Organic Matter Sequestration Research Articles

Unveiling the crucial role of iron oxide transformation in simultaneous immobilization of nanoplastics and organic matter.

Nanoplastics (NPs) have been found in natural environments. However, the sequestration of NPs and natural organic matter (NOM) coupled with the Fe(III) hydrolysis and subsequent iron oxides transformation remains unclear. Here, we investigated the behaviors of NPs during the dynamic transformation process of iron oxides in the presence of humic acids (HA). The quantification results of europium chelate-labeled polystyrene (PS) NPs and HA indicate that 87.60% of NPs and 49.45% of HA were sequestered in the precipitate by the end of the transformation (240h). High-angle annular dark-field-scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (HAADF-STEM-EDS) images show that NPs were doped into iron oxides during the recrystallization of ferrihydrite aggregates, while HA were adsorbed or penetrated into the nanoscale pores on the mineral surfaces, suggesting the formation of a stable iron oxides-NPs-NOM ternary nanocomplex with a core-shell structure. Fourier transform infrared spectrometer (FTIR) and two-dimensional correlation spectroscopy (2D-COS) analysis indicate that functional groups of iron oxides and HA, including hydroxyl, carboxyl, and FeO bonds, played a role in the binding process. In the presence of HA, the stability of the coprecipitation system was enhanced due to the increased electrostatic repulsion, which facilitated the full incorporation of NPs with iron oxides. These findings provide a new insight into the simultaneous immobilization of NPs and NOM.

Sequestration of Labile Organic Matter by Secondary Fe Minerals from Chemodenitrification: Insight into Mineral Protection Mechanisms.

Labile organic matter (OM) immobilized by secondary iron (Fe) minerals from chemodenitrification may be an effective way to immobilize organic carbon (OC). However, the underlying mechanisms of coupled chemodenitrification and OC sequestration are poorly understood. Here, OM immobilization by secondary Fe minerals from chemodenitrification was investigated at different C/Fe ratios. Kinetics of Fe(II) oxidation and nitrite reduction rates decreased with increasing C/Fe ratios. Despite efficient sequestration, the immobilization efficiency of OM by secondary minerals varied with the C/Fe ratios. Higher C/Fe ratios were conducive to the formation of ferrihydrite and lepidocrocite, with defects and nanopores. Three contributions, including inner-core Fe-O and edge- and corner-shared Fe-Fe interactions, constituted the local coordination environment of mineral-organic composites. Microscopic analysis at the molecular scale uncovered that labile OM was more likely to combine with secondary minerals with poor crystallinity to enhance its stability, and OM distributed within nanopores and defects had a higher oxidation state. After chemodenitrification, high molecular weight substances and substances high in unsaturation or O/C ratios including phenols, polycyclic aromatics, and carboxylic compounds exhibited a stronger affinity to Fe minerals in the treatments with lower C/Fe ratios. Collectively, labile OM immobilization can occur during chemodenitrification. The findings on OM sequestration coupled with chemodenitrification have significant implications for understanding the long-term cycling of Fe, C, and N, providing a potential strategy for OM immobilization in anoxic soils and sediments.

Introducing a new method to assess the benefits of resources recovered from wastewater to the natural environment

Resources recovery can improve the economic efficiency and reduce the negative environmental impacts of municipal wastewater treatment plants (MWWTP). The recovered resources can also actively benefit the natural environment enabling a reciprocal relationship between human society and nature. Focusing on these benefits can reveal new resources recovery opportunities. Moreover, for certain environmental impact categories such as emissions of reactive nitrogen, mere damage reduction is insufficient because these emissions are already beyond planetary limits. However, quantitative methods to assess nature benefits are lacking. A new method is developed to calculate the potential nature benefits in three categories: Freshwater restoration, biomass assimilation of nutrients, and soil organic matter sequestration and it is demonstrated on a real-life MWWTP. Focusing on resources recovery helps to purify the wastewater sufficiently for discharge and to benefit the natural environment. Treated wastewater discharge into a river can support freshwater restoration depending on the effluent quality. High quality is achieved by the sufficient removal of the nutrients and organic matter and discharging into a high-flow stream. The recovery of nutrients helps to close the nutrient cycle through biomass assimilation. To maximize this benefit, the nutrient recovery efficiency from the MWWTP must be maximized. But, increasing the nutrient uptake efficiency in agriculture is also crucial, especially for nitrogen. The wastewater sludge products can be applied to soil to sequester organic matter and the products with low volatile solids should be preferred. The development of the new method is a start to recognizing and assessing the potentially positive role of humans in nature.

