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1. Mg zonation and heterogeneity in low-Mg calcite microcrystals of a depositional chalk

   https://doi.org/10.2110/jsr.2020.173  

   Rinderknecht, Chanse J. ; Hasiuk, Franek J. ; Oborny, Stephan C. ( August 2021 , Journal of Sedimentary Research)

   null (Ed.)

   ABSTRACT Diagenetic low-magnesium calcite (LMC) microcrystals constitute the framework that hosts most micropores in limestone reservoirs and therefore create the storage capacity for hydrocarbons, water, and anthropogenic CO2. Limestones dominated by LMC microcrystals are also commonly used for paleoclimate reconstructions and chemostratigraphic correlations. LMC microcrystals are well known to exhibit a range of textures (e.g., granular, fitted, clustered), but there exists uncertainty with regard to how these textures form. One hypothesis is that during crystal growth, Mg is incorporated into diagenetic overgrowths (cement), where the chemical zonation and microtexture may reflect diagenetic processes. To evaluate small-scale geochemical zonation in LMC microcrystals, this study uses scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) to measure the Mg/Ca ratio across the interiors of LMC granular microcrystals from a Late Cretaceous marine chalk from the Tor Fm. (Norwegian North Sea). Mg/Ca zonation was identified in all LMC microcrystals with a diameter > 5 μm. Generally, the cores of large crystals have lower Mg/Ca (≈ 5.9 mmol/mol) and the rims have elevated Mg/Ca (≈ 13 mmol/mol). Smaller microcrystals (< 5 μm) show no resolvable zonation, but do exhibit a wide range in Mg/Ca content from 2.9 to 32.2 mmol/mol. Measured Mg/Ca values are arbitrarily divided into three populations: low Mg (average ≈ 5.9 mmol/mol), intermediate Mg (average ≈ 13.3 mmol/mol), and high Mg (average ≈ 20 mmol/mol). The observed zonation and Mg enrichment within LMC microcrystals is interpreted to reflect depositional as well as multiple diagenetic signals, such as constructive precipitation through recrystallization and pore-filling cementation. Although chalk from the Tor Fm. is dominated by granular euhedral LMC microcrystals, using SEM-EDS to find Mg/Ca heterogeneity in other LMC microcrystal textures may provide insight into the diagenetic processes that create textural variations in micropore-dominated limestones. The Mg data also more broadly suggest that there is useful, measurable diagenetic information in material that is otherwise considered homogeneous. Distinguishing between possible primary compositions and secondary cementation has implications for studies that rely on the primary chemistry of fine-grained carbonate deposits (e.g., micrite), such as paleoclimatology, Mg paleothermometry, and chemostratigraphy. 

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2. The Transformation of Aragonite to Calcite in the Presence of Magnesium: Implications for Marine Diagenesis

   Hashim, M. ; Kaczmarek, S.E. ( September 2021 , Earth and planetary science letters)

   null (Ed.)

   Magnesium (Mg) in natural waters plays a critical role in governing carbonate mineral formation, dissolution, and diagenesis. Previous laboratory experiments show that Mg can strongly inhibit direct calcite precipitation as well as aragonite to calcite diagenetic transformation. Data from natural settings, however, suggest that diagenetic calcite in most Phanerozoic limestones has formed in the shallow marine burial realm in the presence of ample Mg. Thus, the diagenetic conditions under which aragonite-rich sediments convert to calcite-rich limestones are poorly understood. Here, we present data from laboratory experiments whereby aragonite is converted to calcite at 70◦C in Mg-bearing solutions to investigate the effects of fluid:solid ratio (F:S), which varies greatly across diagenetic environments, on Mg inhibition and incorporation in calcite. Our data show that not only can the transformation of aragonite to calcite occur in solutions with higher [Mg] than previously shown possible in laboratory experiments, but that progressively lower F:S increase the rate at which aragonite stabilizes to calcite. For example, in experiments with an F:S of 0.3 mL/g, which corresponds to sediments in a closed system with 50% porosity, aragonite stabilizes to calcite in solution with [Mg]=30 mM (Mg/Ca=5.14) when an initial high degree of undersaturation with respect to aragonite is used and in a solution with [Mg]=20 (Mg/Ca=5.14) when a low degree of undersaturation is used. In contrast, aragonite does not stabilize to calcite after nearly 3000 h in experiments with an F:S of 100 mL/g, which is more typical of an open system, even in a solution with [Mg]=5 mM (Mg/Ca=5.14) regardless of the degree of undersaturation. Our results also show that the amount of Mg incorporated into calcite products increases linearly with the increase of F:S. Collectively, these observations further point to F:S as an important factor in carbonate diagenesis with broad implications. First, the observations that transformation of aragonite to calcite is inhibited at high [Mg] and F:S imply that calcite precipitation is unlikely to occur in marine diagenetic environments that are in direct hydrologic contact with seawater. This leaves aragonite dissolution as the dominant diagenetic process in these environments, which may represent an underrated source of alkalinity to the open ocean. Second, transformation from aragonite-rich sediments to the calcite-rich limestones that dominate the rock record is likely promoted by a decrease in the F:S and the development of a closed system during progressive burial. 

