Modeling of ore-forming and geoenvironmental systems: Roles of fluid flow and chemical reaction processes

Ore-forming and geoenviromental systems commonly involve coupled fluid flowand chemical reaction processes. The advanced numerical methods and computational modeling have become indispensable tools for simulating such processes in recent years. This enables many hitherto unsolvable geoscience problems to be addressed using numerical methods and computational modeling approaches. For example, computational modeling has been successfully used to solve ore-forming and mine site contamination/remediation problems, in which fluid flow and geochemical processes play important roles in the controlling dynamic mechanisms. The main purpose of this paper is to present a generalized overview of: (1) the various classes and models associated with fluid flow/chemically reacting systems in order to highlight possible opportunities and developments for the future; (2) some more general issues that need attention in the development of computational models and codes for simulating ore-forming and geoenviromental systems; (3) the related progresses achieved on the geochemical modeling over the past 50 years or so; (4) the general methodology for modeling of oreforming and geoenvironmental systems; and (5) the future development directions associated with modeling of ore-forming and geoenviromental systems.

Benchmarking the simulation of Cr isotope fractionation

A benchmark problem set consisting of four problem levels was developed for the simulation of Cr isotope fractionation in 1D and 2D domains. The benchmark is based on a recent field study where Cr(VI) reduction and accompanying Cr isotope fractionation occurs abiotically by an aqueous reaction with dissolved Fe 2+ (Wanner et al., 2012., Appl. Geochem., 27, 644–662). The problem set includes simulation of the major processes affecting the Cr isotopic composition such as the dissolution of various Cr(VI) bearing minerals, fractionation during abiotic aqueous Cr(VI) reduction, and non-fractionating precipitation of Cr(III) as sparingly soluble Cr-hydroxide. Accuracy of the presented solutions was ensured by running the problems with four well-established reactive transport modeling codes: TOUGHREACT, MIN3P, CRUNCHFLOW, and FLOTRAN. Results were also compared with an analytical Rayleigh-type fractionation model. An additional constraint on the correctness of the results was obtained by comparing output from the problem levels simulating Cr isotope fractionation with the corresponding ones only simulating bulk concentrations. For all problem levels, model to model comparisons showed excellent agreement, suggesting that for the tested geochemical processes any code is capable of accurately simulating the fate of individual Cr isotopes.

Implementation and evaluation of permeability-porosity and tortuosity-porosity relationships linked to mineral dissolution-precipitation

Changes of porosity, permeability, and tortuosity due to physical and geochemical processes are of vital importance for a variety of hydrogeological systems, including passive treatment facilities for contaminated groundwater, engineered barrier systems (EBS), and host rocks for high-level nuclear waste (HLW) repositories. Due to the nonlinear nature and chemical complexity of the problem, in most cases, it is impossible to verify reactive transport codes analytically, and code intercomparisons are the most suitable method to assess code capabilities and model performance. This paper summarizes model intercomparisons for six hypothetical scenarios with generally increasing geochemical or physical complexity using the reactive transport codes CrunchFlow, HP1, MIN3P, PFlotran, and TOUGHREACT. Benchmark problems include the enhancement of porosity and permeability through mineral dissolution, as well as near complete clogging due to localized mineral precipitation, leading to reduction of permeability and tortuosity. Processes considered in the benchmark simulations are advective-dispersive transport in saturated media, kinetically controlled mineral dissolution-precipitation, and aqueous complexation. Porosity changes are induced by mineral dissolution-precipitation reactions, and the Carman-Kozeny relationship is used to describe changes in permeability as a function of porosity. Archie’s law is used to update the tortuosity and the pore diffusion coefficient as a function of porosity. Results demonstrate that, generally, good agreement is reached amongst the computer models despite significant differences in model formulations. Some differences are observed, in particular for the more complex scenarios involving clogging; however, these differences do not affect the interpretation of system behavior and evolution.

Geochemical and isotopic characterization of the Bodélé Depression dust source and implications for transatlantic dust transport to the Amazon Basin

