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We report an effective and environmentally sustainable water treatment approach using enzymes encapsulated in biogenic vault nanoparticles. Manganese peroxidase (MnP), whose stability was remarkably extended by encapsulating into vaults, rapidly catalyzed the biotransformation of endocrine-disrupting compounds, including bisphenol A (BPA), bisphenol F (BPF), and bisphenol AP (BPAP). The vault-encapsulated MnP (vMnP) treatment removed 80-95% of each of the tested bisphenols (BPs) at lower enzyme dosage, while free native MnP (nMnP) only resulted in a 19-36% removal, over a 24-h period. Treatment by vMnP and nMnP resulted in considerable disparities in product species and abundance, which were consistent with the observed changes in the estrogenic activities of BPs. To test if vMnP-catalyzed transformations generated toxic intermediates, we assessed biological hallmarks of BP toxicity, namely, the ability to disrupt reproductive processes. The toxicity of vMnP-treated samples, as measured in the model organism, Caenorhabditis elegans, was dramatically reduced for all three BPs, including the reproductive indicators of BPA exposure such as reduced fertility and increased germ cell death. Collectively, our results indicate that the vMnP system represents an efficient and safe approach for the removal of BPs and promise the development of vault-encapsulated customized enzymes for treating other targeted organic compounds in contaminated waters.

The influence of growth medium water chemistry, specifically carbon/nitrogen (C/N) molar ratios, on the characteristics and development of biofilms of the model microorganism Pseudomonas aeruginosa was investigated. C/N = 9 had a unique effect on biofilm composition as well as quorum sensing (QS) pathways, with higher concentrations of carbohydrates and proteins in the biofilm and a significant upregulation of the QS gene lasI in planktonic cells. The effect of C/N ratio on total attached biomass was negligible. Principal component analysis revealed a different behavior of most outputs such as carbohydrates and QS chemicals at C/N = 9, and pointed to correlations between parameters of biofilm formation and steady state distribution of cells and extracellular components. C/N ratio was also shown to influence organic compound utilization by both planktonic and sessile organisms, with a maximum chemical oxygen demand (COD) removal of 83% achieved by biofilms at C/N = 21. Planktonic cells achieved higher COD removal rates, but greater overall rates after six days occurred in biofilms. The development of a dual-species biofilm of P. aeruginosa and Nitrobacter winogradskyi was also influenced by C/N, with increase in the relative abundance of the slower-growing N. winogradskyi above C/N = 9. These results indicate that altering operational parameters related to C/N would be relevant for mitigating or promoting biofilm formation and function depending on the desired industrial application or treatment configuration.

Unlike growth on tissue, microbes can grow freely on implantable devices with minimal immune system intervention and often form resilient biofilms that continuously pump out pathogenic cells. The efficacy of antibiotics used to treat infection is declining due to increased rates of pathogenic resistance. A simple, one-step zwitterionic surface modification is developed to significantly reduce protein and microbial adhesion to synthetic materials and demonstrate the successful modification of several clinically relevant materials, including recalcitrant materials such as elastomeric polydimethylsiloxane. The treated surfaces exhibit robust adhesion resistance against proteins and microorganisms in both static and flow conditions. Furthermore, the surface treatment prevents the adhesion of mammalian fibroblast cells while displaying no cytotoxicity. To demonstrate the clinical efficacy of the novel technology in the real-world, a surface-treated, commercial silicone foley catheter is developed that is cleared for use by the U.S. Food and Drug Administration (K192034). 16long-term catheterized patients received surface-treated catheters and completed a Patient Global Impression of Improvement (PGI-I) questionnaire. 10out of 16patients described their urinary tract condition post implantation as "much better" or "very much better" and 72% (n=13) of patients desire to continue using the surface-treated catheter over conventional latex or silicone catheters.

Microbial enzymes catalyze various reactions inside and outside living cells. Among the widely studied enzymes, fungal enzymes have been used for some of the most diverse purposes, especially in bioremediation, biosynthesis, and many nature-inspired commercial applications. To improve their stability and catalytic ability, fungal enzymes are often immobilized on assorted materials, conventional as well as nanoscale. Recent advances in fungal enzyme immobilization provide effective and sustainable approaches to achieve improved environmental and commercial outcomes. This review aims to provide a comprehensive overview of commonly studied fungal enzymes and immobilization technologies. It also summarizes recent advances involving immobilized fungal enzymes for the degradation or assembly of compounds used in the manufacture of products, such as detergents, food additives, and fossil fuel alternatives. Furthermore, challenges and future directions are highlighted to offer new perspectives on improving existing technologies and addressing unexplored fields of applications.

1,4-Dioxane is a probable carcinogen and trace contaminant that is difficult to remove from water because of its high solubility and low volatility. Removal of 1,4-dioxane from aqueous solutions by a set of potential adsorbents was investigated using batch experiments that revealed Titanium Silicate-1 (TS-1) as a high-capacity adsorbent (85.17 mg/g) with rapid kinetics (2 min equilibration time). The specific adsorption mechanisms at the molecular level were investigated using multiple approaches including FTIR spectra and molecular dynamics simulation of 1,4-dioxane adsorption on TS-1, which imply that the shape and size of 1,4-dioxane fits tightly into the hydrophobic straight channels of TS-1 with a diameter of 0.56 nm, and thus TS-1 provides strong van der Waals attraction within the channels. Additionally, 1,4-dioxane-water complexation was observed to connect to the frame oxygens of TS-1 via hydrogen bonds inside the channels. The calculated adsorption free energy of 1,4-dioxane was between −24.59 and −27.17 kJ/mol, which was consistent with the value of −24.89 kJ/mol derived from the adsorption isotherms at 298 K. The strong adsorption competition from nonpolar compounds 1,1,1-trichloroethane (TCA) and benzene onto TS-1 further confirmed that the adsorption was attributed to a combined mechanism of host-guest interactions including van der Waals interactions, hydrophobic interactions, and hydrogen bonding. Furthermore, 1,4-dioxane-loaded TS-1 was found to be efficiently regenerated by an enriched bacterial consortium (BD1) with recovery efficiencies for three cycles of 88.2%, 96.47% and nearly 100%, suggesting that TS-1 holds promise as a cost-effective renewable absorbent for eliminating hydrophilic organics from contaminated water supplies.

