Deep Carbon Research Articles

Marine N2-fixer Crocosphaera waterburyi.

Marine N2-fixing cyanobacteria, including the unicellular genus Crocosphaera, are considered keystone species in marine food webs. Crocosphaera are globally distributed and provide new sources of nitrogen and carbon, which fuel oligotrophic microbial communities and upper trophic levels. Despite their ecosystem importance, only one pelagic, oligotrophic, phycoerythrin-rich species, Crocosphaera watsonii, has ever been identified and characterized as widespread. Herein, we present a new species, named Crocosphaera waterburyi, enriched from the North Pacific Ocean. C. waterburyi was found to be phenotypically and genotypically distinct from C. watsonii, active in situ, distributed globally, and preferred warmer temperatures in culture and the ocean. Additionally, C. waterburyi was detectable in 150- and 4000-meter sediment export traps, had a relatively larger biovolume than C. watsonii, and appeared to aggregate in the environment and laboratory culture. Therefore, it represents an additional, previously unknown link between atmospheric CO2 and N2 gas and deep ocean carbon and nitrogen export and sequestration.

Ca3[C2O5]2[CO3] is a pyrocarbonate which can be formed at p, T-conditions prevalent in the Earth’s transition zone

Understanding the fate of subducted carbonates is a prerequisite for the elucidation of the Earth’s deep carbon cycle. Here we show that the concomitant presence of Ca[CO3] with CO2 in a subducting slab very likely results in the formation of an anhydrous mixed pyrocarbonate, Ca3C2O52CO3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{\\rm{Ca}}}}}_{3}{\\left[{{{{\\rm{C}}}}}_{2}{{{{\\rm{O}}}}}_{5}\\right]}_{2}\\left[{{{{\\rm{CO}}}}}_{3}\\right]$$\\end{document}, at moderate pressure ( ≈ 20 GPa) and temperature ( ≈ 1500 K) conditions. We show that at these conditions Ca3C2O52CO3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{\\rm{Ca}}}}}_{3}{\\left[{{{{\\rm{C}}}}}_{2}{{{{\\rm{O}}}}}_{5}\\right]}_{2}\\left[{{{{\\rm{CO}}}}}_{3}\\right]$$\\end{document} can be obtained by reacting Ca[CO3] with CO2 in a laser-heated diamond anvil cell. The crystal structure was obtained from synchrotron-based single crystal X-ray diffraction data. Density Functional Perturbation Theory calculations in combination with experimental Raman spectroscopy results unambiguously confirmed the structural model. The crystal structure of Ca3C2O52CO3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{\\rm{Ca}}}}}_{3}{\\left[{{{{\\rm{C}}}}}_{2}{{{{\\rm{O}}}}}_{5}\\right]}_{2}\\left[{{{{\\rm{CO}}}}}_{3}\\right]$$\\end{document} is characterized by the presence of CO32−\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\left[{{{{\\rm{CO}}}}}_{3}\\right]}^{2-}$$\\end{document}- and C2O52−\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\left[{{{{\\rm{C}}}}}_{2}{{{{\\rm{O}}}}}_{5}\\right]}^{2-}$$\\end{document}-groups. The results presented here imply that the formation of Ca3C2O52CO3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{\\rm{Ca}}}}}_{3}{\\left[{{{{\\rm{C}}}}}_{2}{{{{\\rm{O}}}}}_{5}\\right]}_{2}\\left[{{{{\\rm{CO}}}}}_{3}\\right]$$\\end{document} needs to be taken into account when constructing models of the deep carbon cycle of the Earth.

