Types Of Soot Research Articles

Simulated contrail-processed aviation soot aerosols are poor ice-nucleating particles at cirrus temperatures

Abstract. Aviation soot surrogates processed in contrails are believed to become potent ice nuclei at cirrus temperatures. This is not verified for real aviation soot, which can have vastly different physico-chemical properties. Here, we sampled soot particles from in-use commercial aircraft engines and quantified the effect of contrail processing on their ice nucleation ability at T< 228 K. We show that aviation soot becomes compacted upon contrail processing, but that does not change their ice nucleation ability in contrast to other soot types. The presence of H2SO4 condensed in soot pores, the highly fused nature of the soot primary particles and their arrangement are what limit the volume of pores generated upon contrail processing, in turn limiting sites for ice nucleation. Furthermore, we hypothesized that contrail-processed aviation soot particles emitted from alternative jet fuel would also be poor ice-nucleating particles if their emission sizes remain small (< 150 nm).

Online Raman spectroscopy for quantitative detection and characterization of aerosolized soot

Ex-situ Raman spectroscopy is a well-established method for the structural characterization of soot but necessitates a sampling step before analysis is made. This work studied the potential to perform Raman spectroscopic measurements of soot directly in the combustion exhaust gases, i.e., online Raman measurements. Two types of soot were produced from a Mini-CAST soot generator, one immature with high organic content and one mature with low organic content. Also, two different measurement configurations were used, a 90-degree and a backscattering configuration, as well as different polarization combinations of the laser radiation and the detected photons. Spectrally resolved Raman signals were successfully recorded and analyzed for the two soot types showing differences between the characteristic D and G peaks as well as the photoluminescence signal. Additionally, the Raman cross section was determined for both soot types and found to be higher for the immature soot. It was also found that a horizontally polarized laser excitation and a 90-degree collection angle had the best potential to reduce the interference from ambient gases. This study can be seen as a first step towards remote sensing of soot.

Observation of Structural Changes during Oxidation of Black and Brown Soot Using Raman Spectroscopy

In this study, Raman spectroscopy has been used to evaluate the evolution of the structural modification of soot during oxidation processes at various preset temperatures up to 700 °C. Two types of well-characterized mini-CAST soot, representing black soot and brown soot, were examined. The major difference between the signals from the two types of soot was the higher photoluminescence (PL) signal for brown soot compared with black soot, in addition to some variations in the first-order Raman signatures such as oxygenated groups and their evolutions during thermal oxidation treatment. An interesting observation was the increase in the PL signal for brown soot at increasing temperatures up to 150 °C probably due to the formation of small oxidized polycyclic aromatic hydrocarbon and defects, followed by a decrease in the PL signal until the soot was fully oxidized. We also demonstrated that brown soot is prone to oxidation in ex situ measurements, a factor that should be considered in the Raman analysis of soot.

Effect of co-combustion of coal with biomass on the morphology of soot

This study performed an experimental investigation to explore the effect of co-combustion of coal with biomass on the morphological parameters and nanostructure of soot. Three types of soot, namely Shenghua coal (SH) soot, Pinewood biomass (PW) soot, and Co-combustion of SH and PW (CC) soot, were collected from the combustion flames of Shenhua coal, Pinewood biomass, and a mixture of coal and biomass. Thereafter, the soot samples were observed and analyzed by means of transmission electron microscope (TEM) and scanning electron microscope (SEM) to obtain their morphological parameters and nanostructure characteristics. The TEM results showed that the size of nascent soot particles generated in co-combustion flame is the largest, rather than between the sizes of PW and SH soot. The nanostructure of the three types of soot primary particles is mainly composed of straight parallel crystal stripes. The separation distance of crystal stripes in SH soot was measured to be larger than that in PW soot, indicating that the crystal structure of soot generated in Pine biomass combustion flame is more compact. It was also observed that both coal-derived primary soot particles and biomass-derived primary soot particles were formed in the co-combustion flame. SEM results indicated that PW soot agglomerates have stronger aggregation performance and more compact structure then SH soot and CC soot. The primary particle size of SH and CC soot agglomerates was mainly concentrated between 50 and 70 nm, while that of PW soot agglomerates was relatively uniform. Furthermore, the number of primary particles in SH soot and CC soot was distributed over a wide range compared to PW soot.

