Evaluation of individual and ensemble probabilistic forecasts of COVID-19 mortality in the United States.

Short-term probabilistic forecasts of the trajectory of the COVID-19 pandemic in the United States have served as a visible and important communication channel between the scientific modeling community and both the general public and decision-makers. Forecasting models provide specific, quantitative, and evaluable predictions that inform short-term decisions such as healthcare staffing needs, school closures, and allocation of medical supplies. Starting in April 2020, the US COVID-19 Forecast Hub (https://covid19forecasthub.org/) collected, disseminated, and synthesized tens of millions of specific predictions from more than 90 different academic, industry, and independent research groups. A multimodel ensemble forecast that combined predictions from dozens of groups every week provided the most consistently accurate probabilistic forecasts of incident deaths due to COVID-19 at the state and national level from April 2020 through October 2021. The performance of 27 individual models that submitted complete forecasts of COVID-19 deaths consistently throughout this year showed high variability in forecast skill across time, geospatial units, and forecast horizons. Two-thirds of the models evaluated showed better accuracy than a naïve baseline model. Forecast accuracy degraded as models made predictions further into the future, with probabilistic error at a 20-wk horizon three to five times larger than when predicting at a 1-wk horizon. This project underscores the role that collaboration and active coordination between governmental public-health agencies, academic modeling teams, and industry partners can play in developing modern modeling capabilities to support local, state, and federal response to outbreaks.

COVID-19 infection data encode a dynamic reproduction number in response to policy decisions with secondary wave implications.

The SARS-CoV-2 virus is responsible for the novel coronavirus disease 2019 (COVID-19), which has spread to populations throughout the continental United States. Most state and local governments have adopted some level of "social distancing" policy, but infections have continued to spread despite these efforts. Absent a vaccine, authorities have few other tools by which to mitigate further spread of the virus. This begs the question of how effective social policy really is at reducing new infections that, left alone, could potentially overwhelm the existing hospitalization capacity of many states. We developed a mathematical model that captures correlations between some state-level "social distancing" policies and infection kinetics for all U.S. states, and use it to illustrate the link between social policy decisions, disease dynamics, and an effective reproduction number that changes over time, for case studies of Massachusetts, New Jersey, and Washington states. In general, our findings indicate that the potential for second waves of infection, which result after reopening states without an increase to immunity, can be mitigated by a return of social distancing policies as soon as possible after the waves are detected.

An Analytical Perspective on Pandemic Recovery.

After implementing restrictions to curb the spread of coronavirus, governments in the United States and around the world are trying to identify the path to social and economic recovery. The White House and the Centers for Disease Control and Prevention have published guidelines to assist US states, counties, and territories in planning these efforts. As the impact of the coronavirus pandemic has not been uniform, these central guidelines need to be translated into practice in ways that recognize variation among jurisdictions. We present a core methodology to assist governments in this task, presenting a case for appropriate actions at each stage of recovery based on scientific data and analysis. Specifically, 3 types of data are needed: data on the spread of disease should be analyzed alongside data on the overall health of the population and data on infrastructure-for example, the capacity of health systems. Local circumstances will produce different needs and present different setbacks, and governments may need to reinstate as well as relax restrictions. Transparent, defensible analysis can assist in making these decisions and communicating them to the public. In the absence of a widely administered vaccine, analysis remains one of our most important tools in addressing the coronavirus pandemic.

Engineering Nanoscale Iron Oxides for Uranyl Sorption and Separation: Optimization of Particle Core Size and Bilayer Surface Coatings.

Herein, we describe engineered superparamagnetic iron oxide nanoparticles (IONPs) as platform materials for enhanced uranyl (UO22+) sorption and separation processes under environmentally relevant conditions. Specifically, monodispersed 8-25 nm iron oxide (magnetite, Fe3O4) nanoparticles with tailored organic acid bilayered coatings have been systematically evaluated and optimized to bind, and thus remove, uranium from water. The combined nonhydrolytic synthesis and bilayer phase transfer material preparation methods yield highly uniform and surface tailorable IONPs, which allow for direct evaluation of the size-dependent and coating-dependent sorption capacities of IONPs. Optimized materials demonstrate ultrahigh sorption capacities (>50% by wt/wt) at pH 5.6 for 8 nm oleic acid (OA) bilayer and sodium monododecyl phosphate (SDP) surface-stabilized IONPs. Synchrotron-based X-ray absorption spectroscopy shows that iron oxide core particle size and stabilizing surface functional group(s) substantially affect U(VI)-removal mechanisms, specifically the ratio of uptake via adsorption versus reduction to U(IV). Taken together, tunable size and surface functionality, high colloidal stability, and favorable affinity toward uranium provide distinct synergistic advantage(s) for the application of bilayered IONPs as part of the next-generation material-based uranium recovery, remediation, and sensing technologies.

