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Natural organic matter (NOM) is a highly active component of soils and sediments, and plays all important role in global C cycling. However, NOM has defied molecular-level structural characterization, owing to variations along the decomposition continuum and its existcnce as highly functionalized polyelectrolytes. We conducted a conrprehensivc systematic overview of spectral signatures and peak positions of major organic molecules that occur as part of NOM using near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The spectra of carbohydrates and amino sugars show resonances between 289.10 and 289.59 eV, attributed to 1s-3p/[[sigma].sup.*] transitions of O-alkyl (C-OH) moieties. They also exhibited distinct peaks between 288.42 and 288.74 eV, representing C 1s-[[pi].sup.*.sub.C=O] transition from COOH functionalities. Amino acids produced a strong signal around 288.70 eV which can be identified as a C [[pi].sup.*.sub.C=O] transition of carboxyl/carbonyl (COOH/ COO-) structures. Spectral features near 285.29 eV were ascribed to C [[pi].sup.*.sub.C=C] transition of ring structure of aromatic amino acids, while spectra between 287.14 and 287.86 eV were attributed to C [[pi].sup.*.sub.C-H] and C 1s-[[sigma].sup.*.sub.C-H/]3p Rydberg-like excitations from CH and C[H.sub.2] groups. Phenols and benzoquinone produced strong resonances between 285.08 and 285.37 eV, attributed to the [[pi].sup.*] orbital of C (C 1s-[[pi].sup.*.sub.C=C]) atoms connected to either C or H (C-H) in the aromatic ring. The next higher excitation common to both phenols and quinone appeared between 286.05 and 286.35 eV, and could be associated with C 1s[[pi].sup.*.sub.C=C] transitioxrs of aromatic C bonded to O atom in phenols, and to C 1s-[[pi].sup.*.sub.C=O] transitions from aromatic C connected to O atom (C-OH) in phenols or to a C=O in p-benzoquinone and some phenols with carbonyl structures, respectively. Nucleobases exhibited complex spectral features with pronounced resonances between 286.02 and 286.84 eV and between 288.01 and 288.70 eV. Molecular markers for black C (benzenecarboxylic acid and biphenyl-4,4'-dicarboxylic acid) exhibit sharp absorption bands between 285.01 and at 285.43 eV, possibly from C 1s-[[pi].sup.*.sub.C=C] transition characteristic of C-H sites or unsaturated C (C=C) on aromatic ring structures. These aromatic carboxylic acids also exhibit broad peaks between 288.35 and 288.48 eV, reflecting C [[pi].sup.*.sub.C=O] transition of carboxyl functional groups bonded to unsaturated C. This investigation provides a more comprehensive NEXAFS spectral library of biogeochemically relevant organic C compounds. The spectra of these reference organic compounds reveal distinct spectral features and peak positions at the C K-edge that arc characteristic of the molecular orbitals bonding C atoms. Detailed structural information can be derived from these distinctive spectral features that could be used to build robust peak assignment criteria to exploit the chemical sensitivity of NEXAFS spectroscopy for in situ molecular-level spatial investigation and fingerprinting of complex organic C compounds in environmental samples. Abbreviations: EDX, energy dispersive x-ray; NEXAFS, near-edge x-ray absorption fine structure spectroscopy; NOM, natural organic matter; SEM, scanning electron microscopy; STXM, scanning transmission x-ray microscopy; TEM transmission electron microscope: XPS, x-ray photoelectron spectroscopy. doi: 10.2136/sssaj2008.0228

Methodological constraints limit the extent to which existing soil aggregation models explain carbon (C) stabilization in soil. We hypothesize that the physical infrastructure of microaggregates plays a major role in determining the chemistry of the occluded C and intimate associations between particulate C, chemically stabilized C and the soil mineral matrix. We employed synchrotron-based scanning transmission X-ray microscopy (STXM) coupled with near-edge X-ray absorption fine structure (C 1s-NEXAFS) spectroscopy to investigate the nanoscale physical assemblage and C chemistry of 150-[micro]m micro-aggregates from a Kenyan Oxisol. Ultra-thin sections were obtained after embedding microaggregates in a sulfur block and sectioning on a cryo-microtome at -55[degrees]C. Principal component and cluster analyses revealed four spatially distinct features: pore surfaces, mineral matter, organic matter, and their mixtures. The occurrence of these features did not vary between exterior and interior locations; however, the degree of oxidation decreased while the complexity and occurrence of aliphatic C forms increased from exterior to interior regions of the microaggregate. At both locations, compositional mapping rendered a nanoscale distribution of oxidized C clogging pores and coating pore cavities on mineral surface. Hydrophobic organic matter of aromatic and aliphatic nature, representing particulate C forms appeared physically occluded in 2- to 5-[micro]m pore spaces. Our findings demonstrate that organic matter in microaggregates may be found as either oxidized C associated with mineral surfaces or aromatic and aliphatic C in particulate form. Using STXM and C 1s-NEXAFS we are for the first time able to resolve the nanoscale biogeocomplexity of unaltered soil microaggregates.

