Molecular signature and sources of biochemical recalcitrance of organic C in Amazonian Dark Earths

Amazonian Dark Earths (ADE) are a unique type of soils developed through intense anthropogenic activities that transformed the original soils into Anthrosols throughout the Brazilian Amazon Basin. We conducted a comparative molecular-level investigation of soil organic C (SOC) speciation in ADE (ages between 600 and 8700 years B.P.) and adjacent soils using ultraviolet photo-oxidation coupled with ¹³C cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR), synchrotron-based Fourier transform infrared-attenuated total reflectance (Sr-FTIR-ATR) and C (1s) near edge X-ray absorption fine structure (NEXAFS) spectroscopy to obtain deeper insights into the structural chemistry and sources of refractory organic C compounds in ADE. Our results show that the functional group chemistry of SOC in ADE was considerably different from adjacent soils. The SOC in ADE was enriched with: (i) aromatic-C structures mostly from H- and C-substituted aryl-C, (ii) O-rich organic C forms from carboxylic-C, aldehyde-C, ketonic-C and quinine-C, and (iii) diverse group of refractory aliphatic-C moieties. The SOC in adjacent soils was predominantly composed of O-alkyl-C and methoxyl-C/N-alkyl-C structures and elements of labile aliphatic-C functionalities. Our study suggests that the inherent molecular structures of organic C due to selective accumulation of highly refractory aryl-C structures seems to be the key factor for the biochemical recalcitrance and stability of SOC in ADE. Anthropogenic enrichment with charred carbonaceous residues from biomass-derived black C (BC) is presumed to be the precursor of these recalcitrant polyaromatic structures. Our results also highlight the complementary role that might be played by organic C compounds composed of O-containing organic C moieties and aliphatic-C structures that persisted for millennia in these anthropic soils as additional or secondary sources of chemical recalcitrance of SOC in ADE. These organic C compounds could be the products of: (i) primary recalcitrant biomolecules from non-BC sources or (ii) secondary processes involving microbial mediated oxidative or extracellular neoformation reactions of SOC from BC and non-BC sources; and stabilized through physical inaccessibility to decomposers due to sorption onto the surface or into porous structures of BC particles, selective preservation or through intermolecular interactions involving clay and BC particles.     

Late Cretaceous eclogite in the Eastern Rhodopes (Bulgaria): evidence for subduction under the Sredna Gora magmatic arc

International Journal of Earth Sciences - The Rhodopes in Bulgaria and Greece represent a nappe stack of high-grade units with polymetamorphic history. Constraining the time of metamorphism in...     

Sensitivity-guided reduction of parametric dimensionality for multi-objective calibration of watershed models

Problem complexity for watershed model calibration is heavily dependent on the number of parameters that can be identified during model calibration. This study investigates the use of global sensitivity analysis as a screening tool to reduce the parametric dimensionality of multi-objective hydrological model calibration problems while maximizing the information extracted from hydrological response data. This study shows that by expanding calibration problem formulations beyond traditional, statistical error metrics to also include metrics that capture indices or signatures of hydrological function, it is possible to reduce the complexity of calibration while maintaining high quality model predictions. The sensitivity-guided calibration is demonstrated using the Sacramento Soil Moisture Accounting (SAC-SMA) conceptual rainfall–runoff model of moderate complexity (i.e., up to 14 freely varying parameters). Using both statistical and hydrological metrics, optimization results demonstrate that parameters controlling at least 20% of the model output variance (through individual effects and interactions) should be included in the calibration process. This threshold generally yields 30–40% reductions in the number of SAC-SMA parameters requiring calibration – setting the others to a priori values – while maintaining high quality predictions. Two parameters are recommended to be calibrated in all cases (percent impervious area and lower zone tension water storage), three parameters are needed in drier watersheds (additional impervious area, riparian zone vegetation, and percent of percolation going to tension storage), and the lower zone parameters are crucial unless the watershed is very dry. Overall, this study demonstrates that a coupled, multi-objective sensitivity and calibration analysis better captures differences between watersheds during model calibration and serves to maximize the value of available watershed response time series. These contributions are particularly important given the ongoing development of more complex integrated models, which will require new tools to address the growing discrepancy between the information content of hydrological data and the number of model parameters that have to be estimated.     

Lightning evolution related to radar-derived microphysics in the 21 July 1998 EULINOX supercell storm

Results of a combined analysis of data from a C-band polarimetric Doppler radar and a 3D VHF interferometric lightning mapping system, as obtained during the European Lightning Nitrogen Oxides project (EULINOX) field campaign, are presented. For 21 July 1998, the lightning data from a supercell thunderstorm weakly indicate a tendency for a bi-level vertical distribution of lightning VHF emissions around the −15°C and −30°C temperature levels. Also, in some parts of the clouds, evidence is found for the presence of a lower positive charge center near the freezing level. However, where strong vertical motions prevail, VHF emissions are not organized in horizontal layers but in oblique or vertical regions. Correlation of VHF signals with radar quantities shows that in the growing storm, peak VHF activity is low and related to reflectivity factors around 30 dBZ, while after the mature stage, the peak VHF activity is about three times larger. The highest density of VHF signals is now found near reflectivity factors of 45 dBZ. A polarimetric hydrometeor classification indicates that during storm development, most lightning activity occurs where graupel and, secondarily, snow and small dry hail are present. In the decaying phase of the supercell hailstorm, however, most lightning VHF emissions stem from the region with hail and heavy rain. Furthermore, while the VHF signal frequency per cubic kilometer in the graupel and rain regions remains nearly constant throughout the supercell life cycle, the signal frequency in the hail region rises during storm decay.     

