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1. Phosphatidylserine affinity for and flip-flop dependence on Ca ²⁺ and Mg ²⁺ ions

   https://doi.org/10.1039/d4fd00206g  

   Hymas, Preston P; Conboy, John C (January 2025, Faraday Discussions)

   Ca²⁺ions are believed to play a crucial role in enzymatic regulation of lipid membrane asymmetry, yet direct effects of Ca²⁺on lipid flip-flop are unknown. Present work examines the influence of Ca–lipid interactions on lipid translocation. 

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2. Phosphatidylinositol 3, 5‐bisphosphate regulates Ca ²⁺ transport during yeast vacuolar fusion through the Ca ²⁺ ATPase Pmc1

   https://doi.org/10.1111/tra.12736  

   Miner, Gregory E.; Sullivan, Katherine D.; Zhang, Chi; Rivera‐Kohr, David; Guo, Annie; Hurst, Logan R.; Ellis, Ez C.; Starr, Matthew L.; Jones, Brandon C.; Fratti, Rutilio A. (June 2020, Traffic)

   Abstract The transport of Ca²⁺across membranes precedes the fusion and fission of various lipid bilayers. Yeast vacuoles under hyperosmotic stress become fragmented through fission events that requires the release of Ca²⁺stores through the TRP channel Yvc1. This requires the phosphorylation of phosphatidylinositol‐3‐phosphate (PI3P) by the PI3P‐5‐kinase Fab1 to produce transient PI(3,5)P₂pools. Ca²⁺is also released during vacuole fusion upontrans‐SNARE complex assembly, however, its role remains unclear. The effect of PI(3,5)P₂on Ca²⁺flux during fusion was independent of Yvc1. Here, we show that while low levels of PI(3,5)P₂were required for Ca²⁺uptake into the vacuole, increased concentrations abolished Ca²⁺efflux. This was as shown by the addition of exogenous dioctanoyl PI(3,5)P₂or increased endogenous production of by the hyperactivefab1^T2250Amutant. In contrast, the lack of PI(3,5)P₂on vacuoles from the kinase deadfab1^EEEmutant showed delayed and decreased Ca²⁺uptake. The effects of PI(3,5)P₂were linked to the Ca²⁺pump Pmc1, as its deletion rendered vacuoles resistant to the effects of excess PI(3,5)P₂. Experiments with Verapamil inhibited Ca²⁺uptake when added at the start of the assay, while adding it after Ca²⁺had been taken up resulted in the rapid expulsion of Ca²⁺. Vacuoles lacking both Pmc1 and the H⁺/Ca²⁺exchanger Vcx1 lacked the ability to take up Ca²⁺and instead expelled it upon the addition of ATP. Together these data suggest that a balance of efflux and uptake compete during the fusion pathway and that the levels of PI(3,5)P₂can modulate which path predominates. 

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3. Simultaneous Determination of I/Ca and Other Elemental Ratios in Foraminifera: Comparing Results From Acidic and Basic Solutions

   https://doi.org/10.1029/2022GC010660  

   Zhou, Xiaoli; Hess, Anya V.; Bu, Kaixuan; Sagawa, Takuya; Rosenthal, Yair (November 2022, Geochemistry, Geophysics, Geosystems)

   Abstract The iodine to calcium ratio in carbonate (I/Ca) has been widely used to indicate ocean oxygenation level in the past. Given the volatility of iodine, I/Ca has been measured in alkaline solutions in previous studies. However, this limits the application of I/Ca with other element/Ca (El/Ca) proxies at the same time and in the same foraminifera because other El/Ca data are preferably analyzed in acidic solutions. This study assesses the reliability of I/Ca measurements in acidic solutions measured with other El/Ca as well as the effects of different sample pre‐treatments on measured foraminiferal I/Ca. Our results show that when samples are measured within hours of prepaparation, the pH of the final solution has an insignificant effect on I/Ca measurements of a carbonate reference material JCp‐1 and a multi‐element standard solution, consistent with the slow kinetics of iodine volatilization. We find, however, that low pH possibly reduces the measured I/Ca in foraminiferal tests in some samples. Our experiments also suggest a resolvable effect of reductive cleaning, yielding lower foraminiferal I/Ca compared to without reductive cleaning. The HNO₃concentration used to dissolve foraminiferal shells has a negligible effect. Despite the different solution pHs and cleaning and dissolving methods, our core top planktic I/Ca data are able to differentiate well‐oxygenated from oxygen‐depleted waters in the upper ocean, and after correcting for cleaning effect, our data are generally consistent with the published studies that analyzed I/Ca without reductive cleaning and in basic solutions. This study shows that measurements of I/Ca within hours of sample dissolutions yield reliable planktic I/Ca data, while also allowing the acquisition of other El/Ca values for paleoceanographic studies. 

