Organic Carbon Preservation Research Articles

Changes in Soil Organic Pool and Carbon Preservation Capacity of Macro- and Micro-aggregates in Response to Land-Use Change in North-Western India

Changes in Soil Organic Pool and Carbon Preservation Capacity of Macro- and Micro-aggregates in Response to Land-Use Change in North-Western India

Evidence for preservation of organic carbon interacting with iron in material displaced from retrogressive thaw slumps: Case study in Peel Plateau, western Canadian Arctic

In northern high latitudes, rapid warming is set to amplify carbon-climate feedbacks by enhancing permafrost thaw and biogeochemical transformation of large amounts of soil organic carbon. However, between 30 % and 80 % of permafrost soil organic carbon is considered to be stabilized by geochemical interactions with the soil mineral pool and thus less susceptible to be emitted as greenhouse gases. Quantification of the nature of and controls on mineral-organic carbon interactions is needed to better constrain permafrost-carbon-climate feedbacks, particularly in ice-rich environments resulting in rapid thaw and development of thermokarst landforms. On sloping terrain, mass wasting features called retrogressive thaw slumps are amongst the most dynamic forms of thermokarst. These multi-decadal disturbances grow due to ablation of an ice-rich headwall, and their enlargement due to warming of the Arctic is mobilizing vast stores of previously frozen materials. Here, we investigate headwall profiles of seven retrogressive thaw slumps and sediments displaced from these mass wasting features from the Peel Plateau, western Canadian Arctic. The disturbances varied in their headwall height (2 to 25 m) and affected land surface area (<1 to > 30 ha). We present total and water extractable mineral element concentrations, mineralogy, and mineral-organic carbon interactions in the headwall layers (active layer, permafrost materials above an early Holocene thaw unconformity, and Pleistocene-aged permafrost tills) and in displaced material (suspended sediments in runoff and material accumulated on the debris tongue). Our data show that the main mechanism of organic carbon stabilization through mineral-organic carbon interactions within the headwall is the complexation with metals (mainly iron), which stabilizes 30 ± 15 % of the total organic carbon pool with higher concentrations in near-surface layers compared to deep permafrost. In the displaced material, this proportion drops to 18 ± 5 %. In addition, we estimate that up to 12 ± 5% of the total organic carbon is stabilized by associations to poorly crystalline iron oxides, with no significant difference between near-surface layers, deep permafrost and displaced material. Our findings suggest that the organic carbon interacting with the sediment mineral pool in slump headwalls is preserved in the material mobilized by slumping and displaced as debris. Overall, up to 32 ± 6 % of the total organic carbon displaced by retrogressive thaw slumps is stabilized by organo-mineral interactions in this region. This indicates that organo-mineral interactions play a significant role in the preservation of organic carbon in the material displaced from retrogressive thaw slumps over years to decades after their development resulting in decadal to centennial scale sequestration of this retrogressive thaw slump-mobilized organic carbon interacting with the soil mineral pool.

Carbon stability and morphotype composition of biochars from feedstocks in the Mekong Delta, Vietnam

