Carbon Samples Research Articles

Interstellar Carbonaceous Dust Erosion Induced by X-Ray Irradiation of Water Ice in Star-forming Regions

The chemical inventory of protoplanetary midplanes is the basis for forming planetesimals. Among them, solid-state reactions based on CO/CO2 toward molecular complexity on interstellar dust grains have been studied in theoretical and laboratory work. The physicochemical interactions between ice, constituted mainly of H2O, and dust surfaces are limited to a few experimental studies focusing on vacuum ultraviolet and cosmic-ray processing. In this work, the erosion of C dust grains induced by X-ray irradiation of H2O ice was systematically investigated for the first time. The work aims to provide a better understanding of the reaction mechanism using selectively isotope-labeled oxygen/carbon species in kinetic analysis. Ultrahigh vacuum experiments were performed to study the interstellar ice analog on submicron, thick C dust at ∼13 K. H2O or O2 ice was deposited on the presynthesized amorphous C dust and exposed to soft X-ray photons (250–1250 eV). Fourier-transform infrared spectroscopy was used to monitor in situ the newly formed species as a function of the incident photon fluence. Field emission scanning electron microscopy was used to monitor the morphological changes of (non-)eroded carbon samples. The X-ray processing of the ice/dust interface leads to the formation of CO2, which further dissociates and forms CO. Carbonyl groups are formed by oxygen addition to grain surfaces and are confirmed as intermediate species in the formation process. The yields of CO and CO2 were found to be dependent on the thickness of the carbon layer. The astronomical relevance of the experimental findings is discussed.

Exploring synergistic effects in physical-chemical activation of Acorus calamus for water treatment solutions

The research proposed a novel method of obtaining sorption material from readily available Acorus calamus biomass through a combination of physical and chemical activation processes. The material with the highest specific surface area (1652 m2 g−1) was obtained by physical activation with CO2, followed by chemical activation with KOH. Reversing the order of activation methods resulted in a lower specific surface area (1014 m2 g−1) of the carbon sample. Chemical activation produced activated carbon with a surface area of 1066 m2 g−1-, while physical activation produced 390 m2 g−1. This confirms the synergistic effect of combining the two activation methods for biocarbon. It was observed that physical activation with CO2 generates a diverse range of pores, including meso- and macropores, while chemical activation induces the formation of micropores. In contrast, reversing the order of these processes leads to the degradation of the porous structure. The application of physical-chemical activation with synergistic effects represents a significant advancement in producing high-quality activated biocarbon for various applications, such as wastewater treatment and energy storage. The combination of the two activation methods resulted in a synergistic effect, leading to the production of carbon material of higher quality. Additionally, the diversified pore sizes will enable the sorption of various pollutants in the aquatic environment and air pollutants, where gas particles are much smaller.

Enhancement of adsorption capacity of Methylene blue, Malachite green, and Rhodamine B onto KOH activated carbon derived from oil palm empty fruit bunches

Enhancement adsorption capacity of Methylene blue (MeB), Malachite green (MaG), and Rhodamine B (RhoB) onto activated carbon derived from oil palm empty fruit bunches (Biochar). The activated carbon was produced by pyrolysis with impregnation in KOH solution. To enhance its efficiency, the activation process was performed twice, yielding the adsorbents 1KAC and 2KAC. The adsorption capacity and equilibrium of the three dyes onto the biochar and activated carbon samples were determined by examining the removal efficiency, capacity, kinetics and isotherm models. The pseudo-second-order model performed better than the pseudo-first-order model in terms of adsorption kinetics. The Langmuir model fits well for all three dye molecules with high correlation coefficient values, suggesting that the activated carbon surface is homogeneous and characterized by a finite number of identical sites. The maximum adsorption capacity was 1123.57, 1315.36, and 982.87 mg/g for MeB, MaG, and RhoB, respectively. This founding indicated a high potential adsorbent more than among KOH activated carbon reported in the literature. The study provides valuable insights into the use of activated carbon derived from oil palm empty fruit bunches for the removal of dyes from wastewater.