Soil organic matter (SOM) is a fundamental component of soil and the global C cycle. We used C (1s) near-edge x-ray absorption fine structure (NEXAFS) and synchrotron-based Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy to speciate C and investigate the influence of land use oil the composition of SOM in the humic substances extracted from clay and silt fractions. Soil samples were collected from natural forest, tea and Cupressus plantations and cultivated fields in Ethiopia. Carbon K-edge spectra revealed multiple C (1s) electron transitions in the fine structure of C NEXAFS region (284-290 eV) indicating the presence of aromatic-C, phenolic-C, aliphatic-C, carboxylic-C, and O-alkyl-C in the humic substances. It also exhibited good selectivity, where specific energy regions correspond to C in discrete functional groups. However, regions of slight overlap between 1s-3p/[sigma] * transition of aliphatic-C and 1s-[pi] * transition of carboxylic-C may not be excluded. Fourier transform infrared-attenuated total reflectance spectroscopy showed larger proportions of aromatic-C (25.5%, 21.9%) and asymmetric and symmetric aliphatic-C (19.7%, 15.2%) groups in the silt than in clay, respectively. However, smaller proportion of polysaccharides (19.3%, 11.5%) was obtained from the silt compared with clay. The proportions of phenols (20.7%, 20.4%), aliphatic deformation of C[H.sub.2] or C[H.sub.3] (13.1%, 14.5%), and carboxylic (9.8%, 8.3%) groups were of similar magnitude in both fractions. The proportion of polysaccharides decreased in the order: natural forests > plantations > cultivated fields, while recalcitrant aromatic-C increased in the order: natural forest plantation < cultivation. Therefore, C (1s) NEXAFS and synchrotron-based FTIR-ATR spectroscopy are powerful, nondestructive techniques that can potentially be used not only to identify and fingerprint complex structural characteristics of organic C macromolecules but also to investigate the impact of long-term anthropogenic management on the composition and biogeochemical cycling of organic C in terrestrial ecosystems.

In Uganda, Ghana and Bangladesh, participatory tools were used for a socio-economic and gender analysis of three topics: climate-smart agriculture (CSA), climate analogue approaches, and climate and weather forecasting. Policy and programme-relevant results were obtained. Smallholders are changing agricultural practices due to observations of climatic and environmental change. Women appear to be less adaptive because of financial or resource constraints, because of male domination in receiving information and extension services and because available adaptation strategies tend to create higher labour loads for women. The climate analogue approach (identifying places resembling your future climate so as to identify potential adaptations) is a promising tool for increasing farmer-to-farmer learning, where a high degree of climatic variability means that analogue villages that have successfully adopted new CSA practices exist nearby. Institutional issues related to forecast production limit their credibility and salience, particularly in terms of women's ability to access and understand them. The participatory tools used in this study provided some insights into women's adaptive capacity in the villages studied, but not to the depth necessary to address women's specific vulnerabilities in CSA programmes. Further research is necessary to move the discourse related to gender and climate change beyond the conceptualization of women as a homogenously vulnerable group in CSA programmes. [ABSTRACT FROM PUBLISHER]

