Tools for uranium characterization in carbonate samples: case studies of natural U–Pb geochronology reference materials

Laser ablation U–Pb analyses of carbonate (LAcarb) samples has greatly expanded the potential for U–Pb dating to a variety of carbonate-producing settings. Carbonates that were previously considered impossible to date using isotope dilution methods may preserve radiogenic domains that can be dated using spatially resolved laser ablation geochronology techniques. Work is ongoing to identify reference materials and to consider best practices for LAcarb. In this study we apply standard and emerging characterization tool sets on three natural samples with the dual goal of enhancing the study of carbonates and establishing a new set of well-characterized natural reference materials for LAcarb studies. We start with the existing carbonate reference material WC-1 from the Permian Reef Complex of Texas, building on the published description to offer a deeper look at U and associated trace elements. We consider a tufa sample from the Miocene Barstow Formation of the Mojave Block, California, as a possible secondary calcite reference material due to its well-behaved U–Pb systematics. There are currently no natural dolomite standards. We present an unusual dolomite sample with very well-behaved U–Pb systematics from the Miocene of the Turkana Basin of Kenya as a possible dolomite reference material for LAcarb dating. In addition to using X-ray fluorescence (XRF) mapping and spectroscopy to better understand U in these natural samples, we have analyzed multiple aliquots of each of them for 87Sr/86Sr by thermal ionization mass spectrometry (TIMS). The Sr isotope compositions are analytically homogeneous within petrographically homogeneous regions of all three samples, and thus these materials could be used as Sr isotope standards as well. While not part of the current contribution, this combination could streamline simultaneous LA analyses of 87Sr/86Sr and U–Pb geochronology.

A Sample Characterization Toolkit for Carbonate U-Pb Geochronology

Laser ablation U-Pb analyses of carbonate (LAcarb) samples has greatly expanded the potential for U-Pb dating to a variety of carbonate producing settings. Carbonates that were previously considered impossible to date using isotope dilution methods may preserve domains that are favorably interrogated when using spatially resolved laser ablation geochronology techniques. Work is ongoing to identify reference materials and to consider best practices for LAcarb. In this study we apply standard and emerging characterization toolsets on three natural samples with the dual goal of enhancing the study of carbonates and in establishing a new set of precisely characterized natural standards for LAcarb studies. We start with the existing carbonate reference material WC-1 from the Permian Reef Complex of Texas, building on the published description to offer a deeper look at U and fluids. We consider a tufa sample from the Miocene Barstow Formation of the Mojave Block, California, as a possible secondary calcite reference material due to its well-behaved U/Pb systematics. There are currently no natural dolomite standards. We present an unusual dolomite sample with very well-behaved U-Pb systematics from the Miocene of the Turkana Basin of Kenya as a possible dolomite reference material for LAcarb dating. In addition to using XRF mapping and spectroscopy to better understand U in these natural samples, we have analyzed multiple aliquots of each of them for 87Sr/86Sr. The Sr isotope compositions are reasonably homogeneous in all three samples, so that these could be used as Sr isotope standards as well. This combination could streamline split stream analyses of 87Sr/86Sr and U/Pb geochronology.

Analysis of Ground Dolomite: Effect of Grinding Time on the Production of Submicron Particles

This paper discusses the effect of grinding time on the production of submicron dolomite by using the impact and abrasion technique of high energy planetary ball mill. It is known that grinding process leads to surface activation other than exhibiting particle size reduction. Most of the energy applied during the process will be dissipated as heat that could lead to harmful effects to the structural pattern of the ground material. Thus in order to study the detrimental effects of grinding towards submicron dolomite, sample was ground at 400 rpm speed with various grinding time; 0.5h, 1h, 2h, 5h, 10h and 20h. It was confirmed using X-Ray Diffraction (XRD) method that the crystalline structure of dolomite did not deform even after 20h of grinding time, thus maintained its crystallinity. The morphological structures of ungrind and ground raw dolomite were shown by Scanning Electron Microscope (SEM) morphology.