This study investigates carbon stability of biochars produced from wood, herbaceous, and fruit agricultural waste products from southern Vietnam. The biochars were produced by pyrolysis to 500 °C, 700 °C, and 900 °C at a heating rate of 10 °C/min. Organic geochemistry and petrology have well-established measurable parameters that define degree of preservation of organic carbon in the Earth's crust. These parameters are utilized, comparatively, to infer the organic carbon stability in biochars relative to that preserved in the geological carbonaceous rocks. The stability of carbon was assessed by measuring incident-light random reflectance (%Ro) to determine the degree of thermally induced aromatization/ordering of the biochar carbon molecules. Additionally, the organic carbon content of the biochars was quantitatively separated into reactive and non-reactive carbon fractions based on thermodynamic stability of CH and CO bonds. The results show increasing carbon stability with increasing pyrolysis temperature and indicate high stability has been achieved at 700 °C and 900 °C where the biochars have the highest total organic carbon (TOC) contents and lowest Hydrogen Index values. Occurrence of a small quantity of readily degradable, labile free hydrocarbons (soluble organic matter; SOM) is due to condensation of the thermally generated hydrocarbons on the surfaces of the biochars. This fraction is minimized in the biochars produced at 700 °C and 900 °C due to volatilization of the free hydrocarbons at higher pyrolysis temperatures. The relatively substantial content of labile hydrocarbons associated with particulate organic matter (POM) in the 500 °C produced biochars is attributed to the incomplete pyrolyzation of the feedstock at this temperature. This fraction declines to near zero at 700 °C and 900 °C as complete carbonization is achieved at these higher temperatures. The overall carbon budget within the biochar shows that irrespective of the biochar type, over 97% of the TOC consists of highly refractory, residual carbon that geochemically is considered to possess long-term stability (“inert”). This is further underpinned by a pronounced increase in biochar mean random reflectance from <2.33% at 500 °C to >4.35% when pyrolyzed at 700 °C, indicating a highly polyaromatized condensed carbon structure. Rice husk is an exception as it yields a mean reflectance of 4.55% at 500 °C suggesting that pyrolysis temperature is not the only factor controlling %Ro and hence carbon stability. Furthermore, the biochar compositions show a relationship between feedstock and pyrolysis temperature. The biochar morphotype composition changes significantly with increasing temperature, but the analyzed biochars are all dominated by fusinoid/solid (primarily fusinoid) morphotypes with the highest initial quantity recorded at 500 °C. This quantity decreases with increasing pyrolysis temperature while porous morphotypes (tenuinetwork, crassinetwork, mixed porous, mixed dense) increase. Variations in morphotype composition observed between the biochars is attributed to the structural nature of the feedstocks.

Soil Carbon, Nitrogen, and Phosphorus Stoichiometry and Fractions in Blue Carbon Ecosystems: Implications for Carbon Accumulation in Allochthonous-Dominated Habitats.

Blue carbon ecosystems (BCEs) including mangroves, saltmarshes, and seagrasses are highly efficient for organic carbon (OC) accumulation due to their unique ability to trap high rates of allochthonous substrates. It has been suggested that the magnitude of OC preservation is constrained by nitrogen (N) and phosphorus (P) limitation in response to climate and anthropogenic changes. However, little is known about the connection of soil OC with N-P and their forms in response to allochthonous inputs in BCEs. By analyzing soil OC, N, and P densities of BCEs from 797 sites globally, we find that, in China, where allochthonous OC provides 50-75% of total OC, soil C/P and N/P ratios are 4- to 8-fold lower than their global means, and 23%, 29%, and 20% of buried OC, N, and P are oxidation-resistant fractions that linked with minerals. We estimate that the OC stocks in China should double over the next 40 years under high allochthonous inputs and elevated N/P ratio scenarios during BCE restoration. Allochthonous-dominated BCEs thus have the capacity to enhance refractory and mineral bound organic matter accumulation. Protection and restoration of such BCEs will provide long-term mitigating benefits against sea level rise and greenhouse gas emissions.

Low content of highly reactive iron in sediments from Prydz Bay and the adjacent Southern Ocean: Controlling factors and implications for sedimentary organic carbon preservation