Development of Non-Spherical Platinum Nanoparticles on Carbon Supports for Oxygen Reduction Reaction

Proton exchange membrane fuel cells are anticipated to play an important role in decarbonizing the global energy system, but the performance of platinum (Pt) catalysts must be improved to make this technology more economical. Studies have identified non-spherical Pt nanoparticles on carbon supports as promising approaches to address this challenge. However, to realize the full benefits of these strategies, the catalyst synthesis procedures must be successfully simplified and scaled up, and the catalyst must perform well in half and full-cell tests. In this study, a surfactant-free one-pot method is developed to synthesize non-spherical Pt nanoparticles on Ketjen Black carbon, which is either non-treated (Pt/KB), acid-treated (Pt/KB-O), or nitrogen-doped (Pt/KB-N). The catalysts are synthesized in both small and large batches to determine the effect of scaling up the synthesis procedure. The nitrogen-doped carbon support shows a nearly identical morphological structure with uniform distribution of non-spherical Pt nanoparticles for both small and large batches’ synthesis compared with non-treated and acid-treated carbon samples. The comparative oxygen reduction reaction (ORR) activity shows that the Pt/KB-N prepared in small and large batches has better ORR activity, which is likely caused by uniformly distributed non-spherical Pt nanoparticles on the nitrogen-doped carbon support. All three catalysts show similar ORR durability, testing from 0.5–1.0 V, while Pt/KB-O displays slightly better durability from 1.0–1.5 V for carbon corrosion. These results will help inform the implementation of shape-controlled Pt catalysts on modified carbon supports in large scale.

Testing carbon structures for metal-free catalytic/photocatalytic ozonation to remove disinfection by-product formation potential

Different graphitic carbon structures were prepared and tested for catalytic and photocatalytic ozonation of the precursors of chlorination disinfection by-products to remove their disinfection formation potential (DBPFP). Commercial graphite was submitted to ball milling and two chemical treatments with ammonium nitrate or potassium oxalate to increase its surface area. Additionally, ozonation in gas phase and liquid phase were used to generate surface oxygen groups in these materials and in commercial graphene. All the carbon samples were tested and compared with commercial graphene oxide in the removal of humic acid solutions. The highest catalytic activity during the catalytic/photocatalytic ozonation of humic acid was observed for commercial graphene, ozonated graphene and for graphene oxide; however, this did not result in high DBPFP removal and the instability of the materials was demonstrated. With a moderate catalytic activity but better stability, ball-milled graphite ozonated in liquid phase, was selected for photocatalytic ozonation of real surface water leading to a high DBPFP removal at the conditions tested (88 % 5-HAAs (haloacetic acids), 70 % 4-THMs (trihalomethanes), 70 % AOX (adsorbable organic halides); conditions: semi-batch experiments; 0.5 L volume; 5 mg L−1 O3; Qg = 10 L h−1; DOC0 = 5 mg L−1; pH = 7.8; 180 min under simulated solar radiation with average irradiance 580 W m−2).

Influence of different curing regimes and accelerated carbonation on the physical, mechanical, and aging performances of fiber cement

The curing process in fiber cement is essential to improving the characteristics of the fiber-matrix interface, physic-mechanical performance, and durability. This work studied the effect of different curing regimes and accelerated carbonation on fiber cement to optimize these materials' production stages and physic-mechanical performance. The fiber cement flat sheets were produced with 10% bleached eucalyptus pulp by slurry-dewatering method to reproduce the commercial Hatschek process. Carbonated and non-carbonated samples were assessed at different regimes and curing ages to provide a comparative parameter. Thermal curing at 60 °C (7 days) and wet curing (28 days) was carried out after carbonation as supplementary curing. The accelerated carbonation was performed in a climatic chamber at 60 °C, 90% RH, and 20% CO2 concentration. Accelerated aging trials were also conducted for durability evaluation. X-ray diffraction, TGA, and scanning electron microscopy analyses determined the mineralogical composition, chemical components, and fiber cement microstructure. Mechanical results presented an average increase of 33% in resistance of carbonated samples compared to non-carbonated fiber cement. Additional curing increased the materials' hydration potential and demonstrated an 11% increase in calcium carbonate amounts. However, there was no statistically significant difference in fiber cement’ physic-mechanical performance with additional curing. The carbonated samples without supplementary curing presented a fiber-matrix interface like that observed in other curing regimes, even after being subjected to a shorter curing time (3 days) and accelerated aging cycles. The accelerated carbonation process enables the materials’ production at reduced ages, achieving physic-mechanical performance and durability like materials produced at more advanced ages with conventional curing regimes.

