Solar-driven abnormal evaporation of nanoconfined water.

Intrinsic water evaporation demands a high energy input, which limits the efficacy of conventional interfacial solar evaporators. Here, we propose a nanoconfinement strategy altering inherent properties of water for solar-driven water evaporation using a highly uniform composite of vertically aligned Janus carbon nanotubes (CNTs). The water evaporation from the CNT shows the unexpected diameter-dependent evaporation rate, increasing abnormally with decreasing nanochannel diameter. The evaporation rate of CNT10@AAO evaporator thermodynamically exceeds the theoretical limit (1.47 kg m-2 hour-1 under one sun). A hybrid experimental, theoretical, and molecular simulation approach provided fundamental evidence of different nanoconfined water properties. The decreased number of H-bonds and lower interaction energy barrier of water molecules within CNT and formed water clusters may be one of the reasons for the less evaporative energy activating rapid nanoconfined water vaporization.

O2-Independent H2O2 Production via Water-Polymer Contact Electrification.

Hydrogen peroxide (H2O2), as a critical green chemical, has received immense attention in energy and environmental fields. The ability to produce H2O2 in earth-abundant water without relying on low solubility oxygen would be a sustainable and potentially economic process, applicable even to anaerobic microenvironments, such as groundwater treatment. However, the direct water to H2O2 process is currently hindered by low selectivity and low production rates. Herein, we report that poly(tetrafluoroethylene) (PTFE), a commonly used inert polymer, can act as an efficient triboelectric catalyst for H2O2 generation. For example, a high H2O2 production rate of 24.8 mmol gcat-1 h-1 at a dosage of 0.01 g/L PTFE was achieved under the condition of pure water, ambient atmosphere, and no sacrificial agents, which exceeds the performance of state-of-the-art aqueous H2O2 powder catalysts. Electron spin resonance and isotope experiments provide strong evidence that water-PTFE tribocatalysis can directly oxidize water to produce H2O2 under both anaerobic and aerobic conditions, albeit with different synthetic pathways. This study demonstrates a potential strategy for green and effective tribocatalytic H2O2 production that may be particularly useful toward environmental applications.

A General Strategy to Synthesize Fluidic Single Atom Electrodes for Selective Reactive Oxygen Species Production.

Fine-tuning the geometric and electronic structure of catalytic metal centers via N-coordination engineering offers an effective design for the electrocatalytic transformation of O2 to singlet oxygen (1O2). Herein, we develop a general coordination modulation strategy to synthesize fluidic single-atom electrodes for selective electrocatalytic activation of O2 to 1O2. Using a single Cr atom system as an example, >98% 1O2 selectivity can be achieved from electrocatalytic O2 activation due to the subtle engineering of Cr-N4 sites. Both theoretical simulations and experimental results determined that "end-on" adsorption of O2 onto the Cr-N4 sites lowers the overall activation energy barrier of O2 and promotes the breakage of Cr-OOH bonds to form •OOH intermediates. In addition, the flow-through configuration (k = 0.097 min-1) endowed convection-enhanced mass transport and improved charge transfer imparted by spatial confinement within the lamellar electrode structure compared to that of batch reactor (k = 0.019 min-1). In a practical demonstration, the Cr-N4/MXene electrocatalytic system exhibits a high selectivity toward electron-rich micropollutants (e.g., sulfamethoxazole, bisphenol A, and sulfadimidine). The flow-through design of the fluidic electrode achieves a synergy with the molecular microenvironment that enables selective electrocatalytic 1O2 generation, which could be used in numerous ways, including the treatment of environmental pollution.

Centurial Persistence of Forever Chemicals at Military Fire Training Sites.

