Gregory M. Dipple

Biologically induced mineralization of dypingite by cyanobacteria from an alkaline wetland near Atlin, British Columbia, Canada

BackgroundThis study provides experimental evidence for biologically induced precipitation of magnesium carbonates, specifically dypingite (Mg5(CO3)4(OH)2·5H2O), by cyanobacteria from an alkaline wetland near Atlin, British Columbia. This wetland is part of a larger hydromagnesite (Mg5(CO3)4(OH)2·4H2O) playa. Abiotic and biotic processes for magnesium carbonate precipitation in this environment are compared.ResultsField observations show that evaporation of wetland water produces carbonate films of nesquehonite (MgCO3·3H2O) on the water surface and crusts on exposed surfaces. In contrast, benthic microbial mats possessing filamentous cyanobacteria (Lyngbya sp.) contain platy dypingite (Mg5(CO3)4(OH)2·5H2O) and aragonite. Bulk carbonates in the benthic mats (δ13C avg. = 6.7‰, δ18O avg. = 17.2‰) were isotopically distinguishable from abiotically formed nesquehonite (δ13C avg. = 9.3‰, δ18O avg. = 24.9‰). Field and laboratory experiments, which emulated natural conditions, were conducted to provide insight into the processes for magnesium carbonate precipitation in this environment. Field microcosm experiments included an abiotic control and two microbial systems, one containing ambient wetland water and one amended with nutrients to simulate eutrophic conditions. The abiotic control developed an extensive crust of nesquehonite on its bottom surface during which [Mg2+] decreased by 16.7% relative to the starting concentration. In the microbial systems, precipitation occurred within the mats and was not simply due to the capturing of mineral grains settling out of the water column. Magnesium concentrations decreased by 22.2% and 38.7% in the microbial systems, respectively. Laboratory experiments using natural waters from the Atlin site produced rosettes and flakey globular aggregates of dypingite precipitated in association with filamentous cyanobacteria dominated biofilms cultured from the site, whereas the abiotic control again precipitated nesquehonite.ConclusionMicrobial mats in the Atlin wetland create ideal conditions for biologically induced precipitation of dypingite and have presumably played a significant role in the development of this natural Mg-carbonate playa. This biogeochemical process represents an important link between the biosphere and the inorganic carbon pool.

Verifying and quantifying carbon fixation in minerals from serpentine-rich mine tailings using the Rietveld method with X-ray powder diffraction data

Abstract Most carbon on Earth is bound within minerals, and increasing the uptake of atmospheric carbon dioxide into minerals may reduce the greenhouse gas content of the atmosphere. We document carbon disposal through the mineralization of mine tailings at Clinton Creek, Yukon Territory, and Cassiar, British Columbia. We confirm crystallographic binding of carbon in these tailings and quantify carbon dioxide uptake using quantitative phase analysis with the Rietveld method for X-ray powder diffraction data. Planar disorder in the structures of the kaolinite-serpentine group minerals makes Rietveld refinements of X-ray powder diffraction data for serpentinites problematic. Using structureless pattern fitting and with the addition of a known quantity of a well-crystallized material, the problem of structural disorder is overcome by considering the serpentine minerals as amorphous phases. We test the accuracy and precision of this refinement method using synthetic serpentine-rich mine tailings of known composition. Estimates of the abundance of hydrated magnesium carbonates in these tailings have a precision of approximately 5% relative for mineral species present in amounts greater than 10 wt%. Precise estimates of carbonate mineral content and crystallographically bound atmospheric CO2 are made for samples of serpentine-rich tailings from Clinton Creek and Cassiar. Results for mine tailings are also compared to mineralogically similar samples from a carbonate playa at Atlin, British Columbia. The potential for decomposition of metastable hydrated magnesium carbonate phases to geologically stable magnesite may represent long-term stability of the products of mineral sequestration in mine tailings.

Accelerated Carbonation of Brucite in Mine Tailings for Carbon Sequestration

Atmospheric CO(2) is sequestered within ultramafic mine tailings via carbonation of Mg-bearing minerals. The rate of carbon sequestration at some mine sites appears to be limited by the rate of CO(2) supply. If carbonation of bulk tailings were accelerated, large mines may have the capacity to sequester millions of tonnes of CO(2) annually, offsetting mine emissions. The effect of supplying elevated partial pressures of CO(2) (pCO(2)) at 1 atm total pressure, on the carbonation rate of brucite [Mg(OH)(2)], a tailings mineral, was investigated experimentally with conditions emulating those at Mount Keith Nickel Mine (MKM), Western Australia. Brucite was carbonated to form nesquehonite [MgCO(3) · 3H(2)O] at a rate that increased linearly with pCO(2). Geochemical modeling indicated that HCO(3)(-) promoted dissolution accelerated brucite carbonation. Isotopic and aqueous chemistry data indicated that equilibrium between CO(2) in the gas and aqueous phases was not attained during carbonation, yet nesquehonite precipitation occurred at equilibrium. This implies CO(2) uptake into solution remains rate-limiting for brucite carbonation at elevated pCO(2), providing potential for further acceleration. Accelerated brucite carbonation at MKM offers the potential to offset annual mine emissions by ~22-57%. Recognition of mechanisms for brucite carbonation will guide ongoing work to accelerate Mg-silicate carbonation in tailings.