Examining iron (Fe) speciation in marine sediments is critical to understand Fe and carbon biogeochemical cycling in polar regions. In this study, we investigated the speciation of Fe in sediments from Prydz Bay and the adjacent Southern Ocean, and examined the factors controlling Fe speciation and its relationship with total organic carbon (TOC). Our results reveal that unreactive silicate Fe (FeU) is the dominant pool of total Fe (FeT), followed by poorly reactive sheet silicate Fe (FePRS), reducible crystalline Fe oxides (Feox2), easily reducible amorphous/poorly crystalline Fe oxides (Feox1), and magnetite (Femag), with carbonate-associated ferrous Fe (Fecarb) being the smallest pool. The highly reactive Fe (FeHR)/FeT ratios (0.13 ± 0.06) in our study area are among the lowest end-member globally, primarily due to weak bedrock weathering and slow glacier melting. The Feox1/FeT ratios are similar to those in continental shelf and marginal seas containing highly weathered materials, while the Feox2/FeT ratios are significantly lower. This result implicates that low temperature inhibits the aging of iceberg melting-sourced Feox1 potentially, and accordingly the regulation of weathering on the FeHR/FeT ratio is mainly reflected in Feox2/FeT ratio. There are no significant correlations between TOC and FeHR, Fecarb, Feox1 or Feox2 in the research region. Four distinct patterns of TOC/FeHR ratio can be discerned by summarizing the global data set: (a) high TOC/FeHR ratios (&amp;gt; 2.5) are likely the result of high marine primary productivity and low chemically weathered source materials; (b) low TOC/FeHR ratios (&amp;lt; 0.6) are caused by high rates of FeHR inputs and OC remineralization; (c) mid-range TOC/FeHR ratios (0.6 – 2.5) typical of most river particulates and marginal sea sediments indicate the same FeHR and OC sources and/or interactions between each other; (d) both low TOC and FeHR content is the result of low marine primary productivity and weak chemical weathering. Our findings provide new insights into the relationship between FeHR and TOC in polar sediments.

Oxygenation of the Earth aided by mineral–organic carbon preservation

Photosynthesis produces molecular oxygen, but it is the burial of organic carbon in sediments that has allowed this O2 to accumulate in Earth’s atmosphere. Yet many direct controls on the preservation and burial of organic carbon have not been explored in detail. For modern Earth, it is known that reactive iron phases are important for organic carbon preservation, suggesting that the availability of particulate iron could be an important factor for the oxygenation of the oceans and atmosphere over Earth history. Here we develop a theoretical model to investigate the effect of mineral–organic preservation on the oxygenation of the Earth, supported by a proxy compilation for terrigenous inputs and the burial of reactive iron phases, and find that changes to the rate of iron input to the global ocean constitute an independent control on atmosphere–ocean O2 and marine sulfate levels. We therefore suggest that increasing continental exposure and denudation may have helped fuel the rise in atmospheric O2 and other oxidants over Earth history. Finally, we show that inclusion of mineral–organic preservation makes the global marine O2 reservoir more resilient to changes in nutrient levels by breaking the link between productivity and organic carbon burial. We conclude that mineral–organic preservation is an important missing process in current assessments of Earth’s long-term carbon cycle.

Intensification of the East Asian winter monsoon resulted in greater preservation of terrestrial organic carbon on the inner shelf of the East China Sea since the last 1400 years

The marine shelves of passive margins receive huge amount of terrestrial organic carbon (OC) exported from adjacent terrestrial ecosystems. Long-term sequestration of terrestrial OC into marine sediments plays an important role in the global carbon cycle on a range of timescales. However, our knowledge of factors affecting the fate of terrestrial OC in continental-marginal settings is incomplete, with ongoing debates regarding rates of degradation during transport and burial. In this paper, we employ analyses of total OC and its stable isotope (δ13C), terrestrial biomarkers and mineral surface area in sediment core 39-A obtained from mud-rich regions of the inner shelf of the East China Sea to investigate terrestrial OC burial history over the last 3000 years. Analysis of terrestrial lipid biomarker and terrestrial OC calculated based on a δ13C-binary mixing model shows increasing trends since ∼1400 yr BP, accompanied by a synchronous increase of terrestrial OC preservation rate. By compiling terrestrial OC records from mud-rich regions of the East China Sea inner shelf, we propose that the most reasonable explanation is the intensification of the East Asian Winter Monsoon. This resulted in a strengthening of coastal currents, which accelerated lateral transport speed (thereby shortening oxygen exposure time) of Changjiang (Yangtze River)-derived terrestrial OC towards the deposition site, resulting in greater terrestrial OC preservation. Moreover, we also found delayed responses of terrestrial OC burial to the East Asian Winter Monsoon in the middle and southern part of the Min-Zhe coastal mud region, implying that the transport of terrestrial OC towards this region took place on a centennial-time scale. Our study sheds new light on mechanisms controlling terrestrial OC transport and burial processes in a typical passive marginal sea.

