Graphene as a rational interface for enhanced adsorption of microcystin-LR from water.

Cyanotoxins such as microcystin-LR (MC-LR) represent a global environmental threat to ecosystems and drinking water supplies. The study investigated the direct use of graphene as a rational interface for removal of MC-LR via interactions with the aromatic ring of the ADDA1 chain of MC-LR and the sp2 hybridized carbon network of graphene. Intra-particle diffusion model fit indicated the high mesoporosity of graphene provided significant enhancements to both adsorption capacities and kinetics when benchmarked against microporous granular activated carbon (GAC). Graphene showed superior MC-LR adsorption capacity of 75.4 mg/g (Freundlich model) compared to 0.982 mg/g (Langmuir model) for GAC. Sorption kinetic studies showed graphene adsorbs 99% of MC-LR in 30 min, compared to zero removal for GAC after 24 hr using the same MC-LR concentration. Density functional theory (DFT), calculations showed that postulated π-based interactions align well with the NMR-based experimental work used to probe primary interactions between graphene and MC-LR adduct. This study proved that π-interactions between the aromatic ring on MC-LR and graphene sp2 orbitals are a dominant interaction. With rapid kinetics and adsorption capacities much higher than GAC, it is anticipated that graphene will offer a novel molecular approach for removal of toxins and emerging contaminants with aromatic systems.

Graphene-Mediated removal of Microcystin-LR in chitosan/graphene composites for treatment of harmful algal blooms.

Water quality can be severely impacted by algal blooms alone, yet cyanotoxins, such as microcystin (MC), are potent underlying hazards produced by various species of cyanobacteria. Currently there is a need for environmentally compatible and economically viable media to address large scale application for HAB impacted waters. This study evaluated the interactions of chitosan/graphene (CSG) composites with three different species of cyanobacteria: Anabaena sp, Synechocystis sp, and Microcystis aeruginosa for both removal of algal optical density and toxins. Although results suggest that CSG has an algae dependent removal of density with a range of 40-90% removal, graphene/CSG is highly effective at MC toxin removal, removing >94% of MC-LR produced by Microcystis aeruginosa. Characterization by SEM and XRD revealed that 750 m2/g surface area graphene, imparts graphene morphology and functionality into the chitosan matrix surface, potentially enabling π-π interactions between graphene and the aromatic ring of microcystin. This proposed π-π removal mechanism of microcystin via the CSG chitosan biopolymer substrate offers a promising sustainable and selective media suitable for deployable treatment of HAB impacted waters.

Identifying degradation products responsible for increased toxicity of UV-Degraded insensitive munitions.

Degradation of insensitive munitions (IMs) by ultraviolet (UV) light has become a topic of concern following observations that some UV-degradation products have increased toxicity relative to parent compounds in aquatic organisms. The present investigation focused on the Army's IM formulation, IMX-101, which is composed of three IM constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). The IM constituents and IMX-101 were irradiated in a UV photo-reactor and then administered to Daphnia pulex in acute (48 h) exposures comparing toxicities relative to the parent materials. UV-degradation of DNAN had little effect on mortality whereas mortality for UV-degraded NTO and NQ (and associated degradation products) increased by factors of 40.3 and 1240, respectively, making UV-degraded NQ the principle driver of toxicity when IMX-101 is UV-degraded. Toxicity investigations for specific products formed during UV-degradation of NQ, confirmed greater toxicity than the parent NQ for degradation products including guanidine, nitrite, ammonia, nitrosoguanidine, and cyanide. Summation of the individual toxic units for the complete set of individually measured UV-degradation products identified for NQ only accounted for 25% of the overall toxicity measured in the exposures to the UV-degraded NQ product mixture. From these toxic unit calculations, nitrite followed by CN- were the principal degradation products contributing to toxicity. Given the underestimation of toxicity using the sum toxic units for the individually measured UV-degradation products of NQ, we conclude that: (1) other unidentified NQ degradation products contributed principally to toxicity and/or (2) synergistic toxicological interactions occurred among the NQ degradation product mixture that exacerbated toxicity.

An integrated theoretical and experimental investigation of insensitive munition compounds adsorption on cellulose, cellulose triacetate, chitin and chitosan surfaces.