Drinking water contamination by per- and polyfluoroalkyl substances (PFAS) is widespread near more than 300 United States (U.S.) military bases that used aqueous film-forming foams (AFFF) for fire training and firefighting activities. Much of the PFAS at these sites consist of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods. Here, we estimate the expected duration and contribution of precursor biotransformation to groundwater PFAS contamination at an AFFF-contaminated military base on Cape Cod, Massachusetts, United States, by optimizing a geochemical box model using measured PFAS concentrations from a multidecadal time series of groundwater and a soil survey in the source zone. A toolbox of analytical techniques used to reconstruct the mass budget of PFAS showed that precursors accounted for 46 ± 8% of the extractable organofluorine (a proxy for total PFAS) across years. Terminal PFAS still exceed regulatory limits by 2000-fold decades after AFFF use ceased. Measurements and numerical modeling show that sulfonamido precursors are retained in the vadose zone and their slow biotransformation into perfluoroalkyl sulfonates (half-life > 66 yr) sustains groundwater concentrations of perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS). The estimated PFAS reservoir in the vadose zone and modeled flux into groundwater suggest PFAS contamination above regulatory guidelines will persist for centuries without remediation.

Insulated Interlaced Surface Electrodes for Bacterial Inactivation and Detachment.

Effective and stable antibiofouling surfaces and interfaces have long been of research interest. In this study, we designed, fabricated, and evaluated a surface coated with insulated interlaced electrodes for bacterial fouling reduction. The electrodes were printed Ag filaments of 100 µm width and 400 µm spacing over an area of 2 × 2 cm2. The insulating Ag electrode coating material was polydimethylsiloxane (PDMS) or thermoplastic polyurethane (TPU) with a thickness of 10 to 40 µm. To evaluate the antibiofouling potential, E. coli inactivation after 2 min contact with the electrified surface and P. fluorescens detachment after 15 and 40 h growth were examined. The extent of bacterial inactivation was related to the insulating material, coating thickness, and applied voltage (magnitude and AC vs DC). A high bacterial inactivation (>98%) was achieved after only 2 min of treatment at 50 V AC and 10 kHz using a 10 µm TPU coating. P. fluorescens detachment after 15 and 40 h incubation in the absence of applied potential was completed with simultaneous cross-flow rinsing and AC application. Higher AC voltages and longer cross-flow rinsing times resulted in greater bacterial detachment with bacterial coverage able to be reduced to <1% after only 2 min of rinsing at 50 V AC and 10 kHz. Theoretical electric field analysis indicated that at 10 V the field strength penetrating the aqueous solution is nonuniform (∼16,000-20,000 V m-1 for the 20 µm TPU) and suggests that dielectrophoresis plays a key role in bacterial detachment. The bacterial inactivation and detachment trends observed in this study indicate that this technique has merit for future antibiofouling surface development.

Nitrifying Microorganisms Linked to Biotransformation of Perfluoroalkyl Sulfonamido Precursors from Legacy Aqueous Film-Forming Foams.

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1-100 pM day-1). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

Pulsed hydraulic-pressure-responsive self-cleaning membrane.

Pressure-driven membranes is a widely used separation technology in a range of industries, such as water purification, bioprocessing, food processing and chemical production1,2. Despite their numerous advantages, such as modular design and minimal footprint, inevitable membrane fouling is the key challenge in most practical applications3. Fouling limits membrane performance by reducing permeate flux or increasing pressure requirements, which results in higher energetic operation and maintenance costs4-7. Here we report a hydraulic-pressure-responsive membrane (PiezoMem) to transform pressure pulses into electroactive responses for in situ self-cleaning. A transient hydraulic pressure fluctuation across the membrane results in generation of current pulses and rapid voltage oscillations (peak, +5.0/-3.2 V) capable of foulant degradation and repulsion without the need for supplementary chemical cleaning agents, secondary waste disposal or further external stimuli3,8-13. PiezoMem showed broad-spectrum antifouling action towards a range of membrane foulants, including organic molecules, oil droplets, proteins, bacteria and inorganic colloids, through reactive oxygen species (ROS) production and dielectrophoretic repulsion.

