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Machine learning enables reconstruction of past fire regimes from charcoal-derived fire intensity and fuel composition

Background Fire is a foundational ecological process that shapes ecosystem structure, diversity, and resilience. Quantifying paleofire regime attributes such as frequency, severity, and intensity is essential for understanding the historical range of variability in fire behavior and its ecological effects. While frequency and severity are often reconstructed in paleofire studies, quantitative reconstructions of fire intensity remain limited. Recent work has shown that maximum pyrolysis temperature—a proxy for fire intensity—and plant species type can be inferred from charcoal using transmission Fourier-transform infrared (FTIR) spectroscopy. However, the sample preparation for transmission FTIR is destructive and time-consuming, limiting application and reuse of materials for other analyses. We evaluated reflectance FTIR spectroscopy as a non-destructive alternative for reconstructing combustion temperature and plant species from laboratory-generated charcoal. We also examined the influence of contrasting airflow environments (ambient air versus nitrogen-rich) on pyrolysis temperature and plant species reconstruction prediction accuracies and compared predictive performance between a novel, neural network–based deep learning model with the traditional modern analogue technique (MAT) using k-nearest neighbor functions. As proof of concept, we apply our enhanced methodology to ancient charcoal to demonstrate applicability at improving long-term fire regime reconstructions and the ability to link paleofire records with contemporary fire ecology. Results Our analysis shows that transmission and reflectance FTIR spectra yield comparable spectral profiles. However, sample preparation for reflectance FTIR is minimal and non-destructive, unlike transmission FTIR which is destructive. We demonstrate that oxygen environments improved reconstruction accuracy relative to nitrogen-rich conditions. Finally, our deep learning neural network (DL) achieved testing accuracies of 98.7% for temperature and 96.2% for species identification, outperforming MAT’s k-NN approach (89.8% and 65.9%, respectively). A Shapley importance analysis identified 5 key spectral regions that greatly influenced the model’s temperature or species categorization. When applied to ancient charcoal, our results show historic fires from the most recent past primarily burned at low intensities (400–500 °C), reflective of natural fire regimes in ponderosa pine forests. Our results corroborate charcoal morphology data that suggests all ancient charcoal originated from burned woody plant types. Conclusions By combining reflectance FTIR spectroscopy with a deep learning approach, we provide the first accuracies high enough to confidently identify both species and temperature from laboratory-produced charcoal, improving quantitative reconstructions of fire intensity and fuel composition from paleofire records. This opens a wide range of research into the link between fire and larger drivers (i.e., climate or human) and greater ecological understanding of fire regimes beyond that of burn scars or recent observations. These methodological improvements have direct relevance for fire management by improving interpretation of historical fire behavior, informing fuel–fire relationships, and providing a scalable analytical framework applicable to both long-term ecological studies and contemporary fire science.

54 ENVIRONMENTAL SCIENCES↗

A Novel Sparse Compositional Technique Reveals Microbial Perturbations

ABSTRACT The central aims of many host or environmental microbiome studies are to elucidate factors associated with microbial community compositions and to relate microbial features to outcomes. However, these aims are often complicated by difficulties stemming from high-dimensionality, non-normality, sparsity, and the compositional nature of microbiome data sets. A key tool in microbiome analysis is beta diversity, defined by the distances between microbial samples. Many different distance metrics have been proposed, all with varying discriminatory power on data with differing characteristics. Here, we propose a compositional beta diversity metric rooted in a centered log-ratio transformation and matrix completion called robust Aitchison PCA. We demonstrate the benefits of compositional transformations upstream of beta diversity calculations through simulations. Additionally, we demonstrate improved effect size, classification accuracy, and robustness to sequencing depth over the current methods on several decreased sample subsets of real microbiome data sets. Finally, we highlight the ability of this new beta diversity metric to retain the feature loadings linked to sample ordinations revealing salient intercommunity niche feature importance. IMPORTANCE By accounting for the sparse compositional nature of microbiome data sets, robust Aitchison PCA can yield high discriminatory power and salient feature ranking between microbial niches. The software to perform this analysis is available under an open-source license and can be obtained at https://github.com/biocore/DEICODE ; additionally, a QIIME 2 plugin is provided to perform this analysis at https://library.qiime2.org/plugins/q2-deicode .

