The North Atlantic marine reservoir effect in the early Holocene: implications for defining and understanding MRE values

The marine reservoir effect (MRE) is a <sup>14</sup>C age offset between the oceanic and atmospheric carbon reservoirs. The MRE is neither spatially nor temporally constant and values may deviate significantly from the global model average provided by the Marine04 curve. Such a deviation is calculated as a ©R value and modern (pre-bomb) values show considerable spatial variations. There is also considerable evidence for temporal variability linked to paleoenvironmental changes identified in paleoclimatic proxy records. Seven new ©R values are presented for the North Atlantic, relating to the period c. 8430 3890 cal. BP (c. 6480 1940 BC). These were obtained from <sup>14</sup>C analysis of multiple samples of terrestrial and marine material derived from seven individual archaeological deposits from Mainland Scotland, the Outer Hebrides and the Orkney Isles. The ©R values vary between 143 ± 20 14C yr and ‑100 ± 15 <sup>14</sup>C yr with the positive values all occurring in the earlier period (8430 5060 cal. BP), and the negative values all coming from later deposits (4820 3890 cal. BP). The nature of MRE values and the potential for spatial and temporal variation in values is the subject of current research interest and these data are placed in the context of (i) other estimates for UK coastal waters and (ii) important questions concerning current approaches to quantifying the MRE

Spatial variation in the MRE throughout the Scottish Post-Roman to late Medieval period: North Sea values (500-1350 BP)

The marine radiocarbon reservoir effect (MRE) occurs as a spatially and temporally dependent variable owing to localized changes in oceanic water composition. This study investigates ΔR values (deviations from the global average MRE whose ΔR = 0) during the period 500–1350 BP for the east coast of Scotland, where a complex estuarine system exists that drains into the semi-enclosed North Sea basin. Due to the availability of suitable archaeological samples, the data set has a distinct Medieval focus that spans the area from Aberdeen in the north to East Lothian in the south. Many of the ΔR values are not significantly different from 0 (the global average), but there are occasional excursions to negative values (max –172 ± 20) indicating the presence of younger water. These values show greater variability compared to other published data for this general region, suggesting that considerable care must be taken when dating marine derived samples from archaeological sites on the east coast of Scotland

Influence of mollusk species on marine DELTA R determinations

Radiocarbon ages were measured on replicate samples of burnt grain and 5 mollusk species collected from a single sealed layer at an archaeological site (Hornish Point) on the west coast of South Uist, Scotland. The aim was to examine the impact of using different mollusk species on ΔR determinations that are calculated using the paired terrestrial/marine sample approach. The mollusk species examined inhabit a range of environments and utilize a variety of food sources within the intertidal zone. Several authors have suggested that these factors may be responsible for observed variations in the 14C activity of mollusk shells that were contemporaneous in a single location. This study found no significant variation in the <sup>14</sup>C ages of the mollusk species, and consequently, no significant variation in calculated values of ΔR. The implication is that in an area where there are no carboniferous rocks or significant local inputs of freshwater to the surface ocean, any of a range of marine mollusk species can be used in combination with short-lived terrestrial material from the same secure archaeological context to accurately determine a ΔR value for a particular geographic location and period in time

Assessment of oxygen plasma ashing as a pre-treatment for radiocarbon dating

This study investigates the potential of low-temperature oxygen plasma ashing as a technique for decontaminating charcoal and wood samples prior to radiocarbon dating. Plasma ashing is demonstrated to be rapid, controllable and surface-specific, and clear differences are identified in the rate of ashing in different organic materials. However, the ability of plasma ashing to selectively remove these different components is limited in heterogeneous sample matrices. This is because oxidation is confined to the immediate sample surface. Comparison of radiocarbon dates obtained from identical aliquots of contaminated ancient charcoal pre-treated by acid-base-acid (ABA), acid-base-oxidation-stepped combustion (ABOx-SC) and plasma ashing suggests that the technique performs as well as the ABA pre-treatment but does not remove as much contamination as the ABOx-SC technique. Plasma-ashing may be particularly useful in cases where sample size is limiting

Radiocarbon analysis of methane at the NERC Radiocarbon Facility (East Kilbride)

Methane is the second most important anthropogenically produced greenhouse gas, and radiocarbon (14C) analysis is extremely valuable in identifying its age and source in the environment. At the NERC Radiocarbon Facility (East Kilbride, UK) we have developed expertise in analysis of methane 14C concentration and methodological approaches to field sampling over the past 20 years. This has opened a wide range of applications, which have mainly focused on (1) the age and source of methane emitted by peatlands and organic soils (e.g. to quantify the release of ancient carbon), (2) the source of aquatic emissions of methane, and (3) the age of methane generated by amenity and illegal landfill. Many of these scientifically important applications involve challenging sampling and measurement considerations, which our development program has continually aimed to overcome. Here, we describe our current methods, and recent improvements to aid field collection of samples in remote locations. We present the results of tests which (1) show the effectiveness of our methods to remove contaminants, especially CO2, (2) quantify the 14C background contribution, and (3) demonstrate the reliability of metal gas storage canisters for sample storage

North Atlantic marine ¹⁴C reservoir effects: implications for late-Holocene chronological studies

We investigated surface ocean–atmosphere 14C offsets for the later Holocene at eight locations in the eastern North Atlantic. This resulted in 11 new ΔR assessments for the west coast of Ireland, the Outer Hebrides, the north coast of the Scottish mainland, the Orkney Isles and the Shetland Isles over the period 1300–500 BP. Assessments were made using a robust Multiple Paired Sample (MPS) approach, which is designed to maximize the accuracy of ΔR determinations. Assessments are placed in context with other available data to enable reconstruction of a realistic picture of surface ocean 14C activity over the Holocene period within the North Atlantic region

