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

Hydropyrolysis: implications for radiocarbon pre-treatment and characterization of Black Carbon

Charcoal is the result of natural and anthropogenic burning events, when biomass is exposed to elevated temperatures under conditions of restricted oxygen. This process produces a range of materials, collectively known as pyrogenic carbon, the most inert fraction of which is known as Black Carbon (BC). BC degrades extremely slowly, and is resistant to diagenetic alteration involving the addition of exogenous carbon making it a useful target substance for radiocarbon dating particularly of more ancient samples, where contamination issues are critical. We present results of tests using a new method for the quantification and isolation of BC, known as hydropyrolysis (hypy). Results show controlled reductive removal of non-BC organic components in charcoal samples, including lignocellulosic and humic material. The process is reproducible and rapid, making hypy a promising new approach not only for isolation of purified BC for 14C measurement but also in quantification of different labile and resistant sample C fractions

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

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

Assessment of hydropyrolysis as a method for the quantification of black carbon using standard reference materials

A wide selection of thermal, chemical and optical methods have been proposed for the quantification of black carbon (BC) in environmental matrices, and the results to date differ markedly depending upon the method used. A new approach is hydropyrolysis (hypy), where pyrolysis assisted by high hydrogen pressures (150 bar) facilitates the complete reductive removal of labile organic matter, so isolating a highly stable portion of the BC continuum (defined as BChypy). Here, the potential of hypy for the isolation and quantification of BC is evaluated using the 12 reference materials from the International BC Ring Trial, comprising BC-rich samples, BC-containing environmental matrices and BC-free potentially interfering materials. By varying the hypy operating conditions, it is demonstrated that lignocellulosic, humic and other labile organic carbon material (defined as non-BChypy) is fully removed by 550 °C, with hydrogasification of the remaining BChypy not commencing until over 575 °C. The resulting plateau in sample mass and carbon loss is apparent in all of the environmental samples, facilitating BC quantification in a wide range of materials. The BChypy contents for all 12 ring trial samples fall within the range reported in the BC inter-comparison study, and systematic differences with other methods are rationalised. All methods for BC isolation, including hypy are limited by the fact that BC cannot be distinguished from extremely thermally mature organic matter; for example in high rank coals. However, the data reported here indicates that BChypy has an atomic H/C ratio of less than 0.5 and therefore comprises a chemically well-defined polyaromatic structure in terms of the average size of peri-condensed aromatic clusters of >7 rings (24 carbon atoms), that is consistent across different sample matrices. This, together with the sound underlying rationale for the reductive removal of labile organic matter, makes hypy an ideal approach for matrix independent BC quantification. The hypy results are extremely reproducible, with BChypy determinations from triplicate analyses typically within ±2% across all samples, limited mainly by the precision of the elemental analyser

Influence of production variables and starting material on charcoal stable isotopic and molecular characteristics

We present a systematic study on the effect of starting species, gas composition, temperature, particle size and duration of heating upon the molecular and stable isotope composition of high density (mangrove) and low density (pine) wood. In both pine and mangrove, charcoal was depleted in o13C relative to the starting wood by up to 1.6% and 0.8%, respectively. This is attributed predominantly to the progressive loss of isotopically heavier polysaccharides, and kinetic effects of aromatization during heating. However, the pattern of o13C change was dependant upon both starting species and atmosphere, with different structural changes associated with charcoal production from each wood type elucidated by Solid-State o13C Nuclear Magnetic Resonance Spectroscopy. These are particularly evident at lower temperatures, where variation in the oxygen content of the production atmosphere results in differences in the thermal degradation of cellulose and lignin. It is concluded that production of charcoal from separate species in identical conditions, or from a single sample exposed to different production variables, can result in significantly different o13C of the resulting material, relative to the initial wood. These results have implications for the use of charcoal isotope composition to infer past environmental change

Antarctic ice sheet discharge driven by atmosphere-ocean feedbacks at the Last Glacial Termination

Reconstructing the dynamic response of the Antarctic ice sheets to warming during the Last Glacial Termination (LGT; 18,000–11,650 yrs ago) allows us to disentangle ice-climate feedbacks that are key to improving future projections. Whilst the sequence of events during this period is reasonably well-known, relatively poor chronological control has precluded precise alignment of ice, atmospheric and marine records, making it difficult to assess relationships between Antarctic ice-sheet (AIS) dynamics, climate change and sea level. Here we present results from a highly-resolved ‘horizontal ice core’ from the Weddell Sea Embayment, which records millennial-scale AIS dynamics across this extensive region. Counterintuitively, we find AIS mass-loss across the full duration of the Antarctic Cold Reversal (ACR; 14,600–12,700 yrs ago), with stabilisation during the subsequent millennia of atmospheric warming. Earth-system and ice-sheet modelling suggests these contrasting trends were likely Antarctic-wide, sustained by feedbacks amplified by the delivery of Circumpolar Deep Water onto the continental shelf. Given the anti-phase relationship between inter-hemispheric climate trends across the LGT our findings demonstrate that Southern Ocean-AIS feedbacks were controlled by global atmospheric teleconnections. With increasing stratification of the Southern Ocean and intensification of mid-latitude westerly winds today, such teleconnections could amplify AIS mass loss and accelerate global sea-level rise