Unexpected exfoliation and activity of nano poly(tetrafluoroethylene) particles from magnetic stir bars: Discovery and implication.

Magnetic stir bars are routinely used by most of researchers in the fields of chemistry, biology and environment etc. An incredible phenomenon, in which the magnetic stirring increased reaction rate by tens of times under ultrasound irradiation, impelled us to explore roles of magnetic stirring. Unexpectedly, the thimbleful nano PTFE particles, from shell of magnetic stir bar, were exfoliated during magnetic stirring and account for ultrahigh tribocatalytic and piezocatalytic activities under ultrasonic irradiation. Reactive oxygen species (ROS), such as hydroxyl radical (OH), superoxide radicals (O2-) and singlet oxygen (1O2) were generated in the present of PTFE under ultrasound irradiation, which is desired in the pollution control. The newly discovered PTFE activity, against the conventional wisdom that PTFE is inert, which also reminds the researchers that the trace amount of PTFE ground during magnetic stirring may inadvertently botch our experiments and introduce false positive results, especially involving routine magnetic stirring and ultrasound irradiation operation in laboratory. In addition, the safety and inertness of PTFE may require further review in PTFE-based commercial, industrial and biomedical settings.

Surface-water/groundwater boundaries affect seasonal PFAS concentrations and PFAA precursor transformations.

Elevated concentrations of per- and polyfluoroalkyl substances (PFAS) in drinking-water supplies are a major concern for human health. It is therefore essential to understand factors that affect PFAS concentrations in surface water and groundwater and the transformation of perfluoroalkyl acid (PFAA) precursors that degrade into terminal compounds. Surface-water/groundwater exchange can occur along the flow path downgradient from PFAS point sources and biogeochemical conditions can change rapidly at these exchange boundaries. Here, we investigate the influence of surface-water/groundwater boundaries on PFAS transport and transformation. To do this, we conducted an extensive field-based analysis of PFAS concentrations in water and sediment from a flow-through lake fed by contaminated groundwater and its downgradient surface-water/groundwater boundary (defined as ≤100 cm below the lake bottom). PFAA precursors comprised 45 ± 4.6% of PFAS (PFAA precursors + 18 targeted PFAA) in the predominantly oxic lake impacted by a former fire-training area and historical wastewater discharges. In shallow porewater downgradient from the lake, this percentage decreased significantly to 25 ± 11%. PFAA precursor concentrations decreased by 85% between the lake and 84-100 cm below the lake bottom. PFAA concentrations increased significantly within the surface-water/groundwater boundary and in downgradient groundwater during the winter months despite lower stable concentrations in the lake water source. These results suggest that natural biogeochemical fluctuations associated with surface-water/groundwater boundaries may lead to PFAA precursor loss and seasonal variations in PFAA concentrations. Results of this work highlight the importance of dynamic biogeochemical conditions along the hydrological flow path from PFAS point sources to potentially affected drinking water supplies.

Dependence of Graphene Oxide (GO) Toxicity on Oxidation Level, Elemental Composition, and Size.

The mass production of graphene oxide (GO) unavoidably elevates the chance of human exposure, as well as the possibility of release into the environment with high stability, raising public concern as to its potential toxicological risks and the implications for humans and ecosystems. Therefore, a thorough assessment of GO toxicity, including its potential reliance on key physicochemical factors, which is lacking in the literature, is of high significance and importance. In this study, GO toxicity, and its dependence on oxidation level, elemental composition, and size, were comprehensively assessed. A newly established quantitative toxicogenomic-based toxicity testing approach, combined with conventional phenotypic bioassays, were employed. The toxicogenomic assay utilized a GFP-fused yeast reporter library covering key cellular toxicity pathways. The results reveal that, indeed, the elemental composition and size do exert impacts on GO toxicity, while the oxidation level exhibits no significant effects. The UV-treated GO, with significantly higher carbon-carbon groups and carboxyl groups, showed a higher toxicity level, especially in the protein and chemical stress categories. With the decrease in size, the toxicity level of the sonicated GOs tended to increase. It is proposed that the covering and subsequent internalization of GO sheets might be the main mode of action in yeast cells.

