Bacterial degradation of perfluoroalkyl acids.

Advances in biological degradation of per- and polyfluoroalkyl substances (PFAS) have shown that bioremediation is a promising method of PFAS mineralization; however, most of these studies focus on remediation of more reactive polyfluorinated compounds. This review focuses on the defluorination of the more recalcitrant perfluorinated alkyl acids (PFAAs) by bacteria. We highlight key studies that report PFAA degradation products, specific bacteria, and relevant genes. Among these studies, we discuss trends in anaerobic versus aerobic conditions with specific bacterial species or consortia. This holistic review seeks to elucidate the state of PFAA biodegradation research and discuss the need for future research for environmental application.

Defluorination of PFAS by Acidimicrobium sp. strain A6 and potential applications for remediation.

Acidimicrobium sp. strain A6 is a recently discovered autotrophic bacterium that is capable of oxidizing ammonium while reducing ferric iron and is relatively common in acidic iron-rich soils. The genome of Acidimicrobium sp. strain A6 contains sequences for several reductive dehalogenases, including a gene for a previously unreported reductive dehalogenase, rdhA. Incubations of Acidimicrobium sp. strain A6 in the presence of perfluorinated substances, such as PFOA (perfluorooctanoic acid, C8HF15O2) or PFOS (perfluorooctane sulfonic acid, C8HF17O3S), have shown that fluoride, as well as shorter carbon chain PFAAs (perfluoroalkyl acids), are being produced, and the rdhA gene is expressed during these incubations. Results from initial gene knockout experiments indicate that the enzyme associated with the rdhA gene plays a key role in the PFAS defluorination by Acidimicrobium sp. strain A6. Experiments focusing on the defluorination kinetics by Acidimicrobium sp. strain A6 show that the defluorination kinetics are proportional to the amount of ammonium oxidized. To explore potential applications for PFAS bioremediation, PFAS-contaminated biosolids were augmented with Fe(III) and Acidimicrobium sp. strain A6, resulting in PFAS degradation. Since the high demand of Fe(III) makes growing Acidimicrobium sp. strain A6 in conventional rectors challenging, and since Acidimicrobium sp. strain A6 was shown to be electrogenic, it was grown in the absence of Fe(III) in microbial electrolysis cells, where it did oxidize ammonium and degraded PFAS.

Modeling the kinetics of perfluorooctanoic and perfluorooctane sulfonic acid biodegradation by Acidimicrobium sp. Strain A6 during the feammox process.

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants of concern due to their health effects and persistence in the environment. Although perfluoroalkyl acids (PFAAs), such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) are very difficult to biodegrade because they are completely saturated with fluorine, it has recently been shown that Acidimicrobium sp. A6 (A6), which oxidizes ammonium under iron reducing conditions (Feammox process), can defluorinate PFAAs. A kinetic model was developed and tested in this study using results from previously published laboratory experiments, augmented with results from additional incubations, to couple the Feammox process to PFAS defluorination. The experimental results show higher Feammox activity and PFAS degradation in the A6 enrichment cultures than in the highly enriched A6 cultures. The coupled experimental and modeling results show that the PFAS defluorination rate is proportional to the rate of ammonium oxidation. The ammonium oxidation rate and the defluorination rate increase monotonically, but not linearly, with increasing A6 biomass. Given that different experiments had different level of Feammox activity, the parameters required to simulate the Feammox varied between A6 cultures. Nonetheless, the kinetic model was able to simulate an anaerobic incubation system and show that PFAS defluorination is proportional to the Feammox activity.

Long-term metal pollution shifts microbial functional profiles of nitrification and denitrification in agricultural soils.

The increasing contamination of heavy metals in agricultural soils and its impact on the nitrogen (N) cycle and N use efficiency have attracted considerable attention in recent years. In this study, agricultural soils neighboring the Dabaoshan copper mining area (DBS) and Qingyuan electronic-waste recycling area (QY), in Guangdong, China, were sampled to study the interaction between heavy metals and nitrification/denitrification processes, especially the related microbial functional profiles. Results showed that the contamination of heavy metals affected nitrifiers and denitrifiers differently. The potential nitrification activity was about four times lower in metal-polluted soils compared with the unpolluted ones, with a significant decrease in the abundance of amoA and nxrB (p < 0.05) in the polluted samples. On the other hand, the potential denitrification activity was more metal-resistant, which attributed to its complex species composition as shown by a slightly higher α-diversity index, and was slightly higher (p > 0.05) in the polluted samples. Among the five denitrifying genes tested, nosZ gene had the highest increase and the nirK gene the most decrease in numbers and in the polluted soils. The metal-polluted soils had fewer correlations among N functional genes based on the co-occurrence network analysis. In addition, the core taxa of the whole bacterial community changed from copiotrophic to oligotrophic bacteria in the presence of heavy metals. Mantel test indicated that heavy metals were the dominant factors determining N-related genes while the bacterial community composition was due to a combination of heavy metal presence and soil properties such as TOC, NO2-, and pH. It is concluded that long-term heavy metals pollution potentially affected nitrifiers and denitrifiers differently as indicated by the shift in N functional genes and the change in nitrification/denitrification processes.

