Elemental Carbon Research Articles

Carbon Isotope Chemistry in Protoplanetary Disks: Effects of C/O Ratios

Carbon isotope fractionation of CO has been reported in the disk around TW Hya, where elemental carbon is more abundant than elemental oxygen ([C/O]elem > 1). We investigated the effects of the [C/O]elem ratio on carbon fractionation using astrochemical models that incorporate isotope-selective photodissociation and isotope exchange reactions. The 12CO/13CO ratio could be lower than the elemental carbon isotope ratio due to isotope exchange reactions when the [C/O]elem ratio exceeds unity. The observed 12CO/13CO and H12CN/H13CN ratios around TW Hya could be reproduced when the [C/O]elem ratio is 2–5. In the vicinity of the lower boundary of the warm molecular layer, the formation of ices leads to the gas-phase [C/O]elem ratio approaching unity, irrespective of the total (gas + ice) [C/O]elem ratio. This phenomenon reduces the variation in the 12CO/13CO ratio across different [C/O]elem ratios.

Characterization of PM2.5 Carbonaceous Components in a Typical Industrial City in China under Continuous Mitigation Measures.

The goals of the "dual carbon" program in China are to implement a series of air pollution policies to reduce the emission of carbon-bearing particulate matter (PM). Following improvements in the reduction in carbon emissions in Handan City, China, fine particulate matter (PM2.5) was collected in the winters from 2016 to 2020 to characterize the concentrations and sources of carbonaceous components in PM2.5. Trend analysis revealed that both organic carbon (OC) and elemental carbon (EC) concentrations significantly decreased. The proportion of total carbon aerosol (TCA) in PM2.5 decreased by 47.0%, highlighting the effective reduction in carbon emissions. Secondary organic carbon (SOC) concentrations increased from 2016 (12.86 ± 14.10 μg·m-3) to 2018 (36.76 ± 21.59 μg·m-3) and then declined gradually. SOC/OC was larger than 67.0% from 2018 to 2020, implying that more effective synergistic emission reduction measures for carbonaceous aerosol and volatile organic compounds (VOCs) were needed. In the winters from 2016 to 2020, primary organic carbon (POC) concentrations reduced by 76.1% and 87.6% under a light/moderate pollution period (LP) and heavy/severe pollution periods (HPs), respectively. The TCA/PM2.5 showed a decreasing trend under LP and HP conditions, decreasing by 42.1% and 54.7%, respectively. Source analysis revealed that carbonaceous components were mainly from biomass burning, coal combustion and automotive exhaust emissions in the winters of 2016 and 2020. OC/EC and K+/EC analysis pointed out that air pollutant reduction measurements should focus on rectification biomass fuels in the next stage. Compared with 2016, the contributions of automotive exhaust emissions decreased in 2020. OC and EC concentrations decreased due to control measures on automotive exhaust emissions.

Characterization and sources of carbonaceous aerosol in ambient PM1 in Qingdao, a coastal megacity of northern China from 2017 to 2022

Organic carbon (OC) and elemental carbon (EC) are major chemical constituents of ambient submicron particles (PM1) and have substantial implications for air quality, climate dynamics, and human health. Long-term observations of daily mean mass concentrations of OC and EC in PM1 were conducted in Qingdao, a typical coastal megacity in northern China, in autumn and winter from Nov. 2017 to Jan. 2023. The variety in OC and EC concentrations under the active emission reduction policies of long-term carbon reduction in China, combined with the impact of the COVID-19 pandemic, were analyzed. OC and EC concentrations decreased noticeably from 8.28 ± 4.59 μg m−3 and 2.00 ± 1.17 μg m−3 during pre-COVID-19 pandemic to 6.34 ± 3.82 μg m−3 and 1.87 ± 1.01 μg m−3 during post-COVID-19 pandemic, respectively. The XGBoost-SHAP model indicated that emission sources had the most significant effect on OC and EC concentrations, followed by meteorological factors. Unfavorable meteorological conditions and a substantial increase in emissions are responsible for the increase of OC and EC concentration in winter. Potential source contribution function results indicated that the southern, eastern, and central Shandong regions were the primary source areas for transporting high concentrations of carbonaceous components. Positive matrix factorization analysis suggested that carbonaceous aerosols in Qingdao predominantly originated from coal/biomass combustion (54.75%–81.78%) and local vehicle emissions (8.72%–28.73%). Compared with that before COVID-19, coal/biomass combustion's contribution to OC and EC decreased by 19% after the COVID-19 pandemic. The contribution of vehicles increased by 110%, possibly due to the increase in motor vehicles and the rapid recovery in diesel consumption in freight transportation. Prohibiting biomass burning, such as open burning of straw, and measures such as promoting low-carbon and clean production of coal-fired industrial furnaces might have played a key role in reducing OC and EC levels. These results contribute to a deeper understanding of the concentration levels and sources of carbonaceous components in PM1 and provide theoretical guidance for environmental management.