Dual-high-frequency from single-piezoelectric crystal for ACE degradation by hybrid advanced oxidation UV-sonochemistry process.

This study investigates the combination of two waves emitted from a single-piezoelectric crystal by use of a dual-frequency generator in a sonochemical reactor. The dual-frequency configurations analyzed were the double-modulated fundamental frequency (376-376 kHz), resonant and second harmonic, termed 376D, 376R and 376H respectively. The effect of the phase shift (Φ) and the percentage of modulation between added waves were described by the total acoustic power distribution (Pt) measured inside the sonoreactor. Moreover, optimal angle alignment and modulation between dual-frequency waves for 376D, 376R and 376H cases were selected in order to evaluate the ultrasonic synergy by sonochemical reactivity in production of H2O2, in degradation rate of a model emerging pollutant ACE, and in the TOC and biodegradability evolution in the treated effluent. Phase shift and percentage of modulation had strong effect on the resulted waveform and on the sonochemical efficiency for all, harmonic and non-harmonic, dual-frequency combinations created. In the 376D case, the best reinforcement conditions are founded at 0° and 360°. In the 376H the maximum power distribution presents a 90° period. Shift phase does not determines any cyclic pattern in the total power distribution for the 376R case. The highest H2O2 production rate was observed for the 376H case followed for 376D and 376R configurations with 1.61, 1.12 and 0.58 µM/min by angle alignment in 105, 0 and 110° respectively. The highest initial degradation rate of ACE was observed for the 376D case followed for 376H and 376R with 0.56, 0.42 and 0.33 µM/min at 100% modulation. Reduced mineralization was observed in all dual-frequency configurations (8.54% for 376D and approximately 4.5% for 376R and 3756H modes). Contrasting results are observed regard to biodegradability ratio following the next sequence 376D < 376H≈376R with 0.9, 2.30 and 2.33 respectively. Relevant intensification in hydroxyl radicals production is observed by the UV-US system increasing up three folds the ACE removal and mineralization and two folds higher biodegradability of effluent in particular for 376R and 376H cases at optimal operation condition of dual-frequency signal.

Comparative and mechanistic toxicity assessment of structure-dependent toxicity of carbon-based nanomaterials.

The wide application of carbon-based nanomaterials (CNMs) has resulted in the ubiquity of CNMs in the natural environment and they potentially impose adverse consequences on ecosystems and human health. In this study, we comprehensively evaluated and compared potential toxicological effects and mechanisms of seven CNMs in three representative types (carbon blacks, graphene nanoplatelets, and fullerenes), to elucidate the correlation between their physicochemical/structural properties and toxicity. We employed a recently-developed quantitative toxicogenomics-based toxicity testing system with GFP-fused yeast reporter library targeting main cellular stress response pathways, as well as conventional phenotype-based bioassays. The results revealed that DNA damage, oxidative stress, and protein stress were the major mechanisms of action for all the CNMs at sub-cytotoxic concentration levels. The molecular toxicity nature were concentration-dependent, and they exhibited both similarity within the same structural group and distinctiveness among different CNMs, evidencing the structure-driven toxicity of CNMs. The toxic potential based on toxicogenomics molecular endpoints revealed the remarkable impact of size and structure on the toxicity. Furthermore, the phenotypic endpoints derived from conventional phenotype-based bioassays correlated with quantitative molecular endpoints derived from the toxicogenomics assay, suggesting that the selected protein biomarkers captured the main cellular effects that are associated with phenotypic adverse outcomes.

Ultrasonic activation of inert poly(tetrafluoroethylene) enables piezocatalytic generation of reactive oxygen species.

