Accurate and precise microscale measurements of boron isotope ratios in calcium carbonates using laser ablation multicollector-ICPMS

2019 ◽  
Vol 34 (3) ◽  
pp. 550-560 ◽  
Author(s):  
Aleksey Sadekov ◽  
Nicholas S. Lloyd ◽  
Sambuddha Misra ◽  
Julie Trotter ◽  
Juan D'Olivo ◽  
...  
Keyword(s):  
Laser Ablation ◽  
Isotope Ratios ◽  
Boron Isotope ◽  
Carbonate Chemistry ◽  
Calcium Carbonates ◽  
Seawater Ph ◽  
Invaluable Tool ◽  
Biogenic Carbonates

The boron isotope compositions (δ11B) of biogenic carbonates have proven to be an invaluable tool for investigating changes in ocean carbonate chemistry, especially the impacts of declining seawater pH due to rising levels of atmospheric CO2.

Boron isotope analysis of coral skeletons by laser ablation MC-ICP-MS: new insights into calcification and environmental reconstruction at high temporal resolution

2020 ◽  
Author(s):  
Gavin L. Foster ◽  
Thomas B. Chalk ◽  
Christopher D. Standish
Keyword(s):  
Laser Ablation ◽  
Trace Element ◽  
Temporal Resolution ◽  
Isotope Analysis ◽  
Coral Skeleton ◽  
Boron Isotope ◽  
High Temporal Resolution ◽  
Carbonate System ◽  
Seawater Ph ◽  
Icp Ms

<p>Despite being some of the largest bio-constructions on the planet, coral reefs are made by many millions of cm- to mm-sized polyps of Scleractinian corals. Calcification occurs in a micron sized space sandwiched between the coral animal and the existing skeleton, known as the extra cellular medium (ECM). The coral animal has a tight control on the carbonate system in this space through deploying enzymatic pumps (e.g. Ca-ATPase) and secreting acidic-rich proteins. Tracking the state of the carbonate system in the ECM is therefore key to forming a mechanistic understanding of how environmental change, such as ocean acidification, influences skeletal formation and ultimately the growth and resilience of these important ecosystems.</p><p>Traditional means to examine ECM composition is through the use of micro-electrodes. While these approaches have revealed many key insights they are, by their nature, invasive.  They also only provide snap shots of information for corals grown in the laboratory. The boron isotopic composition of the coral skeleton and its boron content (expressed as B/Ca ratio) have recently emerged as a viable alternative approach to fully characterise the carbonate system in the ECM.  However, most studies employ bulk sampling techniques which require averaging across both structural elements of the coral skeleton and many months to years of growth. Laser ablation MC-ICP-MS approaches are now available as an alternative sampling protocol (e.g. Standish et al. 2019), and along with B/Ca (and other trace element) measurements this not only allows a reconstruction of the full carbonate system of the ECM from an analysis of the skeleton of any coral (cultured or wild) at unprecedented spatial and temporal resolution, but it also allows an examination of the influence of the carbonate system in the ECM on trace element incorporation. </p><p>Here we present boron isotope and trace element analyses of several tropical, reef-building, corals to examine the nature and magnitude of fine scale variation in ECM composition.  By studying corals from locations where external seawater is well known we also gain insights into trace element incorporation and whether external seawater pH can be accurately reconstructed from the boron-based proxies at weekly (or better) resolution. </p><p> </p><p>Standish, C.D., Chalk, T.B., Babila, T.L., Milton, J.A., Palmer, M.R., Foster, G.L. (2019) The effect of matrix interferences in situ boron isotope analysis by laser ablation MC-ICP-MS, Rapid Communications in Mass Spectrometry 33: 959–968 https://doi.org/10.1002/rcm.8432</p>

scholarly journals δ<sup>11</sup>B as monitor of calcification site pH in marine calcifying organisms

2017 ◽  
Author(s):  
Jill N. Sutton ◽  
Yi-Wei Liu ◽  
Justin B. Ries ◽  
Maxence Guillermic ◽  
Emmanuel Ponzevera ◽  
...  
Keyword(s):  
Isotope Composition ◽  
Dominant Role ◽  
Boron Isotope ◽  
Exchange Reactions ◽  
Saturation State ◽  
Diverse Range ◽  
Inductively Coupled ◽  
Seawater Ph ◽  
Oculina Arbuscula ◽  
Biogenic Carbonates