Oxidative Stress and Acrosomal Status of Human Spermatozoa Subjected to Hydrophobic Carbon Soot Treatments.

The fourth industrial revolution extensively reshapes the reality we are living in by blurring the boundaries of physical, digital and biological worlds. A good example is the previously unthinkable incursion of nanoscale waste materials, such as soot, into the technologies for assisted reproduction. Although the rapeseed oil soot may efficiently enhance the progressive motility of human spermatozoa, it is yet unknown whether this material induces undesirable oxidative stress and premature acrosome reaction, endangering the sperm-oocyte fusion and blastocyst formation. In an attempt to clarify this issue, we reveal that the three-hour incubation of human semen mixed with three main types of soot does not cause oxidative stress and spontaneous acrosome reaction of the sperm. These unique findings are attributed to synchronous elimination and stabilization of the oxidants via hydrogen bonding to the acidic groups of the soot (i.e., C=O and/or C-O-C) and electron donation by its basic chemical sites (i.e., C-OH and/or COOH). Moreover, the soot nanoparticles are electrostatically attracted by discrete positively charged areas on the sperm head, increasing its negative charge and in some cases interfering the acrosome reaction. Such novel mechanistic insights emphasize the credibility of rapeseed oil soot to confidently shift from the purely diagnostic and therapeutic phases in reproductive medicine to research dealing with the effect of carbon nanomaterials on the embryo development and implantation.

Combustion conditions influence toxicity of flame-generated soot to ocular (ARPE-19) cells.

Soot is a prevalent aerosol found both indoors and outdoors that has several sources, such as natural (e.g., wildfires), civilian (e.g., cooking), or military (e.g., burn pit operation). Additionally, within the sources, factors that influence the physicochemical properties of the soot include combustion temperature, oxygen availability, and fuel type. Being able to reproduce soot in the laboratory and systematically assess its toxicity is important in the pursuit of elucidating pathologies associated with its exposure. Of the organs of interest, we targeted the eye given the scant attention received. Yet, air pollution constituents such as soot have been linked to diseases such as age-related macular degeneration and proliferative vitreoretinopathy. We developed a bench-scale system to synthesize different types of soot, that is, soot with a systematically varied physical attributes or chemical composition. We used common analytical techniques to probe such properties, and used statistical analyses to correlate them with toxicity in vitro using ARPE-19 cells. Within the range of flame conditions studied, we find that soot toxicity increases with increasing oxygen concentration in fuel-rich premixed flames, and weakly increases with decreasing flame temperature. Additionally, soot particles produced in premixed flames are generally smaller in size, exhibit a lesser fractal structure, and are considerably more toxic to ARPE-19 cells than soot particles produced in non-premixed flames.

Analysis of heavy pollution weather in Shenyang City and numerical simulation of main pollutants

Abstract In the present research, a statistical analysis of all pollution incidents occurring from 2015 to 2019 in the cities of the urban agglomeration centered on Shenyang was performed. The results indicated that heavy pollution mainly occurred during the heating season, and the main pollutants were (particulate matter) PM2.5 and PM10. It was also determined that the heavy pollution that occurred during the heating season in Shenyang was of the soot type. The weather research forecast-chemistry (WRF-Chem) was used to simulate the meteorological elements and particle concentration during the two heavy pollution periods in 2019 and compared the simulation data with the monitoring data to verify the simulation performance of the model. Results demonstrated that the model had a better simulation effect on temperature and pressure than on wind speed and wind direction. By comparing the hourly particle concentration data, it was found that the simulation results for pollutants obtained with the WRF-Chem model were lower than the measured values. The simulation effect on PM2.5 was better than that on PM10, and the simulation results were basically consistent in the high- and low-value areas, and the time of peak and valley was basically synchronous. It was proven that the selected parameterization scheme properly simulated the weather situation and changes in pollutants during heavy pollution events in the Shenyang area. These results verified the application value of the WRF-Chem model during the investigation of heavy pollution events.

Correlation between Graphitic Carbon and Elemental Carbon in Diesel Particulate Matter in Workplace Atmospheres.

