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At least 109 records · Page 6

Microwave-Assisted dry reforming of toluene as a model tar compound using low-cost iron catalyst for syngas clean-up

Gasification of waste feedstock such as biomass, waste plastics suffers from high tar yields during hydrogen-rich syngas production. The presence of tars result in lower quality syngas, lower syngas yields, reactor blockage, reactor down time, and costly maintenance. Therefore, removal of tar from syngas during gasification is essential. Catalytic reforming of tars via in-situ syngas cleanup is an effective way of mitigating tars. This work explores the possibility of microwave-assisted catalytic dry reforming of tars for syngas production. Further, due to its chemical complexity, toluene, which is one of the main tar constituents, could be used as a model tar compound. Toluene dry reforming was studied using the Fe/Al 2 O 3 catalyst under CO 2 under the temperature range of 400–700 °C. The toluene reforming reaction was conducted using microwave and conventional thermal reactors. Under microwave irradiation, CO 2 and toluene conversions are boosted to 80% at 500 °C. Hydrogen and carbon monoxide yields were approximately five times and ten times higher in the microwave reactor at 500 °C, respectively, compared to the productions obtained in the conventional fixed-bed reactor at 700 °C. Filamentous carbon was also produced as a valuable side product to improve the economy of this process and such value-added carbon was only observed in the microwave reactor. Three reaction pathways were observed during microwave reaction: the toluene decomposition produces an initial hydrogen and carbon deposit on the catalyst; the formation of methane and benzene suggests toluene hydrodemethylation as a secondary reaction; and toluene hydrogenolysis forms light alkanes such as methane, and through reforming reaction under CO 2 to syngas.

10 SYNTHETIC FUELS↗

Risk Assessment in a Chemical Laboratory Following an Explosive Incident Involving a Novel Diazonium Compound: Retrospective Analysis and Lessons Learned

Diazonium compounds are synthetically useful in the production of dyes and textiles, however they are highly explosive under dry conditions. Explosion prevention becomes more difficult when new diazonium compounds are synthesized, because while some syntheses include a counterion to increase their stability, this is not always a reliable method to prevent an explosive incident. Due to the uncertainty surrounding the explosiveness of different diazonium compounds, it is important to understand how to safely clean up after an incident and how to determine when it is safe to return a laboratory to typical operational use, particularly when the incident involves a novel compound where a standard does not exist for instrument calibration. Here, an explosive event is discussed involving the synthesis of 4-bromo-benzenediazonium-2-carboxylate. Following the explosive incident and 3-step cleanup, which involved a precautionary neutralization step, samples were collected from the fume hood where the incident occurred. Because the incident involved an unstable, novel compound that is not commercially available and was deemed unsafe to resynthesize for instrument calibration, we assessed the risk of further explosion by analyzing for the stable decomposition products. Mass spectrometry analysis confirmed that the residue in the fume hood contained 5-bromosalicylic acid, a decomposition product of 4-bromo-benzenediazonium-2-carboxylate. Samples were taken from multiple points in the fume hood and analyzed to estimate the spatial distribution of the decomposition product. Based on this analysis, we inferred that the primary decomposition product was far more abundant than residual energetic, indicating the energetic had been consumed or neutralized to a trace quantity where the risk of further explosion was low. Furthermore, the steps presented here─specifically, initial neutralization and then analyzing the spatial distribution of expected decomposition products to assess risk when a novel explosive material is detonated in a confined space─were our approach to assess further risk following an explosion due to a novel diazonium compound without the need for any further handling or resynthesis of the energetic. Here, we present our approach and critically analyze these steps by discussing retrospective lessons learned and alternative analytical approaches.

Computer simulations↗

Stand Alone Electrical Equipment PRL 227a (Formerly PRL 227 LOC3) Confirmatory Sampling Report Addendum

