The objective of this work is to formulate a novel and physics-based nanomechanics framework to connect geochemical reactions in host rock to the resulting morphological changes at the microscopic lengthscale and to the resulting geomechanical changes at the macroscopic lengthscale. The key idea is to monitor the fraction of minerals based on their mechanical signature. We illustrate this procedure on the Mt. Simon sandstone from the Illinois Basin. To this end, various acidic fluid systems were applied to Mt. Simon sandstone specimens. The chemistry, morphology, microstructure, and mechanical characteristics were investigated across multiple lengthscales. Grid indentation was carried out with a total of 6900 individual indentation tests performed on 24 specimens. A good agreement was observed between the composition computed using statistical nanoindentation and measurements employing independent methods such as scanning electron microscopy, electron-dispersive X-ray spectroscopy, X-ray diffraction analyses, mercury intrusion porosimetry, flow perporometry, and helium pycnometry. An increase in porosity and a decrease in K-feldspar content were observed following the incubation in CO2-saturated brine, suggesting dissolution reactions involving feldspar. Thus, a rigorous methodology is presented to connect geochemical reactions and related compositional changes at the nano- and microscopic scales to alterations of the constitutive behavior at the macroscopic level.
Mixing-driven reactions in porous media are ubiquitous and span natural and engineered environments, yet predicting where and how quickly reactions occur is immensely challenging due to the complex and nonuniform nature of porous media flows. In particular, in many instances, there is an enormous range of spatial and temporal scales over which reactants can mix. This paper aims to review factors that affect mixing-limited reactions in porous media, and approaches used to predict such processes across scales. We focus primarily on the challenges of mixing-driven reactions in porous media at pore scales to provide a concise, but comprehensive picture. We balance our discussion between state-of-the-art experiments, theory and numerical methods, introducing the reader to factors that affect mixing, focusing on the bracketing cases of transverse and longitudinal mixing. We introduce the governing equations for mixing-limited reactions and then summarize several upscaling methods that aim to account for complex pore-scale flow fields. We conclude with perspectives on where the field is going, along with other insights gleaned from this review.
Bench-scale experiments were performed on natural sediments to assess abiotic dechlorination of trichloroethene (TCE) under both aerobic and anaerobic conditions. In the absence of oxygen (<26 µM), TCE dechlorination proceeded via a reductive pathway generating acetylene and/or ethene. Reductive dechlorination rate constants up to 3.1 x 10-5 d-1 were measured, after scaling to in situ solid water ratios. In the presence of oxygen greater than 120 µM, TCE dechlorination proceeded via an oxidative pathway generating formic/glyoxylic and glycolic/acetic acids, and oxidative dechlorination rate constants (again scaled to in situ conditions) up to 7.4 x 10-3 d-1 were measured. These rates correspond to half-lives of 60 and 0.25 years for abiotic TCE dechlorination under anaerobic and aerobic conditions, respectively, indicating the potentially large impact of aerobic TCE oxidation in the field. For both reductive and oxidative TCE dechlorination pathways, measured first-order rate constants increased with increasing ferrous iron content, suggesting the role of iron oxidation. Hydroxyl radical formation was measured and increased with increasing oxygen and ferrous iron content. Rate constants associated with TCE oxidation products increased with increasing hydroxyl radical generation rates, and are zero in the presence of a hydroxyl radical scavenger, suggesting that oxidative TCE dechlorination is a hydroxyl radical driven process.
More than 10% of the global human population is now afflicted with kidney stones, which are commonly associated with other significant health problems including diabetes, hypertension and obesity. Nearly 70% of these stones are primarily composed of calcium oxalate, a mineral previously assumed to be effectively insoluble within the kidney. This has limited currently available treatment options to painful passage and/or invasive surgical procedures. We analyze kidney stone thin sections with a combination of optical techniques, which include bright field, polarization, confocal and super-resolution nanometer-scale auto-fluorescence microscopy. Here we demonstrate using interdisciplinary geology and biology (geobiology) approaches that calcium oxalate stones undergo multiple events of dissolution as they crystallize and grow within the kidney. These observations open a fundamentally new paradigm for clinical approaches that include in vivo stone dissolution and identify high-frequency layering of organic matter and minerals as a template for biomineralization in natural and engineered settings.