Exploring the ability of cations to facilitate binding between inorganic oxyanions and humic acid.

The mobility and fate of inorganic oxyanions in the environment can be greatly influenced by interactions with natural organic matter (NOM). There is increasing evidence that this interaction between two anionic species is facilitated by cationic bridges, but detailed mechanistic studies into this system are challenging due to the heterogeneous nature of NOM. This work examines the ability of cations (FeIII, CrIII, AlIII, or GaIII) to form ternary complexes with Suwannee River humic acid (SRHA) and the oxyanions of As (AsIII and AsV) and Se (SeIV and SeVI). Complexes were characterized by separating SRHA from unbound species using size exclusion chromatography coupled to ICP-MS to determine its metal content. Unlike CrIII and FeIII, the post-transition metal ions AlIII and GaIII proved ineffective at forming ternary complexes with any of the oxyanions, although minor complexation was observed with GaIII, suggesting that electrostatic interactions are not the primary driving force behind the stabilization of these ternary complexes. The results also show differences in the behavior of FeIII and CrIII that may indicate that the two cations stabilize the ternary complexes by different mechanisms.

The influence of environmental conditions on kinetics of arsenite oxidation by manganese-oxides.

BACKGROUND: Manganese-oxides are one of the most important minerals in soil due to their widespread distribution and high reactivity. Despite their invaluable role in cycling many redox sensitive elements, numerous unknowns remain about the reactivity of different manganese-oxide minerals under varying conditions in natural systems. By altering temperature, pH, and concentration of arsenite we were able to determine how manganese-oxide reactivity changes with simulated environmental conditions. The interaction between manganese-oxides and arsenic is particularly important because manganese can oxidize mobile and toxic arsenite into more easily sorbed and less toxic arsenate. This redox reaction is essential in understanding how to address the global issue of arsenic contamination in drinking water. RESULTS: The reactivity of manganese-oxides in ascending order is random stacked birnessite, hexagonal birnessite, biogenic manganese-oxide, acid birnessite, and δ-MnO2. Increasing temperature raised the rate of oxidation. pH had a variable effect on the production of arsenate and mainly impacted the sorption of arsenate on δ-MnO2, which decreased with increasing pH. Acid birnessite oxidized the most arsenic at alkaline and acidic pHs, with decreased reactivity towards neutral pH. The δ-MnO2 showed a decline in reactivity with increasing arsenite concentration, while the acid birnessite had greater oxidation capacity under higher concentrations of arsenite. The batch reactions used in this study quantify the impact of environmental variances on different manganese-oxides' reactivity and provide insight to their roles in governing chemical cycles in the Critical Zone. CONCLUSIONS: The reactivity of manganese-oxides investigated was closely linked to each mineral's crystallinity, surface area, and presence of vacancy sites. δ-MnO2 and acid birnessite are thought to be synthetic representatives of naturally occurring biogenic manganese-oxides; however, the biogenic manganese-oxide exhibited a lag time in oxidation compared to these two minerals. Reactivity was clearly linked to temperature, which provides important information on how these minerals react in the subsurface environment. The pH affected oxidation rate, which is essential in understanding how manganese-oxides react differently in the environment and their potential role in remediating contaminated areas. Moreover, the contrasting oxidative capacity of seemingly similar manganese-oxides under varying arsenite concentrations reinforces the importance of each manganese-oxide mineral's unique properties.

Theoretical predictions of thermodynamic parameters of adsorption of nitrogen containing environmental contaminants on kaolinite.

