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1. Crystallographic and chemical signatures in coral skeletal aragonite

   https://doi.org/10.1007/s00338-021-02198-4  

   Farfan, Gabriela A. ; Apprill, Amy ; Cohen, Anne ; DeCarlo, Thomas M. ; Post, Jeffrey E. ; Waller, Rhian G. ; Hansel, Colleen M. ( November 2021 , Coral Reefs)

   Corals nucleate and grow aragonite crystals, organizing them into intricate skeletal structures that ultimately build the world’s coral reefs. Crystallography and chemistry have profound influence on the material properties of these skeletal building blocks, yet gaps remain in our knowledge about coral aragonite on the atomic scale. Across a broad diversity of shallow-water and deep-sea scleractinian corals from vastly different environments, coral aragonites are remarkably similar to one another, confirming that corals exert control on the carbonate chemistry of the calcifying space relative to the surrounding seawater. Nuances in coral aragonite structures relate most closely to trace element chemistry and aragonite saturation state, suggesting the primary controls on aragonite structure are ionic strength and trace element chemistry, with growth rate playing a secondary role. We also show how coral aragonites are crystallographically indistinguishable from synthetic abiogenic aragonite analogs precipitated from seawater under conditions mimicking coral calcifying fluid. In contrast, coral aragonites are distinct from geologically formed aragonites, a synthetic aragonite precipitated from a freshwater solution, and mollusk aragonites. Crystallographic signatures have future applications in understanding the material properties of coral aragonite and predicting the persistence of coral reefs in a rapidly changing ocean.

    

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2. Thermal equation of state of post-aragonite CaCO3-Pmmn

   https://doi.org/10.2138/am-2020-7279  

   Lv, Mingda ; Liu, Jiachao ; Greenberg, Eran ; Prakapenka, Vitali B. ; Dorfman, Susannah M. ( September 2020 , American Mineralogist)

   null (Ed.)

   Abstract Calcium carbonate (CaCO3) is one of the most abundant carbonates on Earth's surface and transports carbon to Earth's interior via subduction. Although some petrological observations support the preservation of CaCO3 in cold slabs to lower mantle depths, the geophysical properties and stability of CaCO3 at these depths are not known, due in part to complicated polymorphic phase transitions and lack of constraints on thermodynamic properties. Here we measured thermal equation of state of CaCO3-Pmmn, the stable polymorph of CaCO3 through much of the lower mantle, using synchrotron X-ray diffraction in a laser-heated diamond-anvil cell up to 75 GPa and 2200 K. The room-temperature compression data for CaCO3-Pmmn are fit with third-order Birch-Murnaghan equation of state, yielding KT0 = 146.7 (±1.9) GPa and K′0 = 3.4(±0.1) with V0 fixed to the value determined by ab initio calculation, 97.76 Å3. High-temperature compression data are consistent with zero-pressure thermal expansion αT = a0 + a1T with a0 = 4.3(±0.3)×10-5 K-1, a1 = 0.8(±0.2)×10-8 K-2, temperature derivative of the bulk modulus (∂KT/∂T)P = –0.021(±0.001) GPa/K; the Grüneisen parameter γ0 = 1.94(±0.02), and the volume independent constant q = 1.9(±0.3) at a fixed Debye temperature θ0 = 631 K predicted via ab initio calculation. Using these newly determined thermodynamic parameters, the density and bulk sound velocity of CaCO3-Pmmn and (Ca,Mg)-carbonate-bearing eclogite are quantitatively modeled from 30 to 80 GPa along a cold slab geotherm. With the assumption that carbonates are homogeneously mixed into the slab, the results indicate the presence of carbonates in the subducted slab is unlikely to be detected by seismic observations, and the buoyancy provided by carbonates has a negligible effect on slab dynamics. 