Rice–fish coculture system enhances paddy soil fertility, bacterial network stability and keystone taxa diversity

High-input, modern rice farming (MRF) has caused severe soil degradation worldwide, necessitating a transition towards more sustainable practices. The traditional rice–fish coculture (RFC) and manure fertilization (Manure) may provide valuable insights to this transition. However, it remains elusive how long-term agricultural conversion influences microbial community structure, soil fertility, and food supply. Here, we performed six-year conversions of MRF to either RFC or Manure in a hilly area of Sichuan (China). We found that agricultural conversions exerted a greater impact than rice growing stages on bacterial community structure. The RFC bacterial network exhibited the highest modularity and robustness, but also harbored the most diverse keystone taxa, followed by Manure. In contrast, MRF displayed network properties that are characteristic of unstable communities. Importantly, RFC also exhibited the greatest capability in improving the preservation of soil organic carbon, nitrogen, and phosphorus, and has significantly increased soil pH (> 1.5 units). Yet, adopting traditional practices, particularly Manure, decreased rice yields, but fish harvested in RFC could offset the decrease in rice yield. Our field study highlights bacterial network structure and keystone taxa diversity as possible indicators for agriculture sustainability, but also incentivizes the integration of traditional RFC in developing novel sustainable agricultural practices.

Seasonal constraints on the burial of organic carbon in the eutrophic Lake Taihu

Eutrophication alters the function of lake ecosystems through phytoplankton blooms and is a major contributor to organic carbon (OC) burial in lakes worldwide. Although Lake Taihu is notable for its severe eutrophication yet low OC burial, why cyanobacteria-derived OC is ineffectively buried in the lake is unknown. Because seasonal hydrological and ecological dynamics in eutrophic lacustrine ecosystems would significantly modify the preservation and degradation behaviors of OC, seasonal variations in paired particulate samples from both the water column and surface sediment are critical in evaluating cyanobacteria-derived OC burial. In this study, we present the steroid results of water and sediments collected from Meiliang Bay in Lake Taihu across cyanobacteria-bloom and decay seasons (from May 2018 to June 2019) to investigate constraints on the seasonal burial of autochthonous and allochthonous OC. The results indicate that cyanobacteria contribute a considerable amount of OC to the water body in the cyanobacterial bloom season, while terrestrial OC becomes the main contributor during the cyanobacterial decay season. Although OC degradation occurs throughout the water column, substantially more OC degradation was observed at the water-sediment interface. The extensive degradation of OC in the bloom season eventually reverses the seasonal distribution characteristics of particulate OC in the water column, leading to less accumulation of OC under the background of higher cyanobacteria-derived OC input. The combined effect of OC bioavailability, temperature, oxygen exposure, and more importantly microorganism activities, accounts for much higher OC degradation rates in the bloom season. Similar phenomena were observed in subtropical shallow lakes with high primary productivity, suggesting that eutrophication might have a limited influence on OC burial when compared to other factors related to OC degradation.

Shift in the Mode of Carbon Cycling Recorded by Biomarkers and Carbon Isotopic Compositions in the Yanchang Formation, Ordos Basin: Autotrophy vs Heterotrophy.