Natural organic matter (NOM) is a highly active component of soils and sediments, and plays an important role in global C cycling. However, NOM has defied molecular-level structural characterization, owing to variations along the decomposition continuum and its existence as highly functionalized polyelectrolytes. We conducted a comprehensive systematic overview of spectral signatures and peak positions of major organic molecules that occur as part of NOM using near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The spectra of carbohydrates and amino sugars show resonances between 289.10 and 289.59 eV, attributed to 1s-3p/σ* transitions of 0-alkyl (C-OH) moieties. They also exhibited distinct peaks between 288.42 and 288.74 eV, representing C 1s-π*C=O from COOH functionalities. Amino acids produced a strong signal around 288.70 eV, which can be identified as a C 1s-π*C=O transition of carboxyl/carbonyl (COOH/COO-) structures. Spectral features near 285.29 eV were ascribed to C 1s-σ*C=C transition of ring structure of aromatic amino acids, while spectra between 287.14 and 287.86 eV were attributed to C 1s-π*C-H and C 1s-σ*C-H/3p Rydberg-like excitations from CH and CH2 groups. Phenols and benzoquinone produced strong resonances between 285.08 and 285.37 eV, attributed to the π* orbital of C (C 1s-π*C=O) atoms connected to either C or H (C-H) in the aromatic ring. The next higher excitation common to both phenols and quinone appeared between 286.05 and 286.35 eV, and could be associated with C 1s-π*C=O transitions of aromatic C bonded toO atom in phenols, and to C 1s-π*C=O transitions from aromatic C connected to 0 atom (C-OH) in phenols or to a CO in p-benzoquinone and some phenols with carbonyl structures, respectively. Nucleobases exhibited complex spectral features with pronounced resonances between 286.02 and 286.84 eV and between 288.01 and 288.70 eV. Molecular markers forblack C (benzenecarboxylic acid and biphenyl-4,4'-dicarboxylic acid) exhibit sharp absorption bands between 285.01 and at 285.43 eV, possibly from C 1s-π*C=C is-it transition characteristic of C-H sites or unsaturated C (C=C) on aromatic ring structures. These aromatic carboxylic acids also exhibit broad peaks between 288.35 and 288.48 eV, reflecting C 1s-π*C=O) transition of carboxyl functional groups bonded to unsaturated C. This investigation provides a more comprehensive NEXAFS spectral library of biogeochemically relevant organic C compounds. The spectra of these reference organic compounds reveal distinct spectral features and peak positions at the C K-edge that are characteristic of the molecular orbitals bonding C atoms. Detailed structural information can be derived from these distinctive spectral features that could be used to build robust peak assignment criteria to exploit the chemical sensitivity of NEXAFS spectroscopy for in situ molecular-level spatial investigation and fingerprinting of complex organic C compounds in environmental samples. [ABSTRACT FROM AUTHOR]

Black carbon (BC) is a quantitatively important C pool in the global C cycle due to its relative recalcitrance compared with other C pools. However, mechanisms of BC oxidation and accompanying molecular changes are largely unknown. In this study, the long-term dynamics in quality and quantity of BC were investigated in cultivated soil using X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) techniques. BC particles and changes in BC stocks were obtained from soil collected in fields that were cleared from forest by fire at 8 different times in the past (2, 3, 5, 20, 30, 50, 80 and 100 years before sampling) in western Kenya. BC contents rapidly decreased from 12.7 to 3.8 mg C g−1 soil during the first 30 years following deposition, after which they slowly decreased to a steady state at 3.5 mg C g−1 soil. BC-derived C losses from the top 0.1 m over 100 years were estimated at 6,000 kg C ha−1. The initial rapid changes in BC stocks resulted in a mean residence time of only around 8.3 years, which was likely a function of both decomposition as well as transport processes. The molecular properties of BC changed more rapidly on surfaces than in the interior of BC particles and more rapidly during the first 30 years than during the following 70 years. The Oc/C ratios (Oc is O bound to C) and carbonyl groups (C=O) increased over the first 10 and 30 years by 133 and 192%, respectively, indicating oxidation was an important process controlling BC quality. Al, Si, polysaccharides, and to a lesser extent Fe were found on BC particle surfaces within the first few years after BC deposition to soil. The protection by physical and chemical stabilization was apparently sufficient to not only minimize decomposition below detection between 30 and 100 years after deposition, but also physical export by erosion and vertical transport below 0.1 m. [ABSTRACT FROM AUTHOR]

Agricultural researchers and practitioners throughout Africa are conducting soil health-related research and applying the results, though many are not accessing or sharing available knowledge resources effectively. During 2007, 73 respondents (primarily researchers and educators with an interest in soil fertility) in 23 African countries were surveyed to identify: 1) where and how they access soil health and other agricultural information; 2) their use of libraries and agricultural networks; and 3) potential improved pathways for African soil health researchers to locate and share knowledge resources. The survey results suggest that building 1) librarians' capacity for outreach and accessing knowledge resources, and 2) network staff capacity for pro active knowledge brokering could be useful avenues to increase access, sharing and use of soil health research in Africa. Further study of networks and network membership will help determine the potential benefits of increasing inter-network links to share information more effectively among soil health researchers and between scientists and both practitioners and policymakers. Increasing support for collaborative efforts including low or no-cost information resources such as The Essential Electronic Agricultural Library (TEEAL) and AGORA (Access to Global Online Research in Agriculture) and promoting information sources on frequently-visited websites and at conferences could also improve access to soil health knowledge resources in Africa. [ABSTRACT FROM AUTHOR]