The Bodélé Depression (Chad) in the central Sahara/Sahel region of Northern Africa is the most important source of mineral dust to the atmosphere globally. The Bodélé Depression is purportedly the largest source of Saharan dust reaching the Amazon Basin by transatlantic transport. Here, we have undertaken a comprehensive study of surface sediments from the Bodélé Depression and dust deposits (Chad, Niger) in order to characterize geochemically and isotopically (Sr, Nd and Pb isotopes) this dust source, and evaluate its importance in present and past African dust records. We similarly analyzed sedimentary deposits from the Amazonian lowlands in order to assess postulated accumulation of African mineral dust in the Amazon Basin, as well as its possible impact in fertilizing the Amazon rainforest. Our results identify distinct sources of different ages and provenance in the Bodélé Depression versus the Amazon Basin, effectively ruling out an origin for the Amazonian deposits, such as the Belterra Clay Layer, by long-term deposition of Bodélé Depression material. Similarly, no evidence for contributions from other potential source areas is provided by existing isotope data (Sr, Nd) on Saharan dusts. Instead, the composition of these Amazonian deposits is entirely consistent with derivation from in-situ weathering and erosion of the Precambrian Amazonian craton, with little, if any, Andean contribution. In the Amazon Basin, the mass accumulation rate of eolian dust is only around one-third of the vertical erosion rate in shield areas, suggesting that Saharan dust is “consumed” by tropical weathering, contributing nutrients and stimulating plant growth, but never accumulates as such in the Amazon Basin. The chemical and isotope compositions found in the Bodélé Depression are varied at the local scale, and have contrasting signatures in the “silica-rich” dry lake-bed sediments and in the “calcium-rich” mixed diatomites and surrounding sand material. This unexpected finding implies that the Bodélé Depression material is not “pre-mixed” at the source to provide a homogeneous source of dust. Rather, different isotope signatures can be emitted depending on subtle vagaries of dust-producing events. Our characterization of the Bodélé Depression components indicate that the Bodélé “calcium-rich” component, identified here, is most likely released via eolian processes of sand grain saltation and abrasion and may be significant in the overall global budget of dusts carried out by the Harmattan low-level jet during the winter.

Lithium isotope constraints on crust–mantle interactions and surface processes on Mars

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (−0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member. The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl–S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars (BSM) to be 4.2 ± 0.9‰ (2σ). This value is at the higher end of estimates for the Bulk Silicate Earth (BSE; 3.5 ± 1.0‰, 2σ), but overlaps within uncertainty.

Sedimentological processes and environmental variability at Lake Ohrid (Macedonia, Albania) between 637 ka and the present

Lake Ohrid (Macedonia, Albania) is thought to be more than 1.2 million years old and host more than 300 endemic species. As a target of the International Continental scientific Drilling Program (ICDP), a successful deep drilling campaign was carried out within the scope of the Scientific Collaboration on Past Speciation Conditions in Lake Ohrid (SCOPSCO) project in 2013. Here, we present lithological, sedimentological, and (bio-)geochemical data from the upper 247.8 m composite depth of the overall 569 m long DEEP site sediment succession from the central part of the lake. According to an age model, which is based on 11 tephra layers (first-order tie points) and on tuning of bio-geochemical proxy data to orbital parameters (second-order tie points), the analyzed sediment sequence covers the last 637 kyr. The DEEP site sediment succession consists of hemipelagic sediments, which are interspersed by several tephra layers and infrequent, thin (< 5 cm) mass wasting deposits. The hemipelagic sediments can be classified into three different lithotypes. Lithotype 1 and 2 deposits comprise calcareous and slightly calcareous silty clay and are predominantly attributed to interglacial periods with high primary productivity in the lake during summer and reduced mixing during winter. The data suggest that high ion and nutrient concentrations in the lake water promoted calcite precipitation and diatom growth in the epilimnion during MIS15, 13, and 5. Following a strong primary productivity, highest interglacial temperatures can be reported for marine isotope stages (MIS) 11 and 5, whereas MIS15, 13, 9, and 7 were comparably cooler. Lithotype 3 deposits consist of clastic, silty clayey material and predominantly represent glacial periods with low primary productivity during summer and longer and intensified mixing during winter. The data imply that the most severe glacial conditions at Lake Ohrid persisted during MIS16, 12, 10, and 6, whereas somewhat warmer temperatures can be inferred for MIS14, 8, 4, and 2. Interglacial-like conditions occurred during parts of MIS14 and 8.

Experimental determination of barium isotope fractionation during diffusion and adsorption processes at low temperatures

Variations in barium (Ba) stable isotope abundances measured in low and high temperature environments have recently received increasing attention. The actual processes controlling Ba isotope fractionation, however, remain mostly elusive. In this study, we present the first experimental approach to quantify the contribution of diffusion and adsorption on mass- dependent Ba isotope fractionation during transport of aqueous Ba2+ ions through a porous medium. Experiments have been carried out in which a BaCl2 solution of known isotopic composition diffused through u-shaped glass tubes filled with silica hydrogel at 10 C and 25 C for up to 201 days. The diffused Ba was highly fractionated by up to -2.15‰ in d137/134Ba, despite the low relative difference in atomic mass. The time-dependent isotope fractionation can be successfully reproduced by a diffusive transport model accounting for mass-dependent differences in the effective diffusivities of the Ba isotope species (D137Ba/D134Ba = (m134/m137)^b). Values of b extracted from the transport model were in the range of 0.010–0.011. Independently conducted batch experiments revealed that adsorption of Ba onto the surface of silica hydrogel favoured the heavier Ba isotopes (a = 1.00015 ± 0.00008). The contribution of adsorption on the overall isotope fractionation in the diffusion experiments, however, was found to be small. Our results contribute to the understanding of Ba isotope fractionation pro- cesses, which is crucial for interpreting natural isotope variations and the assessment of Ba isotope ratios as geochemical proxies.