Exploring the High-Pressure Phases of Carbon through X-ray Diffraction of Dynamic Compression Experiments on Sandia’s Z Pulsed Power Facility

The carbon phase diagram is rich with polymorphs which possess very different physical and optical properties ideal for different scientific and engineering applications. An understanding of the dynamically driven phase transitions in carbon is particularly important for applications in inertial confinement fusion, as well as planetary and meteorite impact histories. Experiments on the Z Pulsed Power Facility at Sandia National Laboratories generate dynamically compressed high-pressure states of matter with exceptional uniformity, duration, and size that are ideal for investigations of fundamental material properties. X-ray diffraction (XRD) is an important material physics measurement because it enables direct observation of the strain and compression of the crystal lattice, and it enables the detection and identification of phase transitions. Several unique challenges of dynamic compression experiments on Z prevent using XRD systems typically utilized at other dynamic compression facilities, so novel XRD diagnostics have been designed and implemented. We performed experiments on Z to shock compress carbon (pyrolytic graphite) samples to pressures of 150–320 GPa. The Z-Beamlet Laser generated Mn-Heα (6.2 keV) X-rays to probe the shock-compressed carbon sample, and the new XRD diagnostics measured changes in the diffraction pattern as the carbon transformed into its high-pressure phases. Quantitative analysis of the dynamic XRD patterns in combination with continuum velocimetry information constrained the stability fields and melting of high-pressure carbon polymorphs.

Enhanced low-frequency microwave absorption of N-doped biomass derived carbon

Hierarchical porous undoped and N-doped carbon derived from the natural spinach roots was prepared by a facile carbonization process at 600–800 ℃ respectively. The electromagnetic properties were carefully investigated in the range of 1–18 GHz in order to study the effect of the tunable permittivity on the microwave absorbing and shielding performance by modulating the intrinsic polarization of the biomass carbon. Compared with the other samples, the undoped one sintered at 650 ℃ shows the minimum reflection loss (RL) of − 42.93 dB at 16.72 GHz with a thickness of 2.0 mm, while the effective absorbing bandwidth achieves 6.46 GHz at 2.4 mm. With the N-doping, the permittivity is obviously affected by the nitrogen-containing groups and compounds induced dipolar and interfacial polarization. The RLmin of the N-doped carbon sample sintered at 700 ℃ has arrived at − 49.96 dB at 15.88 GHz with a very thin thickness of 1.5 mm. Besides, the impedance matching bandwidth can cover the L-C band in the N-doped carbon with the excellent RL of − 43.195 dB at d= 8.4 mm and f= 2.4 GHz. The competitive and tunable mechanism of the dielectric property are also studied for the tunable impedance and microwave absorption.

CALCIUM CARBONATE ISOLATION FROM EGGSHELL TO MEET PHARMACOPOEIAL STANDARDS AND ITS EFFECTIVENESS AS AN ANTACIDS

Objective: Calcium carbonate is widely used in the pharmaceutical field as excipients and therapeutic agents. Calcium carbonate can be obtained from limestone, chalk, marble and dolomite. Other alternative is from eggshell. Calcium carbonate source from eggshell has several advantages including higher calcium carbonate content, fewer contaminants metal limit, and more brittle. Therefore, in this study, calcium carbonate had been isolated from eggshells which was expected to meet the requirements of Indonesian Pharmacopoeia (sixth edition) and having activity as antacid. Methods: Calcium carbonate were isolated from eggshells by mechanically and physically organic separation. The quality of calcium carbonate was examined according to the Indonesian Pharmacopoeia parameters including loss on drying; acid-insoluble substance, magnesium and alkali salt; limit of arsenic, lead, iron, mercury, heavy metal, and barium. Additional physicochemical characterization of calcium carbonate including particle size analyzer, FTIR and XRD were compared with those of commercial calcium carbonate. Results: The results showed that the isolation produced 98.5±0.5 % of calcium carbonate. The calcium carbonate powder had an average size of 21±1.0 µm, while that of commercial was 8±1.3 µm. The resulted calcium carbonate revealed similar XRD patterns compared with that from commercial Calcium carbonate from the market. Based on database from FTIR instrument, the calcium carbonate sample had 99% similarity level compared with that from the reference. The sample of Calcium carbonate isolated from the eggshell (>mesh 100) had lower antacid activity (23.83 mEq) than that of commercial (24.56 mEq). Conclusion: Calcium carbonate from eggshell fulfilled the requirements of Indonesian Pharmacopoeia.