Garnet‐controlled very low velocities in the lower mantle transition zone at sites of mantle upwelling

Deep mantle plumes and associated increased geotherms are expected to cause an upward deflection of the lower–upper mantle boundary and an overall thinning of the mantle transition zone between about 410 and 660 km depth. We use subsequent forward modelling of mineral assemblages, seismic velocities, and receiver functions to explain the common paucity of such observations in receiver function data. In the lower mantle transition zone, large horizontal differences in seismic velocities may result from temperature‐dependent assemblage variations. At this depth, primitive mantle compositions are dominated by majoritic garnet at high temperatures. Associated seismic velocities are expected to be much lower than for ringwoodite‐rich assemblages at undisturbed thermal conditions. Neglecting this ultralow‐velocity zone at upwelling sites can cause a miscalculation of the lower–upper mantle boundary on the order of 20 km.     

Regime-dependent evaluation of accumulated precipitation in COSMO

Regime-dependent evaluation is a relatively new approach to assess model performance. It consists of classifying the model biases according to a discrete number of regimes and evaluating model output within each regime. In this paper, the regimes are firstly defined by the large-scale atmospheric circulation, based on the objective Jenkinson-Collison classification technique which distinguishes synoptic patterns by strength, direction and vorticity of the geostrophic flow. Eight directional and two vorticity circulation regimes (circulation types) are specified. In this way, it is possible to quantify the model performance for cases with for example westerly winds only, or with cyclonic circulation only. A second regime classification is based on temperature, which allows for detection of temperature-dependent model performance. Modelled accumulated precipitation (mm/6?h) is evaluated with rain gauges for the years 2007 and 2008. Two variants of the COSMO model are evaluated: a fine-resolution version (2.8?km, COSMO-DE) and a coarse-resolution version (7?km, COSMO-EU). In COSMO-EU, a windward/leeward effect becomes visible since circulation is related to dominant wind direction, hence to windward and lee side of orography. In COSMO-DE, no circulation dependent but a height-related bias is identified and further explored, making use of temperature-dependent evaluation which unveils a positive model bias related to solid precipitation.     

A biomarker and δ15N study of thermally altered Silurian cyanobacterial mats

Early Silurian cherts from the Holy Cross and Bardzkie Mountains (Poland) contain abundant microfossils morphologically resembling contemporary cyanobacteria. Most of the organic matter preserved in the cherts is highly mature and extensively degraded because of biological decomposition and progressive thermal alteration. These processes may have changed the original morphology of the deposited microbial remains, so the microfossil origin could be easily misinterpreted. The cherts were therefore examined using organic geochemical and stable isotope techniques to provide support for the presence of cyanobacterial remains. The nitrogen isotopic composition of bulk sediments and extractable organic matter ranged from +0.1‰ to ?2.2‰ and from +1.8‰ to ?1.7‰, respectively. The δ¹⁵N values are thus in good agreement with a contribution of diazotrophic cyanobacteria for both locations. Biomarkers in the Holy Cross Mts. cherts included mid-chain branched monomethyl alkanes, indicative of a cyanobacterial contribution. However, molecular fossils of a cyanobacterial origin were not detected in the Bardzkie Mts. cherts, most likely because of the greater maturity than those from the Holy Cross Mts.     

Analysis of the Moberg et al. (2005) hemispheric temperature reconstruction

The Moberg et al. (Nature 433(7026):613–617, 2005. doi:10.1038/nature03265; M05) reconstruction of northern hemisphere temperature variations from proxy data has been criticised; the M05 method may artificially inflate low-frequency variance relative to reality. We test this assertion by undertaking several pseudoproxy experiments in three climate model simulations—one control run and two forced simulations that include several time-varying radiative forcings. The pseudoproxy series are designed to have the same variance spectra as the real M05 proxies, primarily to mimic the low-resolution character of several series. A simple composite-plus-scale (CPS) method is also analysed. In the CPS case all input data behave like annually resolved proxies. The spectral domain performance of both M05 and CPS is found to be dependent on the noise type and noise level in pseudoproxies, on the variance spectrum of the climate model simulation, and on the degree of data smoothing. CPS performs better than M05 in most investigated cases with the control run, but leads to deflated low-frequency variance in some cases. With M05, low-frequency variance tend to be inflated for the control run but not for one of the forced runs and only very slightly with the other forced simulation. Hence, the M05 approach does not routinely inflate low-frequency variance. In our experiment, the M05 approach performs better in the spectral domain than CPS when applied to forced climate model simulations. The results underscore the importance of evaluating the variance spectrum of climate reconstructions.