59 BASIC BIOLOGICAL SCIENCES↗

GCAM-Demeter-LU

This GCAM-Demeter-LU is made available under the Open Data Commons Attribution License:http://opendatacommons.org/licenses/by/1.0/. The dataset includes the projected global gridded land cover (excluding the Antarctic) for the period of 2015-2100 at 0.05-degree resolution and 5-year time step under fifteen SSP-RCP scenarios driven by five GCMs (i.e., gfdl, hadgem, ipsl, miroc, and noresm), using the Global Change Analysis Model (GCAM) and a geospatial downscaling model (Demeter). The data has been stored in self-describing NetCDF format. The dataset also includes the mean and standard deviation of the results driven by the five GCMs. More specifically, the data in each year includes grid-explicit fraction (in percent) of each of the 32 plant functional types that are widely used in current Earth system models. The NetCDF files are named as “GCAM_Demeter_LU_SSP_RCP_Model_Year.nc”, where “SSP” and “RCP” denote the SSP and RCP scenarios, including 'ssp1_rcp26', 'ssp1_rcp45', 'ssp1_rcp60', 'ssp2_rcp26', 'ssp2_rcp45', 'ssp2_rcp60', 'ssp3_rcp45', 'ssp3_rcp60', 'ssp4_rcp26', 'ssp4_rcp45', 'ssp4_rcp60', 'ssp5_rcp26', 'ssp5_rcp45', 'ssp5_rcp60', and 'ssp5_rcp85'. “Year” denotes the year of the land use data, and “GCM” denotes the source driving forcing data from five global climate models (gfdl, hadgem, ipsl, miroc, and noresm), or the mean (“modelmean”) and the standard deviation (“modelstd”) of the results from the five GCMs.See https://github.com/JGCRI/chen_et_al_2020a for details on how to reproduce this data. Rights and permissions Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. The Creative Commons Public Domain Dedication waiver http://creativecommons.org/publicdomain/zero/1.0/ applies to the metadata files associated with this article

99 GENERAL AND MISCELLANEOUS↗

Sample IEEE123 Bus system for OEDI SI

Time series load and PV data from an IEEE123 bus system. An example electrical system, named the OEDI SI feeder, is used to test the workflow in a co-simulation. The system used is the IEEE123 test system, which is a well studied test system (see link below to IEEE PES Test Feeder), but some modifications were made to it to add some solar power modules and measurements on the system. The aim of this project is to create an easy-to-use platform where various types of analytics can be performed on a wide range of electrical grid datasets. The aim is to establish an open-source library of algorithms that universities, national labs and other developers can contribute to which can be used on both open-source and proprietary grid data to improve the analysis of electrical distribution systems for the grid modeling community. OEDI Systems Integration (SI) is a grid algorithms and data analytics API created to standardize how data is sent between different modules that are run as part of a co-simulation. The readme file included in the S3 bucket provides information about the directory structure and how to use the algorithms. The sensors.json file is used to define the measurement locations.

