Temporal and spatial variations of atmospheric radiocarbon in the Mexico City metropolitan area

This work is licensed under a Creative Commons Attribution 3.0 License.-- et al.Proceedings of the 1st International Radiocarbon in the Environment Conference 18–22 August 2014, Queen’s University Belfast, Belfast, Northern Ireland (UK).The Mexico City Metropolitan Area (MCMA) produces a complex mixture of gases and aerosols from diverse sources, including burning of fossil fuels, biomass, and wastes, with a significant biogenic contribution. We present the first results of ongoing projects to study temporal and spatial variations of 14CO2 in the area. Temporal variations reconstructed from tree rings of Taxodium mucronatum indicate a considerable radiocarbon depletion, in accordance to the vast amount of fossil fuels burnt inside Mexico Valley, with values between 62 and 246‰ lower than background values for the 1962–1968 period, and lower by 51–88‰ for the 1983–2010 period. The lower dilution found for the last decades might indicate an increase in enriched 14CO2 sources. Results from the spatial distribution, as revealed from integrated CO2 samples and grasses from six points within the MCMA collected during the 2013 dry season, show variations between sites and sample types. For integrated CO2 samples, values range from 35.6‰ to 54.0‰, and for grasses between –86.8‰ and 40.7‰. For three of the sampling points, the grasses are significantly depleted, by up to ~133‰, as compared to the corresponding integrated CO2 sample. This may result from differences in the carbon assimilation period and exposure to different CO2 sources. Higher-than-background Δ14C values were found for all integrated CO2 samples, presumably resulting from 14C-enriched CO2 derived from forest fires in the mountains during the sampling period. Results obtained so far confirm the complexity of the 14C cycle in the MCMA.This research is funded by DGAPA-UNAM through project PAPIIT-IN106113. Scholarships from CONACyT for AMJ and AMR and from Instituto de Geología and DGAPA-UNAM for AGS are gratefully acknowledged.Peer Reviewe

Dynamic and Thermodynamic Influences on Precipitation in Northeast Mexico on Orbital to Millennial Timescales

The timing and mechanisms of past hydroclimate change in northeast Mexico are poorly constrained, limiting our ability to evaluate climate model performance. To address this, we present a multiproxy speleothem record of past hydroclimate variability spanning 62.5 to 5.1 ka from Tamaulipas, Mexico. Here we show a strong influence of Atlantic and Pacific sea surface temperatures on orbital and millennial scale precipitation changes in the region. Multiple proxies show no clear response to insolation forcing, but strong evidence for dry conditions during Heinrich Stadials. While these trends are consistent with other records from across Mesoamerica and the Caribbean, the relative importance of thermodynamic and dynamic controls in driving this response is debated. An isotope-enabled climate model shows that cool Atlantic SSTs and stronger easterlies drive a strong inter-basin sea surface temperature gradient and a southward shift in moisture convergence, causing drying in this region

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

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

14C and 13C characteristics of higher plant biomarkers in Washington margin surface sediments

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 105 (2013): 14-30, doi:10.1016/j.gca.2012.11.034.Plant wax lipids and lignin phenols are the two most common classes of molecular markers that are used to trace vascular plant-derived OM in the marine environment. However, their 13C and 14C compositions have not been directly compared, which can be used to constrain the flux and attenuation of terrestrial carbon in marine environment. In this study, we describe a revised method of isolating individual lignin phenols from complex sedimentary matrices for 14C analysis using high pressure liquid chromatography (HPLC) and compare this approach to a method utilizing preparative capillary gas chromatography (PCGC). We then examine in detail the 13C and 14C compositions of plant wax lipids and lignin phenols in sediments from the inner and mid shelf of the Washington margin that are influenced by discharge of the Columbia River. Plant wax lipids (including n-alkanes, n-alkanoic (fatty) acids, n-alkanols, and n-aldehydes) displayed significant variability in both δ13C (-28.3 to -37.5 ‰) and ∆14C values (-204 to +2 ‰), suggesting varied inputs and/or continental storage and transport histories. In contrast, lignin phenols exhibited similar δ13C values (between -30 to -34 ‰) and a relatively narrow range of ∆14C values (-45 to -150 ‰; HPLC-based mesurement) that were similar to, or younger than, bulk OM (-195 to -137 ‰). Moreover, lignin phenol 14C age correlated with the degradation characteristics of this terrestrial biopolymer in that vanillyl phenols were on average ~500 years older than syringyl and cinnamyl phenols that degrade faster in soils and sediments. The isotopic characteristics, abundance, and distribution of lignin phenols in sediments suggest that they serve as promising tracers of recently biosynthesized terrestrial OM during supply to, and dispersal within the marine environment. Lignin phenol 14C measurements may also provide useful constraints on the vascular plant end member in isotopic mixing models for carbon source apportionment, and for interpretation of sedimentary records of past vegetation dynamics. Key words: 14C and 13C composition, radiocarbon age, plant wax lipids, lignin phenols, Washington margin, marine carbon cycling, terrestrial organic matterGrants OCE-9907129, OCE-0137005, and OCE-0526268 (to TIE) from the National Science Foundation (NSF) supported this research