There is a growing need to monitor anthropogenic organic contaminants detected in water sources. DNA aptamers are synthetic single-stranded oligonucleotides, selected to bind to target contaminants with favorable selectivity and sensitivity. These aptamers can be functionalized and are used with a variety of sensing platforms to develop sensors, or aptasensors. In this critical review, we (1) identify the state-of-the-art in DNA aptamer selection, (2) evaluate target and aptamer properties that make for sensitive and selective binding and sensing, (3) determine strengths and weaknesses of alternative sensing platforms, and (4) assess the potential for aptasensors to quantify environmentally relevant concentrations of organic contaminants in water. Among a suite of target and aptamer properties, binding affinity is either directly (e.g., organic carbon partition coefficient) or inversely (e.g., polar surface area) correlated to properties that indicate greater target hydrophobicity results in the strongest binding aptamers, and binding affinity is correlated to aptasensor limits of detection. Electrochemical-based aptasensors show the greatest sensitivity, which is similar to ELISA-based methods. Only a handful of aptasensors can detect organic pollutants at environmentally relevant concentrations, and interference from structurally similar analogs commonly present in natural waters is a yet-to-be overcome challenge. These findings lead to recommendations to improve aptasensor performance.
The environmental impacts of a typical hydraulic fracturing operation for shale gas recovery were evaluated using life cycle assessment, with energy demands for well drilling and fracturing determined from GHGfrack model. Dominant environmental impacts stem from well construction, which are >63% in all categories (e.g., global warming and eutrophication), and mainly due to diesel fuel combustion and steel production. The relative impacts related to water use (i.e., fracturing fluid components, water/wastewater transportation, and wastewater disposal) are relatively small, ranging from 5 to 22% of total impacts in all categories; freshwater consumption for fracturing is also a small fraction of available water resources for the shale play considered. The impacts of replacing slickwater with CO2 or CH4-foam fracturing fluid (≤10 vol % water) were evaluated; total impacts decrease <12%, and relative impacts related to water use decrease to 2–9% of total impacts. Hence, switching to a foam-based fracturing fluid can substantially decrease water-related impacts (>60%) but has only marginal effects on total environmental impacts. Changes in lateral well length, produced to fresh-water ratios, fracturing fluid composition, and LCA control volume do not change these findings. More benefits could potentially be realized by considering water versus foam-related impacts of ecological health and energy production.
Laboratory batch experiments were performed to assess the impacts of temperature and mineralogy on the abiotic dechlorination of tetrachloroethene (PCE) or trichloroethene (TCE) due to the presence of ferrous minerals in natural aquifer clayey soils under anaerobic conditions. A combination of x-ray diffraction (XRD), magnetic susceptibility, and ferrous mineral content were used to characterize each of the 3 natural soils tested in this study, and dechlorination at temperatures ranging from 20 to 55 °C were examined. Results showed that abiotic dechlorination occurred in all 3 soils examined, yielding reduced gas abiotic dechlorination products acetylene, butane, ethene, and/or propane. Bulk first-order dechlorination rate constants (kbulk), scaled to the soil:water ratio expected for in situ conditions, ranged from 2.0 × 10−5 day−1 at 20 °C, to 32 × 10−5 day−1 at 55 °C in the soil with the greatest ferrous mineral content. For the generation of acetylene and ethene from PCE, the reaction was well described by Arrhenius kinetics, with an activation energy of 91 kJ/mol. For the generation of coupling products butane and propane, the Arrhenius equation did not provide a satisfactory description of the data, likely owing to the complex reaction mechanisms associated with these products and/or diffusional mass transfer processes associated with the ferrous minerals likely responsible for these coupling reactions. Although the data set was too limited to determine a definitive correlation, the two soils with elevated ferrous mineral contents had elevated abiotic dechlorination rate constants, while the one soil with a low ferrous mineral content had a relatively low abiotic dechlorination rate constant. Overall, results suggest intrinsic abiotic dechlorination rates may be an important long-term natural attenuation component in site conceptual models for clays that have the appropriate iron mineralogy.