Heat production and heat flow in the mantle lithosphere, Slave craton, Canada

Thermobarometric data for mantle xenoliths from a kimberlite pipe in the NWT, Canada are used to constrain the thermal properties of the lithospheric mantle underlying the Slave craton. We derive an analytical expression for a steady-state conductive mantle geotherm that is independent of the geometry and thermal properties of the crust. The model has an upper boundary coincident with the MOHO at a depth Zm and has temperature Tm and heat flow qm. The mantle is assumed to have constant radiogenic heat production (A) and we allow for a temperature-dependent thermal conductivity [K.T / D Ko.1 C B.T T m//]. Inverting the thermobarometric data through the model geotherm gives limiting values for mantle heat production (A) and bounds on the temperature dependence of K (e.g. B) that are consistent with the mantle P‐T array. We characterize the Slave lithospheric mantle in terms of three critical parameters qm (mW m 2 ), A (m Wm 3 ), Tm (C). The optimal solution has values [15.1, 0.012, 455]. This characterization of thermal state of the Slave mantle is based mainly on petrological data and is not biased by assumptions about crustal thermal properties. Our analysis shows that a substantial range of parameter values can be used to describe the data accurately and the two bounding solutions are [24.2, 0.088, 296] and [12.3, 0, 534], respectively. However, model parameters are strongly correlated and this precludes the arbitrary selection of values of [qm, A, Tm] from these ranges.

Isotopic disequilibrium during uptake of atmospheric CO2 into mine process waters: implications for CO2 sequestration.

Dypingite, a hydrated Mg-carbonate mineral, was precipitated from high-pH, high salinity solutions to investigate controls on carbon fixation and to identify the isotopic characteristics of mineral sequestration in mine tailings. δ(13)C values of dissolved inorganic carbon content and synthetic dypingite are significantly more negative than those predicted for equilibrium exchange of CO(2) gas between the atmosphere and solution. The measured δ(13)C of aqueous carbonate species is consistent with a kinetic fractionation that results from a slow diffusion of atmospheric CO(2) into solution. During dypingite precipitation, dissolved inorganic carbon concentrations decrease and δ(13)C values become more negative, indicating that the rate of CO(2) uptake into solution was outpaced by the rate of carbon fixation within the precipitate. This implies that CO(2) gas uptake is rate-limiting to CO(2) fixation. δ(13)C of carbonate mineral precipitates in mine tailings and of DIC in mine process waters display similar (13)C-depletions that are inconsistent with equilibrium fractionation. Thus, the rate of carbon fixation in mine tailings may also be limited by supply of CO(2). Carbon sequestration could be accelerated by increasing the partial pressure of CO(2) in tailings ponds or by using chemicals that enhance the uptake of gaseous CO(2) into aqueous solution.

Microbially Mediated Mineral Carbonation: Roles of Phototrophy and Heterotrophy

Ultramafic mine tailings from the Diavik Diamond Mine, Canada and the Mount Keith Nickel Mine, Western Australia are valuable feedstocks for sequestering CO₂ via mineral carbonation. In microcosm experiments, tailings were leached using various dilute acids to produce subsaline solutions at circumneutral pH that were inoculated with a phototrophic consortium that is able to induce carbonate precipitation. Geochemical modeling of the experimental solutions indicates that up to 2.5% and 16.7% of the annual emissions for Diavik and Mount Keith mines, respectively, could be sequestered as carbonate minerals and phototrophic biomass. CO₂ sequestration rates are mainly limited by cation availability and the uptake of CO₂. Abundant carbonate mineral precipitation occurred when heterotrophic oxidation of acetate acted as an alternative pathway for CO₂ delivery. These experiments highlight the importance of heterotrophy in producing sufficient DIC concentrations while phototrophy causes alkalinization of waters and produces biomass (fatty acids = 7.6 wt.%), a potential feedstock for biofuel production. Tailings storage facilities could be redesigned to promote CO₂ sequestration by directing leachate waters from tailings piles into specially designed ponds where carbonate precipitation would be mediated by both chemical and biological processes, thereby storing carbon in stable carbonate minerals and potentially valuable biomass.

Subarctic Weathering of Mineral Wastes Provides a Sink for Atmospheric CO2

The mineral waste from some mines has the capacity to trap and store CO(2) within secondary carbonate minerals via the process of silicate weathering. Nesquehonite [MgCO(3)·3H(2)O] forms by weathering of Mg-silicate minerals in kimberlitic mine tailings at the Diavik Diamond Mine, Northwest Territories, Canada. Less abundant Na- and Ca-carbonate minerals precipitate from sewage treatment effluent deposited in the tailings storage facility. Radiocarbon and stable carbon and oxygen isotopes are used to assess the ability of mine tailings to trap and store modern CO(2) within these minerals in the arid, subarctic climate at Diavik. Stable isotopic data cannot always uniquely identify the source of carbon stored within minerals in this setting; however, radiocarbon isotopic data provide a reliable quantitative estimate for sequestration of modern carbon. At least 89% of the carbon trapped within secondary carbonate minerals at Diavik is derived from a modern source, either by direct uptake of atmospheric CO(2) or indirect uptake though the biosphere. Silicate weathering at Diavik is trapping 102-114 g C/m(2)/y within nesquehonite, which corresponds to a 2 orders of magnitude increase over the background rate of CO(2) uptake predicted from arctic and subarctic river catchment data.

