Composition Of Individual Particles Research Articles

Illitization of montmorillonite in ammonium solutions under hydrothermal conditions

In diagenetic solutions, ammonium may be incorporated into smectites as an exchangeable cation and become fixed within the interlayer space of illites and other white micas. To study the potential impact of NH4+ on the smectite-to-illite transformation reaction, a series of hydrothermal experiments were carried out at 100, 150 and 200 °C, spanning reaction duration from 15 to 90 days, and two NH4+ concentrations (0.1 and 0.2 M). The solids resulting from these alteration experiments were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and transmission and analytical electron microscopy (TEM and AEM). The XRD analysis revealed that, under the specified experimental conditions, smectite incorporates NH4+ in the structure, leading to the formation of non-swelling layers, resulting in partial transformation to illite layers and producing packets of disordered illite/smectite (I/S). In addition, a minor XRD peak at ∼10 Å suggests the formation of discrete illite crystals. The FTIR spectra demonstrated the uptake of NH4+, with deformation bands observed at 1400 and 1430 cm−1, corresponding to exchangeable NH4+ in smectite and fixed NH4+ in high-charge layers, respectively. TEM analysis revealed that smectite particles exhibited wavy stacks comprising a few layers with abundant defects and lateral discontinuities. The interlayer spacing in these particles ranged from 12 to 15 Å and became thinner and more plate-like with increasing temperature and time. Moreover, they contained inclusions of 10–10.3 Å layers, either as discrete layers or in packets of several layers, indicating the formation of disordered mixed-layer illite-smectite. Lateral transitions from 12 to 15 Å to 10 Å layers were frequently observed and interpreted as reaction fronts due to local rearrangement. At 150 and 200 °C, isolated packets of 10 Å layers were identified as discrete illite crystals that precipitated directly from solution. Analysis of the chemical composition of individual particles revealed an increase in octahedral charge (MgVI for AlVI substitution) in smectite particles, followed by increase in tetrahedral charge in I/S particles. Interlayer NH4+ played a stabilizing role in the high-charge layers and favored the smectite-to-illite conversion process.

Technical note: Determining chemical composition of atmospheric single particles by a standard-free mass calibration algorithm

Abstract. The chemical composition of individual particles can be revealed by single-particle mass spectrometers (SPMSs). With higher accuracy in the ratio of mass to charge (m/z), more detailed chemical information could be obtained. In SPMSs, the conventional standard-based calibration methods (internal/external) are constrained by the inhomogeneity of ionization lasers and the finite focusing ability of the inlet system, etc.; therefore, the mass accuracy is restricted. In this study, we obtained the detailed and reliable chemical composition of single particles utilizing a standard-free mass calibration algorithm. In the algorithm, the characteristic distributions of hundreds of ions were concluded and collected in a database denoted as prototype. Each single-particle mass spectrum was initially calibrated by a function with specific coefficients. The range of coefficients was constrained by the magnitude of mass deviation to a finite vector space. To find the optimal coefficient vector, the conformity of each initially calibrated spectrum to the prototype dataset was assessed. The optimum calibrated spectrum was obtained with maximum conformity. For more than 98 % ambient particles, a 20-fold improvement in mass accuracy, from ∼ 10 000 ppm (integer) to ∼ 500 ppm (two decimal places), was achieved. The improved mass accuracy validated the determination of adjacent ions with a m/z difference ∼ 0.05 Th. Furthermore, atmospheric particulate trace elements that were poorly studied before are specified. The obtained detailed single-particle-level chemical information could help explain the source apportionment, reaction mechanism, and mixing state of atmospheric particles.

Characterization of particle exposure during tunnel excavation by tunnel boring machines.