Microbial community dynamics were characterized following combined oxidation and biodegradation treatment trains for mixtures of 1,4-dioxane and chlorinated volatile organic compounds (CVOCs) in laboratory microcosms. Bioremediation is generally inhibited by co-contaminate CVOCs; with only a few specific bacterial taxa reported to metabolize or cometabolize 1,4-dioxane being unaffected. Chemical oxidation by hydrogen peroxide (H2O2) as a non-selective treatment demonstrated 50-80% 1,4-dioxane removal regardless of the initial CVOC concentrations. Post-oxidation bioaugmentation with 1,4-dioxane metabolizer Pseudonocardia dioxanivorans CB1190 removed the remaining 1,4-dioxane. The intrinsic microbial population, biodiversity, richness, and biomarker gene abundances decreased immediately after the brief oxidation phase, but recovery of cultivable microbiomes and a more diverse community were observed during the subsequent 9-week biodegradation phase. Results generated from the Illumina Miseq sequencing and bioinformatics analyses established that generally oxidative stress tolerant genus Ralstonia was abundant after the oxidation step, and Cupriavidus, Pseudolabrys, Afipia, and Sphingomonas were identified as dominant genera after aerobic incubation. Multidimensional analysis elucidated the separation of microbial populations as a function of time under all conditions, suggesting that temporal succession is a determining factor that is independent of 1,4-dioxane and CVOCs mixtures. Network analysis highlighted the potential interspecies competition or commensalism, and dynamics of microbiomes during the biodegradation phase, in line with the shifts of predominant genera and various developing directions during different steps of the treatment train. Collectively, this study demonstrated that chemical oxidation followed by bioaugmentation is effective for treating 1,4-dioxane, even in the presence of high levels of CVOC mixtures and residual peroxide, a disinfectant, and enhanced our understanding of microbial ecological impacts of the treatment train. These results will be valuable for predicting treatment synergies that lead to cost savings and improved remedial outcomes in short-term active remediation as well as long-term changes to the environmental microbial communities.

We developed a microbial community capable of biodegrading mixtures of chlorinated ethenes and 1,4-dioxane under varying redox conditions. Achieving the removal of chlorinated ethenes as well as 1,4-dioxane to below health advisory levels in groundwater that has anaerobic and aerobic zones has proven to be challenging. However, our mixed community, composed of the anaerobic chlorinated ethene-degrading consortium KB-1 and aerobic bacterial strain, Pseudonocardia dioxanivorans CB1190, was able to reduce trichloroethene (TCE) in anaerobic environments and oxidize 1,4-dioxane in the presence of oxygen. Aerobic biodegradation of cis-1,2-dichloroethene by CB1190 was also confirmed, thus decreasing the accumulation of TCE transformation products, such as vinyl chloride. The results of this study demonstrate that the assembled microbial community not only survived significant redox changes but sequentially biodegraded chlorinated ethenes and 1,4-dioxane. This approach toward degrading mixed contaminants with a c...

Biodegradation of 1,4-dioxane was examined in packed quartz and soil column flow-through systems. The inhibitory effects of co-contaminants, specifically trichloroethene (TCE), 1,1-dichloroethene (1,1-DCE), and copper (Cu2+) ions, were investigated in the columns either with or without bioaugmentation with a 1,4-dioxane degrading bacterium Pseudonocardia dioxanivorans CB1190. Results indicate that CB1190 cells readily grew and colonized in the columns, leading to significant degradation of 1,4-dioxane under oxic conditions. Degradation of 1,4-dioxane was also observed in the native soil (without bioaugmentation), which had been previously subjected to enhanced reductive dechlorination treatment for co-contaminants TCE and 1,1-DCE. Bioaugmentation of the soil with CB1190 resulted in nearly complete degradation at influent concentrations of 3–10 mg L−1 1,4-dioxane and a residence reaction time of 40–80 h, but the presence of co-contaminants, 1,1-DCE and Cu2+ ions (up to 10 mg L−1), partially inhibited 1,4-dioxane degradation in the untreated and bioaugmented soil columns. However, the inhibitory effects were much less severe in the column flow-through systems than those previously observed in planktonic cultures, which showed near complete inhibition at the same co-contaminant concentrations. These observations demonstrate a low susceptibility of soil microbes to the toxicity of 1,1-DCE and Cu2+ in packed soil flow-through systems, and thus have important implications for predicting biodegradation potential and developing sustainable, cost-effective technologies for in situ remediation of 1,4-dioxane contaminated soils and groundwater.