We investigated the suitability of the graphitic carbon (GC) content of diesel particulate matter (DPM), measured using Raman spectroscopy, as a surrogate measure of elemental carbon (EC) determined by thermal optical analysis. The Raman spectra in the range of 800-1800 cm-1 (including the D mode at ∼1322 cm-1 and the G mode at ∼1595 cm-1) were used for GC identification and quantification. Comparison of the Raman spectra for two certified DPM standards (NIST SRM 1650 and SRM 2975), two types of diesel engine exhaust soot, and three types of DPM-enriched workplace aerosols show that the uncertainty of GC quantification based on the D peak height, G peak height, and the total peak area below D and G peaks was about 6.0, 6.7, and 6.9%, respectively. The low uncertainty for different aerosol types suggested possible use of GC as a surrogate measure of EC in workplace atmospheres. A calibration curve was constructed using two laboratory-aerosolized DPM standards to describe the relationship between GC measured by a portable Raman spectrometer and the EC concentration determined by NIOSH Method 5040. The calibration curve was then applied to determine GC-based estimates of the EC contents of diesel engine exhaust samples from two vehicles and seven air samples collected at a hydraulic fracturing worksite. The GC-EC estimates obtained through Raman measurements agreed well with those found by NIOSH Method 5040 for the same samples at EC filter loadings below 2.86 μg/cm2. The study shows that using an appropriate sample collection method that avoids high filter mass loadings, onsite measurement of GC by a portable or hand-held Raman spectrometer can provide a useful indicator of EC in workplace aerosol.

Activity of Catalytic Ceramic Papers to Remove Soot Particles—A Study of Different Types of Soot

Diesel soot particles are of concern for both the environment and health. To catalytically remove them, it is important to know their structure and composition. There is little described in the literature on how catalysts favor the combustion of different soot fractions. In this work, programmed temperature oxidation (TPO) experiments were carried out using Co,Ce or Co,Ba,K catalysts supported on ceramic papers. Soot particles were obtained by burning diesel fuel in a vessel (LabSoot) or by filtering exhaust gases from a turbo diesel engine in a DPF filter (BenchSoot), and compared with a commercial diesel soot: Printex U. Various characterization techniques were useful to relate the characteristics of both the soot particles and the catalysts with the TPO results. The maximum catalytic soot burn rate (TM) temperatures were in the range of diesel exhaust temperatures that would facilitate in-situ regeneration of the DPF. The Co,Ba,K catalyst showed a higher catalytic effect in LabSoot, as the latter exhibited the largest primary particles and the higher order of graphene layers, for which the potassium-containing catalyst improves the contact between soot and catalyst and favors the combustion of soot, while the Co,Ce catalyst preferentially enhanced the combustion of commercial soot by supplying active oxygen.

Raman signatures of detonation soot

AbstractSoot generated from the detonation of nine explosives was investigated with Raman microspectroscopy and high‐resolution transmission electron microscopy (HRTEM). The first order bands, located at approximately 1,580 (G), 1,350 (D1), 1,620 cm−1 (D2), 1,500 (D3), and 1,200 (D4), are used to provide information on the carbon allotropes and defects. The intensity ratios and the full‐width at half‐maximum provide an indication of the disorder in the material. The Raman spectra of soot acquired from the detonation of nine explosives showed differences which can be used to identify the precursor explosive. Most differences in the spectra were correlated with the presence of amorphous carbon in the soot. In additional to identification of distinct bands in the spectra via deconvolution, principal component analysis was also used to differentiate the different types of soot. HRTEM performed on soot samples with different explosive precursors identified several distinct allotropes of carbon such as nanodiamonds, carbon onions, graphite fibers, and amorphous carbon.

An innovative method for soot deposit quantification using a CO2 sensor: Application to fire studies in research facilities

In industrial facilities handling or manufacturing hazardous materials, fires are one of the major hazards. Therefore, it is important to have tools to better understand the transport and deposition phenomenon of emitted particles in order to take into account their consequences on safety devices. For this purpose and due to the lack of quantitative soot deposition data under realistic fire conditions, an innovative method for soot quantification in experimental facilities devoted to fire research has been developed. This method is based on the quantification of gases emitted during regeneration of a resistive sensor surface and has a higher detection limit than the electrical conductance quantification method previously proposed and validated by (Kort et al., 2021). A proof of feasibility has been shown for two types of soot and a prediction curve has been proposed for deposited masses which vary between 16 and 350 μg (1304 mg m−2 and 28,525 mg m−2). The applicability of this measurement method to realistic industrial fire situation is finally verified taking into account the mean deposition mass per surface area observed in this context.