Tunnel boring machines (TBMs) are used to excavate tunnels in a manner where the rock is constantly penetrated with rotating cutter heads. Fine particles of the rock minerals are thereby generated. Workers on and in the vicinity of the TBM are exposed to particulate matter (PM) consisting of bedrock minerals including α-quartz. Exposure to respirable α-quartz remains a concern because of the respiratory diseases associated with this exposure. The particle size distribution of PM and α-quartz is of special importance because of its influence on adverse health effects, monitoring and control strategies as well as accurate quantification of α-quartz concentrations. The major aim of our study was therefore to investigate the particle size distribution of airborne PM and α-quartz generated during tunnel excavation using TBMs in an area dominated by gneiss, a metamorphic type of rock. Sioutas cascade impactors were used to collect personal samples on 3 separate days. The impactor fractionates the dust in 5 size fractions, from 10 µm down to below 0.25 µm. The filters were weighted, and the α-quartz concentrations were quantified using X-ray diffraction (XRD) analysis and the NIOSH 7500 method on the 5 size fractions. Other minerals were determined using Rietveld refinement XRD analysis. The size and elemental composition of individual particles were investigated by scanning electron microscopy. The majority of PM mass was collected on the first 3 stages (aerodynamic diameter = 10 to 0.5 µm) of the Sioutas cascade impactor. No observable differences were found for the size distribution of the collected PM and α-quartz for the 3 sampling days nor the various work tasks. However, the α-quartz proportion varied for the 3 sampling days demonstrating a dependence on geology. The collected α-quartz consisted of more particles with sizes below 1 µm than the calibration material, which most likely affected the accuracy of the measured respirable α-quartz concentrations. This potential systematic error is important to keep in mind when analyzing α-quartz from occupational samples. Knowledge of the particle size distribution is also important for control measures, which should target particle sizes that efficiently capture the respirable α-quartz concentration.

Single particle mass spectral signatures from on-road and non-road vehicle exhaust particles and their application in refined source apportionment using deep learning

With advances in vehicle emission control technology, updating source profiles to meet the current requirements of source apportionment has become increasingly crucial. In this study, on-road and non-road vehicle particles were collected, and then the chemical compositions of individual particles were analyzed using single particle aerosol mass spectrometry. The data were grouped using an adaptive resonance theory neural network to identify signatures and establish a mass spectral database of mobile sources. In addition, a deep learning-based model (DeepAerosolClassifier) for classifying aerosol particles was established. The objective of this model was to accomplish source apportionment. During the training process, the model achieved an accuracy of 98.49 % for the validation set and an accuracy of 93.36 % for the testing set. Regarding the model interpretation, ideal spectra were generated using the model, verifying its accurate recognition of the characteristic patterns in the mass spectra. In a practical application, the model performed hourly source apportionment at three specific field monitoring sites. The effectiveness of the model in field measurement was validated by combining traffic flow and spatial information with the model results. Compared with other machine learning methods, our model achieved highly automated source apportionment while eliminating the need for feature selection, and it enables end-to-end operation. Thus, in the future, it can be applied in refined and online source apportionment of particulate matter.

Morphological and chemical characterisation of indoor quasi-ultrafine particles

Particles in the nanoscale range have intrinsic physicochemical characteristics that define their interaction with the human body and ultimately their toxicity. Whilst research has focused on engineered nanomaterials or ambient ultrafine particles, little is known about the morphology, size and elemental composition of particles in the nanoscale range collected in indoor environments, where humans spend the longest time. This study aims to characterise the physicochemical properties of quasi-ultrafine particles (qUFP), with an aerodynamic diameter <250 nm, collected with a Sioutas impactor from 5 indoor environments (3 homes and 2 offices). Morphology, size and elemental composition of individual particles were imaged using a Transmission Electron Microscope coupled with X-ray energy dispersive spectroscopy. Most of the single particles and their aggregates were of irregular shapes, and some fibrous rods, elongated rods, spheres and hexagons were also observed. ImageJ software was used to analyse the surface area, roundness and circularity of the particles, as well as individual particle diameter for the spherical particles. For the non-spherical shaped particle, the particles were manually measured to characterise the maximum Feret diameter. Particle main dimensions (i.e. diameter for spheroids and maximum Feret diameter for irregular particles) ranged from 35 ± 59 nm to 103 ± 160 nm. Shapes for non-spherical particles were assigned by visual description. Si, Fe and S were found in nanoparticles from all indoor locations. Other abundant constituents were K, Cr, Na, Ca, Cl found in 60–80% of locations. Minor constituents of indoor nanoparticles were Cu, Sn, Ti, Mo, Al, P, Be, F, Zn, Rb, Pb, Mn and Co. Sources were related to indoor emissions, e.g. printers, stainless-steel tools, electronics, cooking, house chores, particle re-suspension, aerosol and cleaning products as well as to penetration of outdoor nanoparticles from vehicular emissions, soil and secondary aerosols. Detailed investigation of the physicochemical properties of these particles can help understand their associated hazard and their fate in the human body.