Organic-rich shales and mudstones have long been investigated regarding the control of source, environment, climate, etc. on the enrichment of organic carbon. However, little is documented about how autotrophy and heterotrophy influence organic carbon cycling/export. Here, we show molecular and carbon isotopic compositional changes of the shale or mudstone source rocks from the Chang 3 to 7 members of the Yanchang Formation. The Chang 7 member source rocks have higher quality (480-500 mg/g) and total organic carbon (TOC) (15.3% on average) than other member source rocks; the sterane/hopane ratio and the δ13C of organic carbon and kerogen decrease from the Chang 3 to 7 members, but Δδ ([average δ13C of n-C17 + n-C18] - [average δ13C of pristane + phytane]) increases, and no aryl isoprenoids and C40 aromatic carotenoids (e.g., isorenieratane) were observed. These low maturity biomarker features suggest that there were no water stratification, photic zone euxinia (PZE), and no obvious change in the organic matter source, and the water column is generally anoxic. A comparison of the δ13C of Pr and Ph with the δ13C of the n-C17 and n-C18 alkanes reveals a shift in the mode of carbon cycling/export (autotrophy versus heterotrophy) in the Yanchang Formation and that there was dominant heterotrophic bacterial activity or bacterial biomass in the Chang 7 member. The TOC spike in the Chang 7 member may result from boosted carbon cycling/export that improves organic carbon preservation than other members. Possible external forcings on the shift are abundant hydrothermal- or volcanic-derived metal salts as electron acceptors in the palaeowater, which is a reasonable explanation for enhanced heterotrophic bacterial activity. This finding improves our understanding of heterotrophic bacterial activity control on organic matter (OM) preservation and may be a significant supplement for understanding the ecological or environmental forcings in the Yanchang Formation, Ordos Basin.

Preferential preservation of pre-aged terrestrial organic carbon by reactive iron in estuarine particles and coastal sediments of a large river-dominated estuary

Reactive iron (FeR) plays an important role in the preservation of organic carbon (OC) in coastal sediments, yet changes in the OC bound to FeR (OC-FeR), during transport and deposition, remain poorly understood. The main goal of this work is to investigate the variation of the age and composition of OC-FeR from estuarine suspended particulate matter (SPM) to coastal sediments, to further understand the role of FeR in the preservation of terrestrial OC exported from large rivers into marginal seas. We examined OC and its carbon isotopic composition (Δ14Cbulk, δ13Cbulk), specific surface area (SSA), grain size composition, lignin phenols, FeR, Mössbauer spectroscopy, and isotopic signatures of OC-FeR (Δ14COC-FeR, δ13COC-FeR) in SPM and surface sediments of the Changjiang Estuary. Particulate OC (POC) and FeR concentrations in SPM are significantly higher than in surface sediments, with no significant differences between surface- and bottom-water SPM. This indicates that loss of OC and FeR largely occurs at the sediment–water interface due in part, to rapid Fe cycling. The percentage of OC-FeR (fOC-FeR) in SPM (6.6 ± 1.9%) is similar to that in mobile-mud sediment (8.8 ± 1.8%). There are no significant differences in OC-FeR content (p > 0.05) from SPM to mobile-mud sediments, but non-OC-FeR largely decreases, suggesting that terrestrial OC-FeR has greater stability compared to terrestrial non-OC-FeR. Both δ13COC-FeR and Δ14COC-FeR are lower than bulk OC, indicating that FeR is mainly associated with pre-aged soil OC of terrestrial plant origin, especially in estuarine SPM and mobile-mud sediments. Taken together, binding with FeR is a potential long-term protection mechanism for terrestrial OC. Both Δ14Cbulk and Δ14COC-FeR decrease with an increase in the ratio of hematite to (super)paramagnetic Fe3+, indicating that high-crystallinity iron oxide is largely associated with pre-aged terrestrial OC, and there is a potential joint maturation mechanism between FeR and its associated OC. Based on literature comparisons of soils, estuarine SPM, and marine sediments, OC-FeR associations are controlled mainly by sedimentary regimes, FeR compositions, and OC sources. This work supports the notion that FeR plays an important role in the stabilization and transport of river-derived terrestrial OC.

