Structure and Chemical Composition of Soil C-Rich Al-Si-Fe Coprecipitates at Nanometer Scale.

Soil carbon stabilization is mainly driven by organo-mineral interactions. Coprecipitates, of organic matter with short-range order minerals, detected through indirect chemical extraction methods, are increasingly recognized as key carbon sequestration phases. Yet the atomic structure of these coprecipitates is still rather conceptual. We used transmission electron microscopy imaging combined with energy-dispersive X-ray and electron energy loss spectroscopy chemical mappings, which enabled direct nanoscale characterization of coprecipitates from Andosols. A comparison with reference synthetic coprecipitates showed that the natural coprecipitates were structured by an amorphous Al, Si, and Fe inorganic skeleton associated with C and were therefore even less organized than short-range order minerals usually described. These amorphous types of coprecipitates resembled previously conceptualized nanosized coprecipitates of inorganic oligomers with organics (nanoCLICs) with heterogeneous elemental proportions (of C, Al, Si, and Fe) at nanoscale. These results mark a new step in the high-resolution imaging of organo-mineral associations, while shedding further light on the mechanisms that control carbon stabilization in soil and more broadly in aquatic colloid, sediment, and extraterrestrial samples.

Current controversies on mechanisms controlling soil carbon storage: implications for interactions with practitioners and policy-makers. A review.

There is currently an intense debate about the potential for additional organic carbon storage in soil, the strategies by which it may be accomplished and what the actual benefits might be for agriculture and the climate. Controversy forms an essential part of the scientific process, but on the topic of soil carbon storage, it may confuse the agricultural community and the general public and may delay actions to fight climate change. In an attempt to shed light on this topic, the originality of this article lies in its intention to provide a balanced description of contradictory scientific opinions on soil carbon storage and to examine how the scientific community can support decision-making despite the controversy. In the first part, we review and attempt to reconcile conflicting views on the mechanisms controlling organic carbon dynamics in soil. We discuss the divergent opinions about chemical recalcitrance, the microbial or plant origin of persistent soil organic matter, the contribution of particulate organic matter to additional organic carbon storage in soil, and the spatial and energetic inaccessibility of soil organic matter to decomposers. In the second part, we examine the advantages and limitations of big data management and modeling, which are essential tools to link the latest scientific theories with the actions taken by stakeholders. Finally, we show how the analysis and discussion of controversies can guide scientists in supporting stakeholders for the design of (i) appropriate trade-offs for biomass use in agriculture and forestry and (ii) climate-smart management practices, keeping in mind their still unresolved effects on soil carbon storage.

Bioenergetic control of soil carbon dynamics across depth.

Soil carbon dynamics is strongly controlled by depth globally, with increasingly slow dynamics found at depth. The mechanistic basis remains however controversial, limiting our ability to predict carbon cycle-climate feedbacks. Here we combine radiocarbon and thermal analyses with long-term incubations in absence/presence of continuously 13C/14C-labelled plants to show that bioenergetic constraints of decomposers consistently drive the depth-dependency of soil carbon dynamics over a range of mineral reactivity contexts. The slow dynamics of subsoil carbon is tightly related to both its low energy density and high activation energy of decomposition, leading to an unfavourable 'return-on-energy-investment' for decomposers. We also observe strong acceleration of millennia-old subsoil carbon decomposition induced by roots ('rhizosphere priming'), showing that sufficient supply of energy by roots is able to alleviate the strong energy limitation of decomposition. These findings demonstrate that subsoil carbon persistence results from its poor energy quality together with the lack of energy supply by roots due to their low density at depth.

Copper (Cu) speciation in organic-waste (OW) amended soil: Instability of OW-borne Cu(I) sulfide and role of clay and iron oxide minerals.

The geochemistry of copper (Cu) is generally assumed to be controlled by organic matter in soils. However, the role of clay and iron oxide minerals may be understated. Soil density fractionation, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) were combined to assess the long-term behavior of Cu in an agricultural soil subject to organic waste application. Two unprecedented molecular environments of natural Cu (i.e. Cu inherited from the parent rock) in soils are reported: Cu dimer in the interlayer of vermiculite and Cu structurally incorporated within hematite. Moreover, the soil naturally containing Cu-vermiculite, Cu-hematite, but also Cu-kaolinite (Cutotal = 122 mg·kg-1) was amended over 11 years with Cu-rich pig slurry in which Cu was 100 % Cu(I) sulfide. Natural Cu associated with clay and iron oxide minerals persisted in the amended soil, but the exogenous Cu(I) sulfide was unstable. The increase in Cu concentration in the amended soil to 174 mg·kg-1 was accounted for the increase of Cu sorbed to kaolinite and Cu bound to organic matter. These results are important for better understanding the natural occurrence of Cu in soils and for assessing the environmental impacts of organic waste recycling in agricultural fields.