An introduction to the significance of sample size in particle analyses for nuclear forensics and radiological investigations

Particulate isotopic analysis in nuclear forensics has developed rapidly during the past two decades due to technical advances in determining the isotopic composition of individual particles. This paper introduces basic statistical concepts that can be applied by analysts to understand the importance of statistical adequacy when interpretating particle data. While these basic statistical methods provide a useful point-of-entry to particle data analysis, more sophisticated statistical and modeling approaches are needed to extract maximal information from such datasets in the future.

Direct Measurement of Microplastics by Carbon Detection via Single Particle ICP-TOFMS in Complex Aqueous Suspensions.

Multiple analytical techniques to measure microplastics (MPs) in complex environmental matrices are currently under development, and which is most suited often depends on the aim(s) of the research question and the experimental design. Here, we further broaden the suite of possible techniques which can directly detect MPs in suspension while differentiating the carbon contained in MPs from other natural particles and dissolved organic carbon (DOC). Single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) is well suited to measuring particles at trace concentrations, and the use of ICP time-of-flight-MS (ICP-TOFMS) allows one to simultaneously monitor the entire elemental spectrum to assess the full elemental composition of individual particles through developing elemental fingerprints. Because carbon is not detected in a standard operation mode with icp TOF, a dedicated optimization was necessary. Subsequently, to assess the feasibility of monitoring 12C particle pulses for the detection of MPs in more complex natural waters, two proof-of-principle studies were performed to measure MPs in waters with environmentally relevant DOC backgrounds (≤20 mg/L) and in the presence of other carbon containing particles, here, algae. Elevated DOC concentrations did not impact the enumeration of particles in suspension, and individual MPs, single algae, and aggregates of MPs and algae were clearly distinguished. The simultaneous identification of different analytes of interest allows for multiplexed sp-ICP-TOFMS experiments utilizing elemental fingerprinting of particles and is a step forward in quantifying MPs in aqueous environmental samples.

Probing Individual Particles Generated at the Freshwater-Seawater Interface through Combined Raman, Photothermal Infrared, and X-ray Spectroscopic Characterization.

Sea spray aerosol (SSA) is one of the largest global sources of atmospheric aerosol, but little is known about SSA generated in coastal regions with salinity gradients near estuaries and river outflows. SSA particles are chemically complex with substantial particle-to-particle variability due to changes in water temperature, salinity, and biological activity. In previous studies, the ability to resolve the aerosol composition to the level of individual particles has proven necessary for the accurate parameterization of the direct and indirect aerosol effects; therefore, measurements of individual SSA particles are needed for the characterization of this large source of atmospheric aerosol. An integrated analytical measurement approach is required to probe the chemical composition of individual SSA particles. By combining complementary vibrational microspectroscopic (Raman and optical photothermal infrared, O-PTIR) measurements with elemental information from computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM-EDX), we gained unique insights into the individual particle chemical composition and morphology. Herein, we analyzed particles from four experiments on laboratory-based SSA production using coastal seawater collected in January 2018 from the Gulf of Maine. Individual salt particles were enriched in organics compared to that in natural seawater, both with and without added microalgal filtrate, with greater enrichment observed for smaller particle sizes, as evidenced by higher carbon/sodium ratios. Functional group analysis was carried out using the Raman and infrared spectra collected from individual SSA particles. Additionally, the Raman spectra were compared with a library of Raman spectra consisting of marine-derived organic compounds. Saccharides, followed by fatty acids, were the dominant components of the organic coatings surrounding the salt cores of these particles. This combined Raman, infrared, and X-ray spectroscopic approach will enable further understanding of the factors determining the individual particle composition, which is important for understanding the impacts of SSA produced within estuaries and river outflows, as well as areas of snow and ice melt.