Effects of biochar and fertilizer amendments on soil acidity and soil organic carbon content on Luvic Anthrosols in Russian Far East

The paper presents the results of a study effect of biochar together with fertilizers on the acidic properties and organic content in Luvic Anthrosols in the South of the Russian Far East during two years field experiment. As a result of the study, it was proved that the combination of biochar with organic fertilizers contributes to the preservation of organic carbon in the soil at the end of the growing season, even 16 months after application both on the drainage site and without drainage. The most effective shift of acidity values towards neutral occurs 4 months after the introduction of biochar and combination with fertilizers for all experimental variants on a non-drainage site. After 16 months the acidity values almost return to the original values of the beginning of the growing season.

Effects of Volcanic Activity on Organic Matter Enrichment in the Sediments and its Implications for Oil and Gas Exploration and Development

Volcanic activity is an important geological phenomenon in the evolution and development of the earth and brings rich resources to benefit human society, such as geothermal resources, valuable minerals, petroleum, and natural gas, although volcanic eruptions cause serious threats to the ecological environment of our planet. The co-development of oil and gas and volcanic activity in the same basin is a common phenomenon globally. Volcanic activity can bring abundant nutrients into the basins, conducive to the development of algae and other microorganisms in the water body. After the death of organisms, their remaining settles down to the water bottom and accumulate in the sediments. Meanwhile, reducing gases, releasing along with the volcano eruption, including H2S, CO2, etc., result in anoxia in the water body, benefiting the preservation of organic matter at the bottom and brings a large amount of material basis for the generation of oil and gas. Additionally, volcanic activity and hydrothermal fluids are rich in acid substances, will dissolve part of the minerals in the formation, generates a large number of migration channels for oil and gas migration. Some volcanic rocks are rich in pores, making them natural tanks for oil and gas storage. However, volcanic activity also has destructive effects on oil and gas accumulation. High hydrothermal/volcanic input can dilute primary productivity or reduce the abundance of organic matter due to high deposition rates, while excessive volcanic activity or hydrothermal fluid input can introduce large amounts of sulfate into the water, causing strong bacterial sulfate reduction (BSR). The high consumption of organic matter can hamper the organic matter enrichment. Therefore, how to define appropriate volcanic activity conducive to organic carbon preservation, and to establish the relationship model between volcanic activity and organic matter enrichment, are key scientific issues.

New evidence for preservation of contemporary marine organic carbon by iron in Arctic shelf sediments

The protection of organic carbon through association with iron minerals (FeR) is an important factor in its stabilisation, long-term storage, and burial efficiency in marine sediments. However, large uncertainties still exist concerning the sources, lability, age, and composition of the organic matter associated with FeR in natural sediments. Therefore, the timing and environmental setting of the carbon-iron bonding process remain elusive. Here we use radiocarbon (Δ14C) and stable isotopes (δ13C) of downcore bulk sedimentary organic matter, benthic foraminifera and the organic carbon fraction bound to FeR to interrogate the source and age of the organic carbon pool associated with FeR in Arctic marine sediments. In the Barents Sea, we find that the organic carbon associated with FeR is younger overall than the bulk organic matter and is probably marine derived. The comparison to other investigations of OC-FeR origins reveals that in large parts of Arctic shelf regions FeR associated organic carbon is radiocarbon enriched and has a higher δ13Corg value compared to the bulk sediment, irrespective of sediment depth/age. Our findings suggest a rapid and preferential binding of fresh and marine organic matter with FeR. Hence, labile organic matter prone to decomposition is protected and stabilised, underlining the potential of the organic carbon–iron association as an efficient carbon burial mechanism.