Anaerobic degradation of perfluorooctanoic acid (PFOA) in biosolids by Acidimicrobium sp. strain A6.

Anaerobic incubations were performed with biosolids obtained from an industrial wastewater treatment plant (WWTP) that contained perfluorooctanoic acid (PFOA), and with per- and polyfluoroalkyl substances- (PFAS) free, laboratory-generated, biosolids that were spiked with PFOA. Biosolid slurries were incubated for 150 days as is, after augmenting with either Acidimicrobium sp. Strain A6 or ferrihydrite, or with both, Acidimicrobium sp. Strain A6 and ferrihydrite. Autoclaved controls were run in parallel. Only the biosolids augmented with both, Acidimicrobium sp. Strain A6 and ferrihydrite showed a decrease in the PFOA concentration, in excess of 50% (total, dissolved, and solid associated). Higher concentrations of PFOA in the biosolids spiked with PFOA and no previous PFAS exposure allowed to track the production of fluoride to verify PFOA defluorination. The buildup of fluoride over the incubation time was observed in these biosolid incubations spiked with PFOA. A significant increase in the concentration of perfluoroheptanoic acid (PFHpA) over the incubations of the filter cake samples from the industrial WWTP was observed, indicating the presence of a non-identified precursor in these biosolids. Results show that anaerobic incubation of PFAS contaminated biosolids, after augmentation with Fe(III) and Acidimicrobium sp. Strain A6 can result in PFAS defluorination.

Effects of design parameters, microbial community and nitrogen removal on the field-scale multi-pond constructed wetlands.

Ecological multi-pond constructed wetlands (CWs) are an alternative wastewater treatment technology for nitrogen removal from non-point source pollution. As an important component of nitrogen cycles in the field-scale CWs, microorganisms are affected by design parameters. Nevertheless, the mechanism of design parameters affecting the distribution of microbial community and removal performance remains largely unexplored. In this study, satisfactory nitrogen removal performance was obtained in three multi-pond CWs. The highest mass removal rate per square meter (1104.0 mg/m2/day) and mass removal rate per cubic meter (590.2 mg/m3/day) for total nitrogen removal were obtained in the XY CW system during the wet season. The changes in seasonal parameters accounted for different removal performances and distributions of the microbial community. The combination of wastewater treatment technologies in the XY CW system consisting of ponds, CWs, and eco-floating treatment wetlands enriched the abundances of nitrogen-related functional genera. Correlation network analysis further demonstrated that longer hydraulic residence time and higher nitrogen concentration could intensify the enrichment of nitrogen-related functional genera. Regulating the combination of wastewater treatment technologies, the nitrogen concentration of influent, hydraulic loading rate, and water depth might promote the accumulation of microbial communities and enhance nitrogen removal. Macroscopical spatial/temporal regulation were proposed to enhance the treatment of non-point source pollution. The clarification of driving mechanism on design parameters, microbial community, and removal performance provided a novel perspective on the long-term maintenance of purification performance, practically sustainable applications, and scientific management of field-scale multi-pond CWs.

A critical review of modeling Poly- and Perfluoroalkyl Substances (PFAS) in the soil-water environment.

Due to their health effects and the recalcitrant nature of their CF bonds, Poly- and Perfluoroalkyl Substances (PFAS) are widely investigated for their distribution, remediation, and toxicology in ecosystems. However, very few studies have focused on modeling PFAS in the soil-water environment. In this review, we summarized the recent development in PFAS modeling for various chemical, physical, and biological processes, including sorption, volatilization, degradation, bioaccumulation, and transport. PFAS sorption is kinetic in nature with sorption equilibrium commonly quantified by either a linear, the Freundlich, or the Langmuir isotherms. Volatilization of PFAS depends on carbon chain length and ionization status and has been simulated by a two-layer diffusion process across the air water interface. First-order kinetics is commonly used for physical, chemical, and biological degradation processes. Uptake by plants and other biota can be passive and/or active. As surfactants, PFAS have a tendency to be sorbed or concentrated on air-water or non-aqueous phase liquid (NAPL)-water interfaces, where the same three isotherms for soil sorption are adopted. PFAS transport in the soil-water environment is simulated by solving the convection-dispersion equation (CDE) that is coupled to PFAS sorption, phase transfer, as well as physical, chemical, and biological transformations. As the physicochemical properties and concentration vary greatly among the potentially thousands of PFAS species in the environment, systematic efforts are needed to identify models and model parameters to simulate their fate, transport, and response to remediation techniques. Since many process formulations are empirical in nature, mechanistic approaches are needed to further the understanding of PFAS-soil-water-plant interactions so that the model parameters are less site dependent and more predictive in simulating PFAS remediation efficiency.