Preservation and hydrocarbon generation potential of microalgal organic matter in product aggregates induced by Chlorella sp. MASCC-0008

Microalgae are one of the important sources of organic matter which, if preserved well in sediments, can generate hydrocarbons during burial diagenesis. However, the preservation mode of microalgal organic matter within product aggregates induced by marine microalgae has rarely been examined. Herein, a strain of eukaryotic marine microalgae, Chlorella sp. MASCC-0008, was used to conduct biomineralization experiments in an f/2 medium with a 0.02 mol/L Ca2+ ion concentration and various Mg2+ ion concentrations of 0.05, 0.06, 0.07 and 0.10 mol/L. It was found that the soluble organic matter of the microalgae contains amino acids and fulvic acids which can attract and absorb cations. With an increase in Mg2+ ion concentration in the experimental group with Chlorella sp., the aragonite content of the mineral precipitates increased whereas the calcite content decreased. In contrast, calcite was the sole mineral precipitated in the control experiments with no Chlorella sp.. Due to the porous structure of minerals, their organic matters were preferred to be preserved in aragonite aggregates compared to calcite aggregates. The TOC content of the minerals aggregates is the highest (0.45%) and the hydrocarbon generation potential (S1 + S2) of organic matter is the greatest (3.66 mg/g) in those precipitated in the medium with a Mg2+ ion concentration of 0.10 mol/L. Microalgal organic matter has significant hydrocarbon generation potential due to its effective preservation in the product aggregates formed by the microalgal biomineralization. Squalene is the most abundant alkene detected in the pyrolytic products. These results suggest that microalgae can induce precipitation of carbonate minerals, a process that facilitates the sequestration of organic matter within the product aggregates precipitated, thus potentially preserving this microalgal organic matter into the burial diagenetic realm where, if conditions are appropriate, hydrocarbons may be developed.

Soil Organic Matter in Urban Areas of the Russian Arctic: A Review

Polar ecosystems are the most important storage and source of climatically active gases. Currently, natural biogeochemical processes of organic matter circulation in the soil-atmosphere system are disturbed in urban ecosystems of the cryolithozone. Urbanized ecosystems in the Arctic are extremely under-investigated in terms of their functions in regulating the cycle of climatically active gases. The role of urban soils and soil-like bodies in the sequestration and stabilization of organic matter is of particular interest. The percentage of gravimetric concentrations of organic matter in Arctic urban soils are almost always determined by the method of dichromate oxidation and are subject to extreme variability (from tenths of a percent to more than 90% in man-made soil formations), but the average carbon content in the surface soil horizons can be estimated at 5–7%. The surface humus-accumulative horizons are represented by a variety of morphological forms with the content of organic matter of various origins. The work also focuses on those forms of organic matter, the content of which is extremely small, but very important for the biogeochemical functioning of soils-polycyclic aromatic hydrocarbons and components of petroleum products, as well as labile forms of soil organic matter. We recommend that further studies of the organic matter system be conducted in urbanized areas since the carbon cycle there is severely disrupted, as well as carbon flows. The urbanization and industrialization processes in the Arctic are progressing, which could lead to a radical transformation of carbon ecosystem services.

Rapid Cycling of Bacterial Particulate Organic Matter in the Upper Layer of the Western Pacific Warm Pool

AbstractBacterial metabolism largely drives the sequestration of refractory organic matter in the ocean. However, a lack of understanding exists regarding the abundance and reactivity of bacterial particulate organic matter (POM). Here we report the bacterial contributions to suspended POM collected in the oligotrophic Western Pacific Warm Pool (WPWP). Around 27% of particulate organic carbon (POC) and ∼39% of particulate nitrogen (PN) in the surface ocean were derived from bacteria. Most of the bacterial POM (∼87%) was labile or semi‐labile, and ∼85% of bacterial POM was removed between depths of ∼100–300 m. Bacterial POM constituted only ∼8% and ∼13% of refractory POC and PN, respectively. The rapid cycling of bacterial POM in upper waters was likely related to oligotrophic conditions and facilitated by higher temperatures in the WPWP. Taken together, these observations indicate that bacterial POM plays a crucial role in supplying energy for bacterial respiration.