Time-scales of assembly and thermal history of a composite felsic pluton: constraints from the Emerald Lake area, northern Canadian Cordillera, Yukon

Knowledge of the time-scales of emplacement and thermal history during assembly of composite felsic plutons in the shallow crust are critical to deciphering the processes of crustal growth and magma chamber development. Detailed petrological and chemical study of the mid-Cretaceous, composite Emerald Lake pluton, from the northern Canadian Cordillera, Yukon Territory, coupled with U^Pb and 40 Ar/ 39 Ar geochronology, indicates that this pluton was intruded as a series of magmatic pulses. Intrusion of these pulses produced a strong petrological zonation from augite syenite, hornblende quartz syenite and monzonite, to biotite granite. Our data further indicate that multiple phases were emplaced and cooled to below the mineral closure temperatures over a time-scale on the order of the resolution of the 40 Ar/ 39 Ar technique (V1 Myr), and that emplacement occurred at 94.3 Ma. Simple thermal modelling and heat conduction calculations were used to further constrain the temporal relationships within the intrusion. These calculations are consistent with the geochronology and show that emplacement and cooling were complete in less than 100 kyr and probably 70 < 5 kyr. These results demonstrate that production, transport and emplacement of the different phases of the Emerald Lake pluton occurred essentially simultaneously, and that these processes must also have been closely related in time and space. By analogy, these results provide insights into the assembly and petrogenesis of other complex intrusions and ultimately lead to an understanding of the processes involved in crustal development. ? 2002 Elsevier Science B.V. All rights reserved.

Differential transport of CO2 and CH4 in coalbed aquifers: Implications for coalbed gas distribution and composition

Coalbed gas content and composition are critical for the successful exploration and production of coalbed methane. We investigated the differential transport of a preadsorbed CO2-CH4 gas mixture along a coalbed aquifer by groundwater flow or across a coal bed by upward diffusion through pore water. Consistent analytical approximations and numerical solutions were obtained for typical cases. The results suggest that differential transport of CH4 and CO2 in a water-saturated coal seam is mainly controlled by their adsorption equilibrium in coals and solubilities in water. Although CO2 is about 20 times more soluble than CH4 in water at temperatures lower than 50C, the transport of CO2 from a coal seam is only several times more efficient than that of CH4 because of the stronger adsorption of CO2 than CH4 in coals. Preferential transport of CO2 over CH4 by groundwater advection can substantially accumulate more gas rich in CO2 at downstream or near discharge zones if gas-trapping structures exist, and it may cause low total gas content of CH4 near recharge zones, which may explain the CO2 and CH4 distribution in the San Juan and Powder River basins and the undersaturation of gas in many other coals. The separation and redistribution of coalbed gas by transport processes may also be complicated by late-stage biogenic gas generation with infiltration of meteoric water with nutrients and gas-producing microbes into the coal beds as suggested for some basins. Overall, hydrogeologic systems strongly influence the distribution of coalbed gas content and composition in coal seams.

Modern carbonate microbialites from an asbestos open pit pond, Yukon, Canada

Microbialites were discovered in an open pit pond at an abandoned asbestos mine near Clinton Creek, Yukon, Canada. These microbialites are extremely young and presumably began forming soon after the mine closed in 1978. Detailed characterization of the periphyton and microbialites using light and scanning electron microscopy was coupled with mineralogical and isotopic analyses to investigate the mechanisms by which these microbialites formed. The microbialites are columnar in form (cm scale), have an internal spherulitic fabric (mm scale), and are mostly made of aragonite, which is supersaturated in the subsaline pond water. Initial precipitation is seen as acicular aragonite crystals nucleating onto microbial biomass and detrital particles. Continued precipitation entombs benthic diatoms (e.g. Brachysira vitrea), filamentous algae (e.g. Oedogonium sp.), dinoflagellates, and cyanobacteria. The presence of phototrophs at spherulite centers strongly suggests that these microbes play an important initial role in aragonite precipitation. Substantial growth of individual spherulites occurs abiotically through periodic precipitation of aragonite that forms concentric laminations around spherulite centers while pauses in spherulite growth allow for colonization by microbes. Aragonite associated with biomass (δ(13)C = -4.6‰ VPDB) showed a (13)C-enrichment of 0.8‰ relative to aragonite exhibiting no biomass (δ(13)C = -5.4‰ VPDB), which suggests a modest removal of isotopically light dissolved inorganic carbon by phototrophs. The combination of a low sedimentation rate, high calcification rate, and low microbial growth rate appears to result in the formation of these microbialites. The formation of microbialites at an historic mine site demonstrates that an anthropogenically constructed environment can foster microbial carbonate formation.