In this study thermodynamic parameters of adsorption of nitrogen containing environmental contaminants (NCCs, 2,4,6, trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 3-one-1,2,4-triazol-5-one (NTO)) interacting with the tetrahedral and octahedral surfaces of kaolinite were predicted. Adsorption complexes were investigated using a density functional theory and both periodic and cluster approach. The complexes, modeled using the periodic boundary conditions approach, were fully optimized at the BLYP-D2 level to obtain the structures and adsorption energies. The relaxed kaolinite-NCCs structures were used to prepare cluster models to calculate thermodynamic parameters and partition coefficients at the M06-2X-D3 and BLYP-D2 levels from the gas phase. The entropy effect on the Gibbs free energies of adsorption of NCCS on kaolinite was also studied and compared with available experimental data. The results showed that in all calculated models, the NCCs molecules are physisorbed and they favor a parallel orientation toward both kaolinite surfaces. It was found that all calculated NCCs compounds are more stable on the octahedral than on the tetrahedral surface of kaolinite. The Gibbs free energies and partition coefficients were also predicted for interactions of NCCs with Na-kaolinite from aqueous solution. Calculations revealed adsorption of NCCs is effective from the gas phase on both cation free kaolinite surfaces and on Na-kaolinite from aqueous solution at room temperature. Theoretical data were validated against experimental results, and the reasons for small differences between calculated and measured partition coefficients are discussed.

Characterization of multi-layered fish scales (Atractosteus spatula) using nanoindentation, X-ray CT, FTIR, and SEM.

The hierarchical architecture of protective biological materials such as mineralized fish scales, gastropod shells, ram's horn, antlers, and turtle shells provides unique design principles with potentials for guiding the design of protective materials and systems in the future. Understanding the structure-property relationships for these material systems at the microscale and nanoscale where failure initiates is essential. Currently, experimental techniques such as nanoindentation, X-ray CT, and SEM provide researchers with a way to correlate the mechanical behavior with hierarchical microstructures of these material systems1-6. However, a well-defined standard procedure for specimen preparation of mineralized biomaterials is not currently available. In this study, the methods for probing spatially correlated chemical, structural, and mechanical properties of the multilayered scale of A. spatula using nanoindentation, FTIR, SEM, with energy-dispersive X-ray (EDX) microanalysis, and X-ray CT are presented.

Stability of solid-phase selenium species in fly ash after prolonged submersion in a natural river system.

Selenium (Se) chemistry can be very complex in the natural environment, exhibiting different valence states (-2, 0, +4, +6) representing multiple inorganic, methylated, or complexed forms. Since redox associated shifts among most of known Se species can occur at environmentally relevant conditions, it is important to identify these species in order to assess their potential toxicity to organisms. In June of 2009, researchers from the US Army Engineer Research & Development Center (ERDC) conducted investigations of the fly ash spilled 6 months previously into the Emory River at the TVA Kingston Fossil Plant, TN. Ash samples were collected on site from both the original ash pile (that did not move during the levee failure), from the spill zone (including the Emory River), and from the ash recovery ditch (ARD) containing ash removed during dredging cleanup operations. The purpose of this work was to determine the state of Se in the spilled fly ash and to assess its potential for transformation and resultant chemical stability from its prolonged submersion in the river and subsequent dredging. Sequential chemical extractions suggested that the river environment shifted Se distribution toward organic/sulfide species. Speciation studies by bulk XANES analysis on fly ash samples showed that a substantial portion of the Se in the original ash pile had transformed from inorganic selenite to a mixture of Se sulfide and reduced (organo)selenium (Se(-II)) species over the 6-month period. µ-XRF mapping data showed that significant trends in the co-location of Se domains with sulfur and ash heavy metals. Ten-d extended elutriate tests (EETs) that were bubbled continuously with atmospheric air to simulate worst-case oxidizing conditions during dredging showed no discernible change in the speciation of fly ash selenium. The enhanced stability of the organo- and sulfide-selenium species coincided with the mixture of the ash material with humic materials in the river, corresponding with notable shifts in the ash carbon- and nitrogen-functionality.

Arsenite modifies structure of soil microbial communities and arsenite oxidization potential.