For over two decades, Pd has been the primary hydrogenation metal studied for reductive catalytic water treatment applications. Herein, we report that alternative platinum group metals (Rh, Ru, Pt and Ir) can exhibit substantially higher activity, wider substrate selectivity and variable pH dependence in comparison to Pd. Cross comparison of multiple metals and oxyanion substrates provides new mechanistic insights into the heterogeneous reactions. Activity differences and pH effects mainly originate from the chemical nature of individual metals. Considering the advantages in performance and cost, results support renewed investigation of alternative hydrogenation metals to advance catalytic technologies for water purification and other environmental applications.
Three techniques to measure and understand the contact angle, θ, of a CO2/brine/rock system relevant to geologic carbon storage were performed with Mount Simon sandstone. Traditional sessile drop measurements of CO2/brine on the sample were conducted and a water-wet system was observed, as is expected. A novel series of measurements inside of a Mount Simon core, using a micro X-ray computed tomography imaging system with the ability to scan samples at elevated pressures, was used to examine the θ of residual bubbles of CO2. Within the sandstone core the matrix appeared to be neutrally wetting, with an average θ around 90°. A large standard deviation of θ (20.8°) within the core was also observed. To resolve this discrepancy between experimental measurements, a series of Lattice Boltzmann model simulations were performed with differing intrinsic θ values. The model results with a θ=80° were shown to match the core measurements closely, in both magnitude and variation. The small volume and complex geometry of the pore spaces that CO2 was trapped in is the most likely explanation of this discrepancy between measured values, though further work is warranted.
Recently, N,N-trans Re(O)(LN–O)2X (LN–O = monoanionic N–O chelates; X = Cl or Br prior to being replaced by solvents or alkoxides) complexes have been found to be superior to the corresponding N,N-cis isomers in the catalytic reduction of perchlorate via oxygen atom transfer. However, reported methods for Re(O)(LN–O)2X synthesis often yield only the N,N-cis complex or a mixture of trans and cis isomers. This study reports a geometry-inspired ligand design rationale that selectively yields N,N-trans Re(O)(LN–O)2Cl complexes. Analysis of the crystal structures revealed that the dihedral angles (DAs) between the two LN–O ligands of N,N-cis Re(O)(LN–O)2Cl complexes are less than 90°, whereas the DAs in most N,N-trans complexes are greater than 90°. Variably sized alkyl groups (−Me, −CH2Ph, and −CH2Cy) were then introduced to the 2-(2′-hydroxyphenyl)-2-oxazoline (Hhoz) ligand to increase steric hindrance in the N,N-cis structure, and it was found that substituents as small as −Me completely eliminate the formation of N,N-cisisomers. The generality of the relationship between N,N-trans/cis isomerism and DAs is further established from a literature survey of 56 crystal structures of Re(O)(LN–O)2X, Re(O)(LO–N–N–O)X, and Tc(O)(LN–O)2X congeners. Density functional theory calculations support the general strategy of introducing ligand steric hindrance to favor synthesis of N,N-trans Re(O)(LN–O)2X and Tc(O)(LN–O)2X complexes. This study demonstrates the promise of applying rational ligand design for isomeric control of metal complex structures, providing a path forward for innovations in a number of catalytic, environmental, and biomedical applications.
Palladium (Pd)-based catalysts hold promise as an alternative water treatment technology for nitrate (NO3–), but practical application requires a flow-through reactor that efficiently delivers hydrogen (H2) from gas to water. A trickle bed reactor (TBR) packed with a 0.1 percent by weight (wt%) Pd–0.01 wt% In/γ-Al2O3 (indium and porous aluminum oxide) catalyst was evaluated to address this challenge. Catalytic activity generally increased with H2 superficial velocity (0.65–29.6 m/h) and liquid (deionized water) superficial velocities from 14.8 to 26.6 m/h before decreasing at 38.5 m/h. This decrease corresponded to a change in flow regime and suggests that optimal TBR performance occurs at the transition from pulse to bubble flow. An optimal TBR activity of 19.5 ± 1.3 mg NO3–/min-g Pd was obtained; this is only ~18% of the batch reactor activity as a result of H2 mass transfer limitations, but three to 15 times greater than activities obtained with previous flow-through reactors. Catalyst deactivation occurred in the TBR after 41 days of operation, motivating the need for improved fouling mitigation strategies.
