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

A multiwavelength study of the supernova remnant G296.8-0.3

We report XMM-Newton observations of the Galactic supernova remnant G296.8-0.3, together with complementary radio and infrared data. The spatial and spectral properties of the X-ray emission, detected towards G296.8-0.3, was investigated in order to explore the possible evolutionary scenarios and the physical connexion with its unusual morphology detected at radio frequencies. G296.8-0.3 displays diffuse X-ray emission correlated with the peculiar radio morphology detected in the interior of the remnant and with the shell-like radio structure observed to the northwest side of the object. The X-ray emission peaks in the soft/medium energy range (0.5-3.0 keV). The X-ray spectral analysis confirms that the column density is high (NH \sim 0.64 x 10^{22} cm^{-2}) which supports a distant location (d>9 kpc) for the SNR. Its X-ray spectrum can be well represented by a thermal (PSHOCK) model, with kT \sim 0.86 keV, an ionization timescale of 6.1 x 10^{10} cm^{-3} s, and low abundance (0.12 Z_sun). The 24 microns observations show shell-like emission correlated with part of the northwest and southeast boundaries of the SNR. In addition a point-like X-ray source is also detected close to the geometrical center of the radio SNR. The object presents some characteristics of the so-called compact central objects (CCO). Its X-ray spectrum is consistent with those found at other CCOs and the value of NH is consistent with that of G296.8-0.3, which suggests a physical connexion with the SNR.Comment: Accepted for publication in Astrophysics & Space Scienc

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

20 years of the Atlantic Meridional Transect - AMT

The AMT (www.amt-uk.org) is a multidisciplinary programme which undertakes biological, chemical, and physical oceanographic research during an annual voyage between the UK and a destination in the South Atlantic such as the Falkland Islands, South Africa, or Chile. This transect of >12,000 km crosses a range of ecosystems from subpolar to tropical, from euphotic shelf seas and upwelling systems, to oligotrophic mid-ocean gyres. The year 2015 has seen two milestones in the history of the AMT: the achievement of 20 years of this unique ocean going programme and the departure of the 25th cruise on the 15th of September. Both of these events were celebrated in June this year with an open science conference hosted by the Plymouth Marine Laboratory (PML) and will be further documented in a special issue of Progress in Oceanography which is planned for publication in 2016. Since 1995, the 25 research cruises have involved 242 sea-going scientists from 66 institutes representing 22 countries. AMT was designed from the outset to be a collaborative programme. It was originally conceived by Jim Aiken, Patrick Holligan, Roger Harris, and Dave Robins with Chuck McClain and Chuck Trees at NASA to test and ground truth satellite algorithms of ocean color. The opportunities offered by this initiative meant that this series of repeated biannual cruises rapidly developed into a coordinated study of ocean biodiversity, biogeochemistry, and ocean/atmosphere interactions

Direct evidence from hydropyrolysis for the retention of long alkyl moieties in black carbon fractions isolated by acidified dichromate oxidation

Chemical oxidation with acidified potassium dichromate is one of the more commonly used of a range of available methods for the quantification of black carbon (BC) in soils and sediments. There are potential uncertainties with this method however, with indications that not all non-BC material is susceptible to oxidation. An emerging approach to BC quantification is hydropyrolysis (hypy), in which pyrolysis assisted by high hydrogen pressure facilitates the reductive removal of labile organic matter, so isolating a highly stable portion of the BC continuum that is predominantly composed of >7 ring aromatic domains.\ud \ud Here, results from the hypy of the BC fraction isolated by dichromate oxidation (BCdox) from a BC-rich soil are presented, which demonstrated that 88% of the total carbon initially defined as BC was stable under hypy conditions (defined as BChypy). More notably, hypy allowed the non-BChypy fraction to be characterised. In addition to a number of PAHs, the non-BChypy fraction was also found to contain a significant abundance of n-alkanes, with a marked predominance of even-numbered homologues. These compounds are probably derived from lipids, hydrogenated during hypy, which survived dichromate oxidation due to their hydrophobic nature. Hypy of the dichromate oxidation residue from a sample of Green River shale, known to contain no BC of pyrogenic origin revealed that the significant apparent BCdox content (BC/OC = 5.7%) was also largely due to the presence of n-alkanes within the oxidation residues. The distribution of these compounds, biased towards longer chain homologues with no significant even/odd preference, indicated that they were largely derived from long n-alkyl chains within this highly aliphatic matrix.\ud \ud Hypy therefore provides compelling direct evidence for the incomplete removal of non-BC material by dichromate oxidation from both a BC-rich soil and a BC-free oil shale, with the molecular characterisation of the non-BChypy fraction allowing the potential sources of this material to be deduced

Evidence for long-term averaging of Sr-87/Sr-86 in bovine enamel using TIMS and LA-MC-ICP-MS.

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