Eroded particles from the source zone could transport a high concentration of perfluoroalkyl acids (PFAAs) to sediments and water bodies. Yet, the contribution of suspended particles has not been systematically reviewed. Analyzing reported studies, we quantitatively demonstrate that suspended particles in surface water can contain significantly higher concentrations of PFAAs than the sediment below, indicating the source of suspended particles are not the sediment but particles eroded and carried from the source zone upstream. The affinity of PFAAs to particles depends on the particle composition, including organic carbon fraction and iron or aluminum oxide content. In soils, most PFAAs are retained within the top 5 m below the ground surface. The distribution of PFAAs in the subsurface varies based on site properties and local weather conditions. The depth corresponding to the maximum concentration of PFAA in soil decreases with an increase in soil organic carbon or rainfall amount received in the catchment areas. We attribute a greater accumulation of PFAAs near the upper layer of the subsurface to an increase in the accumulation of particles eroded from source zones upstream receiving heavy rainfall. Precursor transformation in the aerobic zone is significantly higher than in the anaerobic zone, thereby making the aerobic subsurface zone serve as a long-term source of groundwater pollution. Collectively, these results suggest that suspended particles, often an overlooked vector for PFAAs, can be a dominant pathway for the transport of PFAAs in environments.

The overuse of antibiotics and subsequent enrichment of antibiotic resistant microbes in the natural and built environments is a severe threat to global public health. In this study, a Phanerochaete chrysosporium fungal-luffa fiber system was found to efficiently biodegrade two sulfonamides, sulfadimethoxine (SDM) and sulfadizine (SDZ), in cow urine wastewater. Biodegradation pathways were proposed on the basis of key metabolites identified using high performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry (HPLC-QqTOF-MS). Transcriptomic, metabolomic, and free radical analyses were performed to explore the functional groups and detailed molecular mechanisms of SDM and SDZ degradation. A total of 27 UniGene clusters showed significant differences between luffa fiber and luffa fiber-free systems, which were significantly correlated to cellulose catabolism, carbohydrate metabolism, and oxidoreductase activity. Carbohydrate-active enzymes and oxidoreductases appear to play particularly important roles in SDM and SDZ degradation. Electron paramagnetic resonance (EPR) spectroscopy revealed the generation and evolution of OH and R during the biodegradation of SDM and SDZ, suggesting that beyond enzymatic degradation, SDM and SDZ were also transformed through a free radical pathway. Luffa fiber also acts as a co-substrate to improve the activity of enzymes for the degradation of SDM and SDZ. This research provides a potential strategy for removing SDM and SDZ from agricultural and industrial wastewater using fungal-luffa fiber systems.

Granular activated carbon (GAC) has been used to remove per- and polyfluoroalkyl substances (PFASs) from industrial or AFFF-impacted waters,but its effectiveness can be low because adsorption of short-chained PFASs is ineffective and its sites are exhausted rapidly by co-contaminants. To increase adsorption of anionic PFASs on GAC by electrostatic attractions,we modified GAC's surface with the cationic polymer poly diallyldimethylammonium chloride (polyDADMAC) and tested its capacity in complex water matrices containing dissolved salts and humic acid. Amending with concentrations of polyDADMAC as low as 0.00025% enhanced GAC's adsorption capacity for PFASs,even in the presence of competing ions. This suggests that electrostatic interactions with polyDADMAC's quaternary ammonium functional groups helped bind organic and inorganic ions as well as the headgroup of short-chain PFASs,allowing more overall PFAS removal by GAC. Evaluating the effect of polymer dose is important because excessive addition can block pores and reduce overall PFAS removal rather than increase it. To decrease the waste associated with this adsorption strategy by making the adsorbent viable for more than one saturation cycle,a regeneration method is proposed which uses low-power ultrasound to enhance the desorption of PFASs from the polyDADMAC- GAC with minimum disruption to the adsorbent's structure. Re-modification with the polymer after sonication resulted in a negligible decrease in the sorbent's capacity over four saturation rounds. These results support consideration of polyDADMAC-modified GAC as an effective regenerable adsorbent for ex-situ concentration step of both short and long-chain PFASs from real waters with high concentrations of competing ions and low PFAS loads.

Per- and polyfluoroalkyl substances (PFASs) are anthropogenic amphipathic heat-resistant materials found in some household products and Aqueous Film-Forming Foams (AFFFs) used to extinguish hydrocarbon fires. There is a critical need for developing destructive technologies for the treatment of PFAS-impacted waters because several PFASs are classified as probable carcinogens and endocrine disruptors. We tested the destruction of 7 individual PFASs, a mix of 24 native PFASs (24Mix), and samples of AFFF and concentrated Investigation Derived Waste (IDW) by high-frequency ultrasound (700 kHz – 1040 W) in deionized water, groundwater containing low total dissolved solids (TDS) (388 mg L−1), and high-TDS groundwater (10.2 g L−1). This study demonstrated the degradation of novel PFASs, hexafluoropropylene oxide dimer acid (HFPO-DA) and 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB), with near-stoichiometric fluoride release. The salts and surfactants affect the air-water partitioning coefficients of PFASs and their availability at the ultrasonic cavity, thereby affecting the degradation rates. The degradation rates of sulfonates and short-chain PFASs were 30% to 60% higher in low TDS groundwater than those in deionized water, while the rates were lower in high TDS groundwater. The degradation rates of sulfonates in AFFF were 40% to 60% higher as compared to the 24Mix. The treatment of concentrated, high-TDS IDW resulted in significant defluorination of 41 PFASs, consuming 3 kWh g−1 – 76 kWh g−1 whereas dilute AFFF degradation utilized 5900 kWh g−1. The results inform important parameters for designing and operating ultrasonic reactors for the degradation of PFASs and verify that sonolytic treatment of concentrated PFAS mixtures and AFFF IDWs can effectively degrade and defluorinate PFASs without the formation of disinfection by-products.

