skip to main content


Title: Using Stable Carbon Isotopes to Quantify Radiocarbon Reservoir Age Offsets in the Coastal Black Sea
Abstract Constraining radiocarbon ( 14 C) reservoir age offsets is critical to deriving accurate calendar-age chronologies from 14 C dating of materials which did not draw carbon directly from the atmosphere. The application of 14 C dating to such materials is severely limited in hydrologically sensitive environments like the Black Sea because of the difficulty to quantify reservoir age offsets, which can vary quickly and significantly through time, due to the dynamics of the biogeochemical cycling of carbon. Here we reconstruct 14 C reservoir age offsets (R shell-atm ) of Holocene bivalve shells from the coastal Black Sea relatively to their contemporaneous atmosphere. We show that the 14 C reservoir age offset and the stable carbon isotope composition of bivalve shells are linearly correlated in this region. From a biogeochemical standpoint, this suggests that inorganic stable carbon isotope and 14 C compositions of Black Sea coastal waters are controlled by the balance between autochthonous primary productivity and heterotrophic respiration of allochthonous pre-aged terrestrial organic matter supplied by rivers. This provided an important implication for Black Sea geochronology as the reservoir age offset of 14 C-dated bivalve shell can be inferred from its stable carbon isotope composition. Our results provide a fundamental and inexpensive geochemical tool which will considerably improve the accuracy of Holocene calendar age chronologies in the Black Sea.  more » « less
Award ID(s):
1755125
NSF-PAR ID:
10088647
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Radiocarbon
Volume:
61
Issue:
1
ISSN:
0033-8222
Page Range / eLocation ID:
309 to 318
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. A 2,000 year-long oceanographic history, in sub-centennial resolution, from a Canadian Beaufort Sea continental shelf site (60meters water depth) near the Mackenzie River outlet is reconstructed from ostracode and foraminifera faunal assemblages, shell stable isotopes (delta 18O, delta 13C) and sediment biogenic silica. The chronology of three sediment cores making up the composite section was established using 137Cs and 210Pb dating for the most recent 150 years and combined with linear interpolation of radiocarbon dates from bivalve shells and foraminifera tests.Continuous centimeter-sampling of the multicore and high-resolution sampling of a gravity and piston core yielded a time-averaged faunal record of every approximately 40 years from 0 to 1850 CE and every approximately 24 years from 1850 to 2013 CE. Proxy records were consistent with temperature oscillations and related changes in organic carbon cycling associated with the Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA). Abundance changes in dominant microfossil species, such as the ostracode Paracyprideis pseudopunctillata and agglutinated foraminifers Spiroplectammina biformis and S. earlandi, are used as indicators of less saline, and possibly corrosive/turbid bottom conditions associated with the MCA (approximately 800 to 1200 CE) and the most recent approximately 60 years (1950–2013). During these periods, pronounced fluctuations in these species suggest that prolonged seasonal sea-ice melting, changes in riverine inputs and sediment dynamics affected the benthic environment. Taxa analyzed for stable oxygen isotope composition of carbonates show the lowest delta 18O values during intervals within the MCA and the highest during the late LIA, which is consistent with a 1 degree to 2 degree C cooling of bottom waters. Faunal and isotopic changes during the cooler LIA (1300 to 1850 CE) are most apparent at approximately 1500 to 1850 CE and are particularly pronounced during 1850 to approximately 1900 CE, with an approximate 0.5 per mil increase in delta 18O values of carbonates from median values in the analyzed taxa. This very cold 50-year period suggests that enhanced summer sea ice suppressed productivity,which is indicated by low sediment biogenic silica values and lower delta 13C values in analyzed species. From 1900CE to present, declines in calcareous faunal assemblages and changes in dominant species (Cassidulina reniforme and P. pseudopunctillata) are associated with less hospitable bottom waters, indicated by a peak in agglutinated foraminifera from 1950 to 1990 CE.

     
    more » « less
  2. ABSTRACT The radiocarbon ( 14 C) content of simultaneously deposited substrates in lacustrine archives may differ due to reservoir and detrital effects, complicating the development of age models and interpretation of proxy records. Multi-substrate 14 C studies quantifying these effects remain rare, however, particularly for large, terminal lake systems, which are excellent recorders of regional hydroclimate change. We report 14 C ages of carbonates, brine shrimp cysts, algal mat biomass, total organic carbon (TOC), terrestrial macrofossils, and n -alkane biomarkers from Holocene sediments of the Great Salt Lake (GSL), Utah. 14 C ages for co-deposited aquatic organic substrates are generally consistent, with small offsets that may reflect variable terrestrial organic matter inputs to the system. Carbonates and long-chain n -alkanes derived from vascular plants, however, are ∼1000–4000 14 C years older than other substrates, reflecting deposition of pre-aged detrital materials. All lacustrine substrates are 14 C-depleted compared to terrestrial macrofossils, suggesting that the reservoir age of the GSL was > 1200 years throughout most of the Holocene, far greater than the modern reservoir age of the lake (∼300 years). These results suggest good potential for multi-substrate paleoenvironmental reconstruction from Holocene GSL sediments but point to limitations including reservoir-induced uncertainty in 14 C chronologies and attenuation and time-shifting of some proxy signals due to detrital effects. 