HydroGeoLogic, Inc. (HGL) prepared this Confirmatory Sampling Report Addendum (CSRA) for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida. PRL 227a Location of Concern (LOC) 3 is located on 10th Street, west of the former Vertical Processing Facility (M7-1469), SWMU 077. The Load Break Switches (LBS) were installed in 1986 and are suspected to have formerly contained dielectric fluid that contained polychlorinated biphenyls (PCBs). The LBS were replaced in 1993 with new LBSs that do not contain PCBs. The LBS are located on a concrete pad surrounded by grass that is mowed and maintained. A total of 330 soil samples were collected between June 2020 and December 2022 from 88 locations at depths ranging from 0-0.5 to 19-20 ft bls. In general, soil samples collected from depths less than 5 ft were collected via hand auger and samples collected beyond 5 ft bls were collected using a direct-push technology drill rig. Soil samples collected from greater than 5 ft bls to 20 ft bls were collected to confirm PCBs were not present at depth in the aquifer matrix. Delineation samples were collected using an approximately 20 ft horizontal spacing. PCB impacted soil has been completely delineated to the State of Florida residential soil cleanup target level (SCTL) at PRL 227a horizontally and vertically. PCB concentrations have been identified above the residential and industrial SCTL as well as concentrations greater than or equal to 50 ppm requiring coordination with EPA and disposal at a facility authorized under TSCA. Based upon the CSRA sampling, an interim measure is recommended to remove PCB impacted soil above the residential SCTL. The total volume of PCB impacted soil to be removed is 591.6 cubic yards. This includes approximately 9.3 cubic yards of soil with PCB concentrations greater than or equal to 50 ppm. An interim measure work plan is included as an attachment to this report.

electrical equipment↗

Life-cycle analysis of sustainable aviation fuel production through catalytic hydrothermolysis

Catalytic hydrothermolysis (CH) is a sustainable aviation fuel (SAF) pathway that has been recently approved for use in aircraft fuel production. In alignment with broader sustainable aviation goals, SAF production through CH requires a quantitative assessment of carbon intensity (CI) impacts. In this study, a current-day life-cycle analysis (LCA) was performed on SAF produced via CH to determine the CI. Various oily feedstocks were considered, including vegetable oils (soybean, carinata, camelina and canola) and low-burden oils and greases (corn oil, yellow grease and brown grease). Life-cycle inventory data were collected on all processes within the CH LCA boundary: feedstock cultivation and/or collection, preprocessing, hydrothermal cleanup and CH, biocrude refining, fuel transportation and end use through combustion. Baseline results show that the CH-produced SAF can be generated with CI reductions ranging from 48 to 82% compared with conventional jet fuel. Modest improvements to CI can be achieved through incremental changes to the brown grease CH process, such as relaxing the dewatering specification and implementing renewable natural gas and electricity, which could decrease the CI from 22.9 to 7.9 g CO 2 e/MJ. Total CH fuel production potential was also assessed on the basis of current or near-future feedstock availability and CI. The total biofuel production potential of CH (SAF and renewable fuel co-products) in the US sums to approximately 3487 million gallons per year, with 97% of these volumes having a CI below 50% of that for petroleum jet fuel. The study shows that from an LCA perspective, CH offers a viable SAF pathway that is comparable with existing SAF pathways like hydroprocessed esters and fatty acids.

09 BIOMASS FUELS↗

Impacts on product quality attributes of monoclonal antibodies produced in CHO cell bioreactor cultures during intentional mycoplasma contamination events

Abstract A mycoplasma contamination event in a biomanufacturing facility can result in costly cleanups and potential drug shortages. Mycoplasma may survive in mammalian cell cultures with only subtle changes to the culture and penetrate the standard 0.2‐µm filters used in the clarification of harvested cell culture fluid. Previously, we reported a study regarding the ability of Mycoplasma arginini to persist in a single‐use, perfusion rocking bioreactor system containing a Chinese hamster ovary (CHO) DG44 cell line expressing a model monoclonal immunoglobulin G 1 (IgG1) antibody. Our previous work showed that M. arginini affects CHO cell growth profile, viability, nutrient consumption, oxygen use, and waste production at varying timepoints after M. arginini introduction to the culture. Careful evaluation of certain identified process parameters over time may be used to indicate mycoplasma contamination in CHO cell cultures in a bioreactor before detection from a traditional method. In this report, we studied the changes in the IgG1 product quality produced by CHO cells considered to be induced by the M. arginini contamination events. We observed changes in critical quality attributes correlated with the duration of contamination, including increased acidic charge variants and high mannose species, which were further modeled using principal component analysis to explore the relationships among M. arginini contamination, CHO cell growth and metabolites, and IgG1 product quality attributes. Finally, partial least square models using NIR spectral data were used to establish predictions of high levels (≥10 4 colony‐forming unit [CFU/ml]) of M. arginini contamination, but prediction of levels below 10 4 CFU/ml were not reliable. Contamination of CHO cells with M. arginini resulted in significant reduction of antibody product quality, highlighting the importance of rapid microbiological testing and mycoplasma testing during particularly long upstream bioprocesses to ensure product safety and quality.