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3. Modern Sedimentation and Authigenic Mineral Formation in the Chew Bahir Basin, Southern Ethiopia: Implications for Interpretation of Late Quaternary Paleoclimate Records

   https://doi.org/10.3389/feart.2021.607695  

   Gebregiorgis, Daniel ; Deocampo, Daniel M. ; Foerster, Verena ; Longstaffe, Fred J. ; Delaney, Jeremy S. ; Schaebitz, Frank ; Junginger, Annett ; Markowska, Monika ; Opitz, Stephan ; Trauth, Martin H. ; et al ( April 2021 , Frontiers in Earth Science)

   null (Ed.)

   We present new mineralogical and geochemical data from modern sediments in the Chew Bahir basin and catchment, Ethiopia. Our goal is to better understand the role of modern sedimentary processes in chemical proxy formation in the Chew Bahir paleolake, a newly investigated paleoclimatic archive, to provide environmental context for human evolution and dispersal. Modern sediment outside the currently dry playa lake floor have higher SiO 2 and Al 2 O 3 (50–70 wt.%) content compared to mudflat samples. On average, mudflat sediment samples are enriched in elements such as Mg, Ca, Ce, Nd, and Na, indicating possible enrichment during chemical weathering (e.g., clay formation). Thermodynamic modeling of evaporating water in upstream Lake Chamo is shown to produce an authigenic mineral assemblage of calcite, analcime, and Mg-enriched authigenic illitic clay minerals, consistent with the prevalence of environments of enhanced evaporative concentration in the Chew Bahir basin. A comparison with samples from the sediment cores of Chew Bahir based on whole-rock MgO/Al 2 O 3 , Ba/Sr and authigenic clay mineral δ 18 O values shows the following: modern sediments deposited in the saline mudflats of the Chew Bahir dried out lake bed resemble paleosediments deposited during dry periods, such as during times of the Last Glacial Maximum and Younger Dryas stadial. Sediments from modern detrital upstream sources are more similar to sediments deposited during wetter periods, such as the early Holocene African Humid Period. 

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4. A window to the Early Cretaceous North American Climate and Environment: The ‘Lake Carpenter’ lacustrine strata of the Cedar Mountain Formation

   Suarez, M.B. ; Al-Suwaidi, A. ; Kirkland, J.I. ; Snell, K. ; Moller, A. ; McLean, N. ; Suarez, C.A. ; Montgomery, E. ; Paige, M. ( January 2023 , The Anatomical record Supplement)

   The Cedar Mountain Formation is thought to span a significant portion of the lower Cretaceous and the base of the upper Cretaceous (Valanginian to Cenomanian). As such, the Cedar Mountain Formation is important for understanding the transition of terrestrial ecosystems from those characterized by pre-angiosperm ecosystems of the Jurassic to the angiosperm-dominated ecosystems that characterized the height of dinosaur diversity in the later part of the Cretaceous. Lacustrine strata offer unique opportunities to shed light on environmental and climate conditions of the past. This study presents results from a multi-proxy study of lacustrine strata in the Cedar Mountain Formation termed “Lake Carpenter.” The sequence of strata is about ~30 m thick and located near Arches National Park. The lower ~7 m is characterized by dark organic-rich mudstones, shales, and tan limestones and dolostone. The middle portion between about 7 and 25m consists of more massive carbonate-rich strata with abundant aquatic fossils including ostracodes, charophytes, and fish scales. The upper portion to about 30 m consists of green to tan mudstones with carbonate nodules and increases in siliciclastic content. Carbonate mineralogies include calcite, high-magnesium calcite, and dolomite (including dolomicrites) based on XRD analyses. To put the lacustrine sequence into stratigraphic context, bulk organic C isotope values were utilized to construct a chemostratigraphic record. The carbon isotope values range from -32.3‰ to -21.1‰ vs. VPDB. Zircons from four suspected volcanic ash layers were analyzed for U-Pb using LA-ICP-MS. One of these produced concordant Cretaceous dates. The youngest zircons from this sample was analyzed using CA-ID-TIMS and produced a date of 115.65 ± 0.18 Ma. Based on the chemostratigraphic record and the U-Pb date, the deposition of the lacustrine sequence occurs in the mid to late Aptian and spans a time that is thought to have coincided with a cold snap based on marine records. Carbonate analyses of the carbonates within the lacustrine sequence ranges from -9.2‰ to +5.4‰ vs. VPDB for carbon and -9.3 to -0.3‰ vs. VPDB for oxygen. Overall, carbonate isotope data is positively covariant and along with the minerology, seems to suggest that the lake was a closed-basin, alkaline lake and would have likely experience significant evaporation. To investigate paleotemperature, selected samples were analyzed for clumped isotope values (47) to determine temperature of formation. Preliminary temperature estimates of calcite formation range from 27°C to 41°C. Estimates for dolomite range from 19°C to 21°C. Lacustrine carbonate formation typically is biased toward spring and summer and as such some of these temperatures (particularly the values for dolomites) seem slightly lower than expected for a greenhouse climate but may be consistent with a “cold-snap” during the late Aptian. Palustrine carbonates from the type section of the Ruby Ranch Member range 19.8°C to 44.5°C (Suarez et al. 2021) and suggests the lacustrine strata records a similar range in temperatures during the Aptian Stage in this part of North America. REFERENCES CITED: Suarez, MB, Knight, J, Snell, KE, Ludvigson, GA, Kirkland, JI, Murphy, L 2020. Multiproxy paleoclimate estimates of the continental Cretaceous Ruby Ranch Member of the Cedar Mountain Formation. In: Bojar, A-V, Pelc., A, Lecuyer, C, editors. Stable Isotopes Studies of Water Cycle and Terrestrial Environments. Geol Soc, London, Spec Pub, 507: https://doi.org/10.1144/SP507-2020-85 KEYWORDS: Early Cretaceous, lacustrine, stable isotopes, paleoclimate Presentation Mode: Invited Speaker 