Groundwater flow through aquifer soils or packed bed systems can fluctuate for various reasons, which could affect the concentration of natural colloids and per- and polyfluoroalkyl substances (PFAS) in the pore water. In such cases, PFAS concentration could either decrease due to matrix diffusion of PFAS or increase by the detachment of colloids carrying PFAS. Yet, the effect of flow fluctuation on PFAS transport or release in porous media has not been examined. To examine the relative importance of either process, we interrupted the flow during an injection of groundwater spiked with perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), and bromide as conservative tracer through clay-rich soil, so that diffusive transport would be prominent during flow interruption. After flow interruption, the PFAS concentration did not decrease indicating an insignificant contribution of matrix diffusion. The concentration increased, potentially due to enhanced release of colloid-associated PFAS. Analysis of samples before and after flow interruption by particle size analysis and SEM confirmed an increase in soil colloid concentration after the flow interruption. XRD analysis of soil and the colloids proved that PFAS were associated with specific sites of the colloids. Due to a higher affinity of PFOA to soil colloids, the total PFOA concentration in the effluent samples increased more than PFBA after the flow interruption process. The results indicate that colloids may have a disproportionally higher role in the transport of PFAS in conditions that release colloids from porous media. Thus, fluctuations in groundwater flow can increase this colloid facilitated mobility of PFAS.

Silica materials are attractive protein supports for applications in catalysis, sensing, water purification, and protein therapy. However, current approaches for loading proteins in silica are limited by inefficient protein immobilization, unintended leaching, the requirement for large quantities of silica precipitants, and associated protein inactivation. Here, we report a highly efficient and robust strategy that directly synthesizes protein-embedded silica via a vault protein nanocapsule-templated biomimetic silicification route. The vaults serve as nucleation sites for the deposition and condensation of silica precursors to form vault/silica composites. Using vaults encapsulated with proteins as the templating agent enables direct embedding of proteins in silica composites with nearly 100% immobilization efficiency. The vaults also act as protective shelters to preserve high protein activity during silica condensation. With the dual advantages of vault templating and protection, the proteins immobilized via this strategy retained over 90% activity after 30 reuse cycles and exhibited high activity, minimal leaching, and improved stability, which would be valuable in a broad variety of medical, industrial, and environmental applications.

This study used integrated omics technologies to investigate the potential novel pathways and enzymes for 1,4-dioxane degradation by a consortium enriched from activated sludge of a domestic wastewater treatment plant. An unclassified genus belonging to Xanthobacteraceae increased significantly after magnetic nanoparticle-mediated isolation for 1,4-dioxane degraders. Species with relatively higher abundance (> 0.3%) were identified to present high metabolic activities in the biodegradation process through shotgun sequencing. The functional gene investigations revealed that Xanthobacter sp. 91, Xanthobacter sp. 126, and a Rhizobiales strain carried novel 1,4-dioxane-hydroxylating monooxygenase genes. Xanthobacter sp. 126 contained the genes coding for glycolate oxidase, which was the main enzyme responsible for utilization of 1,4-dioxane intermediates through the TCA cycle, and further proven by the specific glycolate oxidase inhibitor, α-hydroxy-2-pyridinemethanesulfonic acid. An expanded and detailed degradation pathway of 1,4-dioxane was proposed on the basis of the three major intermediates (2-hydroxy-1,4-dioxane, ethylene glycol, and oxalic acid) confirmed by metabolomics. These findings of microbial community and function as well as the novel pathway will be valuable in predicting natural attenuation or reconstruction of a bacterial consortium for enhanced remediation of 1,4-dioxane-contaminated sites as well as wastewater treatment.

Development of a multiple lines of evidence (MLOE) framework to evaluate the intrinsic biodegradation potential of 1,4-dioxane is vital to implementing management strategies at groundwater sites impacted by 1,4-dioxane. A comprehensive MLOE approach was formed to provide significant evidence of natural degradation of 1,4-dioxane comingled with tetrahydrofuran (THF) within a large, diffuse plume. State-of-the art molecular biological analyses and compound-specific isotope analysis (CSIA) were employed to support more traditional approaches for data analysis (concentration trend analyses, spatial distribution, temporal changes, geochemical biodegradation attenuation indicators, plume mass estimates, and fate and transport modeling). The molecular analyses demonstrated that microorganisms capable of both metabolic and cometabolic degradation of 1,4-dioxane were present throughout the groundwater plume, whereas the CSIA data provided supporting evidence of biodegradation. 1,4-Dioxane biomarkers were present and abundant throughout the 1,4-dioxane plume, and our biomarkers tracked the plume with reasonable accuracy. Evidence also suggests that THF-driven cometabolic biodegradation as well as catabolic 1,4-dioxane biodegradation were active at this site. These data supplemented the traditional lines of evidence approaches, which demonstrated that 1,4-dioxane attenuation was occurring across the groundwater plume and that nondestructive physical processes alone did not account for the observed 1,4-dioxane attenuation. This MLOE framework combining new and traditional analyses demonstrates that this site has a significant capacity for intrinsic biodegradation of 1,4-dioxane. ©2016 Wiley Periodicals, Inc.

