Guo, Luanjing | Search NASA

DOE OSTI2019

The AQUA-MER databases and aqueous speciation server: A web resource for multiscale modeling of mercury speciation

To assess the chemical reactivity, toxicity, and mobility of pollutants in the environment, knowledge of their species distributions is critical. Because their direct measurement is often infeasible, speciation modeling is widely adopted. Mercury (Hg) is a representative pollutant for which study of its speciation benefits from modeling. However, Hg speciation modeling is often hindered by a lack of reliable thermodynamic constants. Although computational chemistry (e.g., density functional theory [DFT]) can generate these constants, methods for directly coupling DFT and speciation modeling are not available. Here, we combine computational chemistry and continuum-scale modeling with curated online databases to ameliorate the problem of unreliable inputs to Hg speciation modeling. Our AQUA-MER databases and web server (https://aquamer.ornl.gov) provides direct speciation results by combining web-based interfaces to a speciation calculator, databases of thermodynamic constants, and a computational chemistry toolkit to estimate missing constants. Lastly, although Hg is presented as a concrete use case, AQUA-MER can also be readily applied to other elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

A probabilistic perspective on thermodynamic parameter uncertainties: Understanding aqueous speciation of mercury

Speciation plays an important role in determining the fate and transport of metals in terrestrial surface and subsurface systems. Equilibrium speciation modeling in aqueous systems relies on thermodynamic constants (log K values) of complexes, which are subject to uncertainties. In this study, using Monte Carlo (MC) simulations with Latin hypercube sampling (LHS) we systematically analyze the propagation of thermodynamic constant uncertainty through speciation modeling of an inorganic mercury-sulfide-chloride-water system. We find that seemingly small variances of the input log K normal distributions can lead to output species concentrations spanning multiple orders of magnitude, with highly skewed probability distributions. When equilibrium with mineral metacinnabar (β-HgS(s)) is neglected, the relative uncertainty of each output species is strongly positively correlated with the skewness of its concentration probability distribution, i.e., the lowest uncertainty occurs when the species concentration probability distribution is the most negatively skewed as its concentration approaches the total element concentration limit. The highest uncertainty in the identity of dominant species is located around species equivalence points. For cases where the mineral equilibrium is included, we derive analytical probability density functions for the log concentrations of all major species in the system. The mineral log K uncertainty is found to be an important contributor to all output concentration uncertainties. The analysis of combined effects of both pH and total sulfide concentration on output concentration uncertainties shows that high concentration uncertainties occur under highly sulfidic alkaline conditions and low uncertainties at low pH and sulfide concentrations. Finally, an analysis as presented here can distinguish between conditions that require a full uncertainty analysis and those for which the classical deterministic speciation modeling suffices.

58 GEOSCIENCES↗