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5. The formation of high-Sr/Y plutons in cordilleran-arc crust by crystal accumulation and melt loss

   https://doi.org/10.1130/GES02400.1  

   Brackman, Adam J. ; Schwartz, Joshua J. ( February 2022 , Geosphere)

   Bulk-rock data are commonly used in geochemical studies as a proxy for melt compositions in order to understand the evolution of crustal melts. However, processes of crystal accumulation and melt migration out of deep-crustal, crystal-rich mush zones to shallower storage regions raise questions about how faithfully bulk-rock compositions in plutons approximate melt compositions. This problem is particularly acute in the lower crust of arcs, where melt reservoirs are subject to periodic melt extraction that leaves behind a cumulate residue. Here, we examine bulk-rock data from the perspective of high-Sr/Y plutonic rocks in the lower crust of a well-exposed Early Cretaceous cordilleran-arc system in Fiordland, New Zealand. We test the validity of using high-Sr/Y bulk-rock compositions as proxies for melts by comparing bulk-rock compositions to melts modeled from >100 major- and trace-element analyses of 23 magmatic clinopyroxene grains from the same samples. The sampling locations of the igneous clinopyroxenes and encompassing bulk rocks are distributed across ~550 km2 of exhumed lower crust and are representative of Mesozoic lower-crustal arc rocks in the Median batholith. We confirm that bulk-rock data have characteristics of high-Sr/Y plutons (Sr/Y >50, Na2O >3.5 wt%, Sr >1000 ppm, and Y <20 ppm), features that have been previously interpreted to indicate the presence of garnet as a residual or fractionating phase. In contrast to bulk rocks, igneous clinopyroxenes have low Sr (<100 ppm), high Y (25–100 ppm), and low molar Mg# [100 × Mg/(Mg + Fe)] values (60–70), which are consistent with derivation from fractionated, low-Sr/Y melts. Chondrite-normalized rare-earth-element patterns and Sm/Yb values in clinopyroxenes also show little to no evidence for involvement of garnet in the source or in differentiation processes. Fe-Mg partitioning relationships indicate that clinopyroxenes are not in equilibrium with their encompassing bulk rocks but could have been in equilibrium with melt compositions determined from chemometry of coexisting igneous hornblendes. Moho-depth calculations based on bulk-rock Sr/Y values also yield Moho depths (average = 69 km) that are inconsistent with Moho depths based on bulk-rock Ce/Y, contact aureole studies, Al-in-horn- blende crystallization pressures, and our modeled clinopyroxene crystallization pressures. These data indicate that most Mesozoic high-Sr/Y bulk rocks in the lower crust of Fiordland are cumulates formed by plagioclase + amphibole + clinopyroxene accumulation and interstitial melt loss from crystal-rich mush zones. Our data do not support widespread fractionation of igneous garnet nor partial melting of a garnet-bearing source in the petrogenesis of these melts. We speculate that melt extraction and the production of voluminous cumulates in the lower crust were aided by unusually high heat flow and high magma addition rates associated with an Early Cretaceous arc flareup. We conclude that bulk-rock compositions are poor proxies for melt compositions in the lower crust of the Median batholith, and geochemical modeling of these high-Sr/Y bulk rocks would overemphasize the role of garnet in their petrogenesis. 

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