Development and preservation mechanism of deep and ultra-deep carbonate reservoirs

Development and preservation mechanism of deep and ultra-deep carbonate reservoirs

Unraveling abiotic organic synthesis pathways in the mafic crust of mid-ocean ridges

The aqueous alteration of the oceanic lithosphere provides significant energy that impacts the synthesis and diversity of organic compounds, which are crucial for the deep carbon cycle and may have provided the first building blocks for life. Although abiotic organic synthesis has been documented in mantle-derived rocks, the formation mechanisms and complexity of organic compounds in crustal rocks remain largely unknown. Here, we show the specific association of aliphatic carbonaceous matter with Fe oxyhydroxides in mafic crustal rocks of the Southwest Indian Ridge (SWIR). We determine potential Fe-based pathways for abiotic organic synthesis from CO2 and H2 using multimodal and molecular nano-geochemical tools. Quantum mechanical modeling is further employed to constrain the catalytical activity of Fe oxyhydroxides, revealing that the catalytic cycle of hydrogen may play a key role in carbon-carbon bond formation. This approach offers the possibility of interpreting physicochemical organic formation and condensation mechanisms at an atomic scale. The findings expand our knowledge of the existence of abiotic organic carbon in the oceanic crustal rocks and emphasize the mafic oceanic crust of the SWIR as a potential site for low-temperature abiotic organic synthesis.

Alkali-carbonate melts in the cratonic mantle evidenced by a wehrlite xenolith from the Majuagaa kimberlite, West Greenland

Carbonate melts are critically important for the deep carbon cycle, mantle melting, redox reactions, and transport of highly incompatible elements. The presence of carbonate melts in the cratonic mantle has been inferred from experimental studies, metasomatic transformations, and melt/fluid inclusions in xenoliths, kimberlites, and diamonds. However, the exact composition of such melts is difficult to determine due to their ephemeral nature and highly reactive properties. Once formed, they migrate away from the source and react with silicate mantle minerals, especially orthopyroxene, causing mantle metasomatism. Wehrlite is one of the products of interaction between the carbonate melt and peridotitic mantle and hence is an excellent candidate for locating in situ carbonate melts. Here, we report petrological, geochemical, and melt inclusion data for a garnet wehrlite xenolith in the Majuagaa kimberlite dike, West Greenland. The xenolith, which last equilibrated with the mantle at 4.5 GPa and 1000 °C, contains abundant melt pools composed of dolomite, calcite, serpentine, spinel, apatite, and phlogopite. Although the original magmatic mineralogy was largely destroyed by low-temperature alteration, remnants of the crystallized carbonatitic melt are preserved as primary melt inclusions in the liquidus Ti-Mg-Fe spinel. These melt inclusions, composed of carbonates, alkali carbonates, periclase/brucite, and minor halides, K-sulfide, apatite, and phlogopite, are the first direct evidence for in situ alkali-carbonate melt in the deep cratonic mantle. Compositionally, they are very similar to primary Na-dolomite melt found in experiments and in fluid inclusions within diamonds.

Experimental constraints on serpentinite carbonation in the presence of a H2O–CO2–NaCl fluid

Serpentinite carbonation contributes to the deep carbon (C) cycle. Recently, geophysical and numerical studies have inferred considerable hydrothermal alteration in plate bending faults, opening the possibility of significant C storage in the slab mantle. However, there is a lack of quantitative determination of C uptake in serpentinized mantle rocks. Here, we experimentally constrain serpentinite carbonation in H2O–CO2–NaCl fluids to estimate C uptake in hydrated mantle rocks. We find that serpentinite carbonation results in the formation of talc and magnesite along the serpentinite surface. The presence of porous reaction zones (49.2% porosity) promotes the progress of carbonation reactions through a continuous supply of CO2-bearing fluids to the reaction front. Added NaCl effectively decreases the serpentinite carbonation efficiency, particularly at low salinities (< 5.0 wt%), which is likely attributed to the reduction in fluid pH and the transport rate of reactants, and the increase in magnesite solubility. Based on previous and our experiments, we fit an empirical equation for the reaction rate of serpentinite carbonation. Extrapolation of this equation to depths of plate bending fault systems suggests that serpentinite carbonation may contribute to an influx of up to 7.3–28.5 Mt C/yr in subduction zones. Our results provide new insights into serpentinite carbonation in environments with high fluid salinities and potentially contribute to the understanding of the C cycle in subduction zones.