Glass Transition Temperatures of Individual Submicrometer Atmospheric Particles: Direct Measurement via Heated Atomic Force Microscopy Probe.

The phase (solid, semisolid, or liquid) of atmospheric aerosols is central to their ability to take up water or undergo heterogeneous reactions. In recent years, the unexpected prevalence of viscous organic particles has been shown through field measurements and global atmospheric modeling. The aerosol phase has been predicted using glass transition temperatures (Tg), which were estimated based on molecular weight, oxygen:carbon ratio, and chemical formulae of organic species present in atmospheric particles via studies of bulk materials. However, at the most important sizes for cloud nucleation (∼50-500 nm), particles are complex mixtures of numerous organic species, inorganic salts, and water with substantial particle-to-particle variability. To date, direct measurements of Tg have not been feasible for individual atmospheric particles. Herein, nanothermal analysis (NanoTA), which uses a resistively heated atomic force microscopy (AFM) probe, is combined with AFM photothermal infrared (AFM-PTIR) spectroscopy to determine the Tg and composition of individual particles down to 76 nm in diameter at ambient temperature and pressure. Laboratory-generated proxies for organic aerosol (sucrose, ouabain, raffinose, and maltoheptaose) had similar Tg values to bulk Tg values measured with differential scanning calorimetry (DSC) and the Tg predictions used in atmospheric models. Laboratory-generated phase-separated particles and ambient particles were analyzed with NanoTA + AFM-PTIR showing intraparticle variation in composition and Tg. These results demonstrate the potential for NanoTA + AFM-PTIR to increase our understanding of viscosity within submicrometer atmospheric particles with complex phases, morphologies, and compositions, which will enable improved modeling of aerosol impacts on clouds and climate.

Characterization of Atmospheric Deposition as the Only Mineral Matter Input to Ombrotrophic Bog

Ombrotrophic peatlands contain a very small percentage of mineral matter that they receive exclusively from atmospheric deposition. Mineral matter deposited on the Šijec bog was characterized using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS). We collected solid atmospheric deposition from snow, rainwater, and using passive samplers. Samples were collected at average atmospheric conditions and after two dust events. Size, morphology, and chemical composition of individual particles were determined. We distinguished four main particle groups: silicates, carbonates, organic particles, and Fe-oxyhydroxides. Silicate particles are further divided into quartz and aluminosilicates. Proportions of these groups vary between samples and between sample types. In all samples, silicate particles predominate. Samples affected by dust events are richer in solid particles. This is well observed in passive deposition samples. Carbonates and organic particles represent smaller fractions and are probably of local origin. Iron-oxyhydroxides make up a smaller, but significant part of particles and are, according to their shape and chemical composition, of both geogenic and anthropogenic origin. Estimated quantity and percentage of main groups vary throughout the year and are highly dependent on weather conditions. Dust events represent periods of increased deposition and contribute significantly to mineral matter input to peatlands.