This manuscript reports results of combined computational chemistry and batch adsorption investigation of insensitive munition compounds, 2,4-dinitroanisole (DNAN), triaminotrinitrobenzene (TATB), 1,1-diamino-2,2-dinitroethene (FOX-7) and nitroguanidine (NQ), and traditional munition compound 2,4,6-trinitrotoluene (TNT) on the surfaces of cellulose, cellulose triacetate, chitin and chitosan biopolymers. Cellulose, cellulose triacetate, chitin and chitosan were modeled as trimeric form of the linear chain of 4C1 chair conformation of ß-d-glucopyranos, its triacetate form, ß-N-acetylglucosamine and D-glucosamine, respectively, in the 1➔4 linkage. Geometries were optimized at the M062X functional level of the density functional theory (DFT) using the 6-31G(d,p) basis set in the gas phase and in the bulk water solution using the conductor-like polarizable continuum model (CPCM) approach. The nature of potential energy surfaces of the optimized geometries were ascertained through the harmonic vibrational frequency analysis. The basis set superposition error (BSSE) corrected interaction energies were obtained using the 6-311G(d,p) basis set at the same theoretical level. The computed BSSE in the gas phase was used to correct interaction energy in the bulk water solution. Computed and experimental results regarding the ability of considered surfaces in adsorbing the insensitive munitions compounds are discussed.

Scalable Chitosan-Graphene Oxide Membranes: The Effect of GO Size on Properties and Cross-Flow Filtration Performance.

Chitosan (CS)-graphene oxide (GO) composite films were fabricated, characterized, and evaluated as pressure-driven water filtration membranes. GO particles were incorporated into a chitosan polymer solution to form a suspension that was cast as a membrane via evaporative phase inversion allowing for scale-up for cross-flow testing conditions. Morphology and composition results for nano and granular GO in the CS matrix indicate that the particle size of GO impacts the internal membrane morphology as well as the structural order and the chemical composition. Performance of the membranes was evaluated with cationic and anionic organic probe molecules and revealed charge-dependent mechanisms of dye removal. The CSGO membranes had rejections of at least 95% for cationic methylene blue with mass balances obtained from measurements of the feed, concentrate, and permeate. This result suggests the dominant mechanism of removal is physical rejection for both GO particle sizes. For anionic methyl orange, the results indicate sorption as the dominant mechanism of removal, and performance is dependent on both GO particle size and time, with micrometer-scale GO removing 68-99% and nanometer-scale GO showing modest removal of 29-64%. The pure water flux for CSGO composite membranes ranged from 2-4.5 L/m2 h at a transmembrane pressure of 344 kPa (3.44 bar), with pure water permeance ranging from 5.8 × 10-3 to 0.01 L/m2 h kPa (0.58-1.3 L/m2 h bar). Based on the 41 µm membrane thickness obtained from microscopy, the hydraulic permeability ranged from 0.24-0.54 L µm/m2 h kPa (24.4-54.1 L µm/m2 h bar).

A two-stage extraction procedure for insensitive munition (IM) explosive compounds in soils.

The Department of Defense (DoD) is developing a new category of insensitive munitions (IMs) that are more resistant to detonation or promulgation from external stimuli than traditional munition formulations. The new explosive constituent compounds are 2,4-dinitroanisole (DNAN), nitroguanidine (NQ), and nitrotriazolone (NTO). The production and use of IM formulations may result in interaction of IM component compounds with soil. The chemical properties of these IM compounds present unique challenges for extraction from environmental matrices such as soil. A two-stage extraction procedure was developed and tested using several soil types amended with known concentrations of IM compounds. This procedure incorporates both an acidified phase and an organic phase to account for the chemical properties of the IM compounds. The method detection limits (MDLs) for all IM compounds in all soil types were <5 mg/kg and met non-regulatory risk-based Regional Screening Level (RSL) criteria for soil proposed by the U.S. Army Public Health Center. At defined environmentally relevant concentrations, the average recovery of each IM compound in each soil type was consistent and greater than 85%. The two-stage extraction method decreased the influence of soil composition on IM compound recovery. UV analysis of NTO established an isosbestic point based on varied pH at a detection wavelength of 341 nm. The two-stage soil extraction method is equally effective for traditional munition compounds, a potentially important point when examining soils exposed to both traditional and insensitive munitions.