Linking microbial community and biological functions to redox potential during black-odor river sediment remediation.

The black-odor phenomenon in polluted urban rivers is a serious environmental problem that has received increasing attention in the recent years. The low redox potential (less than - 100 mV) in the sediment is considered to be the key factor causing the occurrence of black-odor phenomenon. Here, we studied the structure and function of the microbial community during the remediation of urban rivers. Results showed a clear improvement in water quality after undergoing river remediation processes. The on-site treatments showed a succession in the microbial composition and their predicted functions. The primary iron- and sulfur-reducing bacteria (Thiobacillus, Sulfuricurvum, and Sulfursoma) and the related reactions rapidly decreased after the dredging treatment but reappeared after a year. The structure and abundance of nitrogen and methane participants were also affected by river remediation process. These results indicated that although the water quality temporarily improved shortly after a dredging process, a recurrence of the black-odor phenomenon may occur as a result of the rebound in the microbial communities.

Hydrogen peroxide sensor HPCA1 is an LRR receptor kinase in Arabidopsis.

Hydrogen peroxide (H2O2) is a major reactive oxygen species in unicellular and multicellular organisms, and is produced extracellularly in response to external stresses and internal cues1-4. H2O2 enters cells through aquaporin membrane proteins and covalently modifies cytoplasmic proteins to regulate signalling and cellular processes. However, whether sensors for H2O2 also exist on the cell surface remains unknown. In plant cells, H2O2 triggers an influx of Ca2+ ions, which is thought to be involved in H2O2 sensing and signalling. Here, by using forward genetic screens based on Ca2+ imaging, we isolated hydrogen-peroxide-induced Ca2+ increases (hpca) mutants in Arabidopsis, and identified HPCA1 as a leucine-rich-repeat receptor kinase belonging to a previously uncharacterized subfamily that features two extra pairs of cysteine residues in the extracellular domain. HPCA1 is localized to the plasma membrane and is activated by H2O2 via covalent modification of extracellular cysteine residues, which leads to autophosphorylation of HPCA1. HPCA1 mediates H2O2-induced activation of Ca2+ channels in guard cells and is required for stomatal closure. Our findings help to identify how the perception of extracellular H2O2 is integrated with responses to various external stresses and internal cues in plants, and have implications for the design of crops with enhanced fitness.

Phylogenetic and Molecular Evolutionary Analysis of Mitophagy Receptors under Hypoxic Conditions.

As animals evolved to use oxygen as the main strategy to produce ATP through the process of mitochondrial oxidative phosphorylation, the ability to adapt to fluctuating oxygen concentrations is a crucial component of evolutionary pressure. Three mitophagy receptors, FUNDC1, BNIP3 and NIX, induce the removal of dysfunctional mitochondria (mitophagy) under prolonged hypoxic conditions in mammalian cells, to maintain oxygen homeostasis and prevent cell death. However, the evolutionary origins and structure-function relationships of these receptors remain poorly understood. Here, we found that FUN14 domain-containing proteins are present in archaeal, bacterial and eukaryotic genomes, while the family of BNIP3 domain-containing proteins evolved from early animals. We investigated conservation patterns of the critical amino acid residues of the human mitophagy receptors. These residues are involved in receptor regulation, mainly through phosphorylation, and in interaction with LC3 on the phagophore. Whereas FUNDC1 may be able to bind to LC3 under the control of post-translational regulations during the early evolution of vertebrates, BINP3 and NIX had already gained the ability for LC3 binding in early invertebrates. Moreover, FUNDC1 and BNIP3 each lack a layer of phosphorylation regulation in fishes that is conserved in land vertebrates. Molecular evolutionary analysis revealed that BNIP3 and NIX, as the targets of oxygen sensing HIF-1α, showed higher rates of substitution in fishes than in mammals. Conversely, FUNDC1 and its regulator MARCH5 showed higher rates of substitution in mammals. Thus, we postulate that the structural traces of mitophagy receptors in land vertebrates and fishes may reflect the process of vertebrate transition from water onto land, during which the changes in atmospheric oxygen concentrations acted as a selection force in vertebrate evolution. In conclusion, our study, combined with previous experimental results, shows that hypoxia-induced mitophagy regulated by FUDNC1/MARCH5 might use a different mechanism from the HIF-1α-dependent mitophagy regulated by BNIP3/NIX.