASs in the diluted discharge samples from each fab were 1490, 78 700, and 2170 ng L–1. Our findings are essential for developing alternative photolithography chemicals or informing the implementation of advanced wastewater treatment technologies at fabs.
One potential source of per- and polyfluoroalkyl substances (PFASs) in electronics fabrication wastewater are the organofluorine-containing compounds used in photolithography materials such as ...photoresists and top antireflective coatings (TARCs). However, the exact identities of these constituents are unknown and transformation reactions that may occur during photolithography may result in the formation of unknown or unexpected PFASs. To address this knowledge gap, we acquired five commercially relevant photolithography materials, characterized the occurrence of organofluorine-containing compounds in each material, and performed simulated photolithography experiments to stimulate any potential transformation reactions. We found that photoresists and TARCs have total fluorine (TF) concentrations in the g L–1 range, similar to the levels of other industrial and commercial products. However, the target and suspect PFASs present in these materials can only explain up to 20% of the TF in a material. We evaluated wastewater samples collected after simulated photolithography experiments and used a mass balance approach to assess the extent of transformations. Although a number of target, suspect, and nontarget PFASs were identified in the wastewater samples, the extent of transformation was limited and the fluorine contained in the PFASs could not explain more than an additional 1% of the TF in the photolithography materials.
Per- and polyfluorinated alkyl substances (PFAS), such as perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), and ammonium perfluoro-2-propoxypropionate (GenX), contaminate ground and ...surface waters throughout the world. The cost and performance limitations of current PFAS removal technologies motivate efforts to develop selective and high-affinity adsorbents. Covalent organic frameworks (COFs) are unexplored yet promising adsorbents because of their high surface area and tunable pore sizes. Here we show that imine-linked two-dimensional (2D) COFs bearing primary amines adsorb GenX rapidly at environmentally relevant concentrations. COFs with partial amine incorporation showed the highest capacity and fastest removal, suggesting that the synergistic combination of the polar group and hydrophobic surfaces are responsible for GenX binding. A COF with 28% amine loading also removed more than 90% of 12 out of 13 PFAS. These results demonstrate the promise of COFs for PFAS removal and suggest design criteria for maximizing adsorbent performance.
Per- and poly fluorinated alkyl substances (PFASs), notably perfluorooctanoic acid (PFOA), contaminate many ground and surface waters and are environmentally persistent. The performance limitations ...of existing remediation methods motivate efforts to develop effective adsorbents. Here we report a β-cyclodextrin (β-CD)-based polymer network with higher affinity for PFOA compared to powdered activated carbon, along with comparable capacity and kinetics. The β-CD polymer reduces PFOA concentrations from 1 μg L–1 to <10 ng L–1, at least 7 times lower than the 2016 U.S. EPA advisory level (70 ng L–1), and was regenerated and reused multiple times by washing with MeOH. The performance of the polymer is unaffected by humic acid, a component of natural organic matter that fouls activated carbons. These results are promising for treating PFOA-contaminated water and demonstrate the versatility of β-CD-based adsorbents.
The global occurrence in water resources of organic micropollutants, such as pesticides and pharmaceuticals, has raised concerns about potential negative effects on aquatic ecosystems and human ...health. Activated carbons are the most widespread adsorbent materials used to remove organic pollutants from water but they have several deficiencies, including slow pollutant uptake (of the order of hours) and poor removal of many relatively hydrophilic micropollutants. Furthermore, regenerating spent activated carbon is energy intensive (requiring heating to 500-900 degrees Celsius) and does not fully restore performance. Insoluble polymers of β-cyclodextrin, an inexpensive, sustainably produced macrocycle of glucose, are likewise of interest for removing micropollutants from water by means of adsorption. β-cyclodextrin is known to encapsulate pollutants to form well-defined host-guest complexes, but until now cross-linked β-cyclodextrin polymers have had low surface areas and poor removal performance compared to conventional activated carbons. Here we crosslink β-cyclodextrin with rigid aromatic groups, providing a high-surface-area, mesoporous polymer of β-cyclodextrin. It rapidly sequesters a variety of organic micropollutants with adsorption rate constants 15 to 200 times greater than those of activated carbons and non-porous β-cyclodextrin adsorbent materials. In addition, the polymer can be regenerated several times using a mild washing procedure with no loss in performance. Finally, the polymer outperformed a leading activated carbon for the rapid removal of a complex mixture of organic micropollutants at environmentally relevant concentrations. These findings demonstrate the promise of porous cyclodextrin-based polymers for rapid, flow-through water treatment.