    more » « less
  3. Stable isotope proxies measured in the proteinaceous fraction of archaeological mollusc shell represents an increasingly important archive for reconstructing past ecological and biogeochemical conditions of nearshore environments. A major issue, however, is understanding the impact of diagenetic alteration in sub-fossil shell isotope values. “Bulk” stable isotope values of nitrogen (δ15N), and especially carbon (δ13C) often shift strongly with increasing C/N ratios in degraded shell, resulting in unreliable data. Here, we examine preservation of an entirely new set of shell paleo-proxies, compound-specific isotopes of amino acids (CSI-AA). We examine carbon (δ13CAA) and nitrogen (δ15NAA) patterns and values from the organic fraction of California mussel (Mytilus californianus) shells from the California Channel Islands. Archaeological shell samples ranging in age from ca. 6,100 to 250 cal BP exhibiting a wide range of degradation states were collected from varied depositional environments (e.g., exposed coastal bluff, buried strata, etc.), and were directly compared to modern shells of the same species and region. Our results indicate organic matter C/N ratios as the best bulk diagnostic indicator of the relative degradation state of shell organic fraction, including changes at the molecular level. Modern shell organic C/N ratios ranged from 2.8 to 3.5, while those in archaeological shell were substantially elevated (3.4–9.5), exhibiting strong and significant negative correlations with bulk δ13C values, weight %C, and weight %N, and a significant but weaker correlation with δ15 N values. An additional “cleaning” step using weak NaOH helped to remove possible exogenous contaminants and improved bulk values of some samples. However, relative molar AA abundances revealed that some AAs, especially the two most abundant, Glycine and Alanine, progressively decreased with increasing C/N ratio. The loss of these amino acids permanently alters bulk isotope values regardless of removal of contaminants. Modeling the bulk isotope change expected due to amino acid molar composition showed major and predictable shifts in bulk δ13C values from selected AA loss, and similarly large but far more variable impacts from exogenous contaminants. In contrast to bulk data, key CSI-AA values and patterns remained almost entirely unaltered, even in the most degraded shell samples, closely matching expected biosynthetic isotope patterns in modern mussel shell. AA isotope proxies for “baseline” (δ15N-Phenylalanine and average δ13C-Essential AAs) and planktonic trophic structure (δ15N-Glutamic Acid and δ15N-Phenylalanine) were not statistically altered with degradation in any sample. Overall, we conclude that while bulk isotopes, particularly δ13C, are very likely to be unreliable in archaeological or subfossil shell with C/N ratios higher than ∼4.0, CSI-AA proxies can still be used to reconstruct past climatic and ecological conditions of the nearshore marine environment. 
    more » « less
  4. ABSTRACT Radiocarbon (14C) ages cannot provide absolutely dated chronologies for archaeological or paleoenvironmental studies directly but must be converted to calendar age equivalents using a calibration curve compensating for fluctuations in atmospheric 14C concentration. Although calibration curves are constructed from independently dated archives, they invariably require revision as new data become available and our understanding of the Earth system improves. In this volume the international 14C calibration curves for both the Northern and Southern Hemispheres, as well as for the ocean surface layer, have been updated to include a wealth of new data and extended to 55,000 cal BP. Based on tree rings, IntCal20 now extends as a fully atmospheric record to ca. 13,900 cal BP. For the older part of the timescale, IntCal20 comprises statistically integrated evidence from floating tree-ring chronologies, lacustrine and marine sediments, speleothems, and corals. We utilized improved evaluation of the timescales and location variable 14C offsets from the atmosphere (reservoir age, dead carbon fraction) for each dataset. New statistical methods have refined the structure of the calibration curves while maintaining a robust treatment of uncertainties in the 14C ages, the calendar ages and other corrections. The inclusion of modeled marine reservoir ages derived from a three-dimensional ocean circulation model has allowed us to apply more appropriate reservoir corrections to the marine 14C data rather than the previous use of constant regional offsets from the atmosphere. Here we provide an overview of the new and revised datasets and the associated methods used for the construction of the IntCal20 curve and explore potential regional offsets for tree-ring data. We discuss the main differences with respect to the previous calibration curve, IntCal13, and some of the implications for archaeology and geosciences ranging from the recent past to the time of the extinction of the Neanderthals. 
    more » « less
  5. We compiled a database of previously published oxygen and carbon isotope data from archaeological, archival, and modern marine molluscs from the North American coast of the Northeast Pacific (32oN to 50oN). This database includes oxygen and carbon isotope data from over 550 modern, archaeological, and sub-fossil shells from 8880 years before present (BP) to the present, from which there are 4,845 total δ¹³C and 5,071 total δ¹⁸O measurements. Database includes the following parameters: paper of original publication, publication year, unique shell identification, unique subsample identification, sample number (given by original authors), subsample number (given by original author), number of subsamples per shell (added here), age in years before present, species, source (midden or modern), latitude, longitude, calculated sea surface temperature (only if published by original authors), tidal height, life mode, habitat, archaeological trinomial (when applicable), oxygen isotope value, and carbon isotope value. Shell dating and sampling strategies vary among studies (1-118 samples per shell) and vary significantly by journal discipline. Data are from various bivalves and gastropod species, with Mytilus spp. being the most commonly analyzed taxon. This novel database can be used to investigate changes in nearshore sea surface conditions including warm-cool oscillations, heat waves, and upwelling intensity, and provides nearshore calcite δ¹³C and δ¹⁸O values that can be compared to the vast collections of offshore foraminifera calcite δ¹³C and δ¹⁸O data from marine sediment cores. By utilizing previously published geochemical data from midden and museum shells rather than sampling new specimens, future scientific research can reduce or omit the alteration or destruction of culturally valued specimens and sites. 
    more » « less