Removal of natural organic matter fractions by adsorptive asymmetric ceramic membrane functionalized with in situ phytogenic nanoscale zero valent iron: Performance and Fenton cleaning strategy

AbstractExtant literature has demonstrated that conventional water treatment processes especially in developing countries struggle in completely removing detrimental organic loads. Emerging research delineates nanomaterials such as nanoscale zero valent iron (nZVI) to have excellent performance in organic matter removal from aqueous media. In this work, nZVI particles were prepared from the liquor of commercially available green tea and supported on kaolin (K‐nZVI) and investigated as an adsorbent for natural organic matter (NOM) sequestration from aquatic media. Further, the asymmetric ceramic membrane was prepared by incorporating the developed adsorbent on a concrete support for the removal of NOM. A Fenton cleaning strategy was developed to mitigate fouling. The Brunauer–Emmett–Teller (BET) results revealed the developed adsorbent surface area was greater compared to raw kaolin (27.07 and 11.64 m3 g−1, respectively). The scanning electron microscopy (SEM) imagery of the developed adsorbent showed the particle staking was presented as paper slices of varying sizes, an indication of dispersed particles with characteristic plate‐like fragments. The synthesized membrane exhibited a pHZPC value of 4.79 ± 0.03. This meant at pH above 4.79 ± 0.03, the membrane would be negatively charged, and conversely at pH below the pHZPC value. Membrane fouling due to bovine serum albumin (BSA) deposition showed a 50% flux decline in the first 60 min, coinciding with the rapid adsorption capacity within the same time frame. The optimal cleaning parameters of pH (4.5) and H2O2 (5 mM) gave the best flux recovery rates. This work demonstrated an efficient Fenton cleaning strategy to regenerate the developed membrane.

Orbitally forced organic matter accumulation recorded in an Early Permian mid-latitude palaeolake

Organic matter (OM) sequestration acts as a significant sink of the CO2 in Earth's carbon cycle and is tightly associated with the climate and depositional environments. However, the dominant factors controlling OM burial in different depositional settings and the orbitally forced variations in the lacustrine OM accumulation remain poorly constrained. Here, we investigate the depositional environment of the Lucaogou Formation in southern Junggar Basin, northwestern China and further decipher the astronomically forced OM accumulation in different depositional environments. Sedimentological and cyclostratigraphic studies show that both shallow lake and semi-deep to deep lake deposits recorded significant Milankovitch signals among of which ∼405 kyr, ∼91 kyr, 34.5–37.4 kyr, and 17.3–22.8 kyr are interpreted to be long eccentricity, short eccentricity, obliquity, and precession cycles, respectively. A linkage among the lithofacies, natural gamma ray (NGR), and total organic carbon (TOC) content suggests that the depositional environment and OM accumulation were in pace with the hydrological cycle and lake-level changes, in response to the astronomically forced changes in the ice volume and monsoonal intensity. In the semi-deep to deep lake, TOC content tightly tracks the lithofacies and shows an in-phase relationship with NGR. However, this phase relationship has changed with sedimentary facies. The gypsiferous shale deposited in the restricted environment during lowstand intervals has higher TOC content than highstand dolomitic mudstone, demonstrating an anti-phase relationship with NGR data. Our study indicates that the OM sequestration is a dynamically cumulative process of supply and degradation. The different responses of the OM sequestration to the climate change in different environments suggest that detailed sedimentological studies are essential for the cyclostratigraphic analysis.