Abstract. The isotope composition of boron (B) in marine biogenic carbonates has been predominantly studied as a proxy for monitoring past changes in seawater pH and carbonate chemistry. In order to derive seawater pH from boron isotope ratio data, a number of assumptions related to chemical kinetics and themodynamic isotope exchange reactions are necessary. Furthermore, the boron isotope composition (δ11B) of biogenic carbonates (δ11BCaCO3) is assumed to reflect the δ11B of dissolved borate (B(OH)4−) in seawater. Here we report the development of methodology for measuring the δ11B in biogenic carbonate samples at the multi-collector inductively coupled mass spectrometry facility at Ifremer (Plouzané, France) and the evaluation of δ11BCaCO3 in a diverse range of marine calcifying organisms. We evaluated the δ11BCaCO3 of 6 species of marine calcifiers (a temperate coral, Oculina arbuscula; a coralline red alga, Neogoniolithion sp.; a tropical urchin, Eucidaris tribuloides; a temperate urchin, Arbacia punctulata; a serpulid worm, Hydroides crucigera; and an American oyster, Crassostrea virginica) that were reared for 60 days in isothermal seawater (25 °C) equilibrated with an atmospheric pCO2 of ca. 409 μatm. We observe large inter-species variability in δ11BCaCO3 (ca. 20 ‰) and significant discrepancies between measured δ11BCaCO3 and δ11BCaCO3 expected from established relationships between δ11BCaCO3 and seawater pH. We discuss these results in the context of various proposed mechanisms of biocalcification, including the potential dominant role that internal calcifying site pH plays in regulating CaCO3 saturation state and borate δ11B at the site of calcification and, thus, the δ11B composition of calcifers’ shells and skeletons.

scholarly journals In-situ determination of antimony isotope ratios in Sb minerals by femtosecond LA-MC-ICP-MS

2021 ◽  
Author(s):  
Andreas Benjamin Kaufmann ◽  
Marina Lazarov ◽  
Stefan Kiefer ◽  
Juraj Majzlan ◽  
Stefan Weyer
Keyword(s):  
Laser Ablation ◽  
Femtosecond Laser ◽  
Femtosecond Laser Ablation ◽  
Isotope Ratios ◽  
Icp Ms

Here we present a method for in-situ determination of stable antimony (Sb) isotope compositions by ultraviolet (UV)-femtosecond-laser-ablation-multi-collector-ICP-MS (fs-LA-MC-ICP-MS). Metallic antimony and a number of Sb minerals (stibnite, senarmontite, chalcostibite, tetrahedrite,...

scholarly journals Revisiting carbonate chemistry controls on planktic foraminifera Mg /  Ca: implications for sea surface temperature and hydrology shifts over the Paleocene–Eocene Thermal Maximum and Eocene–Oligocene transition

2016 ◽  
Vol 12 (4) ◽  
pp. 819-835 ◽  
Author(s):  
David Evans ◽  
Bridget S. Wade ◽  
Michael Henehan ◽  
Jonathan Erez ◽  
Wolfgang Müller
Keyword(s):  
Laser Ablation ◽  
Inductively Coupled Plasma ◽  
Data Sets ◽  
Carbonate Chemistry ◽  
Surface Hydrology ◽  
Planktic Foraminifera ◽  
Inductively Coupled ◽  
Accurate Picture ◽  
Thermal Maximum ◽  
The Relationship

Abstract. Much of our knowledge of past ocean temperatures comes from the foraminifera Mg / Ca palaeothermometer. Several nonthermal controls on foraminifera Mg incorporation have been identified, of which vital effects, salinity, and secular variation in seawater Mg / Ca are the most commonly considered. Ocean carbonate chemistry is also known to influence Mg / Ca, yet this is rarely examined as a source of uncertainty, either because (1) precise pH and [CO32−] reconstructions are sparse or (2) it is not clear from existing culture studies how a correction should be applied. We present new culture data of the relationship between carbonate chemistry and Mg / Ca for the surface-dwelling planktic species Globigerinoides ruber and compare our results to data compiled from existing studies. We find a coherent relationship between Mg / Ca and the carbonate system and argue that pH rather than [CO32−] is likely to be the dominant control. Applying these new calibrations to data sets for the Paleocene–Eocene Thermal Maximum (PETM) and Eocene–Oligocene transition (EOT) enables us to produce a more accurate picture of surface hydrology change for the former and a reassessment of the amount of subtropical precursor cooling for the latter. We show that pH-adjusted Mg / Ca and δ18O data sets for the PETM are within error of no salinity change and that the amount of precursor cooling over the EOT has been previously underestimated by  ∼ 2 °C based on Mg / Ca. Finally, we present new laser-ablation data of EOT-age Turborotalia ampliapertura from St. Stephens Quarry (Alabama), for which a solution inductively coupled plasma mass spectrometry (ICPMS) Mg / Ca record is available (Wade et al., 2012). We show that the two data sets are in excellent agreement, demonstrating that fossil solution and laser-ablation data may be directly comparable. Together with an advancing understanding of the effect of Mg / Casw, the coherent picture of the relationship between Mg / Ca and pH that we outline here represents a step towards producing accurate and quantitative palaeotemperatures using this proxy.

scholarly journals IsoFishR: An application for reproducible data reduction and analysis of strontium isotope ratios (87Sr/86Sr) obtained via laser-ablation MC-ICP-MS

PLoS ONE ◽  
2018 ◽  
Vol 13 (9) ◽  
pp. e0204519 ◽  
Author(s):  
Malte Willmes ◽  
Katherine M. Ransom ◽  
Levi S. Lewis ◽  
Christian T. Denney ◽  
Justin J. G. Glessner ◽  
...  
Keyword(s):  
Laser Ablation ◽  
Data Reduction ◽  
Isotope Ratios ◽  
Strontium Isotope ◽  
Icp Ms ◽  
Strontium Isotope Ratios

scholarly journals Carbonate System Parameters of an Algal-dominated Reef along West Maui