Controlled generation of reactive oxygen species (ROS) is essential in biological, chemical, and environmental fields, and piezoelectric catalysis is an emerging method to generate ROS, especially in sonodynamic therapy due to its high tissue penetrability, directed orientation, and ability to trigger in situ ROS generation. However, due to the low piezoelectric coefficient, and environmental safety and chemical stability concerns of current piezoelectric ROS catalysts, novel piezoelectric materials are urgently needed. Here, we demonstrate a method to induce polarization of inert poly(tetrafluoroethylene) (PTFE) particles ( ~ 1-5 µm) into piezoelectric electrets with a mild and convenient ultrasound process. Continued ultrasonic irradiation of the PTFE electrets generates ROS including hydroxyl radicals (•OH), superoxide (•O2-) and singlet oxygen (1O2) at rates significantly faster than previously reported piezoelectric catalysts. In summary, ultrasonic activation of inert PTFE particles is a simple method to induce permanent PTFE polarization and to piezocatalytically generate aqueous ROS that is desirable in a wide-range of applications from environmental pollution control to biomedical therapy.

Isolating the AFFF Signature in Coastal Watersheds Using Oxidizable PFAS Precursors and Unexplained Organofluorine.

Water supplies for millions of U.S. individuals exceed maximum contaminant levels for per- and polyfluoroalkyl substances (PFAS). Contemporary and legacy use of aqueous film forming foams (AFFF) is a major contamination source. However, diverse PFAS sources are present within watersheds, making it difficult to isolate their predominant origins. Here we examine PFAS source signatures among six adjacent coastal watersheds on Cape Cod, MA, U.S.A. using multivariate clustering techniques. A distinct signature of AFFF contamination enriched in precursors with six perfluorinated carbons (C6) was identified in watersheds with an AFFF source, while others were enriched in C4 precursors. Principal component analysis of PFAS composition in impacted watersheds showed a decline in precursor composition relative to AFFF stocks and a corresponding increase in terminal perfluoroalkyl sulfonates with < C6 but not those with ≥ C6. Prior work shows that in AFFF stocks, all extractable organofluorine (EOF) can be explained by targeted PFAS and precursors inferred using Bayesian inference on the total oxidizable precursor assay. Using the same techniques for the first time in impacted watersheds, we find that only 24%-63% of the EOF can be explained by targeted PFAS and oxidizable precursors. Our work thus indicates the presence of large non-AFFF organofluorine sources in these coastal watersheds.

Prospects of an Electroactive Carbon Nanotube Membrane toward Environmental Applications.

Rapid population growth and industrialization have driven the emergence of advanced electrochemical and membrane technologies for environmental and energy applications. Electrochemical processes have potential for chemical transformations, chloralkali disinfection, and energy storage. Membrane separations have potential for gas, fluid, and chemical purification. Electrochemical and membrane technologies are often used additively in the same unit process, e.g., the chloroalkali process where a membrane is used to separate cathodic and anodic products from scavenging each other. However, to access the maximal potential requires intimate hybridization of the two technologies into an electroactive membrane. The combination of the two discrete technologies results in a range of synergisms such as reduced footprint, increased processing kinetics, reduced fouling, and increased energy efficiency.Due to their high specific surface area, excellent electric conductivity, and desirable robustness, 1D carbon nanotubes (CNTs) hold promise for many applications over a range of industry sectors such as a base material for electrodes and membranes. Importantly, CNT morphology and surface chemistry can be rationally modified and fine-tuning of these CNT physicochemical properties can enhance their functionality toward practical applications. The CNT 1D form allows assembly of a stable thin-film fibrous network by a variety of facile techniques. These CNT networks have pore sizes in the range of 10-500 nm (dpore ∼ 6-8dCNT) and thicknesses of 10-200 µm, both similar to those of classical polymer membranes, thus allowing for straightforward incorporation into commercial membrane devices modified for electroactivity inclusion.In this Account, CNTs and their composites are used as model electroactive porous materials to exemplify the design strategies and environmental applications of emerging electroactive membrane technology. The Account begins with a brief summary of the electroactive membrane design principles and flow processes developed by our groups. After the methodology section, a detailed discussion is provided on the underlying physical-chemical mechanisms that govern the electroactive membrane technology. Then we summarize our findings on the rational design of several flow-through electrochemical CNT filtration systems focused on either anodic oxidation reactions or cathodic reduction reactions. Subsequently, we discuss a recently discovered electrochemical valence-state-regulation strategy that is capable to detoxify and sequester heavy metal ions. Finally, we conclude the Account with our perspectives toward future development of the electroactive membrane technology.