3D nanostructure prediction of porous carbons via gas adsorption

Structural characterization of porous carbon materials is critical for the evaluation of their synthesis procedures and performance. Throughout the last decades, many methods have been employed to determine porosity properties from gas adsorption such as surface area, pore size distribution (PSD) and real density. However, gas adsorption models use 1D structures of carbon nanopores, although adsorption and separation properties of nanoporous carbons are governed by 3D pore parameters. Estimating the 3D nanostructure of nanoporous carbons using gas adsorption would accelerate progress in research and implementation of nanoporous carbons. We report here a promising 3D pore nanostructural characterization from gas adsorption. Using atomistic simulations, we have generated a database of realistic 3D porous carbon structures spanning a wide range of pore sizes and geometries. After calculating their gas adsorption isotherms, we employed a numerical procedure to find the relative contribution for each of the structures to the adsorption isotherm of a nanoporous carbon sample. These contributions allowed us to estimate the surface area and pore size distribution of carbon materials; moreover (and perhaps more importantly!), we will show that the plausible 3D pore structures correlate very well with the local carbon structure as experimentally determined by high-resolution TEM observations and can successfully predict adsorption of different molecules. This is a powerful procedure that can be extended to other materials, and with enough computer power, to larger pore sizes.

Background Tests and Improvements at LAC-UFF Aiming at Sample Size Reduction in Foraminifera 14C Measurement

Foraminifera are widely used in paleoclimatic and paleoceanographic studies, providing information about past ocean conditions. However, in order to use these tracers, it is essential to obtain an accurate chronology. Radiocarbon has proven to be a powerful tool in developing robust chronologies. Sample sizes of a few milligrams of carbonate material are needed for precise radiocarbon determination using accelerator mass spectrometry (AMS). In the specific case of paleoceanographic and paleoenvironmental studies, Foraminifera microfossils are the most important indicator of oceanic conditions. However, for establishing the chronology of deposition, sample availability is often limited. In AMS facilities using solid ion sources, such as the Radiocarbon Laboratory of the Universidade Federal Fluminense (LAC-UFF), in Brazil, CO2 samples need to be converted to graphite after physical and chemical pre-treatment to remove contamination. Reducing the sample sizes increases the relative contribution of contamination and can favor increased background levels. In this work, we tested different amounts of 14C-free carbonate samples as a means to evaluate the pattern of contamination. For the sealed tube Zn/TiH2 graphitization method, we tested prebaking the graphitization tubes and compared storage procedures. As a result, the background for regular-sized samples was decreased, and accurate measurement of carbonate samples containing ca. 0.5 mg C could be performed. Prebaked graphitization tubes can safely be stored in desiccator cabinets for up to 4 weeks. Foraminifera samples with mass as low as 1 mg (ca. 0.1 mg C) can now be measured at the LAC-UFF AMS facility, provided that C contamination can be estimated and corrected. The developments presented in this work allowed for the study of species-specific Foraminifera and other small-sized carbonate samples.

Investigating accelerated carbonation for alkali activated slag stabilized sandy soil

Portland cement as a commonly used material in soil stabilization projects, releases considerable amounts of CO2 into the atmosphere, highlighting the need to use green binders such as ground granulated blast furnace slag as a substitute for cement. On the other side, extensive research is being conducted on accelerated carbonation treatment to decrease the industry’s carbon footprint. Carbonation transforms CO2 into carbonate minerals. This study investigates the influence of accelerated carbonation on the unconfined compressive strength (UCS) of soil stabilized with alkali-activated slag under ambient and oven curing conditions. Effects of curing time, binder content, relative density, and carbonation pressure (100, 200, and 300 kPa) were also studied. Furthermore, a calcimeter test was conducted to determine the amount of carbonate generated, which reflects CO2 sequestration in soil. The results showed that the carbonated samples achieved higher strength than the non-carbonated samples. However, a slight decrease in UCS was observed with the increase in CO2 pressure. The generated carbonate content directly correlated with the UCS of the samples, which explained the higher strength of carbonated samples. Also, the ambient curing condition was more favorable for the samples stabilized with GGBS, which can be attributed to the supply of required moisture. Results from XRD, SEM, and FTIR indicated that the strength development was due mainly to the formation of carbonation products (CaCO3), which facilitated the densification of solidified materials.