Distribution of Molecular Weight of Humic Substances Isolated from Soils of Tallgrass Temperate Rainforests (Chernevaya Taiga)

The boreal forests of Russia are one of the largest forest areas on the planet. As a result of climate change, the rate of carbon sequestration and stabilization of organic matter are important indicators of environmental conservation. To understand mechanisms of stabilization and the structure of soil organic carbon, the molecular-weight (MW) distribution of humic acids (HAs) in soils of the central deciduous-forest zone of boreal forests (Chernevaya taiga, transitional ecotone forest, coniferous forest) was studied. Analysis of the MW distribution of HAs was conducted using size-exclusion chromatography. This approach allowed us to obtain the distribution of high-, medium-, and low-molecular fractions of HAs. It has been revealed that the content of the low-MW fraction prevails over the content of the medium- and high-MW fractions of HAs, which indicates the process of stabilization in soil organic matter. The accumulation of low-molecular-weight fraction occurs with the aromaticity increase in HAs, which indicates that HAs with a relatively high proportion of aromatic fragments have smaller hydrodynamic radius and a lower MW. It has been statistically substantiated that the low-molecular-weight fraction correlates with the content of aromatic compounds and carboxyl structural fragments of HAs, which indicates the resistance of the soil organic matter of Chernevaya taiga to biodegradation.

Optimizing Carbon Sequestration Through Cover Cropping in Mediterranean Agroecosystems: Synthesis of Mechanisms and Implications for Management

Hot and dry Mediterranean ecoregions are characterized by low soil organic carbon content and large potential to become carbon sink when appropriately managed. Soil carbon sequestration may also play an important role in improving the resilience of these vulnerable agroecosystems to increasingly drastic impacts of global climate change. One agricultural practice that aims to increase soil organic carbon stocks, among other beneficial outcomes, is the use of cover crops. Although cover crops can increase soil organic carbon content, recent studies have observed that cover crops may lead to lower soil carbon stocks when considering co-management strategies, especially at greater soil depths. In this review, we outline the current paradigm of soil organic carbon dynamics and aim to apply our current understanding of soil carbon sequestration processes to cover crop management. We review how cover crop practices such as cover crop species selection, growth duration, and termination methodologies may impact soil organic matter sequestration and stabilization processes and provide insights to direct future research and inform cover crop management for C sequestration in Mediterranean agroecosystems.

Green synthesis of kaolin-supported nanoscale zero-valent iron using camellia sinensis extract for effective adsorption of dissolved organic matter: Preparation, adsorption, and Fenton regenerative valorization of “spent” adsorbent

Physical and chemical methods have been used to synthesize zerovalent iron nanoparticles (nZVI) for the treatment of industrial effluents and contaminated water. However, the major limitations of these methods include usage of toxic chemicals such as NaBH4 and high energy consumption. Therefore, alternative green synthesis route for nZVI based on eco-friendly; low-cost; bio-based and nonhazardous methods are required. In this work, nZVI were synthesized from green tea extract (camellia sinensis) and supported on kaolin for natural organic matter (NOM) sequestration from aqueous media by degradation and adsorption. Further, opportunities for Fenton regenerative valorization of spent media were investigated. The research focused on the effect of initial concentration (1 – 25 mg/L), adsorbent dose (0.1–0.9 g), contact time (0 – 180 min) and pH (2 – 9) by batch experiments. The R2 for Langmuir and Freundlich models were comparable (0.975 and 0.977, respectively) meaning the isotherm data could be best described by either of these models. The calculated Qe value (0.1525 mg/g) using the pseudo-second-order model was closer to the experimental values Qe value (0.1382 mg/g). This indicated that the kinetics was delineated better by a pseudo second- order model. While operating at optimal conditions of pH (4.5) and H2O2 dosage (5 mM), no significant reduction in the adsorption capacity of K-nZVI was observed even after four successive adsorption-regeneration cycles. From the results of the study it was established that biosynthesis of nZVI and supporting it on kaolin can serve as a safe, economic and effective natural adsorbent for NOM removal from aqueous media.

Soil alterations by chronosequence of pastures in crop-livestock-forestry systems

The intensive use of land has accelerated the loss of soil quality, a process that can be avoided by adopting conservationist production systems, such as the Integrated Crop-Livestock-Forest (CLFI system). It is noteworthy that in the Southwest of the State of Maranhão a substantial portion of soils in rural properties are degraded and in distinct stages of erosion, since they have been exploited for decades with non-properly managed pastures. Therefore, the objective of this work was to emphasize the importance of physical and chemical changes in the soil of pastures under crop-livestock-forest integration in general and in the Amazon region of state of Maranhão, Brazil. Therefore, a literature review was conducted through a search for studies in the Google Scholar database, which encompasses multiple other databases, such as Scielo, Elsevier, Scopus, Capes, and others. In face of the conditions of degradation in pastures throughout the state of Maranhão and the broad distribution of native forests such as Babassu forests, the use of technology from CLFI systems could allow for their recovery and sustainable status by means of economically and ecologically feasible productivity. Research on this field is therefore necessary to highlight short- and long-term efficiencies regarding carbon sequestration and quality of organic matter on the soil.