123 bus↗

Phisherman v 1.0

Phisherman is an online software tool that was created to help experimenters study phishing. It can potentially be re-purposed to run other human studies. Phisherman enables studies to be run online, so that users can participate from their own computers. This means that experimenters can get data from subjects in their natural settings. Alternatively, an experimenter can also run the app online in a lab-based setting, if that is desired. The software enables the online deployment of a study that is comprised of three main parts: (1) a consent page, (2) a survey, and (3) an identification task, with instruction/transition screens between each part, allowing the experimenter to provide the user with instructions and messages. Upon logging in, the subject is taken to the permission page, where they agree to or do not agree to take part in the study. If the subject agrees to participate, then the software randomly chooses between doing the survey first (and identification task second) or the identification task first (and survey second). This is to balance possible order effects in the data. Procedurally, in the identification task, the software shows the stimuli to the subject, and asks if she thinks it is a phish (yes/no) and how confident she is about her answer. The subject is given 5 levels of certainty to select from, labeled "low" (1), to "medium" (3), to "high" (5), with the option of picking a level between low and medium (2), and between medium and high (4). After selecting his/her confidence level, then the "Next" button activates, allowing a user to move to the next email. The software saves a given subject's progress in the identification task, so that she may log in and out of the site. The consent page is a space for the experimenter to provide the subject with human studies board /internal review board information, and to formally consent to participate in the study. The survey is a space for the experimenter to provide questions and spaces for the users to input answers (allowing both multiple-choice and free-answer options). Phisherman includes administrative pages for managing the stimuli and users. This includes a tool for the experimenter to create, preview, edit, delete (if desired), and manage stimuli (emails). The stimuli may include pictures (uploaded to an appropriate folder) and links, for realism. The software includes a safety feature that prevents the user from going to any link location or opening a file/image. Instead of re-directing the subject's browser, the software provides a pop-up box with the URL location of where the user would have gone. Another administrative page may be used to create fake subject accounts for testing the software prior to deployment, as well as to delete subject accounts when necessary. Data from the experiment can be downloaded from another administrative page.

Kimura, Margot↗

DTLMod: A simulation framework for in situ workflow optimization

In situ processing workflows have become essential for coping with the explosion in data volume and velocity in large-scale scientific computing, providing domain scientists with early insights at runtime. Multiple frameworks implement this paradigm through a data transport layer (DTL), offering different data access modes and deployment schemes, but researchers currently lack the appropriate tools to assess design and deployment options before committing to costly real experiments. We introduce DTLMod, an open-source simulated DTL that enables performance evaluation of in situ workflow configurations at scale. Built on SimGrid, it links into any SimGrid-based simulator and is available in C++ and Python. We evaluate DTLMod along four axes: scalability (tens of thousands of simulated processes across interconnected clusters in seconds, with linear memory scaling), versatility (three implementation variants trading fidelity for speed), accuracy (simulated times faithfully reflecting real behavior), and practical utility (two use cases demonstrating evidence-based workflow design decisions).

Suter, Fred [ORNL] (ORCID:0000000319021955)↗

A browser-based tool for visualization and analysis of diffusion MRI data

Human neuroscience research faces several challenges with regards to reproducibility. While scientists are generally aware that data sharing is important, it is not always clear how to share data in a manner that allows other labs to understand and reproduce published findings. Here we report a new open source tool, AFQ-Browser, that builds an interactive website as a companion to a diffusion MRI study. Because AFQ-Browser is portable—it runs in any web-browser—it can facilitate transparency and data sharing. Moreover, by leveraging new web-visualization technologies to create linked views between different dimensions of the dataset (anatomy, diffusion metrics, subject metadata), AFQ-Browser facilitates exploratory data analysis, fueling new discoveries based on previously published datasets. In an era where Big Data is playing an increasingly prominent role in scientific discovery, so will browser-based tools for exploring high-dimensional datasets, communicating scientific discoveries, aggregating data across labs, and publishing data alongside manuscripts.

