Relative Contributions of Mg Hydration and Molecular Structural Restraints to the Barrier of Dolomite Crystallization: A Comparison of Aqueous and Non-Aqueous Crystallization in (BaMg)CO3 and (CaMg)CO3 Systems

Carbonate mineralization is reasonably well-understood in the Ca–CO2–H2O system but continuously poses difficulties to grasp when Mg is present. One of the outstanding questions is the lack of success in dolomite MgCa(CO3)2 crystallization at atmospheric conditions. The conventional view holds that hydration retards the reactivity of Mg2+ and is supported by solvation shell chemistry. This theory however is at odds with the easy formation of norsethite MgBa(CO3)2, a structural analogue of dolomite, leading to the premise that crystal or molecular structural constrains may also be at play. The present study represents our attempts to evaluate the separate contributions of the two barriers. Crystallization in the Mg–Ba–CO2 system was examined in a non-aqueous environment and in H2O to isolate the effect of hydration by determining the minimal relative abundance of Mg required for norsethite formation. The results, showing an increase from 1:5 to 6:4 in the solution Mg/Ba ratio, represented a ~88% reduction in Mg2+ reactivity, presumably due to the hydration effect. Further analyses in the context of transition state theory indicated that the decreased Mg2+ reactivity in aqueous solutions was equivalent to an approximately 5 kJ/mol energy penalty for the formation of the activated complex. Assuming the inability of dolomite to crystallizes in aqueous solutions originates from the ~40 kJ/mol higher (relative to norsethite) Gibbs energy of formation for the activated complex, a hydration effect was estimated to account for ~12% of the energy barrier. The analyses present here may be simplistic but nevertheless consistent with the available thermodynamic data that show the activated complex of dolomite crystallization reaction is entropically favored in comparison with that of norsethite formation but is significantly less stable due to the weak chemical bonding state.

Daily cyclicity in bivalve shell chemistry: Paleo-weather record or circadian rhythm?

<p>Bivalve shells have a long-standing reputation as archives for high-resolution (seasonal scale) (paleo)climate variability due to their incremental growth, yielding accurate shell chronologies, and their abundance, diversity, and high preservation potential in the fossil record (Schöne and Surge, 2012). Capitalizing on innovations in geochemical techniques, high-resolution sclerochronology can now resolve changes in bivalve shell chemistry beyond the daily resolution (e.g. Sano et al., 2012; Warter et al., 2018). When applied on fossil shells, these ultra-high-resolution records have the potential to bridge the gap between climate and weather reconstructions and yield unprecedented information about bivalve paleobiology, extreme weather events in past climates and even astronomical cycles (Warter and Müller, 2017; de Winter et al., 2020; Yan et al., 2020).</p><p>However, studies of sub-daily scale shell chemistry are almost exclusively limited to giant clams (Tridacna spp.), due to their high growth rates. It is hitherto unknown if and how such diurnal cycles in chemistry differ in other genera across the bivalve clade and/or whether they are exclusive to photosymbiotic clams. In addition, it is not clear whether the daily cycles are formed in response to environmental conditions (e.g. light or temperature sensitivity) or reflect circadian rhythms.</p><p>To answer these questions, we combine ultra-high-resolution (hourly scale) Laser Ablation ICP-MS trace element profiles through shells of various tridacnid species from the tropical Gulf of Aqaba with profiles through the giant scallop (Pecten maximus) from the temperate Atlantic coast of northwestern France. We observe trace element cycles on in the daily frequency domain in both tridacnids and pectinids. This shows that these diurnal cycles are formed regardless of shell mineralogy (aragonite vs. calcite), living environment (tropical inter-tidal vs. temperate sub-tidal) and occur in highly unrelated bivalve taxa. Our data helps the interpretation of similar records from fossil shells in terms of past (extreme) weather events, climate, and shell growth.</p><p> </p><p><strong>References</strong></p><p>de Winter, N. J. et al. Paleoceanography and Paleoclimatology 35, e2019PA003723 (2020).</p><p>Sano, Y. et al. Nature Communications 3, 761 (2012).</p><p>Schöne, B. R. & Surge, D. M. Treatise Online 24, Volume 1, Chapter 14 (2012).</p><p>Warter, V., Erez, J. & Müller, W. Palaeogeography, Palaeoclimatology, Palaeoecology 496, 32–47 (2018).</p><p>Warter, V. & Müller, W. Palaeogeography, Palaeoclimatology, Palaeoecology 465, 362–375 (2017).</p><p>Yan, H. et al. PNAS 117, 7038–7043 (2020).</p>