Particle phase-state variability in the North Atlantic free troposphere during summertime is determined by atmospheric transport patterns and sources

Abstract. Free tropospheric aerosol particles have important but poorly constrained climate effects due to transformations of their physicochemical properties during long-range transport. In this study, we investigate the chemical composition and provide an overview of the phase states of individual particles that have undergone long-range transport over the North Atlantic Ocean in June and July 2014, 2015, and 2017 to the Observatory of Mount Pico (OMP) in the Azores. The OMP is an ideal site for studying long-range-transported free tropospheric particles because local emissions have a negligible influence and contributions from the boundary layer are rare. We used the FLEXible PARTicle Lagrangian particle dispersion model (FLEXPART) to determine the origins and transport trajectories of sampled air masses and found that most of them originated from North America and recirculated over the North Atlantic Ocean. The FLEXPART analysis showed that the sampled air masses were highly aged (average plume age &gt;10 d). Size-resolved chemical compositions of individual particles were probed using computer-controlled scanning electron microscopy with an energy-dispersive X-ray spectrometer (CCSEM-EDX) and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS). CCSEM-EDX results showed that the most abundant particle types were carbonaceous (∼ 29.9 % to 82.0 %), sea salt (∼ 0.3 % to 31.6 %), and sea salt with sulfate (∼ 2.4 % to 31.5 %). We used a tilted stage interfaced within an environmental scanning electron microscope (ESEM) to determine the phase states of individual submicron particles. We found that most particles (∼ 47 % to 99 %) were in the liquid state at the time of collection due to inorganic inclusions. Moreover, we also observed substantial fractions of solid and semisolid particles (∼ 0 % to 30 % and ∼ 1 % to 42 %, respectively) during different transport patterns and events, reflecting the particles' phase-state variability for different atmospheric transport events and sources. Combining phase state measurements with FLEXPART CO tracer analysis, we found that wildfire-influenced plumes can result in particles with a wide range of viscosities after long-range transport in the free troposphere. We also used temperature and RH values extracted from the Global Forecast System (GFS) along the FLEXPART-simulated path to predict the phase state of the particles during transport and found that neglecting internal mixing with inorganics would lead to an overestimation of the viscosity of free tropospheric particles. Our findings warrant future investigation aiming at the quantitative assessment of the influence of internal mixing on the phase states of the individual particles. This study also provides insights into the chemical composition and phase state of free tropospheric particles, which can help models to reduce uncertainties about the effects of ambient aerosol particles on climate.

Impact of dry intrusion events on the composition and mixing state of particles during the winter Aerosol and Cloud Experiment in the Eastern North Atlantic (ACE-ENA)

Abstract. Long-range transport of continental emissions has a far-reaching influence over remote regions, resulting in substantial change in the size, morphology, and composition of the local aerosol population and cloud condensation nuclei (CCN) budget. Here, we investigate the physicochemical properties of atmospheric particles collected on board a research aircraft flown over the Azores during the winter 2018 Aerosol and Cloud Experiment in the Eastern North Atlantic (ACE-ENA) campaign. Particles were collected within the marine boundary layer (MBL) and free troposphere (FT) after long-range atmospheric transport episodes facilitated by dry intrusion (DI) events. Chemical and physical properties of individual particles were investigated using complementary capabilities of computer-controlled scanning electron microscopy and X-ray spectromicroscopy to probe particle external and internal mixing state characteristics. Furthermore, real-time measurements of aerosol size distribution, cloud condensation nuclei (CCN) concentration, and back-trajectory calculations were utilized to help bring into context the findings from offline spectromicroscopy analysis. While carbonaceous particles were found to be the dominant particle type in the region, changes in the percent contribution of organics across the particle population (i.e., external mixing) shifted from 68 % to 43 % in the MBL and from 92 % to 46 % in FT samples during DI events. This change in carbonaceous contribution is counterbalanced by the increase in inorganics from 32 % to 57 % in the MBL and 8 % to 55 % in FT. The quantification of the organic volume fraction (OVF) of individual particles derived from X-ray spectromicroscopy, which relates to the multi-component internal composition of individual particles, showed a factor of 2.06 ± 0.16 and 1.11 ± 0.04 increase in the MBL and FT, respectively, among DI samples. We show that supplying particle OVF into the κ-Köhler equation can be used as a good approximation of field-measured in situ CCN concentrations. We also report changes in the κ values in the MBL from κMBL, non-DI=0.48 to κMBL, DI=0.41, while changes in the FT result in κFT, non-DI=0.36 to κFT, DI=0.33, which is consistent with enhancements in OVF followed by the DI episodes. Our observations suggest that entrainment of particles from long-range continental sources alters the mixing state population and CCN properties of aerosol in the region. The work presented here provides field observation data that can inform atmospheric models that simulate sources and particle composition in the eastern North Atlantic.