Hydrology of a Semiarid Loess‐Paleosol Sequence, and Implications for Buried Soil Connection to the Modern Climate, Plant‐Available Moisture, and Loess Tableland Persistence

AbstractSoil hydrology provides important background for understanding the fate of organic carbon (OC) buried by geomorphic processes as well as the influence of runoff, infiltration, and plant root uptake on long‐term erosion and landscape evolution. We modeled the hydrology of a 4.5‐m loess‐paleosol sequence on an eroding tableland in the U.S. central Great Plains using Hydrus 1D, a numerical unsaturated flow model, parameterized with high resolution measurements of the soil water retention and hydraulic conductivity curves, which were distinct for the loess and paleosols. We hypothesized that (a) the connection of paleosols to modern climate depends on their burial depth, (b) paleosols in the root zone would have broader pore‐size distributions than unweathered loess, and (c) this broader pore‐size distribution increased root water uptake and made vegetation more resilient to drought, increasing the stability of loess tablelands despite high erodibility and high local relief. Four years with varying total annual precipitation were simulated for the observed profile and two hypothetical profiles, one without paleosols and another with a shallow, strongly developed paleosol. In these simulations, soil moisture in shallow paleosols responds quickly to precipitation while a deeply buried paleosol is largely disconnected from the modern climate, contributing to buried OC preservation. Contrary to our expectation, the presence of paleosols did not increase root uptake relative to unweathered loess in either wet or dry years. The unweathered coarse loess we studied may have an optimal pore‐size distribution for root uptake, providing an alternative hypothesis for why highly erodible loess tablelands persist.

Early diagenetic processes in an iron-dominated marine depositional system

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. We explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O2) bottom waters near the coast and oxygen-deficient waters (∼4 µM O2) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling.The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (∼45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates).The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe2+. Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. This study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.

Lipid Biomarker Investigation of the Delivery and Preservation of Autochthonous Organic Carbon in the Pearl River and Its Contribution to the Carbon Sink: Evidence from the Water and Surface Sediment.

The molecular composition of the lipid biomarkers in the surface water, water column, and surface sediments collected along the Pearl River was investigated to identify the mechanisms of the delivery and preservation of autochthonous organic carbon (AOC) and to estimate its contribution to the carbon sink. The spatial distribution of these lipid biomarkers showed that samples collected at high-DIC-concentration sites (DIC: dissolved inorganic carbon) had prominent aquatic autochthonous signatures, while samples collected at low-DIC-concentration sites showed greater terrestrial contributions, which were described as the DIC fertilization effects. In the summer, typically, intense precipitation and flood erosion diluted the biogeochemical composition and carried terrestrial plant detritus. Therefore, the percentage of AOC (auto%) was higher in the winter than in the summer. According to the calculation of the lipid biomarkers, the values of the auto% were 65% (winter) and 54% (summer) in the surface water, 55.9% (winter) and 44.6% (summer) in the below-surface water, and 52.1% (winter) and 43.9% (summer) in the surface sediment, which demonstrated that AOC accounted for a major portion of the TOC. Vertical variability was mainly present in sites with intense flood erosion, which resulted in the mixing and deposition of resuspended sediments. There was a positive correlation of the clay content with the auto% value and the biogeochemical composition, showing that clay adsorbed the organic carbon in the water, vertically deposited it into the sediment, and was the dominant mechanism of the vertical delivery of organic carbon (OC). According to the new karst carbon sink model, based on coupled carbonate weathering and aquatic photosynthesis, the karst carbon sink flux (CSF) in the Pearl River was 2.69 × 106 t/a which was 1.7 times the original estimation (1.58 × 106 t/a), and this did not consider the formation of AOC. This indicated that previously, the contribution of the riverine system to the global karst carbon sink may have been highly underestimated.

The crop residue conundrum: Maintaining long-term soil organic carbon stocks while reinforcing the bioeconomy, compatible endeavors?