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.
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•ATU is a non-specific ammonia oxidation inhibitor.•Inhibition studies using ATU may overestimate contribution of ammonia-oxidizing bacteria.•Ammonia-oxidizing bacteria were highly involved in biotransforming four compounds.•Substitution-type reactions of micropollutants were not inhibited by ATU.
Evaluating the activity of extracellular and intracellular enzymes derived from wastewater microbial communities is essential to improve our fundamental understanding of micropollutant removal during ...wastewater treatment. To study biotransformations with respect to enzyme biogeography, we developed a method to separate soluble extracellular, extracellular polymeric substance (EPS)-bound, and intracellular enzymes from wastewater microbial communities and assessed the protease and peptidase activity of the resulting enzyme pools. We also evaluated the biotransformation of six antibiotics (amoxicillin, ampicillin, clindamycin, daptomycin, linezolid, and vancomycin) in each enzyme pool because we expect that the kinetics, pathways, and biogeography of antibiotic biotransformations influence the selection of antibiotic resistance within wastewater microbial communities and in downstream environments. Our results demonstrated that biotransformation rate constants varied among the tested antibiotics, and that the observed rank order was consistent across three wastewater treatment plants. Importantly, many of the observed biotransformations eliminated the functional groups associated with antibiotic activity. Furthermore, we found that β-lactam hydrolysis and daptomycin hydrolysis were catalyzed by enzymes extracted from the EPS, while none of the tested antibiotics were biotransformed by soluble extracellular enzymes. Finally, our results demonstrated that the number of enzyme-catalyzed antibiotic transformations was larger for intracellular than for extracellular enzymes. Together, this study provides novel insights on the kinetics, pathways, and biogeography of antibiotic biotransformations performed by wastewater microbial communities and can be used to inform pathway prediction or the development of biodegradable chemicals.
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•A method is presented to extract enzymes from wastewater microbial communities.•Intracellular and extracellular biotransformations of antibiotics were assessed.•Biotransformation rate constants varied among antibiotics.•Transformation product analysis revealed extracellular amide hydrolysis.•Functional groups associated with antibiotic activity were eliminated.
Per and polyfluoroalkyl substances (PFASs) have raised great concern due to their ubiquity in aquatic environments, and adsorption technologies are among the most promising treatment solutions. This ...study investigated the key factors that influence the adsorption of anionic PFASs on conventional and emerging adsorbents. Batch adsorption experiments were conducted to evaluate the removal of 20 target PFASs at environmentally relevant concentrations by three different activated carbon (AC) materials and two different β-cyclodextrin polymers (CDPs). Experiments were conducted in Milli-Q water and in groundwater. Major physical properties of the adsorbents were measured, along with general water chemistry parameters for each groundwater sample. Principal component analysis (PCA) was subsequently employed to extract the important associations from the multivariate dataset. The distinct performances of ACs and CDPs were attributed to their different surface chemistry and the distinct nature of their adsorption binding sites. Hydrophobic interactions dominated PFAS adsorption onto ACs while CDPs mostly attracted anionic PFASs via favorable electrostatic interactions. ACs of a smaller average particle size performed better, with our data pointing to an increased external specific surface area as the likely reason. pH and the concentration of cations were the primary contributors to adsorption inhibition in groundwater. Higher pH values limit anionic PFAS adsorption by deprotonating the functional groups on adsorbent surfaces. The elevated levels of cations in some groundwater samples limited the effects of attractive electrostatic interactions. Knowledge of PFAS adsorption mechanisms gained from this study can be used to design more efficient adsorbents and to predict their performance under a range of environmental scenarios.
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•Greater PFAS removal on finer activated carbon attributed to external surface area.•Cyclodextrin polymers outperform activated carbon in real groundwater matrices.•Cyclodextrin polymers and activated carbon have distinct PFAS removal mechanisms.•High pH and inorganic ion concentrations limit PFAS adsorption in aquatic matrices.
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