Measurement of the proton and deuteron structure functions, F2p and F2d, and of the ratio sigma(L)/sigma(T)

The muon-proton and muon-deuteron inclusive deep inelastic scattering cross sections were measured in the kinematic range 0.002 < x < 0.60 and 0.5 < Q2 < 75 GeV2 at incident muon energies of 90, 120, 200 and 280 GeV. These results are based on the full data set collected by the New Muon Collaboration, including the data taken with a small angle trigger. The extracted values of the structure functions F2p and F2d are in good agreement with those from other experiments. The data cover a sufficient range of y to allow the determination of the ratio of the longitudinally to transversely polarised virtual photon absorption cross sections, R= sigma(L)/sigma(T), for 0.002 < x < 0.12 . The values of R are compatible with a perturbative QCD prediction; they agree with earlier measurements and extend to smaller x.Comment: In this replacement the erroneously quoted R values in tables 3-6 for x>0.12, and R1990 values in tables 5-6 for all x, have been corrected, and the cross sections in tables 3-4 have been adapted. Everything else, including the structure functions F2, remained unchanged. 22 pages, LateX, including figures, with two .sty files, and three separate f2tab.tex files for the F2-tables. Accepted for publication in Nucl.Phys.B 199

Climate resilience in marine protected areas and the ‘Protection Paradox’

Restricting human activities through Marine Protected Areas (MPAs) is assumed to create more resilient biological communities with a greater capacity to resist and recover following climate events. Here we review the evidence linking protection from local pressures (e.g., fishing and habitat destruction) with increased resilience. Despite strong theoretical underpinnings, studies have only rarely attributed resilience responses to the recovery of food webs and habitats, and increases in the diversity of communities and populations. When detected, resistance to ocean warming and recovery after extreme events in MPAs have small effect sizes against a backdrop of natural variability. By contrast, large die-offs are well described from MPAs following climate stress events. This may be in part because protection from one set of pressures or drivers (such as fishing) can select for species that are highly sensitive to others (such as warming), creating a ‘Protection Paradox’. Given that climate change is overwhelming the resilience capacity of marine ecosystems, the only primary solution is to reduce carbon emissions. High-quality monitoring data in both space and time can also identify emergent resilience signals that do exist, in combination with adequate reference data to quantify the initial system state. This knowledge will allow networks of diverse protected areas to incorporate spatial refugia against climate change, and identify resilient biological components of natural systems. Sufficient spatial replication further offers insurance against losses in any given MPA, and the possibility for many weak signals of resilience to accumulate

Effects of mineralogy, chemistry and physical properties of basalts on carbon capture potential and plant-nutrient element release via enhanced weathering

Mafic igneous rocks, such as basalt, are composed of abundant calcium- and magnesium-rich silicate minerals widely proposed to be suitable for scalable carbon dioxide removal (CDR) by enhanced rock weathering (ERW). Here, we report a detailed characterization of the mineralogy, chemistry, particle size and surface area of six mined basalts being used in large-scale ERW field trials. We use 1-D reactive transport modelling (RTM) of soil profile processes to simulate inorganic CDR potential via cation flux (Mg2+, Ca2+, K+ and Na+) and assess the release of the essential plant nutrients phosphorus (P) and potassium (K) for a typical clay-loam agricultural soil. The basalts are primarily composed of pyroxene and plagioclase feldspar (up to 71 wt%), with accessory olivine, quartz, glass and alkali feldspar. Mean crushed particle size varies by a factor of 10, owing to differences in the mining operations and grinding processes. RTM simulations, based on measured mineral composition and N2-gas BET specific surface area (SSA), yielded potential CDR values of between c. 1.3 and 8.5 t CO2 ha−1 after 15 years following a baseline application of 50 t ha−1 basalt. The RTM results are comparative for the range of inputs that are described and should be considered illustrative for an agricultural soil. Nevertheless, they indicate that increasing the surface area for slow-weathering basalts through energy intensive grinding prior to field application in an ERW context may not be warranted in terms of additional CDR gains. We developed a function to convert CDR based on widely available and easily measured rock chemistry measures to more realistic determinations based on mineralogy. When applied to a chemistry dataset for >1300 basalt analyses from 25 large igneous provinces, we simulated cumulative CDR potentials of up to c. 8.5 t CO2 ha−1 after 30 years of weathering, assuming a single application of basalt with a SSA of 1 m2 g−1. Our RTM simulations suggest that ERW with basalt releases sufficient phosphorus (P) to substitute for typical arable crop P-fertiliser usage in Europe and the USA offering potential to reduce demand for expensive rock-derived P