Influence of rapid laser heating on differently matured soot with double-pulse laser-induced incandescence

For accurate laser-induced incandescence (LII) measurements of soot properties it is of great importance to understand the nature of the physical processes involved during rapid laser heating. In this work, we investigate how well-characterized differently matured fresh soot from a soot generator responds to rapid laser heating. For this purpose, a double-pulse LII setup is used with 10 μs time separation between the pulses using various combinations of two common LII wavelengths (532 and 1064 nm). Detection is performed at two wavelength bands for fluorescence analysis, and additionally elastic light scattering is used for mass loss analysis during heating. We investigate how the LII signal changes with pre-heating laser energy, specifically by fluence curve analysis to estimate the influence of thermal annealing, sublimation and laser-induced fluorescence interference. It is shown that extensive absorption enhancement occurs for all types of soot as the soot is thermally annealed, which is manifested through decreasing dispersion coefficient ξ and an increasing absorption coefficient E(m,λ). When comparing young and mature soot, a much larger impact of sublimation can be observed in the fluence curves of the mature soot. Also, we observe an enhanced contribution of laser-induced fluorescence for the young soot when performing LII measurements using 532 nm, which is suggested to originate from vaporized carbon fragments with an aromatic structure. This work further shows the potential of utilizing double-pulse arrangements for increasing the detectability of poorly absorbing soot, but also it highlights the impact of laser heating on soot, which may be important to avoid interferences when performing soot diagnostics.

Effect of Diesel Soot on the Heterogeneous Reaction of NO2 on the Surface of γ-Al2O3

Soot and aged soot are often found to be mixed with atmospheric particles, which inevitably affect various atmospheric heterogeneous reactions and secondary aerosol formation. Previous studies have investigated the heterogeneous reaction of NO2 with different types of soot, but there are few studies on the heterogeneous reaction of NO2 with mixtures containing diesel soot (DS) or aged DS and mineral dust particles. In this study, the effects of DS and aged DS on the heterogeneous reaction of NO2 on the surface of γ-Al2O3 were investigated via in-situ diffuse reflectance infrared Fourier transform spectrometry (DRIFTS). The results showed that the DS or DS n-hexane extract significantly inhibited the formation of nitrate on γ-Al2O3 particles and promoted the formation of nitrite. At 58% RH, with the increase of DS or DS n-hexane extract loading amount, the effect of DS or DS n-hexane extract on the formation of nitrate changed from promotion to inhibition, but DS or DS n-hexane extract always promoted the formation of nitrite. The results also showed that light was conducive to the formation of nitrate on the DS-γ-Al2O3 or DS-n-hexane extract-γ-Al2O3 particles. Furthermore, the influence of soot aging on the heterogeneous reaction of NO2 was investigated under light and no light. In the dark, O3-aged DS-γ-Al2O3 or O3-aged DS-n-hexane extract-γ-Al2O3 firstly inhibited the formation of nitrate on the mixed particles and then promoted it, while the effect of aged DS on nitrite formation was complex. Under light, the O3-aged DS-γ-Al2O3 firstly promoted the formation of nitrate on the mixed particles and then inhibited it, while the O3-aged DS-n-hexane extract-γ-Al2O3 promoted the formation of nitrate on the mixed particles. Our results further showed that the production of nitrate on the O3-aged particles under light or no light was greater than that of the UV-nitrate-aged particles. This study is helpful to deeply understand the atmospheric chemical behavior of soot and the heterogeneous conversion of atmospheric NO2.

