The ubiquitous occurrence of organophosphate flame retardants (OPFRs) in aquatic and soil environments poses significant risks to human health and ecosystems. Here, we report on the hydrolysis of six ...OPFRs and three structural analogues in the absence and presence of metal (hydr)oxide minerals. Eight of the target compounds showed marked degradation in alkaline solutions (pH 9–12) with half-lives ranging from 0.02–170 days. Kinetics follow a second-order rate law with apparent rate constants for base-catalyzed hydrolysis (k B) ranging from 0.69–42 000 M–1 d–1. Although hydrolysis in homogeneous solution at circumneutral pH is exceedingly slow (t 1/2 > 2 years, except for tris(2,2,2-trichloroethy) phosphate), rapid degradation is observed in the presence of metal (hydr)oxide minerals, with half-lives reduced to <10 days for most of the target OPFRs in mineral suspensions (15 m2/L mineral surface area loading). LC-qToF-MS analysis of transformation products confirmed ester hydrolysis as the active degradation pathway. Values of k B for individual OPFRs are highly variable and correlate with acid dissociation constants (pK a) of the corresponding alcohol leaving groups. In contrast, kinetic parameters for mineral-catalyzed reactions are much less sensitive to OPFR structure, indicating that other factors like mineral-OPFR interactions are rate controlling. Given the documented recalcitrance of OPFRs to biodegradation and photodegradation, these results suggest that mineral-catalyzed hydrolysis may be a major fate-controlling sink in natural environments.
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•A novel Ce(IV)/HSO3− process was proposed firstly in this study.•Carbamazepine (CBZ) could be oxidized at pHini 3.0–7.0 in Ce(IV)/HSO3− process.•SO4−, HO, and SO5− were identified to ...be reactive species in this process.•SO4− played a major role in the degradation of CBZ in Ce(IV)/HSO3− system.•Pathways of CBZ degradation in Ce(IV)/HSO3− process were proposed.
In this study, the activation of bisulfite by cerium(IV) (Ce(IV)/HSO3− process) is proposed for the first time to degrade organic contaminants. Experiments show that carbamazepine (CBZ), a representative recalcitrant contaminant of emerging concern, is oxidized by Ce(IV)/HSO3− treatment at pHini 3.0–7.0 when O2(aq) is present to promote HSO3− autoxidation. SO4−, HO, and SO5− were identified as active oxidants of CBZ based on the ESR spectra and the results of alcohol quenching experiments. Quantitative analysis indicates that SO4− plays a major role, while HO and other species play minor roles in the degradation of CBZ in the Ce(IV)/HSO3− process. SO4− radicals are derived from the reaction of SO5− with HSO3− and the activation of hydrogen peroxomonosulfate (HSO5−) by Ce(IV). Five degradation pathways of CBZ are proposed based on transformation products identified by UPLC-QToF-MS/MS, and proposed sites for radical attack are supported by the results of frontier electron density calculations. Elevated concentrations of Cl−, Fe(III), and humic acid (HA) inhibit CBZ degradation, while other non-target solutes have minimal effects on CBZ degradation in the Ce(IV)/HSO3− process. Finally, experiments demonstrating degradation of a suite of other organic contaminants suggests that the Ce(IV)/HSO3− system can be applied as a new advanced oxidation process for wastewater treatment.
Lignin is an energy-dense, heterogeneous polymer comprised of phenylpropanoid monomers used by plants for structure, water transport, and defense, and it is the second most abundant biopolymer on ...Earth after cellulose. In production of fuels and chemicals from biomass, lignin is typically underused as a feedstock and burned for process heat because its inherent heterogeneity and recalcitrance make it difficult to selectively valorize. In nature, however, some organisms have evolved metabolic pathways that enable the utilization of lignin-derived aromatic molecules as carbon sources. Aromatic catabolism typically occurs via upper pathways that act as a “biological funnel” to convert heterogeneous substrates to central intermediates, such as protocatechuate or catechol. These intermediates undergo ring cleavage and are further converted via the β-ketoadipate pathway to central carbon metabolism. Here, we use a natural aromatic-catabolizing organism, Pseudomonas putida KT2440, to demonstrate that these aromatic metabolic pathways can be used to convert both aromatic model compounds and heterogeneous, lignin-enriched streams derived from pilot-scale biomass pretreatment into medium chain-length polyhydroxyalkanoates (mcl -PHAs). mcl -PHAs were then isolated from the cells and demonstrated to be similar in physicochemical properties to conventional carbohydrate-derived mcl -PHAs, which have applications as bioplastics. In a further demonstration of their utility, mcl -PHAs were catalytically converted to both chemical precursors and fuel-range hydrocarbons. Overall, this work demonstrates that the use of aromatic catabolic pathways enables an approach to valorize lignin by overcoming its inherent heterogeneity to produce fuels, chemicals, and materials.