60 APPLIED LIFE SCIENCES↗

The evaluation of aluminum and iron metal oxide settling behaviors for Hanford insoluble solids waste preprocessing

The Hanford site is currently one of the largest and most expensive cleanup sites for hazardous, radioactive waste. Over 20% of the waste found at the Hanford site is in the form of a high activity sludge. The insoluble solids in the sludge will need to be concentrated prior to vitrification in the high-level waste (HLW) melter. This will minimize the amount of liquid that will be evaporated during the melting process and expedite the melter processing rate. One proposed option for concentrating the insoluble solids is gravity settling in the storage tanks. Metal oxide compounds containing aluminum and iron make up the majority of the insoluble solids in the sludge, therefore understanding the behavior of these compounds in various tank waste matrices can facilitate sludge pretreatment options. A study of non-radioactive slurry solutions containing Al(OH) 3 (gibbsite), AlO(OH) (boehmite), and Fe 2 O 3 (iron (III) oxide) was conducted to determine the time dependent interface behavior and settling rates of these compounds. Variations in solids loading and sodium concentration were evaluated to represent waste processing conditions and the results of these settling studies were compared with prior tank waste settling tests. Information gathered from these studies can be used to inform future decisions on sludge treatment processes of the insoluble solids processed at the Hanford site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhanced prediction of Cs removal by CST from Hanford tank waste with K accountability

Abstract The treatment of Hanford tank waste is one of the most challenging environmental cleanup activities to date. To expedite the processing of liquid waste stored in underground tanks in Washington State it is necessary to remove the significant dose contributor, 137 Cs. Crystalline silicotitanate ion exchanger is currently used to remove 137 Cs from the aqueous phase of Hanford tank wastes in preparation for vitrification at the Waste Treatment and Immobilization Plant (WTP). Improving the understanding of potassium impacts on ion exchange behavior of Cs will help in the operation of a critical component of one of the most complex treatment processes in the world today. Optimization of this process can result in significant cost savings and less waste production. Toward this effort, a series of batch contact tests varied in potassium concentration were conducted to look at the impact of potassium concentration on Cs distribution. Experimental distribution ratios ( K d ) were compared to the distribution ratios predicted using the ZAM model. A significant underprediction of Cs capacity in the presence of potassium was seen with the existing model. A revision of the equilibrium constants was determined and provided a statistically better fit for determining the Cs K d values in tank waste matrices.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Tip-based Workflow for Sensitive IMAC-based Low Nanogram Level Phosphoproteomics

Analyzing the phosphoproteome at nanoscale poses a significant challenge, mainly due to the substantial sample loss from non-specific surface adsorption during the enrichment of low stoichiometric phosphopeptides. Here, we describe a tandem tip-based phosphoproteomics sample preparation method capable of sequential sample cleanup and enrichment without the need for additional sample transfer, thereby minimizing sample loss. Integration of this method to our recently developed SOP (Surfactant-assisted One-Pot sample preparation) and iBASIL (improved Boosting to Amplify Signal with Isobaric Labeling) approaches creates a streamlined workflow, enabling sensitive, high-throughput nanoscale phosphoproteomics measurements.

Phosphoproteome, Immobilized metal ion affinity ch↗

Exploring Fission–Fusion Synergies to Accelerate Compatibility Understanding

To address the significant commercial interest in fusion energy, it will be necessary to accelerate the compatibility research associated with liquid breeders including Li, eutectic Pb–Li and LiF-BeF 2 (FLiBe) molten salt. Particularly for FLiBe, compatibility understanding is limited especially for fusion relevant materials such as reduced activation ferritic-martensitic steels, SiC and V alloys. The historical knowledge associated with molten salt reactors (MSRs) and recent work to commercialize MSRs can benefit fusion research. Recent experimental and modeling work has improved understanding and this knowledge can be applied to fusion relevant materials. For liquid metals (LMs), the comparisons to Li and Pb–Li are less direct but nevertheless can help guide the pathway toward commercialization. For Pb–Li, Al-rich coatings have been shown to inhibit dissolution and potentially increase operating temperatures. For commercialization, the experience with sensors and on-line cleanup can help guide future developments. Thus, it is worth considering the potential for fission-related research with LMs and molten salts to help accelerate fusion research.

