Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for e.g. biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, 13C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char

Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, ¹³C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char.Keywords: Aromaticity, Stability, Aromatic condensation, Pyrolysis, Char, Biochar, Pyrogenic organic matter, Heat treatment temperatur

Young organic matter as a source of carbon dioxide outgassing from Amazonian rivers

Rivers are generally supersaturated with respect to carbon dioxide, resulting in large gas evasion fluxes that can be a significant component of regional net carbon budgets. Amazonian rivers were recently shown to outgas more than ten times the amount of carbon exported to the ocean in the form of total organic carbon or dissolved inorganic carbon. High carbon dioxide concentrations in rivers originate largely from in situ respiration of organic carbon, but little agreement exists about the sources or turnover times of this carbon. Here we present results of an extensive survey of the carbon isotope composition ({sup 13}C and {sup 14}C) of dissolved inorganic carbon and three size-fractions of organic carbon across the Amazonian river system. We find that respiration of contemporary organic matter (less than 5 years old) originating on land and near rivers is the dominant source of excess carbon dioxide that drives outgassing in mid-size to large rivers, although we find that bulk organic carbon fractions transported by these rivers range from tens to thousands of years in age. We therefore suggest that a small, rapidly cycling pool of organic carbon is responsible for the large carbon fluxes from land to water to atmosphere in the humid tropics

Controls on black carbon storage in soils

[1] Fire-derived black carbon (BC: charcoal and soot) has been thought to be a passive player in soils, contributing to the refractory soil organic carbon (SOC) pool, but playing no role in pedogenesis and regional short-term carbon cycling. This model, however, is at odds with recent results on the role of charcoal in soil fertility and its detection in the dissolved organic carbon (DOC) pool. For example, if BC simply accumulated passively in soils, its pattern of accumulation should match a simple model correlating fire frequency to BC storage. Instead, soil type, climate, biota, and land use practices all appear to play roles in controlling whether BC accumulates or is lost from soils. We summarize current knowledge of BC-soil interactions and construct a new paradigm describing the controls on BC storage in soils. We reconcile the refractory-labile BC paradox by proposing a model where BC storage is controlled by (1) fire frequency, (2) ecosystem presence or absence of aromatic precursor carbon and appropriate combustion conditions, (3) biological or physical mixing to remove BC from the soil surface, where it is vulnerable to combustion in future fires, (4) the presence or absence of soil mineral fractions able to sorb BC into the long-term stable carbon pool, and (5) the presence of microbial communities capable of degrading aromatic carbon. We also recognize that soil BC/SOC ratios are strongly influenced by land-use practices and add (6) human activities as a final control

Carbon isotope geochemistry of the Santa Clara River

The Santa Clara River is a prototypical small mountainous river, with a headwater height greater than 1000 m and a basin area smaller than 10,000 m 2. Although individual small mountainous rivers export trivial amounts of sediment and carbon to the ocean, as a group these rivers may export a major fraction (as much as 50%) of the total global river sediment flux [Milliman and Syvitski, 1992], making their geochemistry relevant the study of the ocean's carbon cycle. In addition, many small rivers export sediment in a few high flux events, causing massive, sporadic discharge of carbon onto coastal shelves, discharge conditions very different from those of large rivers. This class of rivers is an end-member of the river-ocean carbon exchange system,. opposite the Earth's largest river, the Amazon. The carbon mass and isotopic properties of the Santa Clara River are significantly different from previously studied large rivers. During the 1997–1998 winter, all Santa Clara carbon pools were old, with flux-weighted average Δl4C values of−428±76‰ for particulate organic carbon, −73±31‰ for dissolved organic carbon, and−644±58‰ for black carbon. The age of exported carbon is primarily due to the deep erosion of old soils and not to inclusion of fossil fuel carbon. Additionally, the δ13C signatures of exported carbon pools were high relative to terrestrial carbon, bearing a signature quite similar to marine carbon (average particulate organic carbon (POC) δ13C = −22.2±0.8‰). The Santa Clara's estuary is small and drains onto the narrow eastern Pacific coastal margin, exporting this old soil organic matter directly into the ocean. If the Santa Clara export patterns are representative of this class of rivers, they may be a significant source of refractory terrestrial carbon to the ocean

Interdisciplinary intercomparison of black carbon analysis in soil and sediment

Analysis and characterization of black carbon in the environment, Vienna, Austria, 18-19 April 200