Amino-aromatic compounds, 2-amino-4-nitrotoluene (ANT), and 2,4-diaminotoluene (DAT) are carcinogens and environmentally persistent pollutants. In this study, we investigated their degradation by natural manganese peroxidase (nMnP) derived from Phanerochaete chrysosporium and recombinant manganese peroxidase packaged in vaults (vMnP). Encapsulation of manganese peroxidase (MnP) in ribonucleoprotein nanoparticle cages, called vaults, was achieved by creating recombinant vaults in yeast Pichia pastoris. Vault packaging increased the stability of MnP by locally sequestering multiple copies of the enzyme. Within 96 h, both vMnP and nMnP catalyzed over 72% removal of ANT in-vitro, which indicates that vault packaging did not limit substrate diffusion. It was observed that vMnP was more efficient than nMnP and P. chrysosporium for the catalysis of target contaminants. Only 57% of ANT was degraded by P. chrysosporium even when MnP activity reached about 480 U L−1 in cultures. At 1.5 U L−1 initial activity, vMnP achieved 38% of ANT and 51% of DAT degradation, whereas even 2.7 times higher activity of nMnP showed insignificant biodegradation of both compounds. These results imply that due to protection by vault cages, vMnP has lower inactivation rates. Thus, it works effectively at lower dosage for a longer duration compared to nMnP without requiring frequent replenishment. Collectively, these results indicate that fungal enzymes packaged in vault nanoparticles are more stable and active, and they would be effective in biodegradation of energetic compounds in industrial processes, waste treatment, and contaminated environments.

Biological treatment of 1,4-dioxane, a probable human carcinogen and a recalcitrant contaminant of concern, is often complicated by the presence of inhibitory co-contaminants. Due to its use as a solvent, wetting agent, and stabilizer for chlorinated solvents employed in metal vapor degreasing, 1,4-dioxane has often been found to occur with a variety of co-contaminants, including heavy metals such as hexavalent chromium [Cr(VI)]. Cr(VI) also occurs naturally in groundwater due to geological formations, but also has sources that can coincide with 1,4-dioxane from anthropogenic activities such as metal vapor degreasing. Biodegradation of 1,4-dioxane can be accomplished by microbes that use it as a source of carbon or energy as well as those that cometabolize it after growth on other organic substrates. A propanotroph, Mycobacterium austroafricanum JOB5, was grown in planktonic pure cultures and biofilms to determine its ability to cometabolize 1,4-dioxane in the presence of varying concentrations of Cr(VI). 1,4-Dioxane cometabolism by JOB5 planktonic cells was uninhibited by Cr(VI) at levels up to 10 mg/L, while biofilms were only mildly inhibited at 10 mg/L. As an important part of the biofilms commonly found in subsurface aquifers and engineered systems, extracellular polymeric substances (EPS) were found to play an important role in preventing Cr(VI) exposure to cells. We observed that soluble EPS were able to bind to Cr(VI) and theorize that biofilm-associated EPS additionally served to impede penetration of the biofilm structure by Cr(VI), thus mitigating exposure and toxicity. These findings suggest that bioremediation would be a viable treatment strategy for 1,4-dioxane-contaminated waters that contain elevated levels of Cr(VI) in natural and built environments.

Metallic nanoparticles (NPs), the most abundant nanomaterials in consumer and industrial products, are the most probable class to enter the environment. In this study, wetland-derived microcosms were incubated with copper nanoparticles (Cu-NP) and ionic CuCl(2) to investigate acute (10 days) and chronic (100 days) exposure towards nitrogen cycling microorganisms. The microbial ecology of wetlands play a crucial role in balancing nitrogen in pristine environments as well as in areas impacted by high nutrient loads (e.g., at wastewater effluent discharges). Gene abundance and expression changes were monitored using the GeoChip 5.0 high throughput functional gene microarray and metatranscriptomic shotgun sequencing (RNA-seq), respectively. After 10 days, the Cu-NP impacted microbial communities experienced structural shifts within microorganisms associated with dissimilatory nitrogen reduction accompanied by lower nitrate removal as compared to the unexposed controls. By day 100, these differences were largely resolved and nitrate removal was similar to the unexposed control. Furthermore, the Cu-NP exposed microcosms tolerated copper and were more resilient and adaptive than the unexposed controls based on the abundance and expression of other functions, including electron transfer, metal homeostasis, and stress response. These findings suggest sudden influxes of Cu-NPs into wetland systems may impair nitrogen removal initially, but long-term microbial shifts and functional redundancy would promote the net flux of total nitrogen out of the wetlands.