The influence of arsenite [As(III)] on natural microbial communities and the capacity of exposed communities to oxidize As(III) has not been well explored. In this study, we conducted soil column experiments with a natural microbial community exposed to different carbon conditions and a continuous flow of As(III). We measured the oxidation rates of As(III) to As(V), and the composition of the bacterial community was monitored by 454 pyrosequencing of 16S rRNA genes. The diversity of As(III)-oxidizing bacteria was examined with the aox gene, which encodes the enzyme involved in As(III) oxidation. Arsenite oxidation was high in the live soil regardless of the carbon source and below detection in sterilized soil. In columns amended with 200 µmol kg(-1) of As (III), As(V) concentrations reached 158 µmol kg(-1) in the column effluent, while As(III) decreased to unmeasurable levels. Although the number of bacterial taxa decreased by as much as twofold in treatments amended with As(III), some As(III)-oxidizing bacterial groups increased up to 20-fold. Collectively, the data show the large effect of As(III) on bacterial diversity, and the capacity of natural communities from a soil with low initial As contamination to oxidize large inputs of As(III).

Additive and competitive effects of bacteria and Mn oxides on arsenite oxidation kinetics.

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on oxidation state. Arsenite [As(III)] can be oxidized to arsenate [As(V)] by both minerals and microbes in soil however, the interaction between these abiotic and biotic processes is not well understood. In this study, the time dependency of As(III) oxidation by two heterotrophic soil bacteria (Agrobacterium tumefaciens and Pseudomonas fluorescens) and a poorly crystalline manganese (Mn) oxide mineral (δ-MnO(2)) was determined using batch experiments. The apparent rate of As(V) appearance in solution was greater for the combined batch experiments in which bacteria and δ-MnO(2) were oxidizing As(III) at the same time than for either component alone. The additive effect of the mixed cell- δ-MnO(2) system was consistent for short (<1 h) and long (24 h) term coincubation indicating that mineral surface inhibition by cells has little effect the As(III) oxidation rate. Surface interactions between cells and the mineral surface were indicated by sorption and pH-induced desorption results. Total sorption of As on the mineral was lower with bacteria present (16.1 ± 0.8% As sorbed) and higher with δ-MnO(2) alone (23.4 ± 1%) and As was more easily desorbed from the cell-δ-MnO(2) system than from δ-MnO(2) alone. Therefore, the presence of bacteria inhibited As sorption and decreased the stability of sorbed As on δ-MnO(2) even though As(III) was oxidized fastest in a mixed cell-δ-MnO(2) system. The additive effect of biotic (As-oxidizing bacteria) and abiotic (δ-MnO(2) mineral) oxidation processes in a system containing both oxidants suggests that mineral-only results may underestimate the oxidative capacity of natural systems with biotic and abiotic As(III) oxidation pathways.

Electron energy-loss safe-dose limits for manganese valence measurements in environmentally relevant manganese oxides.

Manganese (Mn) oxides are among the strongest mineral oxidants in the environment and impose significant influence on mobility and bioavailability of redox-active substances, such as arsenic, chromium, and pharmaceutical products, through oxidation processes. Oxidizing potentials of Mn oxides are determined by Mn valence states (2+, 3+, 4+). In this study, the effects of beam damage during electron energy-loss spectroscopy (EELS) in the transmission electron microscope have been investigated to determine the "safe dose" of electrons. Time series analyses determined the safe dose fluence (electrons/nm(2)) for todorokite (10(6) e/nm(2)), acid birnessite (10(5)), triclinic birnessite (10(4)), randomly stacked birnessite (10(3)), and δ-MnO(2) (<10(3)) at 200 kV. The results show that meaningful estimates of the mean Mn valence can be acquired by EELS if proper care is taken.

Arsenite oxidation by a poorly-crystalline manganese oxide. 3. Arsenic and manganese desorption.

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese oxides (Mn oxides) have the ability to decrease overall As mobility both by oxidizing toxic arsenite (As(III)) to less toxic arsenate (As(V)), and by sorbing As. However, the effect of competing ions on the mobility of As sorbed on Mn-oxide surfaces is not well understood. In this study, desorption of As(V) and As(III) from a poorly crystalline phyllomanganate (δ-MnO(2)) by two environmentally significant ions is investigated using a stirred-flow technique and X-ray absorption spectroscopy (XAS). As(III) is not observed in solution after desorption under any conditions used in this study, agreeing with previous studies showing As sorbed on Mn-oxides exists only as As(V). However, some As(V) is desorbed from the δ-MnO(2) surface under all conditions studied, while neither desorptive used in this study completely removes As(V) from the δ-MnO(2) surface.