Advances in high-resolution paleoclimate reconstructions using growth experiments, age modelling and clumped isotope analyses

<p>Geochemical records from incremental carbonate archives, such as fossil mollusk shells, contain information on climate and environmental change at the resolution of days to decades (e.g. Schöne and Gillikin, 2013; Ivany, 2012). These high-resolution paleoclimate data, providing snapshots of past climate change on a human scale, complement more conventional reconstructions on a geological timescale of thousands to millions of years. Recent innovations in geochemical techniques such as high-resolution trace element and clumped isotope analyses provide the unique potential to improve the accuracy and resolution of these high-resolution climate reconstructions in the near future (see e.g. de Winter et al., 2020a; b; Caldarescu et al., 2021). However, to be able to make the most out of these new techniques requires a more detailed understanding of the timing and mechanisms of mollusk shell growth as well as the relationship between environment and shell chemistry on daily to weekly timescales.</p><p>The UNBIAS (UNravelling BIvAlve Shell chemistry) project combines investigations on lab-grown modern bivalve shells with reconstructions based on fossil shell material from past greenhouse periods in an attempt to improve our understanding of short-term temperature variability in warm climates. Samples from cultured shells labeled with a novel trace element spiking method are used to calibrate accurate temperature reconstructions from bivalve shells using the state-of-the-art clumped isotope method. As a result, we present a temperature calibration of clumped isotope measurements on aragonitic shell carbonates. New statistical routines are developed to accurately date microsamples within shells relative to the seasonal cycle (ShellChron; de Winter, 2020) and to strategically combine these microsamples for seasonal reconstructions of temperature and salinity from fossil shells (seasonalclumped, de Winter et al., 2020c; de Winter, 2021). We present the first results of this integrated seasonal reconstruction approach on fossil bivalve shells from the Pliocene Warm Period and Late Cretaceous greenhouse of northwestern Europe as well as an outlook on future plans within the UNBIAS project.</p><p> </p><p><strong>References</strong></p><p>Caldarescu, D. E. et al. Geochimica et Cosmochimica Acta 294, 174–191 (2021).</p><p>de Winter, N. J. ShellChron v0.2.8: Builds Chronologies from Oxygen Isotope Profiles in Shells. (2020).</p><p>de Winter, N. J. seasonalclumped v0.3.2: Toolbox for Seasonal Temperature Reconstructions using Clumped Isotope Analyses. (2021).</p><p>de Winter, N. J. et al. Paleoceanography and Paleoclimatology 35, e2019PA003723 (2020a).</p><p>de Winter, N. J. et al. Nature Communications in Earth and Environment (in review; 2020b) doi:10.21203/rs.3.rs-39203/v2.</p><p>de Winter, N., Agterhuis, T. & Ziegler, M. Climate of the Past Discussions 1–52 (2020c) doi:https://doi.org/10.5194/cp-2020-118.</p><p>Ivany, L. C. The Paleontological Society Papers 18, 133–166 (2012).</p><p>Schöne, B. R. & Gillikin, D. P. Palaeogeography, Palaeoclimatology, Palaeoecology 373, 1–5 (2013).</p>

The analysis of freshwater pearl mussel shells using µ-XRF (micro-x-ray fluorescence) and the applicability for environmental reconstruction