60 APPLIED LIFE SCIENCES↗

An Advanced Network and distributed Storage Laboratory (ANDSL) for Data Intensive Science (Final Report)

The original intent of this project was to build and operate an Advanced Network and Distributed Storage Laboratory (ANDSL) for Data Intensive Science that will prepare the Open Science Grid (OSG) community for a new generation of wide area communication capabilities operating at a 100Gb rate. The plan was to engage a team of four dedicated scientists that will design, develop and operate a state of the art laboratory that will be fully integrated into the organizational and operational infrastructure of the OSG. The ANDSL was planned to include host-based hardware and software required to profile, emulate and study real-life distributed storage workloads at rates of 100 Gbps. The laboratory was designed to utilize the Department Of Energy’s Advanced Network Initiative (ANI) 100GbTestbed as connections to the fabric become available so that OSG stakeholders can use it to profile real-life data intensive science applications as well as experiment with advanced storage and data management technologies. The goal of the original program of work was to close the adoption gap, decreasing the time between availability of production 100Gbps links and the end-to-end use of such a network to enable scientific discovery.

100Gb networks↗

County-Level Hourly Renewable Capacity Factor Dataset for the ReEDS Model

This dataset contains hourly capacity factors for each renewable resource class and region (in this case, county). Technologies like large-scale utility PV (UPV), onshore wind, offshore wind, and concentrating solar power (CSP) are included. The dataset contains 7 years of hourly weather data (2007-2013) for different sites across the US and is used as one of the inputs to the ReEDS-2.0 model (see the "ReEDS 2.0 GitHub Repository" resource link below), developed by NREL. The weather profiles apply to any capacity that exists or is built in each region and class. This helps calculate the generation that can be provided using these resources. Open, reference, and limited are 3 scenarios based on land-use allowance, derived from the Renewable Energy Potential (reV) model developed by NREL, which helps generate supply curves for renewable technologies and assess the maximum potential of renewable resources in a designated area. Each zipped file in this dataset corresponds to a technology and contains the respective land-use scenario files required to run that technology in ReEDS. To use this dataset, download and place the extracted files in the locally cloned ReEDS repository inside one of the folders (inputs/variability/multi_year). After completing this copy, upon running the ReEDS model at the county-level spatial resolution for respective analysis purposes, the program will detect the presence of these files and will not fail.

Array↗

G0.253 + 0.016: A MOLECULAR CLOUD PROGENITOR OF AN ARCHES-LIKE CLUSTER

Young massive clusters (YMCs) with stellar masses of 10{sup 4}-10{sup 5} M{sub Sun} and core stellar densities of 10{sup 4}-10{sup 5} stars per cubic pc are thought to be the 'missing link' between open clusters and extreme extragalactic super star clusters and globular clusters. As such, studying the initial conditions of YMCs offers an opportunity to test cluster formation models across the full cluster mass range. G0.253 + 0.016 is an excellent candidate YMC progenitor. We make use of existing multi-wavelength data including recently available far-IR continuum (Herschel/Herschel Infrared Galactic Plane Survey) and mm spectral line (H{sub 2}O Southern Galactic Plane Survey and Millimetre Astronomy Legacy Team 90 GHz Survey) data and present new, deep, multiple-filter, near-IR (Very Large Telescope/NACO) observations to study G0.253 + 0.016. These data show that G0.253 + 0.016 is a high-mass (1.3 Multiplication-Sign 10{sup 5} M{sub Sun }), low-temperature (T{sub dust} {approx} 20 K), high-volume, and column density (n {approx} 8 Multiplication-Sign 10{sup 4} cm{sup -3}; N{sub H{sub 2}}{approx}4 Multiplication-Sign 10{sup 23} cm{sup -2}) molecular clump which is close to virial equilibrium (M{sub dust} {approx} M{sub virial}) so is likely to be gravitationally bound. It is almost devoid of star formation and, thus, has exactly the properties expected for the initial conditions of a clump that may form an Arches-like massive cluster. We compare the properties of G0.253 + 0.016 to typical Galactic cluster-forming molecular clumps and find it is extreme, and possibly unique in the Galaxy. This uniqueness makes detailed studies of G0.253 + 0.016 extremely important for testing massive cluster formation models.