Anthropogenic perturbations have profoundly modified the Earth's biogeochemical cycles, the most prominent of these changes being manifested by global carbon (C) cycling. We investigated long-term effects of human-induced land-use and land-cover changes from native tropical forest (Kenya) and subtropical grassland (South Africa) ecosystems to agriculture on the dynamics and structural composition of soil organic C (SOC) using elemental analysis and integrated 13C nuclear magnetic resonance (NMR), near-edge X-ray absorption fine structure (NEXAFS) and synchrotron-based Fourier transform infrared-attenuated total reflectance (Sr-FTIR-ATR) spectroscopy. Anthropogenic interventions led to the depletion of 76%, 86% and 67% of the total SOC; and 77%, 85% and 66% of the N concentrations from the surface soils of Nandi, Kakamega and the South African sites, respectively, over a period of up to 100 years. Significant proportions of the total SOC (46–73%) and N (37–73%) losses occurred during the first 4 years of conversion indicating that these forest-and grassland-derived soils contain large amounts of labile soil organic matter (SOM), potentially vulnerable to degradation upon human-induced land-use and land-cover changes. Anthropogenic perturbations altered not only the C sink capacity of these soils, but also the functional group composition and dynamics of SOC with time, rendering structural composition of the resultant organic matter in the agricultural soils to be considerably different from the SOM under natural forest and grassland ecosystems. These molecular level compositional changes were manifested: (i) by the continued degradation of O-alkyl and acetal-C structures found in carbohydrate and holocellulose biomolecules, some labile aliphatic-C functionalities, (ii) by side-chain oxidation of phenylpropane units of lignin and (iii) by the continued aromatization and aliphatization of the humic fractions possibly through selective accumulation of recalcitrant H and C substituted aryl-C and aliphatic-C components such as (poly)-methylene units, respectively. These changes appeared as early as the fourth year after transition, and their intensity increased with duration of cultivation until a new quasi-equilibrium of SOC was approached at about 20 years after conversion. However, subtle but persistent changes in molecular structures of the resultant SOM continued long after (up to 100 years) a steady state for SOC was approached. These molecular level changes in the inherent structural composition of SOC may exert considerable influence on biogeochemical cycling of C and bioavailability of essential nutrients present in association with SOM, and may significantly affect the sustainability of agriculture as well as potentials of the soils to sequester C in these tropical and subtropical highland agroecosystems. [ABSTRACT FROM AUTHOR]

Small-scale heterogeneity of organic carbon (C) forms in soils is poorly quantified since appropriate analytical techniques were not available up to now. Specifically, tools for the identification of functional groups on the surface of micrometer-sized black C particles were not available up to now. Scanning Transmission X-ray Microscopy (STXM) using synchrotron radiation was used in conjunction with Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy to investigate nano-scale distribution (50-nm resolution) of C forms in black C particles and compared to synchrotron-based FTJR spectroscopy. A new embedding technique was developed that did not build on a C-based embedding medium and did not pose the risk of heat damage to the sample. Elemental sulfur (5) was melted to 220°C until it polymerized and quenched with liquid N2 to obtain a very viscous plastic S in which the black C could be embedded until it hardened to a noncrystalline state and was ultrasectioned. Principal component and cluster analysis followed by singular value decomposition was able to resolve distinct areas in a black carbon particle. The core of the studied biomass-derived black C particles was highly aromatic even after thousands of years of exposure in soil and resembled the spectral characteristics of fresh charcoal. Surrounding this core and on the surface of the black C particle, however, much larger proportions of carboxylic and phenolic C forms were identified that were spatially and structurally distinct from the core of the particle. Cluster analysis provided evidence for both oxidation of the black C particle itself as well as adsorption of non-black C. NEXAFS spectroscopy has great potential to allow new insight into black C properties with important implications for biogeochemical cycles such as mineralization of black C in soils and sediments, and adsorption of C, nutrients, and pollutants as well as transport in the geosphere, hydrosphere, and atmosphere. [ABSTRACT FROM AUTHOR]

Increasing weather risks threaten agricultural production systems and food security across the world. Maintaining agricultural growth while minimizing climate shocks is crucial to building a resilient food production system and meeting developmental goals in vulnerable countries. Experts have proposed several technological, institutional and policy interventions to help farmers adapt to current and future weather variability and to mitigate greenhouse gas (GHG) emissions. This paper presents the climate-smart village (CSV) approach as a means of performing agricultural research for development that robustly tests technological and institutional options for dealing with climatic variability and climate change in agriculture using participatory methods. It aims to scale up and scale out the appropriate options and draw out lessons for policy makers from local to global levels. The approach incorporates evaluation of climate-smart technologies, practices, services and processes relevant to local climatic risk management and identifies opportunities for maximizing adaptation gains from synergies across different interventions and recognizing potential maladaptation and trade-offs. It ensures that these are aligned with local knowledge and link into development plans. This paper describes early results in Asia, Africa and Latin America to illustrate different examples of the CSV approach in diverse agroecological settings. Results from initial studies indicate that the CSV approach has a high potential for scaling out promising climate-smart agricultural technologies, practices and services. Climate analog studies indicate that the lessons learned at the CSV sites would be relevant to adaptation planning in a large part of global agricultural land even under scenarios of climate change. Key barriers and opportunities for further work are also discussed. [ABSTRACT FROM AUTHOR]