New horizons in microparticle forensics: Actinide imaging and detection of 238Pu and 242mAm in hot particles.

Micrometer-sized pollutant particles are of highest concern in environmental and life sciences, cosmochemistry, and forensics. From their composition, detailed information on origin and potential risks to human health or environment is obtained. We combine secondary ion mass spectrometry with resonant laser ionization to selectively examine elemental and isotopic composition of individual particles at submicrometer spatial resolution. Avoiding any chemical sample preparation, isobaric interferences are suppressed by five orders of magnitude. In contrast to most mass spectrometric techniques, only negligible mass is consumed, leaving the particle intact for further studies. Identification of actinide elements and their isotopes on a Chernobyl hot particle, including 242mAm at ultratrace levels, proved the performance. Beyond that, the technique is applicable to almost all elements and opens up previously unexplored scientific applications.

Structural collapse in phlogopite mica-rich mine tailings induced by mechanochemical treatment and implications to alkali activation potential

The alkali activation of mine tailings is of interest to diminish the impoundment storage of large waste stream from mining industry. However, most of the mine tailings, like phosphate mine tailings generated in Finland, are rather inert and need pre-treatment to induce the reactivity for alkali activation. In this work, mechanochemical treatment was conducted to improve the reactivity of phosphate mine tailings. The ground specimens were subjected to the crystal structural analysis of X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and thermal analyses by Thermogravimetry/Differential Thermal Analysis (TG/DTA), showing the increment of amorphous content and structural degradation as a function of grinding time. The subsequent alkaline reactivity test illustrated incremental alkaline dissolution of Si, Al and K and a schematic diagram of altered phlogopite structure (sources of aluminosilicates in tailings) was also proposed. Additionally, the mineralogical composition of individual particles was carried out by mineral liberation analysis (MLA), thereby evaluating the influence of pre-treatment on the mineralogy of tailings. The results indicate profound micromorphological changes and structural cleavage of the precursor due to grinding, which strongly increase alkaline reactivity.

Emerging investigator series: influence of marine emissions and atmospheric processing on individual particle composition of summertime Arctic aerosol over the Bering Strait and Chukchi Sea.

The Arctic is rapidly transforming due to sea ice loss, increasing shipping activity, and oil and gas development. Associated marine and combustion emissions influence atmospheric aerosol composition, impacting complex aerosol-cloud-climate feedbacks. To improve understanding of the sources and processes determining Arctic aerosol composition, atmospheric particles were collected aboard the Korean icebreaker R/V Araon cruising within the Bering Strait and Chukchi Sea during August 2016. Offline analyses of individual particles by microspectroscopic techniques, including scanning electron microscopy with energy dispersive X-ray spectroscopy and atomic force microscopy with infrared spectroscopy, provided information on particle size, morphology, and chemical composition. The most commonly observed particle types were sea spray aerosol (SSA), comprising ∼60-90%, by number, of supermicron particles, and organic aerosol (OA), comprising ∼50-90%, by number, of submicron particles. Sulfate and nitrate were internally mixed within both SSA and OA particles, consistent with particle multiphase reactions during atmospheric transport. Within the Bering Strait, SSA and OA particles were more aged, with greater number fractions of particles containing sulfate and/or nitrate, compared to particles collected over the Chukchi Sea. This is indicative of greater pollution influence within the Bering Strait from coastal and inland sources, while the Chukchi Sea is primarily influenced by marine sources.