Reductive transformation of perfluorooctanesulfonate by nNiFe0-Activated carbon.

Degradation of linear (L) and branched (Br) perfluorooctanesulfonate (PFOS) using nNiFe° particles supported on activated carbon (AC) and heat is demonstrated for the first time and with several lines of evidence. At 60 °C, PFOS degradation plateaued at 50 ± 6%, while at 50 °C, 94 ± 4.1 % PFOS transformed. The accelerated iron corrosion at the higher temperature is attributed to the lower PFOS transformation at 60 °C. However, at both temperatures, ≥ 97 % of the PFOS transformed was accounted for by the moles of fluoride generated. At 60 °C, PFOS degradation rates were estimated at 0.028 ± 0.003 h-1 and fluoride and sulfite generation rates of 0.70 ± 0.165 h-1 and 0.62 ± 0.157 h-1, respectively, with no differences between L-PFOS and total Br-PFOS. Using time-of-flight mass spectrometry, some organic products were identified in the particle extracts from the 60 °C reaction. Products included single-bonded C8 polyfluoroalkyl sulfonates (F16 to F7) and alkyl acids (PFCAs, C4-C8) and one perfluorinated C8 desulfonated product supporting both defluorination and desulfonation pathways. Most of the organic products were gone after the first 25 h. High PFOS mineralization using nNiFe°-AC technology warrants further investigation for its use in permeable reactive barriers.

Synthesis and Physicochemical Transformations of Size-Sorted Graphene Oxide during Simulated Digestion and Its Toxicological Assessment against an In Vitro Model of the Human Intestinal Epithelium.

In the last decade, along with the increasing use of graphene oxide (GO) in various applications, there is also considerable interest in understanding its effects on human health. Only a few experimental approaches can simulate common routes of exposure, such as ingestion, due to the inherent complexity of the digestive tract. This study presents the synthesis of size-sorted GO of sub-micrometer- or micrometer-sized lateral dimensions, its physicochemical transformations across mouth, gastric, and small intestinal simulated digestions, and its toxicological assessment against a physiologically relevant, in vitro cellular model of the human intestinal epithelium. Results from real-time characterization of the simulated digestas of the gastrointestinal tract using multi-angle laser diffraction and field-emission scanning electron microscopy show that GO agglomerates in the gastric and small intestinal phase. Extensive morphological changes, such as folding, are also observed on GO following simulated digestion. Furthermore, X-ray photoelectron spectroscopy reveals that GO presents covalently bound N-containing groups on its surface. It is shown that the GO employed in this study undergoes reduction. Toxicological assessment of the GO small intestinal digesta over 24 h does not point to acute cytotoxicity, and examination of the intestinal epithelium under electron microscopy does not reveal histological alterations. Both sub-micrometer- and micrometer-sized GO variants elicit a 20% statistically significant increase in reactive oxygen species generation compared to the untreated control after a 6 h exposure.

Toxicity of Single-Walled Carbon Nanotubes (SWCNTs): Effect of Lengths, Functional Groups and Electronic Structures Revealed by a Quantitative Toxicogenomics Assay.