Freshwater pearl mussel is a highly threatened species, and many populations are currently on the brink of local extinction. For example, in south Finland, only two populations are currently viable. Even though the reasons for the mussels’ demise are relatively well known, the long-term impacts of water quality are not completely resolved. Here, µ-XRF analysis and historical records were used to evaluate whether the differences in water chemistry or past environmental changes in three rivers in southern Finland are visible in mussel shell chemistry. The results show that the cracks inside mussel shells, invisible to the naked eye, may greatly affect the elemental composition results. Further, anomalies which could be related to inclusion of detrital matter inside the shells were detected. Manganese (Mn) seems to be related to mussel growth dynamics, especially in the nacreous layer, while high values of iron (Fe) and Mn are also present at the top sections of the prismatic layer. Line scan analysis revealed high variation between replicates. The µ-XRF method could be used as prescreening method in mussel sclerochemistry studies, but more studies are needed to clarify the ability of FPM shells to reliably record the environmental conditions.

Novel Method to Image and Quantify Cogwheel Structures in Foraminiferal Shells

Most studies designed to better understand biomineralization by foraminifera focus mainly on their shell chemistry in order to retrace processes responsible for element uptake and shell formation. Still, shell formation is a combination of not only chemical and biological processes, but is also limited by structural features. Since the processes involved in the formation of the foraminifera shell remains elusive, new focus has been put on potential structural constraints during shell formation. Revealing structural details of shells of foraminifera might increase our mechanistic understanding of foraminifera calcification, and even explain species-specific differences in element incorporation. Recently, shell structures have been studied in increasingly higher resolution and detail. This paper aims to provide new insights on the structural features on foraminifera shells, so-called cogwheels, which can be observed in the shell wall and at its surface. Here, we present a novel method to image and quantify these cogwheel structures, using field specimens from different environments and ecological groups, including benthic and planktonic species. Application of this method allows for comparing shell structures at specimen and species level, to unravel potential drivers of shell formation.

Distribution of chlorine and fluorine in benthic foraminifera

Over the last few decades, a suite of inorganic proxies based on foraminiferal calcite have been developed, some of which are now widely used for palaeoenvironmental reconstructions. Studies of foraminiferal shell chemistry have largely focused on cations and oxyanions, while much less is known about the incorporation of anions. The halogens fluoride and chloride are conservative in the ocean, which makes them candidates for reconstructing palaeoceanographic parameters. However, their potential as a palaeoproxy has hardly been explored, and fundamental insight into their incorporation is required. Here we used nanoscale secondary ion mass spectrometry (NanoSIMS) to investigate, for the first time, the distribution of Cl and F within shell walls of four benthic species of foraminifera. In the rotaliid species Ammonia tepida and Amphistegina lessonii, Cl and F were distributed highly heterogeneously within the shell walls, forming bands that were co-located with the bands observed in the distribution of phosphorus (significant positive correlation of both Cl and F with P; p<0.01). In the miliolid species Sorites marginalis and Archaias angulatus, the distribution of Cl and F was much more homogeneous without discernible bands. In these species, Cl and P were spatially positively correlated (p<0.01), whereas no correlation was observed between Cl and F or between F and P. Additionally, their F content was about an order of magnitude higher than in the rotaliid species. The high variance in the Cl and F content in the studied foraminifera specimens could not be attributed to environmental parameters. Based on these findings, we suggest that Cl and F are predominately associated with organic linings in the rotaliid species. We further propose that Cl may be incorporated as a solid solution of chlorapatite or may be associated with organic molecules in the calcite in the miliolid species. The high F content and the lack of a correlation between Cl and F or P in the miliolid foraminifera suggest a fundamentally different incorporation mechanism. Overall, our data clearly show that the calcification pathway employed by the studied foraminifera governs the incorporation and distribution of Cl, F, P, and other elements in their calcite shells.