Carbon isotope geochemistry of the Santa Clara River

The Santa Clara River is a prototypical small mountainous river, with a headwater height greater than 1000 m and a basin area smaller than 10,000 m 2. Although individual small mountainous rivers export trivial amounts of sediment and carbon to the ocean, as a group these rivers may export a major fraction (as much as 50%) of the total global river sediment flux [Milliman and Syvitski, 1992], making their geochemistry relevant the study of the ocean's carbon cycle. In addition, many small rivers export sediment in a few high flux events, causing massive, sporadic discharge of carbon onto coastal shelves, discharge conditions very different from those of large rivers. This class of rivers is an end-member of the river-ocean carbon exchange system,. opposite the Earth's largest river, the Amazon. The carbon mass and isotopic properties of the Santa Clara River are significantly different from previously studied large rivers. During the 1997–1998 winter, all Santa Clara carbon pools were old, with flux-weighted average Δl4C values of−428±76‰ for particulate organic carbon, −73±31‰ for dissolved organic carbon, and−644±58‰ for black carbon. The age of exported carbon is primarily due to the deep erosion of old soils and not to inclusion of fossil fuel carbon. Additionally, the δ13C signatures of exported carbon pools were high relative to terrestrial carbon, bearing a signature quite similar to marine carbon (average particulate organic carbon (POC) δ13C = −22.2±0.8‰). The Santa Clara's estuary is small and drains onto the narrow eastern Pacific coastal margin, exporting this old soil organic matter directly into the ocean. If the Santa Clara export patterns are representative of this class of rivers, they may be a significant source of refractory terrestrial carbon to the ocean

Data_Sheet_1_Environmental conditions play a key role in controlling the composition and diversity of Colombian biocrust microbiomes.pdf

Drylands soils worldwide are naturally colonized by microbial communities known as biocrusts. These soil microbiomes render important ecosystem services associated with soil fertility, water holding capacity, and stability to the areas they cover. Because of the importance of biocrusts in the global cycling of nutrients, there is a growing interest in describing the many microbial configurations these communities display worldwide. However, comprehensive 16S rRNA genes surveys of biocrust communities do not exist for much of the planet: for example, in the continents of South America and the northern part of Africa. The absence of a global understanding of biocrust biodiversity has lead us to assign a general importance to community members that may, in fact, be regional. Here we report for the first time the presence of biocrusts in Colombia (South America) through 16S rRNA genes surveys across an arid, a semi-arid and a dry subtropical region within the country. Our results constitute the first glance of the Bacterial/Archaeal communities associated with South American biocrust microbiomes. Communities where cyanobacteria other than Microcoleus vaginatus prevail, despite the latter being considered a key species elsewhere, illustrate differentiable results in these surveys. We also find that the coastal biocrust communities in Colombia include halo-tolerant and halophilic species, and that niche preference of some nitrogen fixing organisms deviate from previously described global trends. In addition, we identified a high proportion (ranging from 5 to 70%, in average) of cyanobacterial sequences that did not match any formally described cyanobacterial species. Our investigation of Colombian biocrusts points to highly diverse communities with climatic regions controlling taxonomic configurations. They also highlight an extensive local diversity to be discovered which is central to better design management and restoration strategies for drylands soils currently undergoing disturbances due to land use and global warming. Finally, this field study highlights the need for an improved mechanistic understanding of the response of key biocrust community members to changes in moisture and temperature.</p

Physical controls on dissolved inorganic radiocarbon variability in the California Current

We present depth profiles of Δ14C and δ 13C of dissolved inorganic carbon (DIC) at Station M in the Eastern North Pacific. Several seasonal profiles are presented for the time period between 1991 and 1996. Comparison with GEOSECS data clearly shows changes in ocean radiocarbon profiles since 1973. The Δ14C of DIC shows the most variability at depths of 450, 85, and 25 m, and the lowest variability at depths of 1600 and 2500 m. The largest variability in DIC Δ14C occurs at 450 m, a depth marked by large fluctuations in the radiocarbon signatures of the source waters. The likely controls of DIC Δ14C variability are physical changes in the circulation of the California Current System. A simple two-box model is used to show the importance of wind driven mixing at the surface. We discuss the likely effects of mesoscale eddies and ENSO on the DIC Δ14C values at this site. We also show that remineralization of organic carbon (dissolved or particulate) is not responsible for the variability in the Δ14C of DIC observed at Station M