36 MATERIALS SCIENCE↗

The Impact of Sorbent Amendments for Mercury Remediation on the Viability of Soil Microorganisms

Mercury (Hg) remediation across contaminated environments in the United States is an ongoing project. As part of the Hg cleanup strategy at East Fork Poplar Creek (EFPC), located in Oak Ridge, TN, the deployment of sorbents is considered. However, the impact of sorbents on soil microorganisms is poorly understood. In this study, we investigated the effect of sorbents on soil microorganism viability and biofilm formation to assess soil health during sorbent application for Hg remediation. We specifically investigated the effect of two engineered sorbents, Organoclay PM-199 and Organoclay MRM (which are manufactured from clay minerals formulated for various remediation applications), on two gram-negative organisms ( Serratia marcescens and Burkholderia thailandensis ) isolated from the Hg-contaminated EFPC bank soil. Pure cultures of S. marcescens or B. thailandensis were amended with 5% (w/v) and 25% (w/v) PM-199 and MRM, respectively, for 9 days. The samples were harvested, and bacterial cell viability was determined using a BacLight staining kit. Results showed that the growth of sorbent-amended S. marcescens was inhibited in contrast to that of unamended control. Furthermore, biochemical assays were used to analyze bacterial biofilm formation and integral biofilm components. Our results suggest that biofilm formation by sorbent-amended S. marcescens was negatively affected. In contrast, B. thailandensis amended with low concentrations of MRM showed enhanced growth and notable differences in biofilm morphology. These results suggest that the use of organoclay PM-199 and MRM at higher concentrations in field studies may hinder the growth of specific soil microorganisms.

54 ENVIRONMENTAL SCIENCES↗

An antibody-free platform for multiplexed, sensitive quantification of protein biomarkers in complex biomatrices

Sensitive, multiplexed protein quantification remains challenging despite recent advancements in LC-MS assays for targeted protein biomarker quantification. High-sensitivity protein biomarker measurements usually require immuno-affinity enrichment of target protein; a process which is highly dependent on capture reagent and limited in capability to measure multiple analytes. Herein, we report a novel antibody-free platform, which measures multiple biomarkers from complex matrices employing a strategically optimized solid-phase extraction cleanup and orthogonal multidimensional LC-MS. Eight human protein biomarkers with different specifications were spiked into canine plasma as a model investigation system. The developed strategy achieved the desired sensitivity, robustness, and throughput via the following steps: (1) post digestion mixed-mode cation exchange-reverse phase SPE enrichment cleaned up the sample initially; (2) rapid, high-pH peptide fractionation further eliminated background components efficiently while selectively enriched signature peptides (SP) to provide sufficient sensitivity for multiple targets; and (3) trapping-micro-LC-MS analysis delivered high sensitivity comparable to a nano-LC-MS method but with much better robustness and throughput for the final analysis. Compared with a conventional LC-MS assay with direct protein digestion and limited clean-up, analysis with this antibody-free platform improved the LLOQ by 1–2 orders of magnitude for the eight protein biomarkers, reaching as low as 5 ng/mL in plasma, with feasible robustness and throughput. In conclusion, this platform was applied for the quantification of biomarkers of respiratory conditions in patients with various lung diseases, demonstrating real-world applicability.

59 BASIC BIOLOGICAL SCIENCES↗

Making coal relevant for small scale applications: Modular gasification for syngas/engine CHP applications in challenging environments

Small-scale coal gasification technology, coupled to a reciprocating engine generator, has the potential for making coal a cost competitive resource for meeting the flexible energy needs and resiliency requirements of utilities across the United States. To maintain grid stability and reliability, electrical generation must be regulated to match the load at the proper voltage and frequency. With the expansion of intermittent sources into the grid, such as wind and solar, frequency and voltage regulation become increasingly important and challenging. This work presents the results of a Front End Engineering Design (FEED) effort to detail the engineering and preliminary economics of a small-scale, air blown, fixed-bed gasification process, operating at near-atmospheric pressure, with gas cleanup to provide syngas and pyrolysis liquid fuels for use in reciprocating engine generators for combined heat and power at the University of Alaska Fairbanks. A very detailed assessment of capital and operating costs allows the evaluation of a levelized cost of electricity of 208.06 $/MWh, which can be reduced through the selling of by-products (steam for heating purposes and pyrolysis liquids to be used for power generation in an existing diesel engine). Here, a combined sensitivity analysis, based on the Monte Carlo approach, has been carried out to evaluate the effects of the uncertainties (capital and operating costs and plant annual availability) on the LCOE.