Deep CO2 emissions facilitated by localized shear deformation: A case study of the Karakoram fault system, western Tibet

Strike-slip faults play a significant role in creating deeply penetrating fractures with high permeability, thus promoting rapid migration of CO2-rich fluids to the surface. However, there are rare observations regarding how strike-slip movement could affect deep CO2 emissions. Here, we focus on the Karakoram fault system (KKFS), western Tibet, to estimate diffuse soil CO2 fluxes and to unravel potential controlling factors for CO2 emissions. Average CO2 fluxes of geothermal fields range in 22–2475 g m−2 d−1, significantly higher than the across-fault profiles (6–116 g m−2 d−1). A mass balance model based on δ13C-CO2 and CO2 concentration of soil gases reveals that deep carbon constitutes 49.1–91.5 % (average = 73.9 %) and 0.2–40.5 % (average = 25.5 %) of soil-gas carbon released from geothermal fields and across-fault profiles, respectively. Deep carbon could be produced by thermal decomposition of crustal rocks considering CO2-rich fluids with radiogenic helium isotopes. Strikingly, higher CO2 fluxes preferentially occur in geothermal fields along a bending segment of the KKFS, where localized shear deformation is prominent as documented by high slip rates over geological timescales, dense splay faults, clustering of earthquake events, and elevated strain rates. We suggest that high stress acting on the KKFS bend could enhance the deformation and fracturing of fault zone rocks, leading to production of metamorphic CO2 and efficient release of CO2-rich fluids through the highly permeable fault system. Our results could shed new light on CO2 origins and fluxes of strike-slip faults that are characterized by spatially heterogeneous strain partitioning and thus localized enhanced shear deformation.

Leveraging a decade of Landsat-8 spectral records for mapping blue carbon storage in tidal salt marshes

Tidal salt marsh ecosystems are known to accumulate and store large amounts of “blue” carbon, making them an important component of regional carbon cycle processes and a potential target for ecosystem-based carbon crediting efforts. However, blue carbon content in salt marshes can vary substantially at relatively small spatial scales. Understanding spatial variations of blue carbon storage at the landscape or local scale is important for developing carbon inventories, guiding ecological restorations, and informing habitat management strategies. We investigated the potential of spectral index records from the Landsat-8 Operational Land Imager spanning from 2014 to 2023 for mapping blue carbon storage in the soils of two tidal salt marsh systems in the Mid-Atlantic United States. The decadal mean of a non-photosynthetic vegetation index and standard deviations of a normalized difference vegetation index and a modified normalized difference water index were identified as predictors of blue carbon. These predictors were used to train a gradient boosted trees model for predicting soil organic matter content that achieved a testing set r-squared value of 0.67. We estimated that the two study marshes stored a combined 133-208 gigagrams of organic carbon in the top 30 cm of soil. We emphasize the need for better quantification of deep soil carbon in tidal salt marsh systems, which is likely quite high, and demonstrate the potential for satellite-based mapping of blue carbon within individual tidal wetland systems.

A Sequential Leaching Protocol for δ11B and Trace Element Analyses of Multi‐Phase Carbonate Rocks

AbstractBoron geochemistry from biogenic carbonates offer valuable information about ocean pH and CO2 chemistry. However, application to geological carbonate deposits suffers from analytical difficulties in obtaining geochemical signals exclusively from the carbonate phase. Sequential leaching with reagents and acids has the potential to overcome such an issue. There is, however, little systematic investigation about the efficiency of sequential leaching in isolating carbonate‐associated boron from siliciclastic matrix. Here, we developed a sequential leaching protocol and applied it to methane‐derived‐authigenic‐carbonate samples. Using the leachate δ11B signatures, elemental composition, and mineral composition of residues, we show that the sequential leaching is able to improve the separation of boron from different phases. Buffered hydrogen peroxide removes organic matter and also some silicate phases resulting low δ11B values. Leaching with NH4Ac removes adsorbed boron though may also partially leach some carbonate phases. The first few leaching steps with diluted acetic acid dissolve carbonate phases. Depending on the sample type, these may also capture some remaining adsorbed boron from the preceding NH4Ac leaching. Once the adsorbed boron is completely removed, as indicated by the progressively higher δ11B values during the following acid leaching steps, representative carbonate composition can be derived. The accuracy of this protocol is demonstrated with leaching experiments using artificial deep sea coral carbonate and clay mixtures that give the representative carbonate‐associated δ11B within error of the pure coral value. Our results provide insights into characteristic signatures derived from silicates and organic matter that need to be considered in boron isotope analyses of impure marine carbonates.