Atmosphere-soil carbon transfer as a function of soil depth.

The exchange of carbon between soil organic carbon (SOC) and the atmosphere affects the climate1,2 and-because of the importance of organic matter to soil fertility-agricultural productivity3. The dynamics of topsoil carbon has been relatively well quantified4, but half of the soil carbon is located in deeper soil layers (below 30 centimetres)5-7, and many questions remain regarding the exchange of this deep carbon with the atmosphere8. This knowledge gap restricts soil carbon management policies and limits global carbon models1,9,10. Here we quantify the recent incorporation of atmosphere-derived carbon atoms into whole-soil profiles, through a meta-analysis of changes in stable carbon isotope signatures at 112 grassland, forest and cropland sites, across different climatic zones, from 1965 to 2015. We find, in agreement with previous work5,6, that soil at a depth of 30-100 centimetres beneath the surface (the subsoil) contains on average 47 per cent of the topmost metre's SOC stocks. However, we show that this subsoil accounts for just 19 per cent of the SOC that has been recently incorporated (within the past 50 years) into the topmost metre. Globally, the median depth of recent carbon incorporation into mineral soil is 10 centimetres. Variations in the relative allocation of carbon to deep soil layers are better explained by the aridity index than by mean annual temperature. Land use for crops reduces the incorporation of carbon into the soil surface layer, but not into deeper layers. Our results suggest that SOC dynamics and its responses to climatic control or land use are strongly dependent on soil depth. We propose that using multilayer soil modules in global carbon models, tested with our data, could help to improve our understanding of soil-atmosphere carbon exchange.

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation, mineralogy and microanalysis.

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d < 1.9, 1.9 < d < 2.3 g cm(-3)) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d < 1.9, 1.9 < d < 2.3, 2.3 < d < 2.6, and d > 2.8 g cm(-3)) and are mostly in the 2.3 < d < 2.6 g cm(-3) fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.

New combination of EXAFS spectroscopy and density fractionation for the speciation of chromium within an andosol.

Studying speciation of heavy metals instead of their total concentration in a complex matrix such as soil is a scientific challenge that requires a combination of different analytical techniques. We compared the speciation of Cr within an andosol (island of Réunion) by using X-ray absorption spectroscopy (XAS) and sequential extraction. Contradictory results were obtained since the fraction of Cr bound to organic matter was detected only with the latter method. As bulk soil is rather complex, its fractionation by a densimetric method decreased its heterogeneity. We found that 60% Cr was within chromite-type primary minerals. Weathering of these phases led to Fe and Cr release, eventually resulting in either coprecipitation as mixed FeCr oxyhydroxide (16% total Cr) or precipitation of a Cr oxyhydroxide (5% total Cr). Our results also revealed that 13% Cr was bound to organic matter. The organic matter was complexed with mineral phases to form organomineral complexes with a density ranging from 1.9 to 2.6. The use of an original density fractionation-based sample preparation allowed identification of the role of organic matter in chromium speciation within an andosol and to overcome the difficulties of EXAFS to detect light elements in the vicinity of heavy elements.

Another continental pool in the terrestrial silicon cycle.

Silicon is the second most abundant element on Earth. It is an important nutrient for phytoplankton and is readily absorbed by terrestrial vegetation; it also assists the removal of carbon dioxide from the atmosphere through the weathering of silicates. But the continental cycle of silicon is not well known, and only a few studies have attempted to use silicon stable isotopes (28Si, 29Si and 30Si) to quantify the continental silicon reservoirs. Dissolved silicon in sea and river waters forms a reservoir of mean isotopic value +1.1 per thousand (refs 7, 10). It is enriched in 30Si with respect to the igneous rocks reservoir, which has a mean isotopic value of -0.3 per thousand (refs 4, 9). This enrichment can only be produced by a major fractionation during weathering, and should result in the formation of a continental 30Si-depleted reservoir. Such a reservoir, however, has not been identified to date. Here we analyse silicon isotopes of in situ quartz from a sandstone series in France, using a new-generation secondary ion mass spectrometry apparatus. We show that quartz that precipitates as siliceous cements forms a strongly 30Si-depleted reservoir with isotopic values down to -5.7 per thousand, a more negative value than any previously published for terrestrial samples. Our findings suggest that quartz re-precipitation plays an important role in the biogeochemical cycle of silicon.