01 COAL, LIGNITE, AND PEAT↗

Sorption kinetics and stability of conventional adsorbents for mercury remediation

In-situ remediation of mercury at numerous contaminated sites worldwide is a challenging and costly endeavor due to the persistency of this contaminant. In this study, we evaluated eight commercially available sorbent media ranging from carbon-, clays- and silica-based materials (PBC– Biochar, eSorb – Sorbster, nsPAC – Powdered Activated Carbon, fsPAC – Powdered Activated Carbon with Mackinawite, F300 – Filtrasorb 300, Si-SH – Silica Thiol, eBind – RemBind, Q-Clay – Organoclay PM-199), for their effectiveness in sorbing mercury (Hg 2+ ) and mercury complexed with dissolved organic matter (Hg-DOM). Under the chosen experimental conditions of this study, results showed that in the absence of DOM, the kinetic rates of Hg 2+ sorption onto the evaluated sorbents were in the order of 0.31 min-1 (Si-SH) to 2.98 min -1 (nsPAC), whereas in the presence of DOM, the rates varied from 0.16 min-1 (F300) to 0.95 min -1 (nsPAC). The measured sorption capacity for Hg 2+ in the absence of DOM varied from 3.02 mg/g (Q-Clay) to 35.15 mg/g (Si-SH), whereas in the presence of DOM, calculated partition coefficient (KD) ranged from 69.7 mL/g (Q-Clay) to 41,510 mL/g (Si-SH). Furthermore, kinetic data suggest liquid film diffusion was the rate-limiting steps governing mercury sorption onto the studied media. Overall, the obtained study parameters (kinetics/isotherm) are particularly important in informing robust engineering designs for deployment of the vast majority of evaluated sorbents. Thus, sorbent-based strategies offer viable solutions for cost-effective cleanup of mercury at industrially contaminated sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Kinetic Model of the Long-Term Corrosion of Glass-Ceramic Materials

Multiphase waste forms show promise for increased waste loading and for the ability to dispose of contaminated solid and particulate waste through direct densification. However, achieving predictive capability for long-term durability of multiphase waste forms, and thus assessing their possible deployment, requires expanding the current, limited knowledge base. Here, we describe the development of a corrosion model of a two-phase waste form consisting of crystals of known volume fraction embedded in a glass matrix. This model accounts for the dissolution of both the crystalline and glass phases as well as the hydration of the glass phase through an ion exchange reaction. Because of the large difference in solubility between the two phases, the reactive surface of the crystalline phase is a function of the extent of dissolution of the glass phase in this model. Model parameterization was performed using corrosion data, such as from single-pass flow-through tests, for the individual phases. The parameterized corrosion model was evaluated against static dissolution test data for a glass-ceramic multiphase waste form. This evaluation demonstrated the model’s ability to reproduce the time-dependent release of key tracers of glass and crystalline phase dissolution. Hence, the development of a kinetic model provides a pathway for long-term durability predictions and thus the use of multiphase waste forms in nuclear cleanup missions.

Kerisit, Sebastien N.↗

Integrative Multi-PTM Proteomics Reveals Dynamic Global, Redox, Phosphorylation, and Acetylation Regulation in Cytokine-treated Pancreatic Beta Cells

Studying regulation of protein function at a systems level necessitates an understanding of the interplay among diverse post-translational modifications (PTMs). A variety of proteomics sample processing workflows are currently used to study specific PTMs but rarely characterize multiple types of PTMs from the same sample inputs. Method incompatibilities and laborious sample preparation steps complicate large-scale physiological investigations and can lead to variations in results. The single-pot, solid-phase-enhanced sample preparation (SP3) method for sample cleanup is compatible with different lysis buffers and amenable to automation, making it attractive for high-throughput multi-PTM profiling. Herein, we describe an integrative SP3 workflow for multiplexed quantification of protein abundance, cysteine thiol oxidation, phosphorylation, and acetylation. The broad applicability of this approach is demonstrated using cell and tissue samples, and its utility for studying interacting regulatory networks is highlighted in a time-course experiment of cytokine-treated ß-cells. We observed a swift response in global regulation of protein abundances consistent with rapid activation of JAK-STAT and NF-?B signaling pathways. Regulators of these pathways as well as proteins involved in their target processes displayed multi-PTM dynamics indicative of a complex cellular response stages: acute, adaptation, and chronic (prolonged stress). PARP14, a negative regulator of JAK-STAT, had multiple co-localized PTMs that may be involved in intraprotein regulatory crosstalk. Our workflow provides a high-throughput platform that can profile multi-PTMomes from the same sample set, which is valuable in unraveling the functional roles of PTMs and their co-regulation.