Thermal Decomposition of Dolomite Containing Phosphorus

In this paper,DTA-TG and TEM are used to investigate dolomite containing phosphorus. The investigations suggest that the thermal decomposition of dolomite containing a little bit of phosphorus powder has only one reaction while that of dolomite has two reactions, and the final temperature of the reaction reduces by about 18°C. The oxidation reaction of the phosphorus in dolomite begins at about 500°C, which is 140°C higher than that of the oxidation reaction of phosphorus in standard atmosphere condition. Round-bubble-shape structure gradually appears on the surface of the dolomite sample when observed using TEM. Furthermore, the number and size of this structure increased with the rising of the temperature. Finally, the round-bubble-shape structure breaks to small hollows, showing as teared-shape, and forms a series of protruding and intensive larger hollows and spherical shape. Therefore, the temperature of thermal decomposition of thermal decomposition of dolomite is decreased and the components of thermal decomposition products of dolomite containing phosphorus are almost the same as that of dolomite.

Cyclic Carbonation Calcination Studies of Limestone and Dolomite for CO2 Separation From Combustion Flue Gases

Naturally occurring limestone and dolomite samples, originating from different geographical locations, were tested as potential sorbents for carbonation/calcination based CO2 capture from combustion flue gases. Samples have been studied in a thermogravimetric analyzer under simulated flue gas conditions at three calcination temperatures, viz., 750°C, 875°C, and 930°C for four carbonation calcination reaction (CCR) cycles. The dolomite sample exhibited the highest rate of carbonation than the tested limestones. At the third cycle, its CO2 capture capacity per kilogram of the sample was nearly equal to that of Gotland, the highest reacting limestone tested. At the fourth cycle it surpassed Gotland, despite the fact that the CaCO3 content of the Sibbo dolomite was only 2/3 of that of the Gotland. Decay coefficients were calculated by a curve fitting exercise and its value is lowest for the Sibbo dolomite. That means, most probably its capture capacity per kilogram of the sample would remain higher, well beyond the fourth cycle. There was a strong correlation between the calcination temperature, the specific surface area of the calcined samples, and the degree of carbonation. It was observed that the higher the calcination temperature, the lower the sorbent reactivity. The Brunauer–Emmett–Teller measurements and scanning electron microscope images provided quantitative and qualitative evidences to prove this. For a given limestone/dolomite sample, sorbent’s CO2 capture capacity depended on the number of CCR cycles and the calcination temperature. In a CCR loop, if the sorbent is utilized only for a certain small number of cycles (<20), the CO2 capture capacity could be increased by lowering the calcination temperature. According to the equilibrium thermodynamics, the CO2 partial pressure in the calciner should be lowered to lower the calcination temperature. This can be achieved by additional steam supply into the calciner. Steam could then be condensed in an external condenser to single out the CO2 stream from the exit gas mixture of the calciner. A calciner design based on this concept is illustrated.

Cyclic Carbonation and Calcination Studies of Limestone and Dolomite for CO2 Separation From Combustion Flue Gases

Naturally occurring limestone and dolomite samples, originating from different geographical locations, were tested as potential sorbents for carbonation/calcination based CO2 capture from combustion flue gases. Samples have been studied in a thermo gravimetric analyzer under a simulated flue gas conditions at three calcination temperatures, viz., 750°C, 875°C and 930°C for four Carbonation Calcination Reaction (CCR) cycles. The dolomite sample exhibited the highest rate of carbonation than the tested limestones. At 3rd cycle, its CO2 capture capacity per kg of sample was nearly equal to that of Gotland, the highest reacting limestone tested. At 4th cycle it surpassed Gotland, despite the fact that the CaCO3 content of Sibbo dolomite was only 2/3 of Gotland. Decay coefficients were calculated by a curve fitting exercise and its value is lowest for Sibbo dolomite. That means, most probably its capture capacity per kg of sample would remain higher, well beyond the 4th cycle. There was a strong correlation between the calcination temperature, specific surface area of the calcined samples and degree of carbonation. It was observed that higher the calcination temperature lower the sorbent reactivity. The BET measurements and SEM images provided quantitative and qualitative evidences to prove this. For a given limestone/dolomite sample, sorbent’s CO2 capture capacity was depend on the number of CCR cycles and the calcination temperature. In a CCR loop, if the sorbent is utilized only for a certain small number of cycles (&lt;20), the CO2 capture capacity could be increased by lowering the calcination temperature. According to the equilibrium thermodynamics, the CO2 partial pressure in the calciner should be lowered to lower the calcination temperature. This can be achieved by additional steam supply into the calciner. Steam could then be condensed in an external condenser to single out the CO2 stream from the exit gas mixture of the calciner. A calciner design based on this concept is illustrated.