Lead and Barium Strata-Bound deposits in Eocene Carbonate ramps of Iran: Implications for the Influence of Sedimentary environment characteristics on the Distribution of Ore reserves

In the case of ore deposits that are formed in marine environments, including kuroko deposits, the effect of paleo-sedimentary environment parameters and microfacies changes is very important, but it is often neglected in economic geological research. These factors determine the dispersion and concentration of ore horizons in an ore deposit area, and recognition them leads us to the localization of high concentration ore horizons.In this regard, lead and barite ore deposit area in the southeastern of Tafresh city (the border of Markazi and Qom provinces, Iran) was investigated. This ore deposit is of the kuroko type and is of the early to middle Eocene epoch (Ypresian-Lutetian ages) and was formed in a relatively deep ancient carbonate ramp. Investigating the concentration of different minerals and ore minerals in the mentioned ore deposit area using by remote sensing techniques indicates that the distribution of minerals and ore minerals is non-uniform with a noteworthy correlation unto the carbonate ramp microfacies in the southeastern of Tafresh. The scrutiny of microfacies characteristics and paleo-sedimentary environment showed that the distance from hydrothermal smokers, the action of different seawaves, sedimentological changes, structural features and initial morphology of microfacies have a remarkable impressiveness in the dispersion of ore reserves and the formation of horizons with a high concentration of ore.

Unearthing the impact of land use on deep soil carbon−an example from the southwestern Australian wheatbelt

AbstractClimate change resulting from anthropogenic greenhouse gas (GHG) emissions is both a topic that is gaining greater societal attention and an area where greater efforts are being made for their mitigation. Increasing soil organic carbon (SOC) has been proposed as one of the mechanisms through which atmospheric carbon can be sequestered and has the potential co‐benefit of also improving soil productivity. A wide range of factors have been found to influence SOC contents, especially when depth is considered, and as such regionally specific sampling is useful to understand SOC dynamics. In this study, soil samples from an agricultural property in the West Australian Wheatbelt were analysed. The samples came from four different land uses: salinity revegetation, annual grazing, forage shrub, and perennial grazing. Samples were taken at four depth intervals up to 1 m and their general characteristics as well as each of their total organic carbon, dissolved organic carbon and microbial biomass carbon values analysed. A microbial incubation experiment was conducted over 28 days to assess the stability of the soil carbon and the extent to which this depends on the soil's clay content. This study found that depth and land use were statistically significant in both SOC concentrations and SOC stability. Soil clay content was a significant factor in the stability of SOC, explaining 38% of the variation in SOC stability. Furthermore, the study reveals that excluding soil below 30 cm depth in SOC analysis can result in a global underestimation of SOC values. An understanding of this is important for wheatbelt producers to be better equipped to understand and respond to, the market pressures exerted by societies and industries to move closer to their claimed net‐zero emissions targets.

Deciphering the Intricate Control of Minerals on Deep Soil Carbon Stability and Persistence in Alaskan Permafrost.

Understanding the fate of organic carbon in thawed permafrost is crucial for predicting climate feedback. While minerals and microbial necromass are known to play crucial roles in the long-term stability of organic carbon in subsoils, their exact influence on carbon persistence in Arctic permafrost remains uncertain. Our study, combining radiocarbon dating and biomarker analyses, showed that soil organic carbon in Alaskan permafrost had millennial-scale radiocarbon ages and contained only 10%-15% microbial necromass carbon, significantly lower than the global average of ~30%-60%. This ancient carbon exhibited a weak correlation with reactive minerals but a stronger correlation with mineral weathering (reactive iron to total iron ratio). Peroxidase activity displayed a high correlation coefficient (p < 10-6) with Δ14C and δ13C, indicating its strong predictive power for carbon persistence. Further, a positive correlation between peroxidase activity and polysaccharides indicates that increased peroxidase activity may promote the protection of plant residues, potentially by fostering the formation of mineral-organic associations. This protective role of mineral surfaces on biopolymers was further supported by examining 1451 synchrotron radiation infrared spectra from soil aggregates, which revealed a strong correlation between mineral OH groups and organic functional groups at the submicron scale. An incubation experiment revealed that increased moisture contents, particularly within the 0%-40% range, significantly elevated peroxidase activity, suggesting that ancient carbon in permafrost soils is vulnerable to moisture-induced destabilization. Collectively, this study offers mechanistic insights into the persistence of carbon in thawed permafrost soils, essential for refining permafrost carbon-climate feedbacks.