1,4-Dioxane is a probable human carcinogen and an emerging contaminant that has been detected in surface water and groundwater resources. Many conventional water treatment technologies are not effective for the removal of 1,4-dioxane due to its high water solubility and chemical stability. Biological degradation is a potentially low-cost, energy-efficient approach to treat 1,4-dioxane-contaminated waters. Two bacterial strains, Pseudonocardia dioxanivorans CB1190 (CB1190) and Mycobacterium austroafricanum JOB5 (JOB5), have been previously demonstrated to break down 1,4-dioxane through metabolic and co-metabolic pathways, respectively. However, both CB1190 and JOB5 have been primarily studied in laboratory planktonic cultures, while most environmental microbes grow in biofilms on surfaces. Another treatment technology, adsorption, has not historically been considered an effective means of removing 1,4-dioxane due to the contaminant's low Koc and Kow values. We report that the granular activated carbon (GAC), Norit 1240, is an adsorbent with high affinity for 1,4-dioxane as well as physical dimensions conducive to attached bacterial growth. In abiotic batch reactor studies, 1,4-dioxane adsorption was reversible to a large extent. By bioaugmenting GAC with 1,4-dioxane-degrading microbes, the adsorption reversibility was minimized while achieving greater 1,4-dioxane removal when compared with abiotic GAC (95–98% reduction of initial 1,4-dioxane as compared to an 85–89% reduction of initial 1,4-dioxane, respectively). Bacterial attachment and viability was visualized using fluorescence microscopy and confirmed by amplification of taxonomic genes by quantitative polymerase chain reaction (qPCR) and an ATP assay. Filtered samples of industrial wastewater and contaminated groundwater were also tested in the bioaugmented GAC reactors. Both CB1190 and JOB5 demonstrated 1,4-dioxane removal greater than that of the abiotic adsorbent controls. This study suggests that bioaugmented adsorbents could be an effective technology for 1,4-dioxane removal from contaminated water resources.

Hybridization of a UV-C photoreactor with an electrochemical cell led to the discovery of a distinctive synergistic mechanism for the degradation and mineralization of phenol when free chlorine-producing anodes were utilized in the presence of chloride. After 6 h, photochemical (UV) treatment resulted in 29% phenol mineralization and electrochemical (EL) treatment resulted in 35% and 52% mineralization using boron-doped diamond (BDD) and ruthenium oxide on titanium (DSA-Cl 2 ) anodes, respectively. However, the photo-assisted electrochemical (UVEL) process removed 88% and 96% of total organic carbon (TOC) after 6 h with BDD and DSA-Cl 2 anodes, respectively. The hybrid UVEL process generated highly reactive hydroxyl and chlorine radicals by the photolysis of in situ electrogenerated free chlorine. As a result, the UVEL treatment produced fewer chlorinated by-products compared to EL alone. UVEL with DSA-Cl 2 had the highest TOC removal after 6 h (96%), one of the highest mineralization rates (0.38 h −1 ), and the lowest energy demand per order TOC removed (E EO = 104 kW h m −3 order −1 ) without any residual toxicity after dechlorination. Generally, conventional advanced oxidation processes (UV/O 3 and UV/H 2 O 2 ) were most effective at mineralization up to 50%, but UVEL appeared more cost effective for mineralization beyond 75%.

The effects of feed solution ionic strength, pH and divalent cation content on NF/RO membrane structure and performance were elucidated experimentally and fitted with a modified solution–diffusion transport model that describes polyamide thin film free volume through an effective pore radius and structure factor. All the membranes tested became more hydrophilic and swollen with increasing feed solution ionic strength, pH, and divalent cation concentrations. Generally, water permeabilities of all three membranes decreased with ionic strength and divalent cation content, but increased with pH. For RO membranes, neutral solute rejection decreased with pH and divalent cation content, but increased with ionic strength and the salt rejection remained independent with water chemistry except for very low pH of 3; for a NF membrane, solute rejection was more sensitive to water chemistry and neutral solute rejection decreased with ionic strength and pH, but increased with divalent cation content. The results presented herein provide new insight into the fundamental relationship between changes in NF/RO membrane structure and performance. Ultimately, these new insights may be useful in selection of already commercial or design of new NF/RO membranes for removal of chemicals of emerging concern in water treatment.

1,4-Dioxane (dioxane), a probable human carcinogen, is used as a solvent stabilizer for 1,1,1-trichloroethane (TCA) and other chlorinated solvents. Consequently, TCA and its abiotic breakdown product 1,1-dichloroethene (DCE) are common co-contaminants of dioxane in groundwater. The aerobic degradation of dioxane by microorganisms has been demonstrated in laboratory studies, but the potential effects of environmentally relevant chlorinated solvent co-contaminants on dioxane biodegradation have not yet been investigated. This work evaluated the effects of TCA and DCE on the transformation of dioxane by dioxane-metabolizing strain Pseudonocardia dioxanivorans CB1190, dioxane co-metabolizing strain Pseudonomas mendocina KR1, as well as Escherichia coli expressing the toluene monooxygenase of strain KR1. In all experiments, both TCA and DCE inhibited the degradation of dioxane at the tested concentrations. The inhibition was not competitive and was reversible for strain CB1190, which did not transform the chlorinated solvents. For both strain KR1 and toluene monooxygenase-expressing E. coli, inhibition of dioxane degradation by chlorinated solvents was competitive and irreversible, and the chlorinated solvents were degraded concurrently with dioxane. These data suggest that the strategies for biostimulation or bioaugmentation of dioxane will need to consider the presence of chlorinated solvents during site remediation.

1,4-Dioxane is a contaminant of emerging concern that has been found widespread in groundwater, surface water, and drinking water environments. Many states are implementing lower regulatory advisory levels based on the toxicological profile of 1,4-dioxane and the potential public health risks. However, the unique chemical properties of 1,4-dioxane, such as high water solubility, low Henry's law constant, and importantly, the co-occurrence with chlorinated solvents and other contaminants, increase the challenges to efficiently cleanup 1,4-dioxane. This review summarizes currently available chemical and physical 1,4-dioxane treatment technologies and focuses on recent advances in bioremediation and monitoring tools. We also include laboratory studies and field applications to propose the next steps in 1,4-dioxane bioremediation research. It is important to provide useful references to change the industrial and regulatory perception of 1,4-dioxane biodegradability, to understand treatment mechanisms especially in contaminant mixtures, and to direct research for meeting practical needs.