Carbon isotopic constraints on the degradation and sequestration of organic matter in river‐influenced marginal sea sediments

AbstractOrganic matter degradation and sequestration in marine sediments are important processes involved in carbon cycling in the ocean. Here, we present the results of carbon isotope (14C and 13C) and concentration measurements of sedimentary organic carbon (SOC), pore‐water dissolved organic carbon (DOC), and dissolved inorganic carbon (DIC) in sediments collected from the East China Sea, Yellow/Bohai Sea, and South China Sea. Our results indicated that selective degradation and preservation of organic matter occurred in these sediments, and marine‐derived young organic carbon degraded preferentially and rapidly, resulting in high concentrations of pore‐water DOC and DIC with distinct carbon isotopic signatures. The average 14C age of pore‐water DOC was thousands of years younger than that of SOC in the sediment, suggesting that DOC was newly produced and cycled much faster than SOC. Aged SOC was refractory and preserved in sediments. Using a dual‐isotope three‐end‐member model, the contributions of potential sources to SOC, DOC, and DIC were estimated. Marine‐derived biomass organic carbon contributed the most to DOC, and dissolution of biogenic carbonate contributed the most to DIC. Riverine inputs of pre‐aged soil and fossil organic carbon dominated the SOC pool. Our study demonstrated that marginal sea sediments are important sites of young DOC and DIC fluxes into the water column, thus acting as a major pathway for carbon and nutrient cycling in the ocean.

Dissimilar evolution of soil dissolved organic matter chemical properties during revegetation with arbor and shrub in desertified land of the Mu Us Desert

The chemistry of dissolved organic matter (DOM) in soil determines its bioavailability and is crucial to soil nutrient cycling and vegetation restoration. However, the response of DOM to revegetation in degraded ecosystems is not well understood. This study analyzed soil chronosequences from semifixed (SF) sand in the Mu Us Desert, China that was afforested with arbor and shrub 23–54 years ago. The DOM organic composition and chemical properties were investigated by fluorescence excitation-emission matrix spectrophotometry and UV–visible spectroscopy. As the revegetation progressed, DOM concentration at 0–20 cm continually increased. In arbor land, the DOM was mainly influenced by dissolved organic carbon, and the average concentration significantly increased from 67.5 to 203.2 mg C•kg−1. In the shrubland, changes in DOM were mainly influenced by dissolved organic nitrogen, with the average concentration significantly increasing from 3.7 to 8.9 mg N•kg−1. Arbor afforestation significantly increased the proportion of hydrophobic humic-like components (C1), with a decline in bioactive tryptophan-like components (C3) and higher DOM molecular complexity (i.e., higher molecular weight, aromaticity, and degree of humification). However, in shrubland, the proportions of C1 and C3 were significantly lower than those in arbor forest soil, with DOM molecular complexity slightly increased, and DOM tended to become more bioavailable over time. Linear regression analysis indicated that DOM rich in carbon had a high molecular complexity, while DOM rich in nitrogen is more bioavailable. These findings reveal a dissimilar evolution in the DOM composition and chemistry in the two forest types throughout the SF sand revegetation period. The DOM under arbor forest was more stable and conducive to soil organic matter sequestration, while the DOM under shrub forest contained more bioactive substances and was more favorable for nutrient cycling.