Using nondestructive techniques in mineral carbonation for understanding reaction fundamentals

Mineral carbonation of alkaline earth metals is the conversion of carbon dioxide, in gaseous form or dissolved in water, to form solid inorganic carbonates. Alkaline earth metals can be derived from natural minerals, waste residues, or brines. Calcium and magnesium are the two most abundant of these metals, which when carbonated form a variety of calcium and magnesium carbonates of different mineral compositions and crystal structures. Determining inorganic carbon (IC) content of carbonation solid products with high precision is an essential requisite to quantify the amount of carbon dioxide sequestered by a given process at a given reaction time. It also enables understanding fundamental phenomena about the reactions, including the reaction rate, conversion limitations, and the mineral composition of carbonation products and by-products. The most conventional methods to determine IC content utilize destructive techniques based on acid decomposition (e.g. calcimeter) and thermal decomposition (e.g. thermogravimetric analyzer). The main disadvantage of these methods includes chemical usage, long measurement time, overestimation of IC, and limited ability to differentiate the various mineral forms of carbonates. In this regard, nondestructive techniques (NDT) constitute a valuable alternative to the conventional method for IC determination and carbonates characterization; these include spectroscopic methods (NIR, MIR), X-ray spectroscopy (XRD, XRF, XCT); and microscopic methods (SEM-EDS, TEM, RLM, EPMA). While infrared spectroscopy can be used to quantitatively identify carbonate spectral bands, X-ray diffraction quantitatively identifies the presence of specific crystalline carbonate phases. Elemental chemical information is provided by X-ray fluorescence, and microstructure analysis is done using electron probe microanalysis and micro-tomography. SEM provides visualization of crystal and particle size and morphology, while energy dispersive spectroscopy is used to inspect elemental composition of individual particles or intra-particle layers and grains. This paper presents a critical comparative analysis of the use of these NDT in determining IC content and carbonate composition. Improved understanding of the advantages, limitations, and applicability of each method can enable the development of standard protocols for characterization of carbonation products, which is especially required for carbon sequestration accounting in view of climate change mitigation.

Individual particle analysis of marine aerosols collected during the North\u2013South transect cruise in the Pacific Ocean and its marginal seas

Sea-salt particles are major aerosol constituents in the marine boundary layer (MBL) and are chemically modified by acidic substances from anthropogenic, volcanic, and biogenic sources. When these acidic substances react with sea-salt particles, they can be easily scavenged from the MBL. This scavenging process influences the concentration of cloud condensation nuclei in the MBL. In this study, differences in chemical compositions of sea-salt particles collected over the Pacific Ocean and its marginal seas were investigated based on an individual particle analysis. The sources of the acidic substances that modified sea-salt particles were also estimated. Approximately 70% of the analyzed particles were fresh sea-salt particles. However, a sample collected near Guam was dominated by sulfates and was affected by polluted air masses that originated over the Asian continent. The aerosols collected around the Aleutian Islands included a large number of sulfates and modified sea-salt particles. Individual particle composition analyses indicate that these sea-salt particles were modified by methanesulfonic acid produced from marine biota and sulfuric acid from volcanic gas from the Kamchatka Peninsula. The gravitational deposition velocities of sulfates and modified sea-salt particles were calculated based on measured particle sizes. The results suggested that if acidic substances react with sea-salt particles, their lifetime in the atmosphere could be shortened due to dry deposition. Therefore, it is necessary to consider the scavenging effect of sea-salt particles for estimating the climate cooling effect by clouds over the ocean.