Planetary Waves Drive Horizontal Variations in Trace Species in the Venus Deep Atmosphere

Abstract The deep atmosphere of Venus remains mysterious because of the planet’s high, optically thick cloud decks. While phenomena such as the observed decadal fluctuations in sulfur dioxide abundance above the clouds could shed light on conditions below, poor understanding of vertical and horizontal transport limits such an approach. Nightside spectral windows permit observation of trace gas species in the lower atmosphere, but incomplete understanding of the circulation makes the distribution of these species challenging to interpret. We performed two simulations with the Venus Planetary Climate Model including an age of air calculation to investigate tracer transport (a) between the surface and the stagnant lower haze layer and (b) between the cloud deck and the observable upper atmosphere. We find a timescale on the order of many decades for surface-to-lower haze layer transport and ∼1.4 yr from the lowest cloud deck to 101 km. The extreme slowness of transport from the surface to the clouds makes it unlikely that compositional variability at the surface could affect the upper atmosphere sulfur dioxide abundance on observed timescales. Planetary-scale Rossby waves with a zonal wavenumber of 1 in both hemispheres are found to circumnavigate the planet in the deep atmosphere in 36 Earth days. These waves are associated with gyres that collect tracers and areas of upwelling that transport them to higher altitudes, leading to significantly younger air at polar latitudes in the altitude range of 25–45 km. The existence of chemically enhanced traveling Rossby gyres could explain the observed deep atmosphere carbon monoxide variability.

Deep marine records of Deccan Trap volcanism before the Cretaceous–Paleogene (K–Pg) mass extinction

The Cretaceous−Paleogene boundary is marked by a large impact and coeval mass extinction event that occurred 66 m.y. ago. Contemporaneous emplacement of the volcanic Deccan Traps also affected global climate before, during, and after the mass extinction. Many questions remain about the timing and eruption rates of Deccan volcanism, its precise forcing of climatic changes, and its signature in the marine geochemical sedimentary proxy record. Here, we compile new and existing mercury (Hg) concentration and osmium isotope (187Os/188Os) records for various stratigraphic sections worldwide. Both geochemical proxies have been suggested to reflect past variations in Deccan volcanic activity. New data from deep marine pelagic carbonate records are compared to contemporaneous records from shallower marine sites correlated through high-resolution cyclostratigraphic age models. The robustness of the proxy records is evaluated on a common timeline and compared to two different Deccan eruption history scenarios. Results show that the global 187Os/188Os signal is clearly reproducible, while the global Hg record does not form a consistent pattern. Moreover, the deep marine sections investigated do not record clear variations in the Hg cycle, particularly in the latest Cretaceous, prior to the extinction event. A detailed reevaluation of the precise depth of the redistribution of impactor-sourced platinum group elements does not exclude the possibility of a minor drop in 187Os/188Os corresponding with a pulse of Deccan volcanism ∼50,000 years before the Cretaceous−Paleogene boundary. Simple Os isotope mass balance modeling indicates that the latest Cretaceous was marked by significant levels of basalt weathering. CO2 sequestration during this weathering likely overwhelmed the emission of Deccan volatiles, thereby contributing to the end of the late Maastrichtian warming.