79 ASTRONOMY AND ASTROPHYSICS↗

The Second Boundaries of Stability Zones and the Angular Diagrams of Conductivity for Metals Having Complicated Fermi Surfaces

We consider some general aspects of dependence of magneto-conductivity on a magnetic field in metals having complicated Fermi surfaces. As it is well known, a nontrivial behavior of conductivity in metals in strong magnetic fields is connected usually with appearance of non-closed quasiclassical electron trajectories on the Fermi surface in a magnetic field. The structure of the electron trajectories depends strongly on the direction of the magnetic field and usually the greatest interest is caused by open trajectories that are stable to small rotations of the direction of B. The geometry of the corresponding Stability Zones on the angular diagram in the space of directions of B represents a very important characteristic of the electron spectrum in a metal linking the parameters of the spectrum to the experimental data. Here we will consider some very general features inherent in the angular diagrams of metals with Fermi surfaces of the most arbitrary form. In particular, we will show here that any Stability Zone actually has a second boundary, restricting a larger region with a certain behavior of conductivity. Besides that, we shall discuss here general questions of complexity of the angular diagrams for the conductivity and propose a theoretical scheme for dividing the angular diagrams into “simple” and “complex” diagrams. The proposed scheme will in fact also be closely related to behavior of the Hall conductivity in a metal in strong magnetic fields. In conclusion, we will also discuss the relationship of the questions under consideration to the general features of an (abstract) angular diagram describing the behavior of quasiclassical electron trajectories at all energy levels in the conduction band.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multi-scale modeling of the evolution of structure and properties in materials for nuclear energy applications

Nuclear energy is an important component of an overall strategy to address climate change. Idaho National Laboratory (INL) is the U.S. Department of Energy’s primary facility for research and development in nuclear science and technology for energy generation, supporting the improvement and life extension of the existing reactor fleet and the development and licensing of new reactor designs. Computational modeling is an important component of these activities, particularly in the area of materials for nuclear applications, where experimental data can be very challenging and expensive to acquire, and where data is especially scarce for new reactor designs. INL has used multi-scale modeling – linking atomistic, mesoscale, and engineering scales – to improve the ability to predict the performance of materials for nuclear energy applications. These modeling efforts make extensive of MOOSE (Multiphysics Object-Oriented Simulation Environment), a general-purpose open source finite element framework developed at INL. In this talk, I will give an overview of the approach and tools used, and several examples of application, including performance of nuclear fuels, understanding radiation-driven formation of nanoscale void and gas bubble superlattices, and powder densification through electric field assisted sintering.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multi-scale modeling of the evolution of structure and properties in materials for nuclear energy applications

Nuclear energy is an important component of an overall strategy to address climate change. Idaho National Laboratory (INL) is the U.S. Department of Energy’s primary facility for research and development in nuclear science and technology for energy generation, supporting the improvement and life extension of the existing reactor fleet and the development and licensing of new reactor designs. Computational modeling is an important component of these activities, particularly in the area of materials for nuclear applications, where experimental data can be very challenging and expensive to acquire, and where data is especially scarce for new reactor designs. INL has used multi-scale modeling – linking atomistic, mesoscale, and engineering scales – to improve the ability to predict the performance of materials for nuclear energy applications. These modeling efforts make extensive of MOOSE (Multiphysics Object-Oriented Simulation Environment), a general-purpose open source finite element framework developed at INL. In this talk, I will give an overview of the approach and tools used, and several examples of application, including performance of nuclear fuels, understanding radiation-driven formation of nanoscale void and gas bubble superlattices, and powder densification through electric field assisted sintering.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydration states of AFm cement phases