Atmospheric pollution from ships and its impact on local air quality at a port site in Shanghai

Abstract. Growing shipping activities in port areas have generated negative impacts on climate, air quality and human health. To better evaluate the environmental impact of ship emissions, an experimental characterization of air pollution from ships was conducted in Shanghai Port in the summer of 2016. The ambient concentrations of gaseous NO, NO2, SO2 and O3 in addition to fine particulate matter concentrations (PM2.5), particle size distributions and the chemical composition of individual particles from ship emission were continuously monitored for 3 months. Ship emission plumes were visible at the port site in terms of clear peaks in the gaseous species and particulate matter concentrations. The SO2 and vanadium particle numbers were found to correlate best with ship emissions in Shanghai Port. Single-particle data showed that ship emission particles at the port site mainly concentrated in a smaller size range (&lt;0.4 µm), where their number contributions were more important than their mass contributions to ambient particulate matter. The composition of ship emission particles at the port site suggested that they were mostly freshly emitted particles: their mass spectra were dominated by peaks of sulfate, elemental carbon (EC), and trace metals such as V, Ni, Fe and Ca, in addition to displaying very low nitrate signals. The gaseous NOx composition in some cases of plumes showed evidence of atmospheric transformation by ambient O3, which subsequently resulted in O3 depletion in the area. Quantitative estimations in this study showed that ship emissions contributed 36.4 % to SO2, 0.7 % to NO, 5.1 % to NO2, −0.9 % to O3, 5.9 % to PM2.5 and 49.5 % to vanadium particles in the port region if land-based emissions were included, and 57.2 % to SO2, 71.9 % to NO, 30.4 % to NO2, −16.6 % to O3, 27.6 % to PM2.5 and 77.0 % to vanadium particles if land-based emissions were excluded.

Microscopic morphology and elemental composition of atmospheric particles from seven micro-environments in Xi’an

This paper characterizes the morphological and elemental compositions of individual particles in seven micro-environments of Xi’an. Atmospheric particulate matter samples were collected at one suburban site (Duling Park (DL)), three urban sites (roadside site (RS), clear days (CD), dusty days (DD)) and three indoor sites (hot pot (HP), barbecue (BBQ), hospital (HO)) during March–April in 2017. A total of 469 particles were analysed by a scanning electron microscopy with an energy dispersive X-ray spectroscopy. Seven types of particles were observed, including sulphate particles, iron oxide particles, dust mineral particles, soot, organic aerosols, silicon–aluminium (Si–Al)-rich fly ash and biological particles. Soot accounted for 22% in BBQ, indicating an effect of BBQ coal burning. Sulphate particles were found in high abundance (14–15%) in HP and HO samples, consistent with the occurrence of secondary chemical reactions. Organic aerosols accounted for 13% in HO, 20% in HP and BBQ samples due to cooking of food and human factors. Comparison of samples in indoor and outdoor environments showed that the external transmission of dust mineral particles and Fe oxide particles played a key role in indoor levels. The microscopic analysis also demonstrated that the particles in Xi’an were highly distributed with fine particles (less than 3 µm) and that the morphology of fine particles tended to be spherical.

3D XCT Mesostructure Characterization and Image‐Based Discrete Element (DE) Modelling of Failure Patterns in Coal Gangue Particles (CGPs)

The paper presents an application of milli‐ and micro‐XCT to mesostructure characterization of CGPs and failure patterns analysis using dynamic impact simulations. In this study, XCT scanning experiments are firstly conducted on CGPs, followed by a series of image analyses with qualitative results. Then, the 3D mesomorphological parameters and internal composition of individual particles are quantitatively characterized. Finally, dynamic impact loading in y‐axis direction is modelled to investigate the 3D mesostructure and different impact velocity effects on failure patterns of individual particles. The studies show that the mesomorphological parameters present different distribution characteristics in individual CGPs. The approximate location of gangue phase is the key parameter that should be taken into account to study failure patterns as well as fracture mechanism of the heterogeneous rock materials. The XCT image‐based numerical model proved to be an effective tool that gives insights into the mesodeformation mechanisms of heterogeneous coal rock (HCR) undergoing dynamic impact failure behavior.