Shell chemistry of the boreal Campanian bivalve <i>Rastellum diluvianum</i> (Linnaeus, 1767) reveals temperature seasonality, growth rates and life cycle of an extinct Cretaceous oyster

The Campanian age (Late Cretaceous) is characterized by a warm greenhouse climate with limited land-ice volume. This makes this period an ideal target for studying climate dynamics during greenhouse periods, which are essential for predictions of future climate change due to anthropogenic greenhouse gas emissions. Well-preserved fossil shells from the Campanian (±78 Ma) high mid-latitude (50∘ N) coastal faunas of the Kristianstad Basin (southern Sweden) offer a unique snapshot of short-term climate and environmental variability, which complements existing long-term climate reconstructions. In this study, we apply a combination of high-resolution spatially resolved trace element analyses (micro-X-ray fluorescence – µXRF – and laser ablation inductively coupled plasma mass spectrometry – LA-ICP-MS), stable isotope analyses (IRMS) and growth modeling to study short-term (seasonal) variations recorded in the oyster species Rastellum diluvianum from the Ivö Klack locality. Geochemical records through 12 specimens shed light on the influence of specimen-specific and ontogenetic effects on the expression of seasonal variations in shell chemistry and allow disentangling vital effects from environmental influences in an effort to refine paleoseasonality reconstructions of Late Cretaceous greenhouse climates. Growth models based on stable oxygen isotope records yield information on the mode of life, circadian rhythm and reproductive cycle of these extinct oysters. This multi-proxy study reveals that mean annual temperatures in the Campanian higher mid-latitudes were 17 to 19 ∘C, with winter minima of ∼13 ∘C and summer maxima of 26 ∘C, assuming a Late Cretaceous seawater oxygen isotope composition of −1 ‰ VSMOW (Vienna standard mean ocean water). These results yield smaller latitudinal differences in temperature seasonality in the Campanian compared to today. Latitudinal temperature gradients were similar to the present, contrasting with previous notions of “equable climate” during the Late Cretaceous. Our results also demonstrate that species-specific differences and uncertainties in the composition of Late Cretaceous seawater prevent trace element proxies (Mg∕Ca, Sr∕Ca, Mg∕Li and Sr∕Li) from being used as reliable temperature proxies for fossil oyster shells. However, trace element profiles can serve as a quick tool for diagenesis screening and investigating seasonal growth patterns in ancient shells.

Controlling the structures of organic semiconductor–quantum dot nanocomposites through ligand shell chemistry

Structural insights via small angle X-ray and neutron (SAXS and SANS, respectively) into how nanocrystal quantum dots (QD) functionalized with organic ligands self-assemble with a small molecule organic semiconductor.

Distribution of chlorine and fluorine in benthic foraminifera

Over the last decades a suite of inorganic proxies based on foraminiferal calcite have been developed, of which some are now widely used for paleoenvironmental reconstructions. Studies of foraminiferal shell chemistry have largely focused on cations and oxyanions, while much less is known about the incorporation of anions. The halogens fluoride and chloride are conservative in the ocean, which makes them candidates for reconstructing paleoceanographic parameters. However, their potential as a paleoproxy has hardly been explored, and fundamental insight in their incorporation is required. Here we used nano-scale secondary ion mass spectrometry (NanoSIMS) to investigate, for the first time, the distribution of Cl and F within shell walls of four benthic species of foraminifera. In the rotaliid species Ammonia tepida and Amphistegina lessonii Cl and F were highly heterogeneous and correlated within the shell walls, forming bands that were co-located with the banded distribution of phosphorus. In the miliolid species Sorites marginalis and Archaias angulatus the distribution of Cl and F was much more homogeneous without discernible bands. In these species Cl and P were correlated, whereas no correlation was observed between Cl and F or between F and P. Additionally, their F content was about an order of magnitude higher than in the rotaliid species. The high variance in the Cl and F content in the studied foraminifera could not be attributed to environmental parameters. Based on these findings we suggest that in the rotaliid species Cl and F are predominately associated with organic linings. We further propose that in the miliolid species Cl may be incorporated as a solid solution of chlorapatite or associated with organic molecules in the calcite. The high F content together with the lack of correlation between Cl and F or P in the miliolid foraminifera suggests a fundamentally different incorporation mechanism. Overall, our data clearly show that the calcification pathway employed by the studied foraminifera governs the incorporation and distribution of Cl, F, P and other elements in their calcite shells.