proteomics, PTM, automation, SP3, cysteine thiol o↗

Photon detector response function methodology using MCNP and shift hybrid radiation transport code for wide-area contamination assay applications

Here, radiation transport modeling using the Monte Carlo N-Particle (MCNP) radiation transport code and Monte Carlo code, Shift, were employed to model detector responses for a variety of wide-area photon contamination scenarios. In this study, 2" × 2" and 3" × 3" cylindrical NaI(Tl) scintillation detector configurations at source detector-distances of 0.5 cm, 1 cm, 2.54 cm, 10 cm, and 30 cm were modeled. Media of soil, concrete, and steel were evaluated for contamination depths ranging from surface to a depth of an infinite thickness in each medium for photon energies ranging from 20 keV to 3 MeV, which correspond to the energies that current detectors can discern. Monoenergetic photon surface contamination detector responses for each of the media, source–detector distances, and detectors were estimated using MCNP v6.2. Shift was harnessed for improved variance reduction of particle transport in highly attenuating media to obtain average cell fluxes in the two MCNP NaI(Tl) scintillation detector configurations. Average cell flux values in Shift were coupled with detector responses from MCNP to convert average cell flux in a void to energy distribution of pulses in the NaI(Tl) scintillation detector crystal of interest. An optimized detector response function methodology was developed by coupling the MCNP radiation transport method with the Consistent Adjoint Driven Importance Sampling (CADIS) hybrid radiation transport method built into Shift to significantly decrease the runtime of thousands of MCNP pulse height simulations. The methodology may be utilized to quickly and accurately facilitate the assessment of a broad range of wide-area environmental contamination assay and decommissioning cleanup applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Raman Spectroscopic In Situ Monitoring of Highly Turbid Media

The ability to run chemical processing more efficiently and cost effectively is a need that spans critical materials recovery and legacy nuclear waste cleanup. Sensors integrated to provide online monitoring are essential to addressing this need by providing near-real time feedback on process conditions, which can improve efficiency, aid in decision making, and reduce the need for grab sample measurements. Optical spectroscopy is well-suited for providing online chemical composition information and has been widely applied in varied chemical systems. However, applications in turbid matrices continue to represent substantial challenges to sensor performance, where absorption or scattering of excitation light can cause significant signal interference. Here, in this study, close-focus Raman probes are investigated for use in turbid media as a way to overcome the signal loss from the scattering of the Raman excitation source. This, paired with advanced data science techniques, allowed for the development of chemometric models for the accurate quantification of several analytes of interest (NO 3 – , NO 2 – , and PO 4 3– ) in highly turbid solutions with solids loadings of up to 20 wt %. This work focuses on offline sample measurement and characterization as an initial step toward the development of online monitoring capabilities. Chemical systems of interest were focused on nuclear waste at the Hanford Site, which represents highly complex matrices that could realize significant processing benefits through the integration of online monitoring.

Felmy, Heather M. [Pacific Northwest National Labo↗

Guanidinium-Based Ionic Covalent-Organic Nanosheets for Sequestration of Cr(VI) and As(V) Oxoanions in Water

Chromium- and arsenic-based oxoanions are among the major highly toxic and carcinogenic inorganic pollutants present in groundwater, demanding fast and selective sequestration. Efficient capturing and removal of these highly mobile oxometallates at neutral pH presents a great challenge in groundwater cleanup. In this report, a series of guanidinium-based ionic organic covalent nanosheets (iCONs) with varying hydrogen bonding, steric, and electronic properties was studied to examine the structure–activity relationship in the adsorption and removal of chromium- and arsenic-based oxoanions in water. Structural modulations in iCONs were found to alter the guanidinium acidity, thus regulating the oxoanion uptake limits via ion exchange. The hydrogen bonding, steric, and electrostatic interactions at/near the guanidinium-based anion binding site in iCONs exerted heavy influences on the uptake efficiency and selectivity of arsenate but not on those of chromate. Further analyses revealed that the parallel bidentate hydrogen bonding interactions play a key role in the weak binding of arsenate to the protonated/positively charged guanidine motifs, whereas the strong ion–ion interactions between chromate and guanidinium appear to be more tolerant to the geometric and structural perturbation.

36 MATERIALS SCIENCE↗