•>97% rejection of 42 different PFASs by nanofiltration and reverse osmosis.•Membrane operating conditions marginally impacted PFAS rejection.•Rejection reduced in groundwater matrix.•Hydrophobic ...adsorption of PFASs to membranes, permeate spacer, and membrane system.•Long-term membrane performance was not impacted by adsorption.
The ubiquitous use and manufacturing of per- and polyfluoroalkyl substances (PFASs) have led to the contamination of water resources worldwide. High-pressure membranes, including nanofiltration (NF) and reverse osmosis (RO), are increasingly being deployed for water treatment and may be an effective barrier to PFASs. However, the impact of membrane operating conditions, background water matrix, and solute adsorption on rejection of diverse PFASs by NF and RO remains unclear. Rejection of perfluoroalkyl acids (PFAAs) present in aqueous film-forming foam (AFFF) diluted into a laboratory electrolyte matrix by NF and RO spiral wound elements was >98% and >99%, respectively. Rejection of the same PFAAs present in an AFFF-impacted groundwater matrix by NF was lower, between 92-98%, and was attributed to background water matrix constituents. Operating conditions did not have a significant impact on rejection of PFASs with the exception of shorter chain perfluoroalkyl sulfonic acids (PFSAs) in the AFFF-impacted groundwater matrix, where rejection increased with increasing flux. Structure-activity analysis of 42 PFASs, including 10 PFAAs and 32 PFASs identified in AFFF through high-resolution mass spectrometry suspect screening methods, showed some correlation between rejection and compound molecular weight. Adsorptive losses of PFAAs, most notably longer-chain hydrophobic PFAAs, to the spiral wound membrane elements and the membrane system were observed. Adsorption of PFAAs to the permeate spacer was especially pronounced and may have implications of artificially high rejection values. Still, rejection of PFASs by NF remained consistently >98% over 13 days of continuous operation.
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Permanganate (Mn(VII)) has been widely applied as an oxidant in water treatment plants. However, compared with ozone, Fenton, and other advanced oxidation processes, the reaction rates of some trace ...organic contaminants (TrOCs) with Mn(VII) are relatively low. Therefore, further studies on the strategies for enhancing the oxidation of organic contaminants by Mn(VII) are valuable. In this work, 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), as an electron shuttle, enhanced Mn(VII) oxidation toward various TrOCs (i.e., bisphenol A (BPA), phenol, estrone, sulfisoxazole, etc.). TEMPO sped up the oxidative kinetics of BPA by Mn(VII) greatly, and this enhancement was observed at a wide pH range of 4.0–11.0. The exact mechanism of TEMPO in Mn(VII) oxidation was described briefly as follows: (i) TEMPO was oxidized by Mn(VII) to its oxoammonium cation (TEMPO+) by electron transfer, which was the reactive species responsible for the accelerated degradation of TrOCs and (ii) TEMPO+ could decompose TrOCs rapidly with itself back to TEMPO or TEMPOH (TEMPO hydroxylamine). To further illustrate the interaction between TEMPO and target TrOCs, we explored the transformation pathways of BPA in Mn(VII)/TEMPO oxidation. Compared to Mn(VII) alone, adding TEMPO into the Mn(VII) solution significantly suppressed BPA’s self-coupling and promoted hydroxylation, ring-opening, and decarboxylation. Moreover, the Mn(VII)/TEMPO system was promising for the abatement of TrOCs in real waters for humic acid, and ubiquitous cations/anions had no adverse or even beneficial impact on the Mn(VII)/TEMPO system.