Laser-induced incandescence (2\u03bb and 2C) for estimating absorption efficiency of differently matured soot

Two-wavelength and two-color laser-induced incandescence (2λ–2C-LII) was used to study the absorption properties of three types of cold soot of different maturity from a mini-CAST soot generator. LII fluence curve analysis allowed for estimating absorption wavelength dependence in terms of dispersion coefficients ξ by the use of two excitation wavelengths (532 and 1064 nm). The estimated ξ (based on E(m, λ) ∝ λ1−ξ) spanned from ~ 1.2 for the mature soot, up to 2.3 for the young soot. The results for the mature soot showed good agreement with previous measurement using multi-wavelength extinction. For the young soot, however, some discrepancy was observed suggesting a weaker wavelength dependence (lower ξ) from the LII fluence analysis. Furthermore, an estimation of the E(m, λ) for the different types of soot was done from the experimental fluence curves with temperature analysis in the low-fluence regime and simulations using an LII model. Additionally, uncertainties and limitations were discussed. Finally, it should be pointed out that caution has to be taken when interpreting 2λ-LII results to obtain quantitative absorption properties of less mature soot, which may be influenced by thermal annealing during the laser pulse and by absorption from non-refractory species externally/internally mixed with the soot.

Heterogeneous nucleation of water vapor on different types of black carbon particles

Abstract. The heterogeneous nucleation of water vapor on insoluble particles affects cloud formation, precipitation, the hydrological cycle, and climate. Despite its importance, heterogeneous nucleation remains a poorly understood phenomenon that relies heavily on empirical information for its quantitative description. Here, we examine the heterogeneous nucleation of water vapor on different types of soots as well as cloud drop activation of different types of soots, including both pure black carbon particles and black carbon particles mixed with secondary organic matter. We show that the recently developed adsorption nucleation theory quantitatively predicts the nucleation of water and droplet formation upon particles of the various soot types. A surprising consequence of this new understanding is that, with sufficient adsorption site density, soot particles can activate into cloud droplets – even when completely lacking any soluble material.

Reactive Oxygen Species-Related Inside-to-Outside Oxidation of Soot Particles Triggered by Visible-Light Irradiation: Physicochemical Property Changes and Oxidative Potential Enhancement.

Modifications of the physicochemical properties and oxidative potential (OP) of soot due to visible-light irradiation and its underlying mechanisms during atmospheric aging have not been elucidated. In this study, two types of soot obtained using different air/fuel ratios (A/F) were aged under visible light with or without ozone (O3) at an atmospherically relevant level in an environmental chamber. Physicochemical characteristics and OP of aged soot were systematically measured using the dithiothreitol (DTT) assay (OPDTT). Regardless of the presence of O3, visible light markedly promoted oxidation of soot, which led to consumption of polycyclic aromatic hydrocarbons, formation of oxygen-containing functional groups, and enhancement of OPDTT values. Compared to low-A/F soot, high-A/F soot contained more elemental carbon but less organic carbon and was more sensitive to visible light by exhibiting greater changes. It was proposed that elemental carbon in soot under visible-light irradiation initiated an inside-to-outside oxidation pathway, where reactive oxygen species played an important role. This study clarified the solar irradiation-triggered self-oxidation process in soot, which is important to its atmospheric and health effects.

Modelling the Influence of Different Soot Types on the Radio-Frequency-Based Load Detection of Gasoline Particulate Filters

Gasoline particulate filters (GPFs) are an appropriate means to meet today’s emission standards. As for diesel applications, GPFs can be monitored via differential pressure sensors or using a radio-frequency approach (RF sensor). Due to largely differing soot properties and engine operating modes of gasoline compared to diesel engines (e.g., the possibility of incomplete regenerations), the behavior of both sensor systems must be investigated in detail. For this purpose, extensive measurements on engine test benches are usually required. To simplify the sensor development, a simulation model was developed using COMSOL Multiphysics® that not only allowed for calculating the loading and regeneration process of GPFs under different engine operating conditions but also determined the impact on both sensor systems. To simulate the regeneration behavior of gasoline soot accurately, an oxidation model was developed. To identify the influence of different engine operating points on the sensor behavior, various samples generated at an engine test bench were examined regarding their kinetic parameters using thermogravimetric analysis. Thus, this compared the accuracy of soot mass determination using the RF sensor with the differential pressure method. By simulating a typical driving condition with incomplete regenerations, the effects of the soot kinetics on sensor accuracy was demonstrated exemplarily. Thereby, the RF sensor showed an overall smaller mass determination error, as well as a lower dependence on the soot kinetics.