Catalytic Upgrading of Biomass Model Compounds: Novel Approaches and Lessons Learnt from Traditional Hydrodeoxygenation – a Review

Catalytic hydrodeoxygenation (HDO) is a fundamental process for bio‐resources upgrading to produce transportation fuels or added value chemicals. The bottleneck of this technology to be implemented at commercial scale is its dependence on high pressure hydrogen, an expensive resource which utilization also poses safety concerns. In this scenario, the development of hydrogen‐free alternatives to facilitate oxygen removal in biomass derived compounds is a major challenge for catalysis science but at the same time it could revolutionize biomass processing technologies. In this review we have analysed several novel approaches, including catalytic transfer hydrogenation (CTH), combined reforming and hydrodeoxygenation, metal hydrolysis and subsequent hydrodeoxygenation along with non‐thermal plasma (NTP) to avoid the supply of external H2. The knowledge accumulated from traditional HDO sets the grounds for catalysts and processes development among the hydrogen alternatives. In this sense, mechanistic aspects for HDO and the proposed alternatives are carefully analysed in this work. Biomass model compounds are selected aiming to provide an in‐depth description of the different processes and stablish solid correlations catalysts composition‐catalytic performance which can be further extrapolated to more complex biomass feedstocks. Moreover, the current challenges and research trends of novel hydrodeoxygenation strategies are also presented aiming to spark inspiration among the broad community of scientists working towards a low carbon society where bio‐resources will play a major role.Financial support for this work was provided by the Department of Chemical and Process Engineering of the University of Surrey and the EPSRC grants EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. Authors would also like to acknowledge the Ministerio de Economía, Industriay Competitividad of Spain (Project MAT2013‐45008‐P) and the Chinese Scholarship Council (CSC). LPP also thanks Comunitat Valenciana for her postdoctoral fellow (APOSTD2017)

Catalytic hydropyrolysis of wood to prepare lignin-enriched residues for stable carbon isotope analysis

EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Modern radiocarbon levels for northwestern Mexico derived from tree rings: A comparison with northern hemisphere zones 2 and 3 curves

Proceedings of the 20th International Radiocarbon Conference.-- This work is licensed under a Creative Commons Attribution 3.0 License.-- et al.The radiocarbon variation for northwestern Mexico during the period 1950-2004 was studied by accelerator mass spectrometry (AMS) and liquid scintillation counting (LSC) analyses of tree rings. Two tree-ring sequences of Pseudotsuga menziesii, sampled in a site isolated from urban centers and active volcanoes (26.18°N, 106.3°W, 3000 m asl), were dendrochronologically dated and separated in annual rings prior to 14C analysis. Results obtained show a similar profile to the values reported for the Northern Hemisphere (NH), having significant correlation coefficients with the compilation curves for NH zone 2 (r = 0.987, p < 0.001) and NH zone 3 (r = 0.993, p < 0.001). The maximum peak is centered at 1964.5 with a Δ14C value of 713.15 ± 9.3‰. The values obtained for the period 1958-1965 are lower than zone 2 values and higher than zone 3 values. For the period 1975-2004, the values obtained are higher than the NH compilation curve and other NH records. We attribute the first divergence to the North American monsoon that may have carried 14C-depleted air from the south during the summer months; the second divergence may be attributable to 14C-enriched biospheric CO2. © 2010 by the Arizona Board of Regents on behalf of the University of Arizona.The financial support from DGAPA–UNAM (Project IN-111608) is gratefully acknowledged.Peer Reviewe

Radiocarbon Laboratory at the National Autonomous University of Mexico: First Set of Samples and New 14

This contribution reports the first set of samples and the creation of an internal reference material at the recently opened Radiocarbon Laboratory at the National Autonomous University of Mexico (UNAM). Samples for the initial measurements were selected from archaeological and dating projects on Teotihuacán, one of the largest and best-studied Mesoamerican urban and ceremonial centers. The 14C dates were compared to results obtained by 2 other laboratories in order to assess the results obtained at UNAM and validate the adopted methodology. As part of the quality assurance protocol, an internal reference material was created that consists of charred wood from the Teotihuacán site with a 14C activity in the value range expected for samples from Mesoamerican archaeological sites. Results from 7 analyses have a mean of 1750 +/16 BP (80.43 +/0.16 pMC).The Radiocarbon archives are made available by Radiocarbon and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202

Radiocarbon Laboratory at the National Autonomous University of Mexico: First Set of Samples and New 14C Internal Reference Material

This contribution reports the first set of samples and the creation of an internal reference material at the recently opened Radiocarbon Laboratory at the National Autonomous University of Mexico (UNAM). Samples for the initial measurements were selected from archaeological and dating projects on Teotihuacán, one of the largest and best-studied Mesoamerican urban and ceremonial centers. The 14C dates were compared to results obtained by 2 other laboratories in order to assess the results obtained at UNAM and validate the adopted methodology. As part of the quality assurance protocol, an internal reference material was created that consists of charred wood from the Teotihuacán site with a 14C activity in the value range expected for samples from Mesoamerican archaeological sites. Results from 7 analyses have a mean of 1750 +/16 BP (80.43 +/0.16 pMC).The Radiocarbon archives are made available by Radiocarbon and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202