Crop Litter Has a Strong Effect on Soil Organic Matter Sequestration in Semi-Arid Environments

The agricultural soils in the Mediterranean are characterized by low stocks of soil organic matter (SOM) because of the intensive management practices and constraints on litter inputs to the soil imposed by environmental conditions (low precipitation, high evapotranspiration). To date, several studies have provided evidence for a low potential of Mediterranean agroecosystems, especially on its southern part, to store C, even under soil conservation practices (e.g., non-tillage), questioning the capacity of commonly applied practices to restore soil health, mitigate climate change and improve resilience of agroecosystems to climate extremes. Using paired orchards of avocado and olive trees, we show that soils in the South Mediterranean have a high potential for C storage that depends strongly on crop type and soil properties. Soils planted with avocado trees showed higher SOM contents compared to olive trees mainly in the upper soil layer (0–10 cm) which were linked to higher inputs and litter chemistry. Our findings enable us to re-define achievable thresholds of SOC (≈8%) in Southern Mediterranean soils to store C, to quantify the effect of different cropping systems, and the period required to reach this potential and how this potential is affected by soil properties. Thus, the findings have profound implications for the design of soil conservation practices compatible with Mediterranean conditions and developing initiatives describing achievable targets of SOM restoration depending on soil properties and cropping systems.

Verrucomicrobiota are specialist consumers of sulfated methyl pentoses during diatom blooms

Marine algae annually sequester petagrams of carbon dioxide into polysaccharides, which are a central metabolic fuel for marine carbon cycling. Diatom microalgae produce sulfated polysaccharides containing methyl pentoses that are challenging to degrade for bacteria compared to other monomers, implicating these sugars as a potential carbon sink. Free-living bacteria occurring in phytoplankton blooms that specialise on consuming microalgal sugars, containing fucose and rhamnose remain unknown. Here, genomic and proteomic data indicate that small, coccoid, free-living Verrucomicrobiota specialise in fucose and rhamnose consumption during spring algal blooms in the North Sea. Verrucomicrobiota cell abundance was coupled with the algae bloom onset and accounted for up to 8% of the bacterioplankton. Glycoside hydrolases, sulfatases, and bacterial microcompartments, critical proteins for the consumption of fucosylated and sulfated polysaccharides, were actively expressed during consecutive spring bloom events. These specialised pathways were assigned to novel and discrete candidate species of the Akkermansiaceae and Puniceicoccaceae families, which we here describe as Candidatus Mariakkermansia forsetii and Candidatus Fucivorax forsetii. Moreover, our results suggest specialised metabolic pathways could determine the fate of complex polysaccharides consumed during algae blooms. Thus the sequestration of phytoplankton organic matter via methyl pentose sugars likely depend on the activity of specialised Verrucomicrobiota populations.

Late Quaternary Climate Reconstruction and Lead-Lag Relationships of Biotic and Sediment-Geochemical Indicators at Lake Bolshoe Toko, Siberia

Millennial-scale climate change history in eastern Siberia and relationships between diatom diversity, paleoclimate, and sediment-geochemical lake system trajectories are still poorly understood. This study investigates multi-proxy time series reaching back to the Late Pleistocene derived from radiocarbon dated Lake Bolshoe Toko sediment cores, southeastern Yakutia, Russia. We analyzed diatoms, elements (XRF), minerals (XRD), grain-size, organic carbon, and included chironomid analyses and published pollen-data for quantitative paleoclimate reconstruction. Changes in diatom species abundances reveal repeated episodes of thermal stratification indicated by shifts from euplanktonicAulacoseiratoCyclotellaspecies. Chironomid and pollen-inferred temperature reconstruction reveal that the main shift between these diatom species is related to the onset of Holocene Thermal Maximum (HTM) at 7.1 cal ka BP. Comparison to other paleoclimate records along a north-south transect through Yakutia shows that the HTM was delayed as far south as the Stanovoy mountains. Relationships between sediment-geochemistry, paleoclimate variability and diatom species richness (alpha diversity) was tested in a moving temporal offset approach to detect lead-lag relationships. Sediment-geochemical data, mainly uniform during the Holocene, revealed strongest positive or negative correlations ahead of species richness changes. Mean July air temperature (TJuly) reconstructions correlate with both Hill numbers and relative assemblage changes indicated by sample scores of multidimensional scaling analysis (MDS) over the entire time series. We found that sediment organic carbon revealed distinct positive correlations, i.e., centennial-scale delay to increases in diatom effective richness (Hill numbers N0 and N2). We conclude that a lag of deposited organic carbon concentrations behind changes in diatom alpha diversity reveals that species richness can augment the production and thus sequestration of organic matter in comparable lake systems.

