Trace element and isotope partitioning in carbonates in simulated biological environments

Lead Research Organisation: University of St Andrews
Department Name: Earth and Environmental Sciences

Abstract

Many marine organisms produce calcium carbonate structures e.g. corals produce skeletons, bivalves produce shells and foraminifera (single-celled organisms) produce tests. These mineral structures provide organisms with tissue support and/or protection from predators and the physical environment. The chemistry of calcium carbonate is affected by environment. In particular seawater temperatures affect how trace elements substitute in place of calcium and the ratio of oxygen isotopes (forms of oxygen with different masses) in the mineral structure. Thus the geochemistry of the calcium carbonate structures provides information on the temperature and chemistry of seawater at the time the organism lived and grew. The mineral structures are preserved after the death of the organism e.g. as coral reefs, and the analysis of fossil specimens offers an excellent route to reconstruct records of past environmental conditions. Such records help us to understand past changes and interactions in global climate and to predict 21st century climate change. Understanding how other factors affect the chemistry of the shells and reefs is key to accurate interpretation of the climate information recorded in fossil specimens.

Coral skeletons and foraminifera tests form at specialist calcification sites, either in or adjacent to the organism. The calcification sites contain both soluble and insoluble organic biomolecules (e.g. proteins, lipids), which control and guide the precipitation and growth of the mineral. These biomolecules also affect the chemistry of the mineral. In this research we will analyse modern and fossil corals and foraminifera to determine how the concentrations and compositions of organic biomolecules at the calcification site have varied throughout time. We will then precipitate CaCO3 minerals in vitro under conditions replicating those of past and present calcification sites to determine how variations in biomolecules affect mineral chemistry. In particular we will explore how biomolecules interact with other ions at the calcification site over a range of temperature to control mineral chemistry. We will calculate how relationships between coral skeleton and foraminifera test chemistry and seawater temperature have varied throughout time. By applying these calculations to fossils, we will optimise the accuracy of past seawater temperature estimates. We will also use advanced microscopy techniques to visualise the structure of the mineral precipitated under different conditions and to watch the formation of minerals in real time. These observations will help us to understand how variations in the calcification environment affect the incorporation of trace elements and isotopes in calcium carbonate.

Planned Impact

Our improved palaeoproxy calibrations will increase the accuracy of past seawater temperature for surface and deep ocean waters and ice volume estimates. These data will facilitate understanding of past climate by improving models which explore how interactions in the ocean and atmosphere drive climate change. Such models underpin our current predictions of the magnitude and geography of future climate change. Increasing the accuracy of these models enables us to plan for future climate change more efficiently.

Researchers studying biomineralisation and the impact of future changes in seawater temperature and pCO2 (ocean acidification) will benefit from our research which will demonstrate how biomolecules can facilitate or suppress calcium carbonate precipitation over different temperatures and pH. Understanding this aspect of biomineralisation is crucial to estimating the future behaviours of calcareous organisms which are of key economic importance e.g. shallow and deep water corals provide important habitat space for fisheries while bivalves are a food source. Approximately 1 in 6 people on the planet rely on coral reefs for their livelihoods and understanding the coral biomineralisation processes is fundamental for predicting their futures.

The UK government is committed to reducing UK greenhouse gas emissions by investing in low-carbon energy sources, improving fuel standards in cars and increasing energy efficiency wherever possible. Encouraging the general public to reduce their carbon footprint will be key to successfully implementing these greenhouse gas reductions. Raising awareness of the negative impacts of CO2 emissions at a local and global scale is an important component of this. Our research, exploring the relationships between temperature, pH and biocarbonate production, provides an excellent route to highlight the negative effects of increasing atmospheric CO2 (and ocean acidification) and to demonstrate their wider impacts e.g. reduction in coral reef production and associated loss of tourism income, coastal protection and fisheries, impacts on UK bivalve aquaculture etc. We will communicate our research to school children (through the University of St. Andrews Geobus) and to the general public through exhibits at Dundee Science Centre (Sensations) and the University of St. Andrews Science open day.

Publications

10 25 50
 
Description Coral skeletons and foraminifera tests form at specialist calcification sites, either in or adjacent to the organism. The calcification sites contain both soluble and insoluble organic biomolecules (e.g. proteins, lipids), which control and guide the precipitation and growth of the mineral. Our study has shown that the biomolecules which occur in coral skeletons can both accelerate and inhibit the precipitation of aragonite (the calcium carbonate mineral in the skeleton). These biomolecules also alter the morphology of the mineral crystals and may affect trace element content. Under ocean acidification conditions, the organic content of coral skeletons is increased but the concentration of biomolecules at the coral calcification site is unknown so it is unclear if this increases serves to promote or inhibit formation of the coral skeleton.
Exploitation Route The skeletal chemistry of marine organisms may record information on the local environmental conditions prevailing at the time of their deposition and the analysis of fossil specimens can be used to estimate past climate. Understanding how biomolecules influence the trace element and isotope chemistry of biominerals will enhance the accuracy of these estimates of past climate.
Sectors Environment

 
Description Emerging from lockdown grant: Do organic contaminants influence the formation of calcium carbonate structures in simulated biological environments
Amount £1,500 (GBP)
Organisation Marine Alliance for Science and Technology for Scotland 
Sector Academic/University
Country United Kingdom
Start 06/2021 
End 11/2021
 