The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

36 MATERIALS SCIENCE↗

KBKit: A Python Toolkit for Kirkwood–Buff Theory from Molecular Dynamics

Thermodynamic properties of liquid mixtures govern processes that range from drug delivery to energy storage, yet extracting these properties from molecular simulations remains challenging. Kirkwood–Buff (KB) theory offers a rigorous route by linking microscopic pair distribution functions to macroscopic free energies, but practical use of the theory has been hindered by two obstacles: (i) the long simulations needed to obtain well-converged Kirkwood-Buff integrals (KBIs) and (ii) the specialized corrections required to translate finite-size data to the thermodynamic limit. $\texttt{KBKit}$ is an open-source Python package that removes these barriers. It automatically computes KBIs and derived thermodynamic quantities from GROMACS input files, applies state-of-the-art finite-size corrections, and provides built-in diagnostic tools to quantify statistical uncertainty. Written with modern software-engineering practices—continuous integration, extensive unit testing, and thorough documentation—$\texttt{KBKit}$ is both reliable and easy to extend. By condensing complex KBI analysis into a few intuitive commands, $\texttt{KBKit}$ enables researchers to incorporate KB theory into routine simulation workflows and accelerate the discovery of solution-phase thermodynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Planting a Lyman alpha forest on ABACUSSUMMIT

The full-shape correlations of the Lyman alpha (Ly$α$) forest contain a wealth of cosmological information through the Alcock Paczynski effect. However, these measurements are challenging to model without robustly testing and verifying the theoretical framework used for analyzing them. Here, we leverage the accuracy and volume of the $N$-body simulation suite ABACUSSUMMIT to generate high-resolution Ly$α$ skewers and quasi-stellar object (QSO) catalogs. One of the main goals of our mocks is to aid in the full-shape Ly$α$ analysis planned by the Dark Energy Spectroscopic Instrument (DESI) team. We provide optical depth skewers for six of the fiducial cosmology base-resolution simulations ($L$ box = 2 $h$ -1 Gpc, $N$ = 6912 3 ) at $z$ = 2.5. We adopt a simple recipe based on the Fluctuating Gunn-Peterson Approximation (FGPA) for constructing these skewers from the matter density in an $N$-body simulation and calibrate it against the 1D and 3D Ly$α$ power spectra extracted from the hydrodynamical simulation IllustrisTNG (TNG; $L$ box = 205 $h$ -1 Mpc, $N$ = 2500 3 ). As an important application, we study the non-linear broadening of the baryon acoustic oscillation (BAO) peak and show the cross-correlation between DESI-like QSOs and our Ly$α$ forest skewers. We find differences on small scales between the Kaiser approximation prediction and our mock measurements of the Ly$α$×QSO cross-correlation, which would be important to account for in upcoming analyses. The ABACUSSUMMIT Ly$α$ forest mocks open up the possibility for improved modelling of cross correlations between Ly$α$ and cosmic microwave background (CMB) lensing and Ly$α$ and QSOs, and for forecasts of the 3-point Ly$α$ correlation function. Furthermore, our catalogues and skewers are publicly available on Globus via the National Energy Research Scientific Computing Center (NERSC) (full link under Data Availability).

79 ASTRONOMY AND ASTROPHYSICS↗

Geochemical Modeling of F Area Seepage Basin Composition and Variability

From the 1950s through 1989, the F Area Seepage Basins at the Savannah River Site (SRS) received low level radioactive wastes resulting from processing nuclear materials. Discharges of process wastes to the F Area Seepage Basins followed by subsequent mixing processes within the basins and eventual infiltration into the subsurface resulted in contamination of the underlying vadose zone and downgradient groundwater. For simulating contaminant behavior and subsurface transport, a quantitative understanding of the interrelated discharge-mixing-infiltration system along with the resulting chemistry of fluids entering the subsurface is needed. An example of this need emerged as the F Area Seepage Basins was selected as a key case study demonstration site for the Advanced Simulation Capability for Environmental Management (ASCEM) Program. This modeling evaluation explored the importance of the wide variability in bulk wastewater chemistry as it propagated through the basins. The results are intended to generally improve and refine the conceptualization of infiltration of chemical wastes from seepage basins receiving variable waste streams and to specifically support the ASCEM case study model for the F Area Seepage Basins. Specific goals of this work included: (1) develop a technically-based 'charge-balanced' nominal source term chemistry for water infiltrating into the subsurface during basin operations, (2) estimate the nature of short term and long term variability in infiltrating water to support scenario development for uncertainty quantification (i.e., UQ analysis), (3) identify key geochemical factors that control overall basin water chemistry and the projected variability/stability, and (4) link wastewater chemistry to the subsurface based on monitoring well data. Results from this study provide data and understanding that can be used in further modeling efforts of the F Area groundwater plume. As identified in this study, key geochemical factors affecting basin chemistry and variability included: (1) the nature or chemistry of the waste streams, (2) the open system of the basins, and (3) duration of discharge of the waste stream types. Mixing models of the archetype waste streams indicated that the overall basin system would likely remain acidic much of the time. Only an extended periods of predominantly alkaline waste discharge (e.g., >70% alkaline waste) would dramatically alter the average pH of wastewater entering the basins. Short term and long term variability were evaluated by performing multiple stepwise modeling runs to calculate the oscillation of bulk chemistry in the basins in response to short term variations in waste stream chemistry. Short term (1/2 month and 1 month) oscillations in the waste stream types only affected the chemistry in Basin 1; little variation was observed in Basin 2 and 3. As the largest basin, Basin 3 is considered the primary source to the groundwater. Modeling showed that the fluctuation in chemistry of the waste streams is not directly representative of the source term to the groundwater (i.e. Basin 3). The sequence of receiving basins and the large volume of water in Basin 3 'smooth' or nullify the short term variability in waste stream composition. As part of this study, a technically-based 'charge-balanced' nominal source term chemistry was developed for Basin 3 for a narrow range of pH (2.7 to 3.4). An example is also provided of how these data could be used to quantify uncertainty over the long term variations in waste stream chemistry and hence, Basin 3 chemistry.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Node-Accessible Zirconium MOFs

High-stability, zirconium-based metal–organic frameworks are attractive as heterogeneous catalysts and as model supports for uniform arrays of subsequently constructed heterogeneous catalysts—for example, MOF-node-grafted metal–oxy and metal–sulfur clusters. For hexa-Zr(IV)-MOFs characterized by nodes that are less than 12-connected, sites not used for linkers are ideally occupied by reactive and displaceable OH/H 2 O pairs. Here, the desired pairs are ideal for grafting the aforementioned catalytic clusters, while aqua-ligand lability renders them effective for exposing highly Lewis-acidic Zr(IV) sites (catalytic sites) to candidate reactants. New single-crystal X-ray studies of an eight-connected Zr-MOF, NU-1000, reveal that conventional activation fully removes modulator ligands, but replaces them with three node-blocking formate ligands (from solvent decomposition) and only one OH/H 2 O pair, not four—a largely overlooked complication that now appears to be general for Zr-MOFs. Here we describe an alternative activation protocol that effectively removes modulators, avoids formate, and installs the full complement of terminal OH/H 2 O pairs. It does so via an unusual isolatable intermediate featuring eight aqua ligands and four non-ligated chlorides—again as supported by single-crystal X-ray data. We find that complete replacement of node-blocking modulators/formate with the originally envisioned OH/OH 2 pairs has striking consequences; here we touch upon just three. First, elimination of unrecognized formate renders aqua ligands much more thermally labile, enabling open Zr(IV) sites to be obtained at lower temperature. Second, in the absence of formate, which otherwise links and locks pairs of node Zr(IV) ions, reversible removal of aqua ligands engenders reversible contraction of MOF meso- and micropores, as evidenced by X-ray diffraction. Third, formate replacement with OH/OH 2 pairs renders NU-1000 ca.10× more active for catalytic hydrolytic degradation of a representative simulant of G-type chemical warfare agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