Fractionation of natural algal organic matter and its preservation on the surfaces of clay minerals

The sequestration of algal organic matter (AOM) in clays constitute important carbon sinks in lake sediments. The composition of AOM was proven recently to critically influence its preservation in sediments. Yet it remains unclear which AOM components and types of clay minerals contribute to AOM burial in lake sediments. Here we investigated the AOM fractionation in kaolinite and illite via their adsorption, to ascertain the distribution of AOM components on these clay surfaces. The results showed that the AOM adsorbed quantity was 2-fold higher for illite than kaolinite. The adsorption isotherm data of illite and kaolinite were well fitted by a Freundlich model. The three-dimensional excitation emission matrix fluorescence spectroscopy (3D EEM) with parallel factor analysis (PARAFAC) modeling identified the AOM component under fractionation. The AOM solution mainly consisted of humic acid-like, tyrosine-like, and tryptophan-like components. Notably, large amounts of the hydrophilic tyrosine-like components were adsorbed onto the surface of both kaolinite and illite, whereas the hydrophobic tryptophan-like components were seldom adsorbed onto neither of the clay materials, while humic acid-like components were only adsorbed onto illite. Therefore, illite is more suitable for the preservation of AOM. Both transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDS) and the X-ray photoelectron spectroscopy (XPS) analysis further confirmed the high adsorption of AOM on the surface of illite; i.e., the molar content of carbon in AOM adsorbed to illite was 22.04%, almost a double of that adsorbed to kaolinite (11.59%). Overall, our results demonstrate the selective preservation of AOM on clay surfaces and highlight the role of clay minerals as sequesters of organic matter in eutrophic lakes.

4D Surface Reconstructions to Study Microscale Structures and Functions in Soil Biogeochemistry.

The development of high-resolution microscopy and spectroscopy techniques has allowed the analysis of microscopic 3D objects in fields like nanotechnology and life and soil sciences. Soils have the ability to incorporate and store large amounts of organic carbon. To study this organic matter (OM) sequestration, it is essential to analyze its association with soil minerals at the relevant microaggregate scale. This has been previously studied in 2D. However, 3D surface representations would allow a variable angle and magnification analysis, providing detailed insight on their architecture. Here we illustrate a 4D surface reconstruction workflow able to locate preferential sites for OM deposition with respect to microaggregate topography. We used Helium Ion Microscopy to acquire overlapping Secondary Electron (SE) images to reconstruct the soil topography in 3D. Then we used nanoscale Secondary Ion Mass Spectrometry imaging to chemically differentiate between the OM and mineral constituents forming the microaggregates. This image was projected onto the 3D SE model to create a 4D surface reconstruction. Our results show that organo-mineral associations mainly form at medium curvatures while flat and highly curved surfaces are avoided. This method presents an important step forward to survey the 3D physical structure and chemical composition of microscale biogeochemical systems correlatively.

Long‐term effects of nitrogen and phosphorus fertilization on soil aggregate stability and aggregate‐associated carbon and nitrogen in the North China Plain

AbstractSoil aggregates and carbon storage are important in soil conservation, nutrient supply, and climate change mitigation. The long‐term responses of aggregate‐associated organic C (OC) and nitrogen (N) in surface versus subsoil to N and P fertilization remain unclear. We examined the effects of different N and P fertilization rates on aggregate stability and the associated soil OC (SOC) and N in the North China Plain through a 35‐yr double‐crop field experiment, hypothesizing that higher rates of mineral fertilizer would promote aggregate stability and increase C/N ratios in large macroaggregates. The OC and N were highest in the silt + clay fraction, accounting for 34 to 48% of bulk SOC and 28 to 47% of bulk soil N at 0 to 20 cm, and 38 to 62% of bulk SOC and 40 to 62% of bulk soil N at 20 to 40 cm. After 35 yr, N + P fertilization increased SOC (16–35%) and N (21–27%), especially the 540 kg N + 67.5 kg P treatment; the N + P fertilizer also increased the OC and N of the macroaggregate, microaggregate, and silt + clay fractions at 0 to 20 cm. The N + P fertilizer treatments increased bulk soil C/N ratios; the C/N ratios of large macroaggregates decreased. Nitrogen and P fertilizer did not affect aggregate stability. Long‐term N and P fertilization increased SOC concentrations, and altered OC and N distributions in aggregates. Quantifying the impacts of long‐term fertilization strategies on organic matter sequestration and soil stabilization is important.