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3. Sudden emergence of a shallow aragonite saturation horizon in the Southern Ocean

   https://doi.org/10.1038/s41558-019-0418-8  

   Negrete-García, Gabriela ; Lovenduski, Nicole S. ; Hauri, Claudine ; Krumhardt, Kristen M. ; Lauvset, Siv K. ( April 2019 , Nature Climate Change)
4. Origin of blocky aragonite cement in Cenozoic glaciomarine sediments, McMurdo Sound, Antarctica

   https://doi.org/10.1111/sed.12690  

   Yang, Mingyu ; Frank, Tracy D. ; Fielding, Christopher R. ; Smith, Megan E. ; Swart, Peter K. ; Reijmer, ed., John ( December 2019 , Sedimentology)

   Inorganic aragonite occurs in a wide spectrum of depositional environments and its precipitation is controlled by complex physio‐chemical factors. This study investigates diagenetic conditions that led to aragonite cement precipitation in Cenozoic glaciomarine deposits of McMurdo Sound, Antarctica. A total of 42 sandstones that host intergranular cement were collected from theCIROS‐1 core, located proximal to the terminus of Ferrar Glacier. Standard petrography, Raman spectroscopy and electron microprobe analysis reveal a prominent aragonite cement phase that occurs as a pore‐filling blocky fabric throughout the core. Oxygen isotope compositions (δ¹⁸O = −30·0 to −8·6‰ Vienna Pee‐Dee Belemnite) and clumped isotope temperatures (TΔ₄₇ = 13·1 to 31·5°C) determined from the aragonite cements provide precise constraints on isotopic compositions (δ¹⁸O_w) of the parent fluid, which mostly range from −10·8 to −7·2‰ Vienna Standard Mean Ocean Water. The fluidδ¹⁸O_wvalues are consistent with those of pore water, previously identified as cryogenic brine in the nearbyAND‐2A core. Petrographic and geochemical data suggest that aragonite cement in theCIROS‐1 core precipitated from a similar brine. The brine likely formed and infiltrated sediments in flooded glacial valleys along the western margin of McMurdo Sound during the middle Miocene Climatic Transition, and subsequently flowed basinward in the subsurface. Consequently, the brine forms as a longstanding subsurface fluid that has saturated Cenozoic sediments below southern McMurdo Sound since at least the middle Miocene. Aragonite cementation in theCIROS‐1 core is interpreted to reflect its proximal position to sites of brine formation and greater likelihood of experiencing brines with sustained high carbonate saturation states and Mg/Ca ratios. This unusual occurrence expands the range of known natural occurrences of aragonite cement. Given the potential for cryogenic brine formation in glaciomarine settings, blocky aragonite, as the end member of the spectrum of aragonite cement morphology, may be more widespread in glaciomarine sediments than currently thought.

    

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5. Aragonite saturation states in estuaries along a climate gradient in the northwestern Gulf of Mexico

   https://doi.org/10.3389/fenvs.2022.951256  

   Hu, Xinping ; Yao, Hongming ; McCutcheon, Melissa R. ; Dias, Larissa ; Staryk, Cory J. ; Wetz, Michael S. ; Montagna, Paul A. ( October 2022 , Frontiers in Environmental Science)

   In the northwestern Gulf of Mexico (nwGOM), the coastal climate shifts abruptly from the humid northeast to the semiarid southwest within a narrow latitudinal range. The climate effect plays an important role in controlling freshwater discharge into the shallow estuaries in this region. In addition to diminishing freshwater runoff down the coast, evaporation also increases substantially. Hence, these estuaries show increasing salinity along the coastline due to the large difference in freshwater inflow balance (river runoff and precipitation minus evaporation and diversion). However, this spatial gradient can be disrupted by intense storm events as a copious amount of precipitation leads to river flooding, which can cause temporary freshening of these systems in extreme cases, in addition to freshwater-induced ephemeral stratification. We examined estuarine water aragonite saturation state (Ω arag ) data collected between 2014 and 2018, covering a period of contrasting hydrological conditions, from the initial drought to multiple flooding events, including a brief period that was influenced by a category 4 hurricane. Based on freshwater availability, these estuaries exhibited a diminishing Ω arag fluctuation from the most freshwater enriched Guadalupe Estuary to the most freshwater-starved Nueces Estuary. While Ω arag values were usually much higher than the threshold level (Ω arag = 1), brief freshwater discharge events and subsequent low oxygen levels in the lower water column led to episodic corrosive conditions. Based on previously obtained Ω arag temporal trends and Ω arag values obtained in this study, we estimated the time of emergence (ToE) for Ω arag . Not only did estuaries show decreasing ToE with diminishing freshwater availability but the sub-embayments of individual estuaries that had a less freshwater influence also had shorter ToE. This spatial pattern suggests that planning coastal restoration efforts, especially for shellfish organisms, should emphasize areas with longer ToE. 

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