Understanding the complexity of secondary formation damage: Mechanism and detection strategies during filter cake removal process

Formation damage has a negative impact on the productivity of a well. Hence, its mechanism needs to be well understood to be able to mitigate it. Secondary damage is a form of formation damage that occurs during the removal process of barite filter cake layer but has received less attention. This study focuses on examining the secondary damage that occurs during the removal process of barite filter cake layer using chelating agents. Ethylenediaminetetraacetic acid (EDTA) with a concentration of 20% was employed as an effective treatment solution for removing the barite filter cake. EDTA was prepared as a pure solution (referred to as EDTA-K) and saturated with barium (referred to as EDTA-Ba) to simulate the solution state after the completion of filter cake removal. Experiments were conducted using different rock samples, including a sandstone and a carbonate core, to investigate the interaction between the chelating agent and the formation through a core flooding system. Nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) were applied to evaluate the alterations in the inner pore structure, and pore size distribution due to the EDTA reactivity. Furthermore, the changes in rock samples’ permeability were examined. Results showed that the reactivity of EDTA varies depending on the rock type and the presence of specific ions. EDTA exhibited limited reactivity with sandstone samples because of its weak ability to react with the silicate matrix and limited content of clay minerals containing Al3+ and Mg2+, highlighting a lower potential for secondary formation. In contrast, carbonate samples demonstrated higher reactivity with EDTA, leading to enhanced permeability. However, the precipitation of barium within the pores of carbonate rocks was observed, which can be considered as a significant level of secondary formation damage. Ab initio calculations supported the experimental findings by demonstrating the binding ability of EDTA with different ions.

Tuning the ultra-microporosity in hierarchical porous carbons derived from amorphous cellulose towards a sustainable solution for hydrogen storage

Activated carbons exhibit a high grade of porosity, which together with structural stability, regenerability and cyclability makes them capable of achieving excellent hydrogen adsorption capacity. A further advantage comes from the ease of production and the use of recyclable and biocompatible materials. A simple way to produce activated carbons from amorphous cellulose involves procedures in which a pyrolysis process is combined with physical activation in CO2.We used this approach by optimizing the production process tuning the activation times. The aim is to evaluate the influence of this process parameter on the formation of the specific surface area, the pore volume and fraction of micropores with a typical size <2 nm. The influence of these structural parameters on the hydrogen adsorption properties was then evaluated. The textural and adsorption characteristics were investigated using a commercial volumetric apparatus (ASAP 2460, Micromeritics) at −196 °C and pressures between 0 and 1 bar, while the morphological properties were investigated using scanning electron microscopy.The results show that the nanostructured samples are characterized by a very high degree of ultra-microporosity (<0.7 nm) with an average pore size between 0.5 and 0.6 nm and a high specific surface area, reaching maximum values around 1500 m2/g and micropore volume up to 0.58 cc/g. These morphological characteristics strongly influence the hydrogen adsorption properties, where the molecules adsorbed reach values very close to the coverage of ideal monolayer. The synthesized activated carbon samples show a higher hydrogen adsorption capacity than similar commercial materials tested under the same thermodynamic conditions.

Waste jean derived self N-containing activated carbon as a potential electrode material for supercapacitors.

The rapid rise of the world population increases the annual amount of waste textile products. Textile products create a significant amount of CO2, water, and chemical footprints during production. Therefore, the reusability of textile products has an important environmental and economic impact. Waste denim was used in this study to produce activated carbon (AC) samples as the alternative substance for supercapacitor electrodes. Characterisation studies showed that AC samples contain nitrogen originating from the elastane in the denim structure. Electrochemical characterisation tests proved the pseudocapacitive behaviour of the denim-derived AC due to the nitrogen content. Specific capacitance values observed for the three-electrode and two-electrode cell configurations were 95.93 F/g and 54.64 F/g at 1 A/g, respectively. Good capacitive retention (83.01%) of the cell after 3000 galvanostatic charge-discharge cycles at 1 A/g shows that waste denim can be considered as raw material for energy storage systems.

