A period of calm in Scottish seas: a comprehensive study of ΔR values for the northern British Isles coast and the consequent implications for archaeology and oceanography

The Marine Radiocarbon Reservoir Effect (MRE) is a 14C age offset between contemporaneous marine- and terrestrially-derived carbon. In Northern Hemisphere surface waters it is of the order of 400 years but temporal and spatial deviations, known as ΔR, occur. This study provides a comprehensive dataset of 21 ΔR and MRE values for the east coast of Scotland and 21 recalculated values for the west coast of Scotland and Ireland, for the period c. 3500 BC to 1450 AD. They are presented as mean, site-specific ΔR and MRE values, together with their associated uncertainties, calculated as standard errors for predicted values. The ΔR values range from -320 ± 35 to +150 ± 28 14C years and show no spatial or temporal trends. The MRE values range from 59 ± 40 to 531 ± 26, show an almost identical distribution pattern to the ΔR values and again show no spatial or temporal trends. Results show that ΔR values calculated for a single site using statistically indistinguishable groups of terrestrial and marine radiocarbon age measurements can produce variability of up to 225 14C years. ΔR is an important factor in the accurate calibration of samples containing marine-derived carbon for archaeological interpretation but is often also used as an indicator of changes in 14C specific activity of the oceans, and therefore a proxy for changes in ocean circulation and/or climate. Using the methods outlined in this paper, it is apparent that ΔR values for the northern part of the British Isles have been relatively stable, within our ability to quantify non-random variation in the data. The fact that significant climatic shifts have been recorded during this time, yet these are not visible in the ΔR data, presents a cautionary tale regarding the use of ΔR to infer large-scale oceanographic or climatic changes. Upon the exclusion of 5 outliers from the 42 values, the remaining ΔR values are statistically indistinguishable from one another and range from -142 ± 61 to +40 ± 47 14C years. 34 of these values are from Scottish archaeological sites and can be combined to produce a mean value for Scotland of -47 ± 52 14C years for the period 3500 BC to 1450 AD, to be used only in the absence of site- and period-specific data

Advances in the radiocarbon analysis of carbon dioxide at the NERC radiocarbon facility (East Kilbride) using molecular sieve cartridges

Radiocarbon (14C) analysis of carbon dioxide (CO2) provides unique information on the age, turnover and source of this important greenhouse gas, raising the prospect of novel scientific investigations into a range of natural and anthropogenic processes. To achieve these measurements, cartridges containing zeolite molecular sieves are a reliable and convenient method for collecting CO2 samples. At the NERC Radiocarbon Facility (East Kilbride) we have been refining our molecular sieve methods for over twenty years to achieve high-quality, reproducible and precise measurements. At the same time, we have been developing novel field sampling methods to expand the possibilities in collecting gas from the atmosphere, soil respiration and aquatic environments. Here, we present our latest improvements to cartridge design and procedures. We provide the results of tests used to verify the methods using known 14C content standards, demonstrating reliability for sample volumes of 3 mL CO2 (STP; 1.6 mg C) collected in cartridges that had been prepared at least three months earlier. We also report the results of quality assurance standards processed over the last two years, with results for 22 out of 23 international 14C standards being within measurement uncertainty of consensus values. We describe our latest automated procedures for the preparation of cartridges prior to use

Holocene variations in the Scottish marine radiocarbon reservoir effect

We assessed the evidence for variations in the marine radiocarbon reservoir effect (MRE) at coastal, archaeological Iron Age sites in north and west Scotland by comparing AMS measurements of paired marine and terrestrial materials (4 pairs per context). DeltaR values were calculated from measurements on material from 3 sites using 6 sets of samples, all of which were deposited around 2000 BP. The weighted mean of the DeltaR determinations was -79 +/- 17 C-14 yr, which indicates a consistent, reduced offset between atmospheric and surface ocean C-14 specific activity for these sites during this period, relative to the present day (DeltaR = similar to0 C-14 yr). We discuss the significance of this revised AR correction by using the example of wheelhouse chronologies at Hornish Point and their development in relation to brochs. In addition, we assess the importance of using the concepts of MRE correction and AR variations when constructing chronologies using C-14 measurements made on materials that contain marine- derived carbon