Ca–Zn isotope fractionation during fluid–rock interaction in subduction zones and its implication for deep carbon cycle

Subducting slabs transport Earth's surface carbon into the deep mantle, with a portion of this carbon potentially recycled through volcanic eruptions at mid-ocean ridges or ocean islands. Non-traditional stable isotopes such as calcium (Ca) and zinc (Zn) are increasingly used to trace this deep carbon cycle. However, the potential for Ca and Zn isotope fractionation in the subduction zone, critical for the successful application of these tracers, remains insufficiently explored. In this study, we investigate high-pressure carbonated metamafic rocks and enclosed vein systems from a Paleo-oceanic subduction complex (SW Tianshan) to explore the possible fractionation of Ca and Zn isotope during subduction-related metamorphism and fluid–rock interaction. The δ44/40Ca (0.77 ‰–0.90 ‰) and δ66Zn isotope compositions (0.20 ‰–0.39 ‰) of greenschist-, blueschist- and eclogite-facies metabasites are consistent with their protoliths (OIBs and MORBs). We observe no systematic fractionation of either Ca and Zn isotopes across prograde metamorphism and associated dehydration. However, the precipitation of carbonate in surrounding rock along fluid pathways leads to an increase in the δ44/40Ca of residual fluids (>0.90 ‰). More significantly, we find detectable Zn isotope fractionation (ΔA-H = ẟ66Znaltered - ẟ66Znhost of 0.06–0.10 ‰) during fluid-mediated metasomatism of some blueschists/eclogites. Light Zn isotopes are preferentially released into the infiltrating fluid, resulting in an elevated δ66Zn isotope composition in the immediate carbonated eclogites along the vein. The modified slab fluids during migration are likely charactered by heavy δ44/40Ca and light δ66Zn compositions, which may play a crucial role in determining the low δ66Zn values found in some arc lavas. However, the MORB-like δ44/40Ca compositions observed in global arc magmatic rocks suggest that the slab-released Ca (possibly along with some carbon) is probably sequestered and stored along the migration path of the fluid, thereby hindering the slab–arc carbon recycling. Our study emphasizes that intraslab fluid–rock interaction results in similar δ44/40Ca and δ66Zn signature in carbonate-bearing eclogites compared to sedimentary carbonates. Consequently, deeply subducted carbonate-bearing eclogites –not necessarily sedimentary carbonates– might carry light δ44/40Ca and heavy δ66Zn signatures into the deep mantle, potentially influencing the corresponding Ca-Zn isotope compositions of some mantle-derived basalts.

Shock-induced phase transitions in siderite up to 90 GPa and implications for deep carbon cycle

The phase stability of carbonates under mantle conditions is important for understanding the global carbon cycle. In this study, the Hugoniot data of a natural siderite (FeCO3) were measured up to 90 GPa using the plane-plate impact method. Two successive phase transitions were observed at 38–40 GPa and 65–69 GPa, respectively. In comparison with the static compression results, the first phase transition was identified as a spin transition, and the second is attributed to the self-redox reaction. The volume change during the self-redox transition is consistent with the reaction products of tetrairon orthocarbonate Fe4C3O12 and diamond. Using the measured Hugoniot data, we estimated the density of Fe4C3O12 along the lower mantle conditions and found it to be higher than the seismic values. Our results suggest siderite plays an important role in the deep carbon cycle.

Deep‐eutectic‐solvent‐assisted hydrothermal carbonization of sewage sludge for green wood bioadhesive production

AbstractThis study reports the use of deep‐eutectic‐solvent‐ (DES‐) assisted hydrothermal carbonization (HTC) to disrupt the floc structure of sewage sludge (SS) for deep carbonization, with the resulting hydrochars employed in the preparation of formaldehyde‐free plywood bioadhesives. Sewage‐sludge‐based bioadhesive exhibits an excellent wet shear strength, complying with the requirements of Chinese national standard GB/T 9846–2015 (≥0.7 MPa). The molecular weight of proteins and the formation of covalent bonds via dehydration have a notable role in improving adhesive performance (wet shear strength). The Maillard reaction is a key reaction during HTC to destroy the secondary structure of proteins, resulting in the release of more OH and NH2. The main reaction during hot‐press treatment is dehydration. High ash content in bioadhesives improves flame resistance potential, particularly on addition of DES. A plausible mechanism is proposed for this. This work provides a new method for the valorization of SS‐derived hydrochars and contributes to the development of greener formaldehyde‐free wood bioadhesives.