Crop residues are a key bulk feedstock for supplying renewable carbon for bioenergy production and the broader bioeconomy without compromising food security. However, it is frequently advised to harvest no more than half of this potential to ensure the preservation of soil organic carbon (SOC) stocks. In this study, we challenge this recommendation and demonstrate that the crop residue potential allowing to maintain long-term SOC stocks is spatially differentiated and strongly dependent upon the bioeconomy conversion pathway for which it is intended. We assessed the interaction between the residues' usage for the bioeconomy and the maintenance of SOC stocks over 100 years by considering the coproduct return to soils from five bioeconomy pathways: pyrolysis, gasification, hydrothermal liquefaction, anaerobic digestion, and lignocellulosic ethanol production. To compare the long-term SOC changes from these scenarios against a reference where crop residues are unharvested, we developed a novel framework, applicable to any site or region, by coupling a SOC model that includes recalcitrant organic matter deriving from a bioeconomy calculation module. The adapted SOC model considers the recalcitrance to degradation of each coproduct, while the bioeconomy module determines the share of carbon from the crop residues ending in the coproducts. The framework was tested and applied with a high spatial resolution (>60,000 simulation units) to the context of French croplands over the period of 2020–2120, with state-of-the-art sensitivity analyses. The case study results revealed, among others, that an additional crop residue potential equivalent to 71–225 PJ (pathway-dependent) could be available for the French bioeconomy without SOC decreases, compared to applying a stringent removal limit of 31.5%.

The Fate of Sedimentary Reactive Iron at the Land‐Ocean Interface: A Case Study From the Amazon Shelf

AbstractReactive iron (Fe) oxides in marine sediments may represent a source of bioavailable Fe to the ocean via reductive dissolution and sedimentary Fe release or can promote organic carbon preservation and long‐term burial. Furthermore, enrichments of reactive Fe (sum of Fe oxides, carbonates and sulfides normalized to total Fe) in ancient sediments are utilized as a paleo‐proxy for anoxic conditions. Considering the general importance of reactive Fe oxides in marine biogeochemistry, it is important to quantify their terrestrial sources and fate at the land‐ocean interface. We applied sequential Fe extractions to sediments from the Amazon shelf to investigate the transformation of river‐derived Fe oxides during early diagenesis. We found that ∼22% of the Amazon River‐derived Fe oxides are converted to Fe‐containing clay minerals in Amazon shelf sediments. The incorporation of reactive Fe into authigenic clay minerals (commonly referred to as reverse weathering) is substantiated by the relationship between Fe oxide loss and potassium (K) uptake from sedimentary pore waters, which is in agreement with the previously reported Fe/K stoichiometry of authigenic clay minerals. Mass balance calculations suggest that widely applied sequential extractions do not separate Fe‐rich authigenic clay minerals from reactive Fe oxides and carbonates. We conclude that the balance between terrestrial supply of reactive Fe and reverse weathering in continental margin sediments has to be taken into account in the interpretation of sedimentary Fe speciation data.

Iron-bound organic carbon dynamics in peatland profiles: The preservation equivalence of deep and surface soil

More than half of the carbon pools in peatlands are stored in the soil layers below 30 cm, yet little is known about the carbon stabilizing factors at these depths. Although iron oxide minerals are considered to be important for stabilizing organic carbon (OC), their role in the preservation of OC in peatlands, especially in the deep layers, is poorly understood. Here, we collected 1 m soil profiles from six peatlands in Central and West China to quantitatively study the vertical distribution characteristics of iron-bound OC (Fe-bound OC), and the influencing physicochemical properties of the soil. The results showed that the content of reactive iron (FeR) was enriched in the top layer and decreased gradually with depth. While Fe-bound OC was positively correlated with FeR, its concentration did not decrease with depth in the peat profile. There were no obvious trends in the distributions of FeR and Fe-bound OC with water level fluctuations in the peat profile. In addition, the proportion of Fe-bound OC to soil organic carbon in the deep peat (31 to 100 cm) was equivalent to that in the surface peat (0 to 30 cm), indicating that iron oxide mineral provides comparable protection of OC in both layers. According to upper estimates of global peatland carbon storage (612 Pg), it could be predicted that 23.81 ± 11.75 Pg of OC is protected by association with FeR. These results indicated that iron oxide minerals are the effective "rusty sink" of OC sequestration in peatland, and a key factor for its long-term preservation. The results from this study make a valuable contribution to the carbon dynamics knowledgebase for peatlands, and provide a basis for improved predictive simulations.