Performance of the rebuilt SUERC single-stage accelerator mass spectrometer

The SUERC bipolar single-stage accelerator mass spectrometer (SSAMS) has been dismantled and rebuilt to accommodate an additional rotatable pre-accelerator electrostatic spherical analyser (ESA) and a second ion source injector. This is for the attachment of an experimental positive-ion electron cyclotron resonance (ECR) ion source in addition to a Cs-sputter source. The ESA significantly suppresses oxygen interference to radiocarbon detection, and remaining measurement interference is now thought to be from 13C injected as 13CH molecule scattering off the plates of a second original pre-detector ESA

8.2 ka event North Sea hydrography determined by bivalve shell stable isotope geochemistry

The abrupt 8.2 ka cold event has been widely described from Greenland and North Atlantic records. However, its expression in shelf seas is poorly documented, and the temporal resolution of most marine records is inadequate to precisely determine the chronology of major events. A robust hydrographical reconstruction can provide an insight on climatic reaction times to perturbations to the Atlantic Meridional Overturning Circulation. Here we present an annually-resolved temperature and water column stratification reconstruction based on stable isotope geochemistry of Arctica islandica shells from the Fladen Ground (northern North Sea) temporally coherent with Greenland ice core records. Our age model is based on a growth increment chronology obtained from four radiometrically-dated shells covering the 8290–8100 cal BP interval. Our results indicate that a sudden sea level rise (SSLR) event-driven column stratification occurred between ages 8320–8220 cal BP. Thirty years later, cold conditions inhibited water column stratification but an eventual incursion of sub-Arctic waters into the North Sea re-established density-driven stratification. The water temperatures reached their minimum of ~3.7 °C 55 years after the SSLR. Intermittently-mixed conditions were later established when the sub-Arctic waters receded

Deciphering diet and monitoring movement: multiple stable isotope analysis of the Viking Age settlement at Hofstaðir, Lake Mývatn, Iceland

Objectives: A previous multi-isotope study of archaeological faunal samples from Skútustaðir, an early Viking age settlement on the southern shores of Lake Mývatn in north-east Iceland, demonstrated that there are clear differences in δ34S stable isotope values between animals deriving their dietary protein from terrestrial, freshwater, and marine reservoirs. The aim of this study was to use this information to more accurately determine the diet of humans excavated from a nearby late Viking age churchyard. Materials and Methods: δ13C, δ15N, and δ34S analyses were undertaken on terrestrial animal (n = 39) and human (n = 46) bone collagen from Hofstaðir, a high-status Viking-period farmstead ∼10 km north-west of Skútustaðir. Results: δ34S values for Hofstaðir herbivores were ∼6‰ higher relative to those from Skútustaðir (δ34S: 11.4 ± 2.3‰ versus 5.6 ± 2.8‰), while human δ13C, δ15N, and δ34S values were broad ranging (−20.2‰ to −17.3‰, 7.4‰ to 12.3‰, and 5.5‰ to 14.9‰, respectively). Discussion: Results suggest that the baseline δ34S value for the Mývatn region is higher than previously predicted due to a possible sea-spray effect, but the massive deposition of Tanytarsus gracilentus (midges) (δ34S: −3.9‰) in the soil in the immediate vicinity of the lake is potentially lowering this value. Several terrestrial herbivores displayed higher bone collagen δ34S values than their contemporaries, suggesting trade and/or movement of animals to the region from coastal areas. Broad ranging δ13C, δ15N, and δ34S values for humans suggest the population were consuming varied diets, while outliers within the dataset could conceivably have been migrants to the area

Chemical characteristics of macroscopic pyrogenic carbon following millennial-scale environmental exposure

Pyrogenic Carbon (PyC) is ubiquitous in global environments, and is now known to form a significant, and dynamic component of the global carbon cycle, with at least some forms of PyC persisting in their depositional environment for many millennia. Despite this, the factors that determine the turnover of PyC remain poorly understood, as do the physical and chemical changes that this material undergoes when exposed to the environment over tens of thousands of years. Here, we present the results of an investigation to address these knowledge gaps through chemical and physical analysis of a suite of wood PyC samples exposed to the environment for varying time periods, to a maximum of >90,000 years. This includes an assessment of the quantity of resistant carbon, known as Stable Polyaromatic Carbon (SPAC) versus more chemically labile carbon in the samples. We find that, although production temperature is likely to determine the initial ‘degradation potential’ of PyC, an extended exposure to environmental conditions does not necessarily mean that remaining PyC always progresses to a ‘SPAC-dominant’ state. Instead, some ancient PyC can be composed largely of chemical components typically thought of as environmentally labile, and it is likely that the depositional environment drives the trajectory of preservation versus loss of PyC over time. This has important implications for the size of global PyC stocks, which may have been underestimated, and also for the potential loss of previously stored PyC, when its depositional environment alters through environmental or climatic changes