Green wood bio-adhesives from cellulose-derived bamboo powder hydrochars

The development of formaldehyde-free plywood bio-adhesives is becoming a hot research topic. This contribution reports, for the first time, formaldehyde-free plywood bio-derived adhesives using hydrochar from bamboo powder, which has no nutritional ingredients, to address the poor anti-mildew properties of this material. The highest wet shear strength of bio-adhesives (BD-BP-APP) was 0.93 MPa, which meets the Chinese national standard GB/T 9846–2015 (≥0.7 MPa). Deep carbonization decreased the number of active functional groups on the surface of the hydrochar, reducing wet shear strength. The formation of covalent bonds was a key factor in improving wet shear strength during hot-pressing treatment.

Diagenetic evolution and cementation mechanism in deep Carbonate reservoirs: A case study of Dengying Fm. 2 in Penglai, Sichuan Basin, China

The Dengying Formation in the Penglai region of the Sichuan Basin is renowned for hosting high-quality dolomite reservoirs. However, the understanding of their formation mechanisms and spatial distribution patterns remains enigmatic. This study undertakes a comprehensive petrographic analysis of the second member of the Dengying Formation, primarily focusing on its burial history, reservoir characteristics, and an examination of the types, stages, and developmental patterns of cementation within the dolomite reservoir. This is achieved through the application of isotopic geochemistry, inclusion temperature analysis, and laser U-Pb dating. The findings reveal that cements within the second member of the Dengying Formation predominantly occur in pores and fractures, often exhibiting euhedral and subhedral morphologies. These cements also exhibit evidence of replacing original non-skeletal grains and micrites in semi-euhedral and other forms. Broadly, the cements can be classified into four types: calcium cement (the most abundant), dolomite cement, quartz, and pyrite. The formation of calcareous and siliceous cements closely aligns with the sedimentation and burial processes of the Dengying Formation as a whole. The early to late stages of early-middle diagenesis play a crucial role in the formation of dolomite within the second member. Notably, the degree of euhedral dolomite formation directly correlates with the specific diagenetic stage. Our research indicates that the development of high-quality reservoirs in deep-to-ultra-deep microbial dolomites is a result of complex multi-factor interactions and multi-stage discontinuous modifications, leading to strong heterogeneity within the reservoirs. Microbial dolomite carbonates inherently exhibit high initial porosity, with the favorable sedimentary facies serving as the fundamental basis for reservoir development. Dissolution processes during the syngenetic and quasi-syngenetic periods, in conjunction with epigenetic karstification, further augment porosity and expand the reservoir's capacity. During burial and deep burial stages, various acidic fluids play a pivotal role in preserving and modifying the early-formed pores. In the deep environment characterized by high temperature and pressure, microbial dolomite reservoirs undergo intricate diagenetic evolution and possess complex pore preservation mechanisms. Remarkably, even under exceptional ultra-deep conditions, high-quality microbial dolomite carbonate reservoirs can still develop and be preserved, presenting significant potential for oil and gas exploration.

Natural deep eutectic solvent-functionalized multiwall carbon nanotubes for lead removal from wastewater

In this study, two natural deep eutectic solvents (NADESs) were prepared from natural hydrogen bond donors (HBDs) based on sugar, namely fructose and sucrose, alongside H2O, and choline chloride as a hydrogen bond acceptor (HBA). The prepared NADESs were used as functionalizing agents with multiwall carbon nanotubes (MWCNTs), and the functionalized MWCNTs were used as adsorbents of Pb(II) lead ions from aqueous solution. The analyses demonstrated that MWCNTs functionalized with sucrose-based NADES to have more sub-stems and functional groups than the MWCNTs functionalized with fructose-based NADES, providing more possible sites for Pb(II) adsorption. The time dependence of Pb(II) adsorption onto these novel adsorbents was found to be better described by a pseudo-second-order kinetic model. Additionally, the Langmuir model better fits the adsorption data due to its higher coefficient of determination. Finally, the operating conditions (pH, adsorbent concentration, and contact time) were optimized using the Box-Behnken model, which demonstrated pH to exert greater influence on the adsorption process than the other studied factors. To the best of our knowledge, this study is the first to apply NADESs as emerging functionalizing agents for carbon nanomaterials in the removal of heavy metals from synthetic wastewater.