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4. Accuracy and Reproducibility of Coral Sr/Ca SIMS Timeseries in Modern and Fossil Corals

   https://doi.org/10.1029/2021GC010068  

   Sayani, Hussein R.; Cobb, Kim M.; Monteleone, Brian; Bridges, Heather (August 2022, Geochemistry, Geophysics, Geosystems)

   Abstract Coral strontium‐to‐calcium ratios (Sr/Ca) provide quantitative estimates of past sea surface temperatures (SST) that allow for the reconstruction of changes in the mean state and climate variations, such as the El Nino‐Southern Oscillation, through time. However, coral Sr/Ca ratios are highly susceptible to diagenesis, which can impart artifacts of 1–2°C that are typically on par with the tropical climate signals of interest. Microscale sampling via Secondary Ion Mass Spectrometry (SIMS) for the sampling of primary skeletal material in altered fossil corals, providing much‐needed checks on fossil coral Sr/Ca‐based paleotemperature estimates. In this study, we employ a set modern and fossil corals from Palmyra Atoll, in the central tropical Pacific, to quantify the accuracy and reproducibility of SIMS Sr/Ca analyses relative to bulk Sr/Ca analyses. In three overlapping modern coral samples, we reproduce bulk Sr/Ca estimates within ±0.3% (1σ). We demonstrate high fidelity between 3‐month smoothed SIMS coral Sr/Ca timeseries and SST (R = −0.5 to −0.8;p < 0.5). For lightly‐altered sections of a young fossil coral from the early‐20th century, SIMS Sr/Ca timeseries reproduce bulk Sr/Ca timeseries, in line with our results from modern corals. Across a moderately‐altered section of the same fossil coral, where diagenesis yields bulk Sr/Ca estimates that are 0.6 mmol too high (roughly equivalent to −6°C artifacts in SST), SIMS Sr/Ca timeseries track instrumental SST timeseries. We conclude that 3–4 SIMS analyses per month of coral growth can provide a much‐needed quantitative check on the accuracy of fossil coral Sr/Ca‐derived estimates of paleotemperature, even in moderately altered samples. 

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5. Impact of Intra‐Skeletal Calcite on the Preservation of Coral Geochemistry and Implications for Paleoclimate Reconstruction

   https://doi.org/10.1029/2023PA004730  

   Weerabaddana, Mudith M; Thompson, Diane M; Reed, Emma V; Farfan, Gabriela A; Kirk, Jason D; Kojima, Alice C; Dettman, David L; de_Brum, Kalena; Kabua, Emma; Edwards, Florence (May 2024, Paleoceanography and Paleoclimatology)

   Abstract The geochemistry of tropical coral skeletons is widely used in paleoclimate reconstructions. However, sub‐aerially exposed corals may be affected by diagenesis, altering the aragonite skeleton through partial dissolution, or infilling of secondary minerals like calcite. We analyzed the impact of intra‐skeletal calcite on the geochemistry (δ¹⁸O, Sr/Ca, Mg/Ca, Li/Mg, Li/Ca, U/Ca, B/Ca, Ba/Ca, and Mn/Ca) of a sub‐aerially exposedPoritessp. coral. Each micro‐milled coral sample was split into two aliquots for geochemistry and X‐ray diffraction (XRD) analysis to quantify the direct impact of calcite on geochemistry. We modified the sample loading technique for XRD to detect low calcite levels (1%–2%; total uncertainty = 0.33%, 2σ) in small samples (∼7.5 mg). Calcite content ranged from 0% to 12.5%, with higher percentages coinciding with larger geochemical offsets. Sr/Ca, Li/Mg, Li/Ca, and δ¹⁸O‐derived sea‐surface temperature (SST) anomalies per 1% calcite were +0.43°C, +0.24°C, +0.11°C, and +0.008°C, respectively. A 3.6% calcite produces a Sr/Ca‐SST signal commensurate with local SST seasonality (∼1.5°C), which we propose as the cut‐off level for screening calcite diagenesis in paleo‐temperature reconstructions. Inclusion of intra‐skeletal calcite decreases B/Ca, Ba/Ca, and U/Ca values, and increases Mg/Ca values, and can therefore impact reconstructions of paleoclimate and the carbonate chemistry of the semi‐isolated calcifying fluid in corals. This study emphasizes the importance of quantifying fine‐scale calcite diagenesis to identify coral preservation levels and assure robust paleoclimate reconstructions. 

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