Arsenite oxidation by a poorly crystalline manganese-oxide 1. Stirred-flow experiments.

Manganese-oxides (Mn-oxides) are quite reactive, with respect to arsenite (As(III)) oxidation. However, studies regarding the pathways of As(III) oxidation, over a range of time scales, by poorly crystalline Mn-oxides, are lacking. In stirred-flow experiments, As(III) oxidation by δ-MnO2 (a poorly crystalline form of hexagonal birnessite) is initially rapid but slows appreciably after several hours of reaction. Mn(II) is the only reduced product of δ-MnO2 formed by As(III) oxidation during the initial, most rapid phase of the reaction. There seems to be evidence that the formation of Mn(III) observed in previous studies is a result of conproportionation of Mn(II) sorbed onto Mn(IV) reaction sites rather than from direct reduction of Mn(IV) by As(III).The only evidence of arsenic (As) sorption during As(III) oxidation by δ-MnO2 is during the first 10 h of reaction, and As sorption is greater when As(V) and Mn(II) occur simultaneously in solution. Our findings indicate that As(III) oxidation by poorly crystalline δ-MnO2 involves several simultaneous reactions and reinforces the importance of studying reaction mechanisms over time.

Arsenite oxidation by a poorly crystalline manganese-oxide. 2. Results from X-ray absorption spectroscopy and X-ray diffraction.

Arsenite (As(III)) oxidation by manganese oxides (Mn-oxides) serves to detoxify and, under many conditions, immobilize arsenic (As) by forming arsenate (As(V)). As(III) oxidation by Mn(IV)-oxides can be quite complex, involving many simultaneous forward reactions and subsequent back reactions. During As(III) oxidation by Mn-oxides, a reduction in oxidation rate is often observed, which is attributed to Mn-oxide surface passivation. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) data show that Mn(II) sorption on a poorly crystalline hexagonal birnessite (δ-MnO2) is important in passivation early during reaction with As(III). Also, it appears that Mn(III) in the δ-MnO2 structure is formed by conproportionation of sorbed Mn(II) and Mn(IV) in the mineral structure. The content of Mn(III) within the δ-MnO2 structure appears to increase as the reaction proceeds. Binding of As(V) to δ-MnO2 also changes as Mn(III) becomes more prominent in the δ-MnO 2 structure. The data presented indicate that As(III) oxidation and As(V) sorption by poorly crystalline δ-MnO2 is greatly affected by Mn oxidation state in the δ-MnO2 structure.

Evaluating environmental influences on AsIII oxidation kinetics by a poorly crystalline Mn-oxide.

The oxidation of arsenite (As(III)) via Mn-oxides is an important process for natural arsenic (As) cycling and for developing in situ strategies for remediation of As-contaminated waters. In this study, the influence of goethite (alpha-FeOOH), phosphate, and bacteria/biopolymer coatings on the initial As(III) oxidation kinetics by a hydrous Mn-oxide (delta-MnO(2)) is examined via both batch experiments and rapid scan ATR-spectroscopy. Under natural conditions the presence of various mineral surfaces, bacteria, organic matter, and ions in solution can block Mn-oxide reaction sites, alter reaction rates, and thus inhibit As(III) oxidation. Previous studies of As-Mn systems demonstrate rapid oxidation of As(III), catalyzed by Mn-oxides, producing less toxic and mobile arsenate (As(V)). Subsequent to oxidation, reaction products from reductive dissolution of delta-MnO(2) by As(III), bind to and passivate the mineral surface. This study demonstrates enhanced passivation through interaction with phosphate and bacteria. Increased As oxidation with high concentrations of goethite is observed, attributed to As(V) sorption to alpha-FeOOH and diminished surface passivation of delta-MnO(2). Specific competition between phosphate and As(V) for delta-MnO(2) was confirmed through diminished As sorption and decreased As(V) production when oxidation occurred in the presence of phosphate. Kinetic experiments reveal that the extent of initial As(III) oxidation in the presence of low phosphate and alpha-FeOOH concentration is reduced; however, initial reaction rates are generally not affected. Reaction rates are reduced when bacterial adhesion and high phosphate concentrations strongly passivate delta-MnO(2) and reduce As(III) interactions with the mineral surface. The data presented in this study highlight the importance of considering natural heterogeneity when investigating reaction mechanisms and initial reaction kinetics.