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Radiocarbon Dating of Marine Samples: Methodological Aspects, Applications and Case Studies

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Radiocarbon Dating of Marine Samples: Methodological Aspects, Applications and Case Studies water Article Radiocarbon Dating of Marine Samples: Methodological Aspects, Applications and Case Studies Gianluca Quarta 1,* , Lucio Maruccio 2, Marisa D’Elia 2 and Lucio Calcagnile 1 1 CEDAD (Centre for Applied Physics, Dating and Diagnostics), Department of Mathematics and Physics, “Ennio De Giorgi”, University of Salento, INFN-Lecce Section, 73100 Lecce, Italy; [email protected] 2 CEDAD (Centre for Applied Physics, Dating and Diagnostics), Department of Mathematics and Physics, “Ennio De Giorgi”, University of Salento, 73100 Lecce, Italy; [email protected] (L.M.); [email protected] (M.D.) * Correspondence: [email protected] Abstract: Radiocarbon dating by AMS (Accelerator Mass Spectrometry) is a well-established absolute dating technique widely used in different areas of research for the analysis of a wide range of organic materials. Precision levels of the order of 0.2–0.3% in the measured age are nowadays achieved while several international intercomparison exercises have shown the high degree of reproducibility of the results. This paper discusses the applications of 14C dating related to the analysis of samples up-taking carbon from marine carbon pools such as the sea and the oceans. For this kind of samples relevant methodological issues have to be properly addressed in order to correctly interpret 14C data and then obtain reliable chronological frameworks. These issues are mainly related to the so-called “marine reservoirs effects” which make radiocarbon ages obtained on marine organisms apparently older than coeval organisms fixing carbon directly from the atmosphere. We present the strategies used to correct for these effects also referring to the last internationally accepted and recently released Citation: Quarta, G.; Maruccio, L.; calibration curve. Applications will be also reviewed discussing case studies such as the analysis of D’Elia, M.; Calcagnile, L. Radiocarbon marine biogenic speleothems and for applications in sea level studies. Dating of Marine Samples: Methodological Aspects, Applications Keywords: radiocarbon dating; Accelerator Mass Spectrometry; marine environment and Case Studies. Water 2021, 13, 986. https://doi.org/10.3390/w13070986 Academic Editor: Hong Yang 1. Introduction Radiocarbon dating is a well-established and mature absolute dating method widely Received: 9 March 2021 applied in different research fields spanning from Archaeological sciences, to Earth, Ma- Accepted: 1 April 2021 rine and Life sciences. In the last years important methodological advancements such as Published: 3 April 2021 those related to refined data analysis and calibration procedures and, at the same time, the development of new dedicated, high precision and throughput, compact instruments Publisher’s Note: MDPI stays neutral significantly enhanced the impact of this method in different fields. Nowadays advanced with regard to jurisdictional claims in statistical tools, mainly based on Bayesian approaches, are routinely used for the anal- published maps and institutional affil- ysis of sets of radiocarbon data in different fields while precision levels of 0.2–0.3% are iations. routinely achieved, corresponding to uncertainties of ±20/30 years on radiocarbon age determinations. In marine sciences radiocarbon dating is widely and routinely used in different areas such as the analysis of sedimentary records for climate or ecology studies, of corals and bio-constructions for the reconstruction of the calibration curve, of water for Copyright: © 2021 by the authors. ocean circulation modelling, of marine samples (fossil fish and shells) for coastal geomor- Licensee MDPI, Basel, Switzerland. phology and sea-level variation studies. In this paper we will briefly review the basics This article is an open access article of AMS (Accelerator Mass Spectrometry) radiocarbon dating in particular discussing the distributed under the terms and specific issues associated with the analysis of marine samples such as, mainly, the so-called conditions of the Creative Commons Attribution (CC BY) license (https:// marine-reservoir effect. Different case studies will be also presented in different application creativecommons.org/licenses/by/ fields spanning from the study of the evolution of marine bioconstructions and sea-level 4.0/). rise studies using different types of sea-level indicators. Aim of the paper is then to give Water 2021, 13, 986. https://doi.org/10.3390/w13070986 https://www.mdpi.com/journal/water Water 2021, 13, 986 2 of 10 Water 2021, 13, x FOR PEER REVIEW 2 of 11 an overview of the specificities connected with the use of radiocarbon dating of marine rise studies using different types of sea-level indicators. Aim of the paper is then to give samples, discussing the relevant advantages and drawbacks of the method in this field. an overview of the specificities connected with the use of radiocarbon dating of marine 