Effect of concentration and flow rate of electrolyte on electrochemical regeneration of activated carbon at pilot-plant scale

Few research has investigated the problem of regeneration of activated carbon once it has been saturated by organic and inorganic contaminants. Among the regeneration methods, electrochemical technology is one of the most advanced, demonstrating its effectiveness in pilot-plant scale experiments using samples obtained from drinking water treatment plants. In the present study, the optimization of a parallel plate electrochemical reactor with a capacity of 15 kg of activated carbon, has been achieved regarding the electrolyte concentration and flow rate. A regeneration efficiency of approximately 90% was achieved with a 0.25 M H2SO4 concentration, while lower concentrations resulted in a voltage exceeding the acceptable limits for this type of installation. In addition, higher flow rates imply a higher recovery of the porous texture of the regenerated activated carbon. This is, to the best of our knowledge, the first report where these two experimental variables are optimized in a pilot-scale process with real saturated activated carbon samples with different types of pollutants adsorbed in the activated carbon.

Estimating Permeability of Porous Media from 2D Digital Images

Digital rock physics (DRP) has been widely used as an effective approach for estimating the permeability of porous media. However, conventional implementation of DRP requires the reconstruction of three-dimensional (3D) pore networks, which suffer from intensive memory and underlying uncertainties. Therefore, it is highly significant to develop an approach only based on two-dimensional (2D) cross-sections of parent samples without 3D reconstruction. In this study, we present a novel approach that combines the Kozeny–Carman equation with fractal theory to derive a bridge function that links 2D cross-sectional images and 3D pore structures of parent samples in flow equivalence. Using this bridge function, we predicted the physical properties of the parent samples, including the permeability, bulk porosity, tortuosity, and pore fractal dimension. To validate our model, we performed Lattice Boltzmann (LB) simulations on nine carbonate samples and compared the LB simulation results with our model’s predictions. We also compared our predicted results with available data on various porous materials, such as sandstone, glass beads, and carbonate, in the literature. Our findings demonstrate that without reconstructing 3D pore networks, our method provides a reliable estimation of sample permeability using 2D cross-sectional images. This approach not only simplifies the determination of sample permeability in heterogeneous porous media but also sheds new light on the inherent correlations between 2D cross-sectional information and 3D pore structures of parent samples. Moreover, the derived model may be conducible to a better understanding of flow in reservoirs during the extraction of unconventional onshore and offshore oil/gas.

Influence of carbon nanodots on the Carbonate/CO2/Brine wettability and CO2-Brine interfacial Tension: Implications for CO2 geo-storage

Understanding the interfacial and wettability phenomena of the CO2-brine and rock-CO2-brine system plays a key role in the geo-storage of CO2 and in their security containment. Carbon nanodots (CNDs) have been identified as a promising surface-active agent for altering the wettability from strongly oil-wet into water-wet in the carbonate reservoirs, thus it contributed for the oil recovery increment in the carbonate formations. However, no consideration was given to the application of CNDs for the enhancement of CO2 geological storage and containment security in the carbonate formations. In the current study, we assessed the impact of CNDs on the residual and structural trapping of CO2 in the carbonate reservoir. The contact angles (θ) of the CO2-brine-carbonate rock system were studied before and after the treatment of CNDs for both the clean and crude oil-aged samples. Subsequently, we also investigated the CO2-seawater interfacial tensions (IFT) with and without CNDs addition. All these measurements were performed as a function of CNDs concentration (0–1000 ppm), temperature (20–80 °C) and pressure (14.7–3000 psi). The results showed that the clean carbonate rock remained strongly water-wet before and after CNDs-treatment. The oil-wet carbonate sample was turned into CO2-wet at all investigated temperatures when the pressures increased to 1000 psi, however, it turns to be weakly water-wet upon treatment with CNDs at the highest pressure (3000 psi). Specifically, at 3000 psia and 20 °C, the contact angle of oil-wet carbonate reduced from 122° to 86° with the addition of CNDs at the increased concentration of 1000 ppm. Such wettability modifications in carbonate formations will enhance the efficacy of CO2 storage potential, and eventually, this will help to de-risk their security containment. The θ generally demonstrated a declining trend with the increase of CNDs concentration but it slightly increased with the rise in temperature and pressure. These results suggest that warmer reservoirs and increased storage depth could be unfavorable for CO2 storage in carbonate formations. Thus, the pre-injection of a minimal concentration of CNDs in the formation would improve CO2 storage effectively. Also, no significant change was observed in the CO2-seawater IFT in the presence of CNDs, which indicates that the capillary trapping of CO2 could be favorable due to their lower contact angle and high CO2-brine IFT as the most suitable condition to maintain the high capillarity. The study demonstrates that the highly stable, freely soluble, easy detectable, scalable, and economically viable CNDs has the potency to enhance the containment security of CO2 in carbonate formation.