Literature works reported that organic cocontaminants could be degraded during Cr(VI), a contaminant, reduction by sulfite (Cr(VI)/sulfite process). However, the role of Cr(V) and Cr(IV) ...intermediates in the Cr(VI)/sulfite process has been overlooked. In this study, we confirmed the generation of Cr(V) and proposed a new mechanism for the decomposition of coexisting organic contaminants during Cr(VI)/sulfite reactions occurring in oxygenated solutions at pHini 4.0 with the molar ratio of sulfite to Cr(VI) of 10.0. UV–visible and electron paramagnetic resonance (EPR) spectra indicate that Cr(V) was the predominant Cr intermediates in oxygenated solutions, while Cr(IV) accumulated in deoxygenated solutions. The contribution of Cr(V) to the degradation of organic contaminants was verified by the EPR spectra collected at 2 K and using methyl phenyl sulfoxide as a probe compound. Both Cr(V) and SO4 •– contributed to the decomposition of organic contaminants in oxygenated solutions, with the relative contributions from each species being strongly dependent on properties of the target organic cocontaminants. The key mechanisms responsible for Cr(V) accumulation were supported by DFT calculations, and the degradation kinetics of organic cocontaminants was simulated with the program Kintecus 6.51. This work advances the fundamental understanding of the oxidative transformation of coexisting organic contaminants in this process.
Permanganate (Mn(VII)) is extensively applied in water purification due to its stability and ease of handling, but it is a mild oxidant for trace organic contaminants (TrOCs). Hence, there is ...significant interest in strategies for enhancing reaction kinetics, especially in combination with efficient and economical carbocatalysts. This study compared the performance of four carbocatalysts (graphite, graphene oxide (GO), reduced-GO (rGO), and nitrogen-doped rGO (N-rGO)) in accelerating sulfisoxazole (SSX) oxidation by Mn(VII) and found that GO exhibited the greatest catalytic performance. Besides, the Mn(VII)/GO system shows desirable capacities to remove a broad spectrum of TrOCs. We proposed that the degradation of SSX in Mn(VII)-GO suspensions follows two routes: (i) direct oxidation of SSX by Mn species both Mn(VII) and
formed MnO
and (ii) a carbocatalyst route, where GO acts as an electron mediator, accepting electrons from SSX and transferring them to Mn(VII). We developed a mathematical model to show the contribution of each parallel pathway and found one-electron transfer is primarily responsible for accelerating SSX removal in the Mn(VII)/GO system. Findings in this study showed that GO provides a simple and effective strategy for enhancing the reactivity of Mn(VII) and provided mechanistic insights into the GO-catalyzed redox reaction between SSX and Mn(VII).
The incomplete elimination of pharmaceuticals and personal care products (PPCPs) during wastewater treatment has resulted in their detection in the environment. PPCP biodegradation is a potential ...removal mechanism; however, the microorganisms and pathways involved in soils are generally unknown. Here, the biodegradation of diclofenac (DCF), carbamazepine (CBZ) and triclocarban (TCC) in four agricultural soils at concentrations typically detected in soils and biosolids (50 ng g−1) was examined. Rapid DCF removal (<7 days) was observed under aerobic conditions, but only limited biodegradation was noted under other redox conditions. CBZ and TCC degradation under aerobic conditions was slow (half-lives of 128–241 days and 165–190 days for CBZ and TCC). Phylotypes in the Proteobacteria, Gemmatimonadales and Actinobacteria were significantly more abundant during DCF biodegradation compared to the controls (no DCF). For CBZ, those in the Bacteroidetes, Actinobacteria, Proteobacteria and Verrucomicrobia were enriched compared to the controls. Actinobacteria and Proteobacteria were also enriched during TCC biodegradation. Such differences could indicate these microorganisms are associated with the biodegradation of these compounds, as they appear to be benefiting from their removal. The impact of these PPCPs on the KEGG pathways associated with metabolism was also examined. Four pathways were positively impacted during DCF biodegradation (propanoate, lysine, fatty acid & benzoate metabolism). These pathways are likely common in soils, explaining the rapid removal of DCF. There was limited impact of CBZ on the metabolic pathways. TCC removal was linked to genes associated with the degradation of simple and complex substrates. The results indicate even low concentrations of PPCPs significantly affect soil communities. The recalcitrant nature of TCC and CBZ suggests soils receiving biosolids could accumulate these chemicals, representing risks concerning crop uptake.