2.samples, AMS Radiocarbon discussing the Dating relevant advantages and drawbacks of the method in this field. Radiocarbon (14C) is the radioactive isotope of carbon which exists in nature also in 2. AMS Radiocarbon Dating the two stable isotopic form of 12C and 13C. Radiocarbon is a cosmogenic nuclide produced in theRadiocarbon upper terrestrial (14C) atmosphere is the radioactive trough theisotope interaction of carbon of secondary which exists neutrons, in nature produced also in bythe cosmic two stable rays, isotopic with the form atmospheric of 12C and nitrogen: 13C. Radiocarbon is a cosmogenic nuclide produced in the upper terrestrial atmosphere trough the interaction of secondary neutrons, pro- 14 14 duced by cosmic rays, with the atmospheric7 N + n ! nitrogen:6 C + p − − Through this nuclear reaction 2.02 atoms→ cm 2 s 1 of 14C atoms are continuously pro- duced [1]. When produced 14C is oxidised by O and OH atmospheric molecules to 14CO Through this nuclear reaction 2.02 atoms 2cm−2 s−1 of 14C atoms are continuously pro-2 entering, trough different mechanisms14 and following the same bio-chemical pathways14 as duced [1].12 When produced13 C is oxidised by O2 and OH atmospheric molecules to CO2 the “light” CO2 and CO2 molecules, the different terrestrial carbon pools. For terrestrial entering, trough14 different mechanisms and following the same bio-chemical pathways as organisms CO2 is fixed from the atmosphere either directly through photosynthesis or the “light” 12CO2 and 13CO2 molecules, the different terrestrial carbon pools. For terrestrial indirectly through the food chain. Marine organisms fix (radio)carbon from the marine pool organisms 14CO2 is fixed from the atmosphere either directly through photosynthesis or where it is dissolved from the atmosphere (Figure1). In this way all the living organisms indirectly through the food chain. Marine organisms fix (radio)carbon from the marine exhibit a 14C concentration in their tissues mirroring the concentration in the reservoir they pool where it is dissolved from the atmosphere (Figure 1). In this way all the living organ- are in equilibrium with (such as the atmosphere or the sea). When an organism dies the isms exhibit a 14C concentration in their tissues mirroring the concentration in the reservoir uptake of radiocarbon from the reservoir ceases and the 14C, β-decaying to14N: they are in equilibrium with (such as the atmosphere or the sea). When an organism dies the uptake of radiocarbon from the14 reservoir14 ceases− and the 14C, β-decaying to14N: 6 C ! 7 N + e + n → ̅ is not compensated by the uptake from the environment. Its concentration starts to decrease 14 byis followingnot compensated the well-known by the uptake radioactive from exponential the environment. decay law. Its concentration If we then express starts the to de-C concentration in a sample, relative to the constant concentration of 12C, we can write the crease by following the well-known radioactive exponential decay law. If we then express 14C 14the 1214C concentration in a sample, relative to the constant concentration6 of 12C, we can C/ C isotopic ratio in sample at the time t after the death 12 as: 6 C write the 14C/12C isotopic ratio in sample at the time t after the deatht as: ! ! 14C 14C − (ln 2) × t 6 = 6 e t1/2 12 12 C C / 6 t 6 0 14C 6 wherewhere 12 indicates thethe isotopicisotopic ratioratio atatthe the time time of of death death and andt1/2 t1/2is is the the radiocarbon radiocarbon 6C 0 half-lifehalf-life of of 5700 5700± ± 3030 yearsyears [[2].2]. FigureFigure 1. 1. SchematicSchematic representation of the the mechanism mechanism un underlyingderlying the the uptake uptake of of carbon carbon from from ma- ma- rinerine organisms. organisms. Water 2021, 13, x FOR PEER REVIEW 3 of 11 Water 2021, 13, 986 3 of 10 By reversing this equation one can then calculate, assuming that the isotopic ratios and are known, the time elapsed since the death of the organisms [3]. The By reversing this equation one can then calculate, assuming that the isotopic ratios principle14C of the14C method is then simple though, as we will discuss in the following, the 6 and 6 are known, the time elapsed since the death of the organisms [3]. The 12C 12C estimation6 t and6 the0 measurement of these two quantities rises important issues. principle of the method is then simple though, as we will discuss in the following, the estimation2.1. Instrumental and the measurement of these two quantities rises important issues. 2.1. Instrumental 14 12 The term represents the ratio between the C and the C concentrations in 14C The term 6 represents the ratio between the 14C and the 12C concentrations in the sample to be12C dated. The complexity of the experimental approaches needed to meas- 6 t theure sample this term to be is dated.related The to complexitythe low natural of the abundance experimental of approaches 14C (in a modern needed tosample measure the 14C/12C thisratio term is of is the related order to theof 10 low−12 natural) which abundance requires an of 14extremelyC (in a modern high samplesensitivity the 14 analyticalC/12C tech- rationique.
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