Characterizing nighttime vertical profiles of atmospheric particulate matter and ozone in a megacity of south China using unmanned aerial vehicle measurements

Daytime atmospheric pollution has received wide attention, while the vertical structures of atmospheric pollutants at night play a crucial role in the photochemical process on the following day, which is still less reported. Focusing on Guangzhou, a megacity of South China, we established an unmanned aerial vehicle (UAV) equipped with micro detectors to collect consecutive high-resolution samples of fine particle (PM2.5), submicron particle (PM1.0), black carbon (BC) and ozone (O3) concentrations in the atmosphere, as well as the air temperature (AT) and relative humidity (RH) within a 500 m altitude during nighttime from Oct. 24th to Nov. 6th, 2018. The measurements showed that PM2.5, PM1.0, and BC decreased with altitude and were influenced by the nighttime shallow planetary boundary layer (PBL) where BC was more accumulated and fluctuated. In contrast, O3 was positively correlated with altitude. Backward trajectory clustering and Pasquill stability classification showed that advection and convection significantly influenced the vertical distribution of all pollutants, particularly particulate matter. External air masses carrying high concentrations of pollutants increased PM1.0 and PM2.5 levels by 145% and 455%, respectively, compared to unaffected periods. The ratio of BC to PM2.5 indicated that local emissions had a minor role in nighttime particulate matter. Vertical transport caused by atmospheric instability reduced the differences in pollutant concentrations at various heights. Geodetector and generalized additive model showed that RH and BC accumulation in the PBL were significant factors influencing vertical changes of the secondary aerosol intensity as indicated by the ratio of PM1.0 to PM2.5. The joint explanation of RH and atmospheric stability with other variables such as BC is essential to understand the generation of secondary aerosols. These findings provide insights into regional and local measures to prevent and control night-time particulate matter pollution.

Substantial incorporation of isotopically heavy reduced U species into marine carbonate sediments

The uranium (U) isotope ratio (238U/235U, reported as δ238U) in marine carbonates is an important proxy for reconstructing changes in past oceanic redox conditions, based on the essential assumption that U in carbonates originates from dissolved U(VI) in seawater. However, diagenetic processes may induce the addition of isotopically heavy U(IV) into the carbonates, complicating the application of the U isotope proxy. So far, the valence states of trace amounts of U and its relation with U isotope composition in marine carbonate sediments have not been directly studied. In this study, we have calibrated an ion-exchange chromatographic method to separate U(IV) from U(VI) in geological carbonate samples (e.g., modern and fossil corals, stalagmites, cold seep carbonates) and quantified their contents by mass spectrometry. Our study confirms that modern coral carbonates are faithful archives of U(VI) sourced from seawater. Surprisingly, drill core samples from a modern coral carbonate platform, which bear no sign of alteration inferred from conventional diagenetic proxies (e.g., Mn/Sr), show significant positive correlation between U(IV) fraction and bulk carbonate δ238U, suggesting U(IV) is present in the marine carbonates and drives δ238U toward higher values than that of seawater. We therefore suggest that coupled valence and isotope analyses of U in marine carbonates could provide critical constraints toward reliable reconstruction of marine redox evolution in the Earth’s history.