This study investigated the impacts of individual chlorinated solvents and their mixtures on aerobic 1,4-dioxane biodegradation by Pseudonocardia dioxanivorans CB1190. The established association of these co-occurring compounds suggests important considerations for their respective biodegradation processes. Our kinetics and mechanistic studies demonstrated that individual solvents inhibited biodegradation of 1,4-dioxane in the following order: 1,1-dichloroethene (1,1-DCE) > cis-1,2-diochloroethene (cDCE) > trichloroethene (TCE) > 1,1,1-trichloroethane (TCA). The presence of 5 mg L(-1) 1,1-DCE completely inhibited 1,4-dioxane biodegradation. Subsequently, we determined that 1,1-DCE was the strongest inhibitor of 1,4-dioxane biodegradation by bacterial pure cultures exposed to chlorinated solvent mixtures as well as in environmental samples collected from a site contaminated with chlorinated solvents and 1,4-dioxane. Inhibition of 1,4-dioxane biodegradation rates by chlorinated solvents was attributed to delayed ATP production and down-regulation of both 1,4-dioxane monooxygenase (dxmB) and aldehyde dehydrogenase (aldH) genes. Moreover, increasing concentrations of 1,1-DCE and cis-1,2-DCE to 50 mg L(-1) respectively increased 5.0-fold and 3.5-fold the expression of the uspA gene encoding a universal stress protein. In situ natural attenuation or enhanced biodegradation of 1,4-dioxane is being considered for contaminated groundwater and industrial wastewater, so these results will have implications for selecting 1,4-dioxane bioremediation strategies at sites where chlorinated solvents are present as co-contaminants.

© 2016 SETAC. Although interactions of metallic nanoparticles (NPs) with various microorganisms have been previously explored, few studies have examined how metal sensitivity impacts NP toxicity. The present study investigated the effects of copper NPs (Cu-NP) exposure on the model alga Chlamydomonas reinhardtii in the presence and absence of the essential micronutrient copper. The toxic ranges for Cu-NPs and the ionic control, CuCl2, were determined using a high-throughput adenosine triphosphate (ATP)-based fluorescence assay. The Cu-NPs caused similar mortality in copper-replete and copper-deplete cells (median inhibitory concentration [IC50]: 14-16mg/L) but were less toxic than the ionic control, CuCl2(IC50: 7mg/L). Using this concentration range, the Cu-NP impacts on cell morphology, copper accumulation, chlorophyll content, and expression of stress genes under both copper supply states were assessed. Osmotic swelling, membrane damage, and chloroplast and organelle disintegration were observed by transmission electron microscopy at both conditions. Despite these similarities, copper-deplete cells showed greater accumulation of loosely bound and tightly bound copper after exposure to Cu-NPs. Furthermore, copper-replete cells experienced greater loss of chlorophyll content, 19% for Cu-NPs, compared with only an 11% net decrease in copper-deplete cells. The tightly bound copper was bioavailable as assessed by reverse-transcriptase quantitative polymerase chain reaction analysis of CYC6, a biomarker for Cu deficiency. The increased resistance of copper-deplete cells to Cu-NPs suggests that these cells potentially metabolize excess Cu-NPs or better manage sudden influxes of ions. The results suggest that toxicity assessments must account for the nutritional status of impacted organisms and use toxicity models based on estimations of the bioavailable fractions. Environ Toxicol Chem 2016;35:1148-1158.

Biofouling and virus penetration are two significant obstacles in water treatment membrane filtration. Biofouling reduces membrane permeability, increases energy costs, and decreases the lifetime of membranes. In order to effectively remove viruses, nanofiltration or reverse osmosis (both high energy filtration schemes) must be used. Thus, there is an urgent demand for low pressure membranes with anti-biofouling and antiviral properties. The antibacterial properties of silver are well known, and silver nanoparticles (nAg) are now incorporated into a wide variety of consumer products for microbial control. In this study, nAg incorporated into polysulfone ultrafiltration membranes (nAg-PSf) exhibited antimicrobial properties towards a variety of bacteria, including Escherichia coli K12 and Pseudomonas mendocina KR1, and the MS2 bacteriophage. Nanosilver incorporation also increased membrane hydrophilicity, reducing the potential for other types of membrane fouling. XPS analysis indicated a significant loss of silver from the membrane surface after a relatively short filtration period (0.4 L/cm2) even though ICP analysis of digested membrane material showed that 90% of the added silver remained in the membrane. This silver loss resulted in a significant loss of antibacterial and antiviral activity. Thus, successful fabrication of nAg-impregnated membranes needs to allow for the release of sufficient silver ions for microbial control while preventing a rapid depletion of silver.