Raman spectra of atmospheric aerosol particles: Clusters and time-series for a 22.5 hr sampling period

An automated Aerosol Raman Spectrometer (ARS) was used to measure approximately 100,000 Raman spectra (RS) during a 24-hour sampling period. The approximately 9000 RS that exceeded thresholds for Raman or fluorescence intensity were studied. Unstructured cluster analysis of the initial RS and the RS remaining after approximated fluorescence was removed resulted in clusters which had Raman peaks consistent with quartz, calcite, dolomite, gypsum, anhydrite, iron oxides, biological materials and calcium oxalates, and materials that exhibit D and G bands (e.g., soots). A set of RS which are dominated by a broad fluorescence and include only not-detectable or very small Raman peaks were assigned to a “fluorescent materials” category with approximately 900 spectra. The temporal changes in the numbers of RS consistent with different materials are illustrated. The highest numbers of RS consistent with oxalates appear during the nighttime. The numbers of RS consistent with some type of soot increased during the day. This increase occurred after PM10 concentration increased.

Impact of isolated atmospheric aging processes on the cloud condensation nuclei activation of soot particles

Abstract. The largest contributors to the uncertainty in assessing the anthropogenic contribution in radiative forcing are the direct and indirect effects of aerosol particles on the Earth's radiative budget. Soot particles are of special interest since their properties can change significantly due to aging processes once they are emitted into the atmosphere. Probably the largest obstacle for the investigation of these processes in the laboratory is the long atmospheric lifetime of 1 week, requiring tailored experiments that cover this time span. This work presents results on the ability of two types of soot, obtained using a miniCAST soot generator, to act as cloud condensation nuclei (CCN) after exposure to atmospherically relevant levels of ozone (O3) and humidity. Aging times of up to 12 h were achieved by successful application of the continuous-flow stirred tank reactor (CSTR) concept while allowing for size selection of particles prior to the aging step. Particles of 100 nm diameter and rich in organic carbon (OC) that were initially CCN inactive showed significant CCN activity at supersaturations (SS) down to 0.3 % after 10 h of exposure to 200 ppb of O3. While this process was not affected by different levels of relative humidity in the range of 5 %–75 %, a high sensitivity towards the ambient/reaction temperature was observed. Soot particles with a lower OC content required an approximately 4-fold longer aging duration to show CCN activity at the same SS. Prior to the slow change in the CCN activity, a rapid increase in the particle diameter was detected which occurred within several minutes. This study highlights the applicability of the CSTR approach for the simulation of atmospheric aging processes, as aging durations beyond 12 h can be achieved in comparably small aerosol chamber volumes (<3 m3). Implementation of our measurement results in a global aerosol-climate model, ECHAM6.3-HAM2.3, showed a statistically significant increase in the regional and global CCN burden and cloud droplet number concentration.

Novel Carbon Nanoparticles Derived from Biodiesel Soot as Lubricant Additives.

The objective of this study was to investigate the roles and tribological mechanisms of onion-like carbon nanoparticles derived from biodiesel soot (BDS) when applied in water (H2O) and liquid paraffin (LP). In this study, we prepared nitric acid-treated BDS (NA-BDS) as an additive to H2O and NA-BDS modified with oleylamine (NA-BDS-OLA) as an additive to LP. Raman spectroscopy, field-emission transmission electron microscopy, Fourier transform infrared spectroscopy, and zeta potentiometry were used to characterize the results of the nitric acid treatment and oleylamine modification. The tribological behaviors and corresponding mechanisms of the new onion-like carbon nanoparticles were evaluated using a ball-on-disc reciprocating tribometer, as well as field-emission scanning electron microscopy, three-dimensional laser scanning microscopy, and Raman spectroscopy. The results indicated that the additives NA-BDS and NA-BDS-OLA, which were onion-like carbon nanoparticles with sizes ranging from 35 to 40 nm, enhanced the antiwear and friction reduction properties of H2O and LP, respectively. Through tribo-mechanisms, these types of soot can serve as spacers and ball bearings between the rubbing surfaces. Moreover, exfoliation under a high load as a result of the formation of a graphitic layer facilitates easy shearing.