Single-walled carbon nanotubes (SWCNTs) are a group of widely used carbon-based nanomaterials (CNMs) with various applications, which raise increasing public concerns associated with their potential toxicological effect and risks on human and ecosystems. In this report, we comprehensively evaluated the nanotoxicity of SWCNTs with their relationship to varying lengths, functional groups and electronic structures, by employing both newly established quantitative toxicogenomics test, as well as conventional phenotypic bioassays. The objective is to reveal potential cellular toxicity and mechanisms of SWCNTs at the molecular level, and to probe their potential relationships with their morphological, surface, and electronic properties. The results indicated that DNA damage and oxidative stress were the dominant mechanisms of action for all SWCNTs and, the toxicity level and characteristics varied with length, surface functionalization and electronic structure. Distinguishable molecular toxicity fingerprints were revealed for the two SWCNTs with varying length, with short SWCNT exhibiting higher toxicity level than the long one. In terms of surface properties, SWCNT functionalization, namely carboxylation and hydroxylation, led to elevated overall toxicity, especially genotoxicity, as compared to unmodified SWCNT. Carboxylated SWCNT induced a greater toxicity than the hydroxylated SWCNT. The nucleus is likely the primary target site for long, short, and carboxylated SWCNTs and mechanical perturbation is likely responsible for the DNA damage, specifically related to degradation of the DNA double helix structure. Finally, dramatically different electronic structure-dependent toxicity was observed with metallic SWCNT exerting much higher toxicity than the semiconducting one that exhibited minimal toxicity among all SWCNTs.

Synergism of ozonation and electrochemical filtration during advanced organic oxidation.

Here, we investigated the synergistic effect towards phenol degradation and mineralization between ozonation (O3) and electrochemical filtration (ECF) using perforated titanium as cathode and porous carbon nanotube (CNT) networks as anode. A flow rate of 1.6 mL min-1, 10 mM of sodium sulfate electrolyte, 1.0 mM of phenol (model aromatic compound), and an ozone dose of 12 mgO3 L-1 were used. Insight into the synergistic mechanism was achieved via carbon anode morphology characterization and phenol degradation kinetics analysis. Improved kinetic performance was observed for the combined process (O3-ECF) as compared to the sum of the individual processes, not only towards phenol degradation (3.2-fold increase), but also towards phenol mineralization (2.2-fold increase). Scanning electron microscopy revealed a significant decrease of polymer formation and deposition on CNT after the hybrid O3-ECF process as compared to the ECF alone. Voltage-dependent (0-2.5 V) ozone CNT functionalization was investigated at pH 7-11 to assist in elucidation of the synergistic mechanism. X-Ray photoelectron spectroscopy indicated increases up to 26-fold in CNT oxygen content post-ozonation at pH 7 comparing to fresh CNT. Various potential O3-ECF synergistic reaction mechanisms for organic aromatic oxidation and mineralization are discussed.

Dataset and detailed methodology for structure and performance characterization of modified polymeric membranes.

The data contained in this publication refers to protocols adopted characterization of clay nanoparticles (CN) membranes with and without the use of polyethylene oxide (PEO) as pore former. The membrane casting solutions were produced by dissolving PS (18% w/w) in NMP with addition of CN (1-5% w/w CN/PS) and/or PEO (1-5% w/w PEO/PS) when applicable. Membranes with no CN or PEO were used as a control. Pure water permeability of cast membranes was determined using the cross-flow cell unit. Viscosity was measured for most casting solution compositions and contact angle was measured for all membranes. The control membrane was further compared in detail to the highest permeability membranes with only CN (1.5%), only PEO (5%), 1.5% CN and 5% PEO (combination of optimal individual permeabilities), and 4.5% CN and 5% PEO (optimal combined permeability) regarding thickness, porosity, rejection, fouling resistance, surface charge, and thermal/mechanical properties. The relevance of the data presented here is to show details about methods for characterizing membranes for future comparison of performance and eventual improvement of characterization methods.