Physical, chemical, and biological interactions between groundwater and sedimentary rock directly control the fundamental subsurface properties such as porosity, permeability, and flow. This is true for a variety of subsurface scenarios, ranging from shallow groundwater aquifers to deeply buried hydrocarbon reservoirs. Microfluidic flow cells are now commonly being used to study these processes at the pore scale in simplified pore structures meant to mimic subsurface reservoirs. However, these micromodels are typically fabricated from glass, silicon, or polydimethylsiloxane (PDMS), and are therefore incapable of replicating the geochemical reactivity and complex three-dimensional pore networks present in subsurface lithologies. To address these limitations, we developed a new microfluidic experimental test bed, herein called the Real Rock-Microfluidic Flow Cell (RR-MFC). A porous 500 μm-thick real rock sample of the Clair Group sandstone from a subsurface hydrocarbon reservoir of the North Sea was prepared and mounted inside a PDMS microfluidic channel, creating a dynamic flow-through experimental platform for real-time tracking of subsurface reactive transport. Transmitted and reflected microscopy, cathodoluminescence microscopy, Raman spectroscopy, and confocal laser microscopy techniques were used to (1) determine the mineralogy, geochemistry, and pore networks within the sandstone inserted in the RR-MFC, (2) analyze non-reactive tracer breakthrough in two- and (depth-limited) three-dimensions, and (3) characterize multiphase flow. The RR-MFC is the first microfluidic experimental platform that allows direct visualization of flow and transport in the pore space of a real subsurface reservoir rock sample, and holds potential to advance our understandings of reactive transport and other subsurface processes relevant to pollutant transport and cleanup in groundwater, as well as energy recovery.
Catalytic reduction of nitrate in ion exchange (IX) waste brine for reuse is a promising option for reducing IX costs and environmental impacts. A recycling trickle bed reactor (TBR) was designed and optimized using 0.5 percent byweight (wt%) palladium–0.05 wt% indium catalysts supported on US mesh size 12 × 14 or 12 × 30 activated carbon particles. Various liquid superficial velocities (Ur) and hydrogen gas superficial velocities (Ug-H2) were evaluated to assess performance in different flow regimes; catalyst activity increased with Ug-H2 at all Ur for both catalysts and was greatest for the 12 × 30 catalyst at thelowest Ur (8.9 m/h). The 12 × 30 catalyst demonstrated up to 100% higher catalytic activity and 280% higher mass transfer rate compared with the 12 × 14 catalyst. Optimal TBR performance was achieved with both catalysts in thetrickle flow regime. The results indicate that the TBR is a promising step forward, and continued improvements are possible to overcome remaining mass transfer limitations.
Members of the Geobacteraceae family are ubiquitous metal reducers that utilize conductive ‘nanowires’ to reduce Mn(IV) and Fe(III) oxides in anaerobic sediments. However, it is not currently known if and to what extent the Mn(IV) and Fe(III) oxides in soil grains and low permeability sediments that are sequestered in pore spaces too small for cell passage can be reduced by long-range extracellular electron transport via Geobacter nanowires, and what mechanisms control this reduction. We developed a microfluidic reactor that physically separates Geobacter sulfurreducens from the Mn(IV) mineral birnessite by a 1.4 μm thick wall containing <200 nm pores. Using optical microscopy and Raman spectroscopy, we show that birnessite can be reduced up to 15 μm away from cell bodies, similar to the reported length of Geobacter nanowires. Reduction across the nanoporous wall required reducing conditions, provided by Escherichia coli, and an exogenous supply of riboflavin. Our results discount electron shuttling by dissolved flavins, and instead support their role as bound redox cofactors in electron transport from nanowires to metal oxides. We also show that upon addition of a soluble electron shuttle (i.e., AQDS), reduction extends beyond the reported nanowire length up to 40 μm into a layer of birnessite.