Stable isotopes of subfossil bat guano as a long-term environmental archive: insights from a Grand Canyon cave deposit

We investigated the utility of subfossil bat guano as a paleoenvironmental archive by comparing elemental ratios and d13C, d15N, and dD values of various simple extracts from bulk material. Solvent-extracted guano yielded consistent C:N and N:H ratios, and d13C values of solvent-extracted guano exhibited strong covariation with dD values, as well as with the d13C values of other simple extracts (bulk guano, bulk lipid). The results suggest that reliable records are easily recovered for d13C, and also indicate that d15N values may have utility as a paleoenvironmental archive. Despite coeval d13C values of bulk guano and solvent-extracted guano, 14C ages of the different fractions did not always yield similar ages, indicating that future refinement of a suitable extraction protocol is required. Applying these protocols to an ancient bat guano deposit allowed us to infer that climate at the Grand Canyon during the late Pleistocene was more variable and generally cooler and wetter, relative to Holocene climate. We conclude that guano deposits are an underutilized, yet powerful continental paleoenvironmental archive of climate change for semi-arid and tropical regions

Reservoirs and radiocarbon: ¹⁴C dating problems in Myvatnssveit, Northern Iceland

This paper examines 2 potential sources of the radiocarbon offset between human and terrestrial mammal (horse) bones recovered from Norse (~AD 870–1000) pagan graves in Mývatnssveit, north Iceland. These are the marine and freshwater 14C reservoir effects that may be incorporated into human bones from dietary sources. The size of the marine 14C reservoir effect (MRE) during the Norse period was investigated by measurement of multiple paired samples (terrestrial mammal and marine mollusk shell) at 2 archaeological sites in Mývatnssveit and 1 site on the north Icelandic coast. These produced 3 new ΔR values for the north coast of Iceland, indicating a ΔR of 106 ± 10 14C yr at AD 868–985, and of 144 ± 28 14C yr at AD 1280–1400. These values are statistically comparable and give an overall weighted mean ΔR of 111 ± 10 14C yr. The freshwater reservoir effect was similarly quantified using freshwater fish bones from a site in Mývatnssveit. These show an offset of between 1285 and 1830 14C yr, where the fish are depleted in 14C relative to the terrestrial mammals. This is attributed to the input of geothermally derived CO2 into the groundwater and subsequently into Lake Mývatn. We conclude the following: i) some of the Norse inhabitants of Mývatnssveit incorporated non-terrestrial resources into their diet that may be identified from the stable isotope composition of their bone collagen; ii) the MRE off the north Icelandic coast during the Norse period fits a spatial gradient of wider North Atlantic MRE values with increasing values to the northwest; and iii) it is important to consider the effect that geothermal activity could have on the 14C activity of samples influenced by groundwater at Icelandic archaeological sites

Temporal and spatial variations in freshwater 14C reservoir effects: Lake Myvatn, Northern Iceland

Lake Mývatn is an interior highland lake in northern Iceland that forms a unique ecosystem of international scientific importance and is surrounded by a landscape rich in archaeological and palaeoenvironmental sites. A significant Freshwater 14C Reservoir Effect (FRE) has been identified in carbon from the lake at some Norse (c.870-1000 AD) archaeological sites in the wider region (Mývatnssveit). Previous AMS measurements indicated this FRE was ~1500-1900 14C years. Here we present the results of a study using stable isotope and 14C measurements to quantify the Mývatn FRE for both the Norse and modern periods. This work has identified a temporally variable FRE that is greatly in excess of previous assessments. New, paired samples of contemporaneous bone from terrestrial herbivores and omnivores (including humans) from Norse sites demonstrate at least some omnivore diets incorporated sufficient freshwater resources to result in a herbivore-omnivore age offset of up to 400 14C yrs. Modern samples of benthic detritus, aquatic plants, zooplankton, invertebrates and freshwater fish indicate an FRE in excess of 5000 14C yrs in some species. Likely geothermal mechanisms for this large FRE are discussed, along with implications for both chronological reconstruction and integrated investigation of stable and radioactive isotop

Variability in oxidative degradation of charcoal: influence of production variables and environmental exposure

<p>Charcoal is a key component of the Black Carbon (BC) continuum, where BC is characterized as a recalcitrant, fire-derived, polyaromatic material. Charcoal is an important source of palaeoenvironmental data, and of great interest as a potential carbon sink, due to its high apparent environmental stability. However, at least some forms of charcoal are clearly susceptible to environmental alteration and degradation over relatively short timescales. Although these processes have importance for the role of charcoal in global biogeochemistry, they remain poorly understood.</p> <p>Here we present results of an investigation into the susceptibility of a range of charcoal samples to oxidative degradation in acidified potassium dichromate. The study examines both freshly-produced charcoal, and charcoal exposed to environmental conditions for up to 50,000 years. We compare the proportion of carbon present in different forms between the samples, specifically with respect to the relative chemical resistance of these forms. This was undertaken in order to improve understanding of the post-depositional diagenetic changes affecting charcoal within environmental deposits.</p> <p>A wide range in chemical compositions are apparent both within and between the sample groups. In freshly-produced charcoal, material produced at 300 °C contains carbon with more labile forms than charcoal produced at ≥400 °C, signifying a key chemical change over the 300–400 °C temperature range. Charcoal exposed to environmental depositional conditions is frequently composed of a highly carboxylated aromatic structure and contains a range of carbon fractions of varying oxidative resistance. These findings suggest that a significant number of the environmental charcoals have undergone post-depositional diagenetic alteration. Further, the data highlight the potential for the use of controlled progressive oxidative degradation as a method to characterize chemical differences between individual charcoal samples.</p&gt