Dynamics of Charcoal Alteration in a Tropical Biome: A Biochar-Based Study

Pyrogenic carbon (PyC) is a polyaromatic residue of the incomplete combustion of biomass or fossil fuels. There is a growing recognition that PyC forms an important part of carbon budgets, due to production rates of 116–385 Tg C yr, and the size and ubiquity of PyC stocks in global carbon reservoirs. At least a proportion of PyC exists in a highly recalcitrant chemical form, raising the prospect of long-term carbon sequestration through soil amendment with “biochar,” which is generally produced with the aim of making a particularly recalcitrant form of PyC. However, there is growing evidence that some PyC, including biochar, can be both physically and chemically altered and degraded upon exposure to the environment over annual timescales, yet there is a lack of information concerning the mechanisms and determining factors of degradation. Here, we investigate three main factors; production temperature, feedstock composition, and the characteristics of the environment to which the material is exposed (e.g., pH, organic matter composition, oxygen availability) by analysis of biochar samples in a litterbag experiment before and after a year-long field study in the tropical rainforests of northeast Australia. We find that non-lignocellulosic feedstock has lower aromaticity, plus lower O/C and H/C ratios for a given temperature, and consequently lower carbon sequestration potential. The rate at which samples are altered is production temperature-dependant; however even in the highest temperature samples loss of the semi-labile aromatic carbon component is observed over 1 year. The results of 13C-MAS-NMR measurements suggest that direct oxygenation of aromatic structures may be even more important than carboxylation in environmental alteration of biochar (as a subset of PyC). There is a clear effect of depositional environment on biochar alteration even after the relatively short timescale of this study, as changes are most extensive in the most oxygenated material that was exposed on the soil surface. This is most likely the result of mineral ingress and colonization by soil microbiota. Consequently, oxygen availability and physical or chemical protection from sunlight and/or rainwater is vital in determining the alteration trajectory of this material

Alkali extraction of archaeological and geological charcoal: evidence for diagenetic degradation and formation of humic acids

Charcoal forms a crucial source of archaeological and palaeoenvironmental data, providing a record of cultural activities, past climatic conditions and a means of chronological control via radiocarbon (<sup>14</sup>C) dating. Key to this is the perceived resistance of charcoal to post-depositional alteration, however recent research has highlighted the possibility for alteration and degradation of charcoal in the environment. An important aspect of such diagenesis is the potential for addition of exogenous 'humic acids' (HAs), to affect the accuracy of archaeological and palaeoenvironmental reconstructions based upon chemical analyses of HA-containing charcoal. However the release of significant quantities of HA from apparently pristine charcoals raises the question whether some HA could be derived via diagenetic alteration of charcoal itself. Here we address this question through comparison of freshly produced charcoal with samples from archaeological and geological sites exposed to environmental conditions for millennia using elemental (C/H/O) and isotopic (δ<sup>13</sup>C) measurements, Fourier Transform Infrared Spectroscopy (FTIR) and proton Liquid-State Nuclear Magnetic Resonance (<sup>1</sup>H NMR). The results of analyses show that the presence of highly carboxylated and aromatic alkali-extractable HA in charcoal from depositional environments can often be attributable to the effects of post-depositional processes, and that these substances can represent the products of post-depositional diagenetic alteration in charcoal

Investigation of growth responses in saprophytic fungi to charred biomass

We present the results of a study testing the response of two saprophytic white-rot fungi species, Pleurotus pulmonarius and Coriolus versicolor, to charred biomass (charcoal) as a growth substrate. We used a combination of optical microscopy, scanning electron microscopy, elemental abundance measurements, and isotope ratio mass spectrometry (<sup>13</sup>C and <sup>15</sup>N) to investigate fungal colonisation of control and incubated samples of Scots Pine (Pinus sylvestris) wood, and charcoal from the same species produced at 300 °C and 400 °C. Both species of fungi colonise the surface and interior of wood and charcoals over time periods of less than 70 days; however, distinctly different growth forms are evident between the exterior and interior of the charcoal substrate, with hyphal penetration concentrated along lines of structural weakness. Although the fungi were able to degrade and metabolise the pine wood, charcoal does not form a readily available source of fungal nutrients at least for these species under the conditions used in this study