2018 ◽  
Author(s):  
Nancy G. Prouty ◽  
Kimberly K. Yates ◽  
Nathan Smiley ◽  
Chris Gallagher ◽  
Olivia Cheriton ◽  
...  
Keyword(s):  
Coral Reef ◽  
Reef Flat ◽  
Sampling Period ◽  
Total Alkalinity ◽  
Carbonate Chemistry ◽  
Diurnal Variability ◽  
Carbon Chemistry ◽  
Sources Of Pollution ◽  
Seawater Ph ◽  
Chemistry Dynamics

Abstract. Constraining coral reef metabolism and carbon chemistry dynamics are fundamental for understanding and predicting reef vulnerability to rising coastal CO2 concentrations and decreasing seawater pH. However, few studies exist along reefs occupying densely inhabited shorelines with known input from land-based sources of pollution. The shallow coral reefs off Kahekili, West Maui, are exposed to nutrient-enriched, low-pH submarine groundwater discharge (SGD) and are particularly vulnerable to the compounding stressors from land-based sources of pollution and lower seawater pH. To constrain the carbonate chemistry system, nutrients and carbonate chemistry were measured along the Kahekili reef flat every 4 h over a 6-d sampling period in March 2016. Abiotic process – primarily SGD fluxes – controlled the carbonate chemistry adjacent to the primary SGD vent site, with nutrient-laden freshwater decreasing pH levels and favoring undersaturated aragonite saturation (Ωarag) conditions. In contrast, diurnal variability in the carbonate chemistry at other sites along the reef flat was driven by reef community metabolism. Superimposed on the diurnal signal was a transition during the second sampling period to a surplus of total alkalinity (TA) and dissolved inorganic carbon (DIC) compared to ocean end-member TA and DIC measurements. A shift from net community production and calcification to net respiration and carbonate dissolution was identified. This transition occurred during a period of increased SGD-driven nutrient loading, lower wave height, and reduced current speeds. This detailed study of carbon chemistry dynamics highlights the need to incorporate local effects of nearshore oceanographic processes into predictions of coral reef vulnerability and resilience.

In situ determination of precise stable Si isotope ratios by UV-femtosecond laser ablation high-resolution multi-collector ICP-MS

2008 ◽  
Vol 249 (1-2) ◽  
pp. 155-166 ◽  
Author(s):  
Jérôme Chmeleff ◽  
Ingo Horn ◽  
Grit Steinhoefel ◽  
Friedhelm von Blanckenburg
Keyword(s):  
Laser Ablation ◽  
High Resolution ◽  
Femtosecond Laser ◽  
Femtosecond Laser Ablation ◽  
Isotope Ratios ◽  
Icp Ms ◽  
Si Isotope

No ion is an island: Multiple ions involved during boron incorporation into CaCO3

2021 ◽  
Author(s):  
Michael Henehan ◽  
Christa Klein-Gebbinck ◽  
Gavin Foster ◽  
Jill Wyman ◽  
Mathis Hain ◽  
...  
Keyword(s):  
Calcium Carbonate ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Boron Isotope ◽  
Minor Role ◽  
Growth Mechanisms ◽  
Minor Elements ◽  
Vital Effects ◽  
Biogenic Carbonates ◽  
Trace And Minor Elements

&lt;p&gt;Boron isotope ratios, as measured in marine calcium carbonate, are a proven tracer of past seawater and calcifying fluid pH and thus a powerful tool for the reconstruction of past atmospheric CO&lt;sub&gt;2&lt;/sub&gt; and monitoring of coral physiology. For such applications, understanding the inorganic baseline upon which foraminiferal vital effects or coral pH upregulation are superimposed should be an important prerequisite. Yet, investigations into boron isotope fractionation in synthetic CaCO&lt;sub&gt;3&amp;#160;&lt;/sub&gt;polymorphs have often reported variable and even conflicting results, implying that we may not fully understand pathways of boron incorporation into calcium carbonate. &amp;#160;Here we address this topic with experimental data from calcite and aragonite precipitated across a range of pH in the presence of both Mg and Ca. We confirm the results of previous studies that the boron isotope composition of inorganic aragonite precipitates closely reflects that of aqueous borate ion, but that calcites display a higher degree of scatter, and diverge from the boron isotope composition of borate ion at low pH. We discuss these findings with reference to the simultaneous incorporation of other trace and minor elements, and highlight a number of mechanisms by which crystal growth mechanisms may influence the concentration and isotope composition of boron in CaCO&lt;sub&gt;3&lt;/sub&gt;. In particular, we highlight the potential importance of surface electrostatics in driving variability in published synthetic carbonate datasets. Importantly for palaeo-reconstruction, however, these electrostatic effects are likely to play a much more minor role during natural precipitation of biogenic carbonates.&lt;/p&gt;

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