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Soil degradation is one of the most serious threats to sustainable crop production in many tropical agroecosystems where extensification rather than intensification of agriculture has occurred. In the highlands of western Kenya, we investigated soil nitrogen (N) and phosphorus (P) constraints to maize productivity across a cultivation chronosequence in which land-use history ranged from recent conversion from primary forest to 100 years in continuous cropping. Nutrient treatments included a range of N and P fertilizer rates applied separately and in combination. Maize productivity without fertilizer was used as a proxy measure for indigenous soil fertility (ISF). Soil pools of mineral nitrogen, strongly bound P and plant-available P decreased by 82%, 31% and 36%, and P adsorption capacity increased by 51% after 100 years of continuous cultivation. For the long rainy season (LR), grain yield without fertilizer declined rapidly as cultivation age increased from 0 to 25 years and then gradually declined to a yield of 1.6Mgha � 1 , which was maintained as time under cultivation increased from 60 to 100 years. LR grain yield in the old conversions was only 24% of the average young conversion grain yield (6.4Mgha � 1 ). Application of either N or P alone significantly increased grain yield in both the LR and short rainy (SR) seasons, but only application of 120kgNha � 1 on the old conversion increased yield by 41Mgha � 1 . In both SR and LR, there was a greater average yield increment response to N and P when applied together (ranging from 1 to 3.8Mgha � 1 for the LR), with the greatest responses on the old conversions. The benefit‐cost ratio (BCR) for applying 120kgNha � 1 alone was o1 except on the old conversions, while BCRs were41 for applying 25kgPha � 1 alone at all levels of conversion for both seasons. Application of both N (120kgNha � 1 ) and P (25kgPha � 1 ) on the old conversions resulted in the greatest BCRs. This study clearly indicates that maize productivity responses to N and P fertilizer are significantly affected by the age of cultivation and its influence on ISF, but that loss of productivity can be restored rapidly when these limiting nutrients are applied. Management strategies should consider ISF and economic factors to determine optimal N and P input requirements for achieving and sustaining profitable crop production on degraded soils.

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 13 C 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.

Methodological constraints limit the extent to which existing soil aggregationmodels explaincarbon(C) stabilization insoil. Wehypothesize 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-mm microaggregates from a Kenyan Oxisol. Ultra-thin sections were obtained after embedding microaggregates in a sulfur block and sectioning on a cryo-microtome at 255C. 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-mm 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.

Black Carbon (BC) may significantly affect nutrient retention and play a key role in a wide range of biogeochemical processes in soils, especially for nutrient cycling. Anthrosols from the Brazilian Amazon (ages between 600 and 8700 yr BP) with high contents of biomassderived BC had greater potential cation exchange capacity (CEC measured at pH 7) per unit organic C than adjacent soils with low BC contents.Synchrotron-based near edge X-ray absorption fine structure (NEXAFS) spectroscopy coupled with scanning transmission X-ray microscopy (STXM) techniques explained the source of the higher surface charge of BC compared with non-BC by mapping crosssectional areas of BC particles with diameters of 10 to 50 mm for C forms. The largest cross-sectional areas consisted of highly aromatic or only slightly oxidized organic C most likely originating from the BC itself with a characteristic peak at 286.1 eV, which could not be found in humic substance extracts, bacteria or fungi. Oxidation significantly increased from the core of BC particles to their surfaces as shown by the ratio of carboxyl-C/aromatic-C. Spotted and non-continuous distribution patterns of highly oxidized C functional groups with distinctly different chemical signatures on BC particle surfaces (peak shift at 286.1 eV to a higher energy of 286.7 eV) indicated that non-BC may be adsorbed on the surfaces of BC particles creating highly oxidized surface. As a consequence of both oxidation of the BC particles themselves and adsorption of organic matter to BC surfaces, the charge density (potential CEC per unit surface area) was greater in BC-rich Anthrosols than adjacent soils. Additionally, a high specific surface area was attributable to the presence of BC, which may contribute to the high CEC found in soils that are rich in BC.

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 on 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/σ* transition of aliphatic-C and 1s-π* 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 CH 2 or CH 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.