An actinomycete strain (CB1190T) was previously isolated from industrial sludge contaminated with 1,4-dioxane. The cells of this culture are Gram-positive and exhibit branching aerial and vegetative mycelium. Analysis of the 16S rRNA gene sequence indicates that the strain belongs to the genus Pseudonocardia, closely related to Pseudonocardia hydrocarbonoxydans, P. sulfidoxydans and P. halophobica. Physiological and biochemical characteristics of CB1190T are different from those of other known Pseudonocardia species. The novel organism described here is distinguished by its ability to grow on 1,4-dioxane, which is a probable human carcinogen. This culture can also grow on tetrahydrofuran, gasoline aromatics and several other toxic environmental contaminants. Strain CB1190T is capable of fixing dinitrogen. The predominant fatty acids are 16 : 0 iso, 16 : 1 iso cis9 and 17 : 1 iso cis9. The major phospholipid fatty acids are 16 : 0 iso, 16 : 0 10-Me and 17 : 0 10-Me. The peptidoglycan belongs to type A1γ, meso-diaminopimelic acid. The major menaquinone is MK-8 (H4). Mycolic acids are absent. The G+C content is 74 mol%. Based on morphological, physiological, chemotaxonomic and phylogenetic evidence, it is proposed that strain CB1190T (=ATCC 55486T=DSM 44775T) be classified as the type strain of a novel species, Pseudonocardia dioxanivorans sp. nov. Further studies with this organism will provide insights into metabolic pathways, responsible enzymes, kinetics and the fate of 1,4-dioxane in the environment.

Bacterial multicomponent monooxygenase gene targets in Pseudonocardia dioxanivorans CB1190 were evaluated for their use as biomarkers to identify the potential for 1,4-dioxane biodegradation in pure cultures and environmental samples. Our studies using laboratory pure cultures and industrial activated sludge samples suggest that the presence of genes associated with dioxane monooxygenase, propane monooxygenase, alcohol dehydrogenase, and aldehyde dehydrogenase are promising indicators of 1,4-dioxane biotransformation; however, gene abundance was insufficient to predict actual biodegradation. A time course gene expression analysis of dioxane and propane monooxygenases in Pseudonocardia dioxanivorans CB1190 and mixed communities in wastewater samples revealed important associations with the rates of 1,4-dioxane removal. In addition, transcripts of alcohol dehydrogenase and aldehyde dehydrogenase genes were upregulated during biodegradation, although only the aldehyde dehydrogenase was significantly correlated with 1,4-dioxane concentrations. Expression of the propane monooxygenase demonstrated a time-dependent relationship with 1,4-dioxane biodegradation in P. dioxanivorans CB1190, with increased expression occurring after over 50% of the 1,4-dioxane had been removed. While the fraction of P. dioxanivorans CB1190-like bacteria among the total bacterial population significantly increased with decrease in 1,4-dioxane concentrations in wastewater treatment samples undergoing active biodegradation, the abundance and expression of monooxygenase-based biomarkers were better predictors of 1,4-dioxane degradation than taxonomic 16S rRNA genes. This study illustrates that specific bacterial monooxygenase and dehydrogenase gene targets together can serve as effective biomarkers for 1,4-dioxane biodegradation in the environment.

Pseudonocardia dioxanivorans CB1190 is the first bacterium reported to be capable of growth on the environmental contaminant 1,4-dioxane and the first member of the genus Pseudonocardia for which there is an annotated genome sequence. Preliminary analysis of the genome (chromosome and three plasmids) indicates that strain CB1190 possesses several multicomponent monooxygenases that could be involved in the aerobic degradation of 1,4-dioxane and other environmental contaminants.

1,4-Dioxane biodegradation was investigated in microcosms prepared with groundwater and soil from an impacted site in Alaska. In addition to natural attenuation conditions (i.e., no amendments), the following treatments were tested: (a) biostimulation by addition of 1-butanol (a readily available auxiliary substrate) and inorganic nutrients; and (b) bioaugmentation with Pseudonocardia dioxanivorans CB1190, a well-characterized dioxane-degrading bacterium, or with Pseudonocardia antarctica DVS 5a1, a bacterium isolated from Antarctica. Biostimulation enhanced the degradation of 50 mg L(-1) dioxane by indigenous microorganisms (about 0.01 mg dioxane d(-1) mg protein(-1)) at both 4 and 14 degrees C, with a simultaneous increase in biomass. A more pronounced enhancement was observed through bioaugmentation. Microcosms with 50 mg L(-1) initial dioxane (representing source-zone contamination) and augmented with CB1190 degraded dioxane fastest (0.16 +/- 0.04 mg dioxane d(-1) mg protein(-1)) at 14 degrees C, and the degradation rate decreased dramatically at 4 degrees C (0.021 +/- 0.007 mg dioxane d(-1) mg protein(-1)). In contrast, microcosms with DVS 5a1 degraded dioxane at similar rates at 4 degrees C and 14 degrees C (0.018 +/- 0.004 and 0.015 +/- 0.006 mg dioxane d(-1) mg protein(-1), respectively). DVS 5a1 outperformed CB1190 when the initial dioxane concentration was low (500 microg L(-1), which is representative of the leading edge of plumes). This indicates differences in competitive advantages of these two strains. Natural attenuation microcosms also showed significant degradation over 6 months when the initial dioxane concentration was 500 microg L(-1). This is the first study to report the potential for dioxane bioremediation and natural attenuation of contaminated groundwater in sensitive cold-weather ecosystems such as the Arctic.

The recent advances in nanotechnology and the corresponding increase in the use of nanomaterials in products in every sector of society have resulted in uncertainties regarding environmental impacts. The objectives of this review are to introduce the key aspects pertaining to nanomaterials in the environment and to discuss what is known concerning their fate, behavior, disposition, and toxicity, with a particular focus on those that make up manufactured nanomaterials. This review critiques existing nanomaterial research in freshwater, marine, and soil environments. It illustrates the paucity of existing research and demonstrates the need for additional research. Environmental scientists are encouraged to base this research on existing studies on colloidal behavior and toxicology. The need for standard reference and testing materials as well as methodology for suspension preparation and testing is also discussed.