Wettability is a key reservoir characteristic influencing geological carbon sequestration (GCS) processes, such as CO2 transport and storage capacity. Wettability is often determined on a limited number of reservoir samples by measuring the contact angle at the CO2/brine/mineral interface, but the ability to predict this value remains a challenge. In this work, minerals comprising a natural reservoir sample were identified, and the influence of their surface roughness and mineralogy on the contact angle was quantified to evaluate predictive models and controlling mechanisms. The natural sample was obtained from the Mount Simon formation, a representative siliciclastic reservoir that is the site of a United States Department of Energy CO2 injection project. A thin section of the Mount Simon sandstone was examined with compound light microscopy and environmental scanning electron microscopy (ESEM) coupled with energy-dispersive X-ray spectroscopy (EDS). Quartz and feldspar were identified as dominant minerals and were coated with various reddish black precipitates consistent with illite clay and iron oxide hematite. Contact angle (θ) measurements were conducted for the four representative minerals and the Mount Simon sample over a range of pressures (2–25 MPa) at 40 °C. At supercritical conditions, all samples are strongly water-wet, with contact angles between 27° and 45°. Several predictive models for contact angle were evaluated for the mineral and Mount Simon samples, including the Wenzel and Cassie–Baxter models, plus newly proposed modifications of these that account for the fraction of different minerals comprising the reservoir sample surface, the surface roughness, and the extent that roughness pits are filled with brine. Modeling results suggest that the fraction of mineral surfaces containing roughness pits filled with brine is the most important reservoir characteristic that controls wettability in the Mount Simon sandstone, followed by surface mineralogy. To our knowledge, this is one of the few studies to investigate the effects of individual minerals on the wettability of a natural reservoir sample.
Well-defined palladium–gold nanoparticles (PdAuNPs) with randomly alloyed structures and broadly tunable compositions were studied in catalytic nitrite (NO2–) reduction. The catalysts were synthesized using a microwave-assisted polyol coreduction method. PdxAu100–xNPs with systematically varied compositions (x = 18–83) were supported on amorphous silica (SiO2) and studied as model catalysts for aqueous NO2– reduction in a batch reactor, using H2 as the electron donor. The reactions followed pseudo-first-order kinetics for ≥80% NO2– conversion. The PdxAu100–xNP-SiO2 catalysts showed a volcano-like correlation between NO2– reduction activity and x; the highest activity was observed for Pd53Au47, with an associated first-order rate constant of 5.12 L min–1 gmetal–1. Alloy NPs with greater proportions of Au were found to reduce the loss in catalytic activity due to sulfide fouling. Density functional theory calculations indicate that this is because Au weakens sulfur binding at PdAuNP surfaces due to atomic ensemble, electronic, and strain effects and thus reduces sulfur poisoning. The environmental relevance of the most active supported catalyst was evaluated by subjecting it to five cycles of catalytic NO2– reduction. The catalytic activity decreased over multiple cycles, but analysis of the postreaction PdxAu100–xNP-SiO2 materials using complementary techniques indicated that there were no significant structural changes. Most importantly, we show that PdxAu100–xNP-SiO2 alloys are significantly more active NO2– reduction catalysts in comparison to pure Pd catalysts.