Description Groundtruthing the d11B pH proxy in coral aragonite
Amount £36,000 (GBP)
Funding ID IMF689/0519 
Organisation Natural Environment Research Council 
Sector Public
Country United Kingdom
Start 12/2020 
End 12/2021
 
Description NERC Discipline Hopping for Discovery Science Fund: How do biomolecules alter the material properties of biominerals?
Amount £21,131 (GBP)
Organisation Natural Environment Research Council 
Sector Public
Country United Kingdom
Start 01/2023 
End 03/2023
 
Description St Leonards Global leading PhD scholarship
Amount £100,000 (GBP)
Organisation University of St Andrews 
Sector Academic/University
Country United Kingdom
Start 10/2022 
End 03/2026
 
Description St Leonards World leading PhD scholarship, The role of lipids in coral biomineralisation
Amount £100,000 (GBP)
Organisation University of St Andrews 
Sector Academic/University
Country United Kingdom
Start 09/2020 
End 03/2024
 
Description Article on chiral amino acid analysis for Chemistry World, Mar 2020 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Article on chiral amino acid analysis and its importance for understanding the past; Chemistry World, Mar 2020
Year(s) Of Engagement Activity 2020
URL https://www.chemistryworld.com/news/unlocking-geological-time-capsules-with-analytical-chemistry/401...
 
Description Contributer to 'Dive In- Protecting our Oceans' exhibition at the Wardlaw Museum, St. Andrews 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Public/other audiences
Results and Impact This exhibition ran for 4 months and highlighted stressors in the marine environment and how these could be reduced by individuals decision making.
Year(s) Of Engagement Activity 2021,2022
URL https://divein.wp.st-andrews.ac.uk/?msclkid=11c6e22da5d811eca909bfdeea0451f7
 
Description Departmental seminar - Aberystwyth University 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Professional Practitioners
Results and Impact Departmental seminar at Aberystwyth University
Year(s) Of Engagement Activity 2020
 
Description Departmental seminar - University of Oxford 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Professional Practitioners
Results and Impact Departmental seminar at the University of Oxford
Year(s) Of Engagement Activity 2021
 
Description Dundee Science Festival 2020 
Form Of Engagement Activity Engagement focused website, blog or social media channel
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact An online video demonstration of how corals build skeletons and how this is affected by ocean acidification
Year(s) Of Engagement Activity 2020
URL https://www.dundeesciencefestival.org/corals-and-ocean-acidification.html
 
Description Mapping Ocean Change workshop 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Public/other audiences
Results and Impact Guided walk for 25 people collecting intertidal organisms and follow up microscope session discussing impacts of seawater temperature rise and ocean acidification on marine organisms.
Year(s) Of Engagement Activity 2022
URL https://www.mappingoceanchange.org/events/mapping-ocean-change-workshop-scottish-oceans-institute
 
Description Meet the 2020 Blavatnik Award UK Chemistry Honorees youtube video 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact A youtube video about the winners of the 2020 Blavatnik chemistry honorees. The video feactures a section on Kirsty Penkman's research.
Year(s) Of Engagement Activity 2020
URL https://www.youtube.com/watch?v=_iX_AqNxMNU
 
Description Poster at INQUA conference, Dublin, July 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Poster Presentation at the 2019 INQUA (International Quaternary) congress, Dublin. Details:
Kirsty Penkman, Beatrice Demarchi, Molly Crisp, Peter Tomiak, Marc Dickinson, Lucy Wheeler, Martina Conti & Sheila Taylor, 2019. Through the Looking-Glass, and What Amino Acids Found There. INQUA 2019 Congress, Dublin, Ireland.
Year(s) Of Engagement Activity 2019
URL http://www.inqua2019.org/
 
Description Prepared and contributed specimens to Chaos Terrain sculpture by Ilana Halperin 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Public/other audiences
Results and Impact I prepared and contributed pieces of coral to a sculpture by Ilana Halperin which is now displayed in the Bute Building at the University of St. Andrews. The sculpture was unveiled during an event for ~ 30 people and is now on permanent display.
Year(s) Of Engagement Activity 2022
URL https://museumblog.wp.st-andrews.ac.uk/2022/11/09/marble-preservation-society/
 
Description School visit (Madras High school, St. Andrews) 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact We held workships on climate change and ocean acidifcation for S1 pupils (ages 12-13) at the local high school. Pupils discussed the causes and consequences of climate change and reported that they felt better informed after the workshops.
Year(s) Of Engagement Activity 2020
 
Description Talk at QRA conference, Leeds, 2020 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Keynote presentation at the QRA Annual Discussion Meeting, Leeds, 2020. Details:
Kirsty Penkman, 2020. Through the Looking-Glass, and What Amino Acids Found There. QRA Annual Discussion Meeting, Leeds, 2020
Year(s) Of Engagement Activity 2020
URL https://qraleeds2020.com/
 
Description Talk at University Open Day, Sep 2019 
Form Of Engagement Activity Engagement focused website, blog or social media channel
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Schools
Results and Impact Research talk at University of York Open Day, showcasing inter-disciplinary science.
Year(s) Of Engagement Activity 2019
 
Description Talk for Manchester Literary & Philosophical Society 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact Talk given to a scientific society; sparked questions & discussions afterwards.
Year(s) Of Engagement Activity 2022
URL https://www.manlitphil.ac.uk/resources/summer-2022-programme