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•Pharmaceuticals and personal care products are commonly found in soils.•Diclofenac, carbamazepine & triclocarban removal in soils was examined.•The phylotypes and metabolic pathways impacted were also investigated.•The methods involved LC-ESI-MS/MS, Illumina sequencing, STAMP and PiCRUST.•Hypotheses were generated regarding the metabolic pathways involved in biodegradation.
The widespread use of aqueous film-forming foam (AFFF) for firefighting activities (e.g., fire training to extinguish fuel-based fires at aircraft facilities) has led to extensive groundwater and ...soil contamination by per- and polyfluoroalkyl substances (PFASs) that are highly recalcitrant to destruction using conventional treatment technologies. This study reports on the hydrothermal alkaline treatment of diverse PFASs present in AFFFs. Quantitative and semiquantitative high-resolution mass spectrometry analyses of PFASs demonstrate a rapid degradation of all 109 PFASs identified in two AFFFs (sulfonate- and fluorotelomer-based formulations) in water amended with an alkali (e.g., 1–5 M NaOH) at near-critical temperature and pressure (350 °C, 16.5 MPa). This includes per- and polyfluoroalkyl acids and a range of acid precursors. Most PFASs were degraded to nondetectable levels within 15 min, and the most recalcitrant perfluoroalkyl sulfonates were degraded within 30 min when treated with 5 M NaOH. 19F NMR spectroscopic analysis and fluoride ion analysis confirm the near-complete defluorination of PFASs in both dilute and concentrated AFFF mixtures, and no stable volatile organofluorine species were detected in reactor headspace gases by the gas chromatography–mass spectrometry analysis. These findings indicate a significant potential for application of hydrothermal treatment technologies to manage PFAS waste streams, including on-site treatment of unused AFFF chemical stockpiles, investigation-derived wastes, and concentrated source zone materials.
Ion exchange is widely used to treat nitrate-contaminated groundwater, but high salt usage for resin regeneration and management of waste brine residuals increase treatment costs and add ...environmental burdens. Development of palladium-based catalytic nitrate treatment systems for brine treatment and reuse has showed promising activity for nitrate reduction and selectivity towards the N2 over the alternative product ammonia, but this strategy overlooks the potential value of nitrogen resources. Here, we evaluated a hybrid catalytic hydrogenation/membrane distillation process for nitrogen resource recovery during treatment and reuse of nitrate-contaminated waste ion exchange brines. In the first step of the hybrid process, a Ru/C catalyst with high selectivity towards ammonia was found to be effective for nitrate hydrogenation under conditions representative of waste brines, including expected salt buildup that would occur with repeated brine reuse cycles. The apparent rate constants normalized to metal mass (0.30 ± 0.03 mM min−1 gRu−1 under baseline condition) were comparable to the state-of-the-art bimetallic Pd catalyst. In the second stage of the hybrid process, membrane distillation was applied to recover the ammonia product from the brine matrix, capturing nitrogen as ammonium sulfate, a commercial fertilizer product. Solution pH significantly influenced the rate of ammonia mass transfer through the gas-permeable membrane by controlling the fraction of free ammonia species (NH3) present in the solution. The rate of ammonia recovery was not affected by increasing salt levels in the brine, indicating the feasibility of membrane distillation for recovering ammonia over repeated reuse cycles. Finally, high rates of nitrate hydrogenation (apparent rate constant 1.80 ± 0.04 mM min−1 gRu−1) and ammonia recovery (overall mass transfer coefficient 0.20 m h−1) with the hybrid treatment process were demonstrated when treating a real waste ion exchange brine obtained from a drinking water utility. These findings introduce an innovative strategy for recycling waste ion exchange brine while simultaneously recovering potentially valuable nitrogen resources when treating contaminated groundwater.
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•Introduce a hybrid ion exchange/catalytic hydrogenation/membrane distillation process.•Ru/C shows high activity for selective nitrate reduction to ammonia.•Membrane distillation used to recover ammonia product as a fertilizer.•Nitrate hydrogenation and ammonia recovery demonstrated with real IX waste brine.
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