Four sets of nonreactive solute transport experiments were conducted with micromodels. Each set consisted of three experiments with one variable, i.e., flow velocity, grain diameter, pore-aspect ratio, and flow-focusing heterogeneity. The data sets were offered to pore-scale modeling groups to test their numerical simulators. Each set consisted of two learning experiments, for which all results were made available, and one challenge experiment, for which only the experimental description and base input parameters were provided. The experimental results showed a nonlinear dependence of the transverse dispersion coefficient on the Peclet number, a negligible effect of the pore-aspect ratio on transverse mixing, and considerably enhanced mixing due to flow focusing. Five pore-scale models and one continuum-scale model were used to simulate the experiments. Of the pore-scale models, two used a pore-network (PN) method, two others are based on a lattice Boltzmann (LB) approach, and one used a computational fluid dynamics (CFD) technique. The learning experiments were used by the PN models to modify the standard perfect mixing approach in pore bodies into approaches to simulate the observed incomplete mixing. The LB and CFD models used the learning experiments to appropriately discretize the spatial grid representations. For the continuum modeling, the required dispersivity input values were estimated based on published nonlinear relations between transverse dispersion coefficients and Peclet number. Comparisons between experimental and numerical results for the four challenge experiments show that all pore-scale models were all able to satisfactorily simulate the experiments. The continuum model underestimated the required dispersivity values, resulting in reduced dispersion. The PN models were able to complete the simulations in a few minutes, whereas the direct models, which account for the micromodel geometry and underlying flow and transport physics, needed up to several days on supercomputers to resolve the more complex problems.
Characterizing subsurface properties is crucial for reliable and cost-effective groundwater supply management and contaminant remediation. With recent advances in sensor technology, large volumes of hydrogeophysical and geochemical data can be obtained to achieve high-resolution images of subsurface properties. However, characterization with such a large amount of information requires prohibitive computational costs associated with “big data” processing and numerous large-scale numerical simulations. To tackle such difficulties, the principal component geostatistical approach (PCGA) has been proposed as a “Jacobian-free” inversion method that requires much smaller forward simulation runs for each iteration than the number of unknown parameters and measurements needed in the traditional inversion methods. PCGA can be conveniently linked to any multiphysics simulation software with independent parallel executions. In this paper, we extend PCGA to handle a large number of measurements (e.g., 106 or more) by constructing a fast preconditioner whose computational cost scales linearly with the data size. For illustration, we characterize the heterogeneous hydraulic conductivity (K) distribution in a laboratory-scale 3-D sand box using about 6 million transient tracer concentration measurements obtained using magnetic resonance imaging. Since each individual observation has little information on the K distribution, the data were compressed by the zeroth temporal moment of breakthrough curves, which is equivalent to the mean travel time under the experimental setting. Only about 2000 forward simulations in total were required to obtain the best estimate with corresponding estimation uncertainty, and the estimated K field captured key patterns of the original packing design, showing the efficiency and effectiveness of the proposed method.
Ion exchange (IX) is the most common approach to treating nitrate-contaminated drinking water sources, but the cost of salt to make regeneration brine, as well as the cost and environmental burden of waste brine disposal, are major disadvantages. A hybrid ion exchange-catalyst treatment system, in which waste brine is catalytically treated for reuse, shows promise for reducing costs and environmental burdens of the conventional IX system. An IX model with separate treatment and regeneration cycles was developed, and ion selectivity coefficients for each cycle were separately calibrated by fitting experimental data. Of note, selectivity coefficients for the regeneration cycle required fitting the second treatment cycle after incomplete resin regeneration. The calibrated and validated model was used to simulate many cycles of treatment and regeneration using the hybrid system. Simulated waste brines and a real brine obtained from a California utility were also evaluated for catalytic nitrate treatment in a packed-bed, flow-through column with 0.5 wt%Pd–0.05 wt%In/activated carbon support (PdIn/AC). Consistent nitrate removal and no apparent catalyst deactivation were observed over 23 d (synthetic brine) and 45 d (real waste brine) of continuous-flow treatment. Ion exchange and catalyst results were used to evaluate treatment of 1 billion gallons of nitrate-contaminated source water at a 0.5 MGD water treatment plant. Switching from a conventional IX system with a two bed volume regeneration to a hybrid system with the same regeneration length and sequencing batch catalytic reactor treatment would save 76% in salt cost. The results suggest the hybrid system has the potential to address the disadvantages of a conventional IX treatment systems.
Rapid reduction of aqueous ClO4– to Cl– by H2 has been realized by a heterogeneous Re(hoz)2–Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx– intermediates formed during reactions with concentrated ClO4– promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4– reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2– intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4– reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx– scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx– intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2–Pd/C, the new Re(hoz)(htz)–Rh/C catalyst exhibits similar ClO4– reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated “challenge” solution containing 1000 ppm of ClO4–. This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications.