Smith, Jeremy Christopher

DOE OSTI2020

Multi-Scale Modeling Framework for Mercury Biogeochemistry

Multi-Scale modeling of mercury (Hg) geochemical speciation and reactions has been performed by integrating atomistic quantum chemical calculations with continuum scale speciation models. Major progress has been made in the improvement of quantum chemical models to calculate critical thermodynamic data for Hg complexes in aquatic environments. Rapid and reliable quantum chemical approaches have been developed for calculating acid dissociation constants (pK a ) and stability constants (log K), with calculated mean unsigned errors of 0.5 and 1.5 log units, respectively for ligand molecules and Hg complexes. At the continuum scale, systematic analysis of uncertainty propagation in mercury (Hg) speciation modeling has been conducted and was used to identify environmental conditions under which thermodynamic constant uncertainties are significant and recommended to be accounted for. The integrated framework for multi-scale modeling of mercury geochemistry is open to the research community through the web-based multiscale modeling aqueous speciation resource, AQUA-MER. The improved quantum chemical approaches for thermodynamic constant calculations are accessible through AQUA-MER and can be used to provide the missing constants in the continuum scale speciation calculations. In addition to low molecular mass Hg complex speciation, modeling natural aquatic environments also involve the transport of high molecular weight dissolved organic matter (DOM) in reactive flows simultaneously with equilibrium and kinetic reactions. To this end, atomistic MD simulations were performed to capture the details of aggregation, mechanisms and distribution of functional groups in DOM at the molecular level. The elemental composition and calculated bulk properties of the DOM models are in close agreement with experimental measurements. A travel-time based reactive transport model in the hyporheic zone of stream corridors was established for the multicomponent Hg-DOM-S system and implemented through PFLOTRAN.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2016

Using Unmanned Air Systems to Monitor Methane in the Atmosphere

Methane is likely to be an important contributor to global warming, and our current knowledge of its sources, distributions, and transport is insufficient. It is estimated that there could be from 7.5 to 400 billion tons carbon-equivalent of methane in the arctic region, a broad range that is indicative of the uncertainty within the Earth Science community. Unmanned Air Systems (UASs) are often used for combat or surveillance by the military, but they also have been used for Earth Science field missions. In this study, we will analyze the utility of the NASA Global Hawk and the Aurora Flight Sciences Orion UASs compared to the manned DC-8 aircraft for conducting a methane monitoring mission. The mission will focus on the measurement of methane along the boundaries of Arctic permafrost thaw and melting glaciers. The use of Long Endurance UAS brings a new range of possibilities including the ability to obtain long- term and persistent observations and to significantly augment methane measurements/retrievals collected by satellite. Furthermore, we discuss the future of long endurance UAS and their potential for science applications in the next twenty to twenty-five years.

Clow, Jacqueline↗