Characteristics and Sources of Organic Aerosol in PM2.5 at Yangbajing in Tibetan Plateau

The climate and environment of the Tibetan Plateau (TP) are sensitive to human activities. As a key component highly influencing global climate and environment, organic aerosol over the TP is investigated in this study, especially in organic composition and its sources. This study aims to explore the composition characteristics, seasonal variation, and potential sources of organic aerosol including two episodes through one-year sampling at the Yangbajing (YBJ) site in the TP. A total of 120 primary and secondary organic species as well as organic carbon (OC) and elemental carbon (EC) were measured in PM2.5. The annual average concentrations of OC, EC, and organic species were 3.12 ± 3.73 μgC/m3, 0.28 ± 0.18 μgC/m3 and 104 ± 36.6 ng/m3, respectively. High ratio of OC to EC (OC/EC) and low ratio of fatty acids to n-alkanes were found for aerosol in the TP. The OC/EC ratio was 11.8 ± 10.2 on average at the YBJ site and strongly correlated with levoglucosan, a tracer for biomass burning, but not so with typical secondary species, indicating that the high ratio of OC/EC over the TP was more influenced by biomass burning than secondary formation. The ratio of fatty acids to n-alkanes at YBJ was 1.39 ± 0.29 on average, lower than those reported over urban areas (3.13 ± 1.49), probably owing to less residential cooking activities. Seasonally, the non-monsoon season had significant increases in primary organic aerosol (POA) tracers, among which biomass burning tracers had a higher increase percentage than other specific tracers. On the contrary, the levels of secondary organic aerosol (SOA) tracers, especially isoprene- and monoterpene-derived SOA tracers were enhanced in the monsoon season (summer time), largely resulting from high emissions of biogenic volatile organic compounds. Two episodes characterized with much higher concentrations of organic species (1215 and 688 ng/m3) were observed in this study. One was characterized by significant enhancement of POA tracers with the air masses originated from South Asia, and the other showed large increases in SOA and POA tracers with the air masses transported across multiple regions. This study could help to better understand the influence of human activities on atmospheric organic aerosol in remote regions and how POA and SOA vary with seasons and in different episodes.

Distinct Photochemistry of Odd-Carbon PAHs from the Even-Carbon Ones During the Photoaging and Analysis of Soot.

Polycyclic aromatic hydrocarbons (PAHs) are the primary organic carbons in soot. In addition to PAHs with even carbon numbers (PAHeven), substantial odd-carbon PAHs (PAHodd) have been widely observed in soot and ambient particles. Analyzing and understanding the photoaging of these compounds are essential for assessing their environmental effects. Here, using laser desorption ionization mass spectrometry (LDI-MS), we reveal the substantially different photoreactivity of PAHodd from PAHeven in the aging process and their MS detection through their distinct behaviors in the presence and absence of elemental carbon (EC) in soot. During direct photooxidation of organic carbon (OC) alone, the PAHeven are oxidized more rapidly than the PAHodd. However, the degradation of PAHodd becomes preponderant over PAHeven in the presence of EC during photoaging of the whole soot. All of these observations are proposed to originate from the more rapid hydrogen abstraction reaction from PAHodd in the EC-photosensitized reaction, owing to its unique structure of a single sp3-hybridized carbon site. Our findings reveal the photoreactivity and reaction mechanism of PAHodd for the first time, providing a comprehensive understanding of the oxidation of PAHs at a molecular level during soot aging and highlight the enhanced effect of EC on PAHodd ionization in LDI-MS analysis.

Optimization of Vertical Fixed-Bed Pyrolysis for Enhanced Biochar Production from Diverse Agricultural Residues.

This study examines the pyrolysis of agricultural residues, namely, coconut shells, rice husks, and cattle manure, in a vertical fixed-bed reactor at varying temperatures from 300 to 800 degrees Celsius for biochar production. The research aimed to evaluate the potential of biochar as biofuels, adsorbents, and soil amendments. Proximate, ultimate, and elemental analyses were conducted to determine their composition and caloric values. Several analytical techniques were used in the physical and chemical characterization of the biochar (SEM, FTIR, BET). The results indicated that the highest SBET values were achieved under different conditions for each biochar: 89.58 m2/g for BC-CS-700, 202.39 m2/g for BC-RH-600, and 42.45 m2/g for BC-CD-800. Additionally, all three biochars exhibited the highest caloric values at 600 °C. The results showed that 600 °C is the general optimal temperature to produce biochar from an assortment of biomass materials, considering their use for a variety of purposes. BC-CS-800 had the highest elemental carbon content at 93%, accompanied by a relative decrease in oxygen content. The van Krevelen diagram of biochar products shows that biochars derived from coconut shells and rice husks are suitable for use as fuels. Furthermore, FTIR analysis revealed the presence of oxygen-containing functional groups on the biochar surface, enhancing their pollutant adsorption capabilities. This study provides valuable insights into the scalable and environmentally sustainable production of biochar, emphasizing its role in improving soil quality, increasing energy density, and supporting sustainable agricultural practices.

High-pressure dysprosium carbides containing carbon dimers, trimers, chains, and ribbons

Exploring the chemistry of materials at high pressure leads to discoveries of previously unknown compounds and phenomena. Here chemical reactions between elemental dysprosium and carbon were studied in laser-heated diamond anvil cells at pressures up to 95 GPa and temperatures of ∼2800 K. In situ single-crystal synchrotron X-ray diffraction (SCXRD) analysis of the reaction products revealed the formation of novel dysprosium carbides, γ-DyC2, Dy5C9, and γ-Dy4C5, along with previously reported Dy3C2 and Dy4C3. The crystal structures of γ-DyC2 and Dy5C9 feature infinite flat carbon polyacene-like ribbons and cis-polyacetylene-type chains, respectively. In the structure of γ-Dy4C5, carbon atoms form dimers and non-linear trimers. Dy3C2 contains ethanide-type carbon dumbbells, and Dy4C3 is methanide featuring single carbon atoms. Density functional theory calculations reproduce well the crystal structures of high-pressure dysprosium carbides and reveal conjugated π-electron systems in novel infinite carbon polyanions. This work demonstrates that complex carbon homoatomic species previously unknown in organic chemistry can be synthesized at high pressures by direct reactions of carbon with metals.

Associations between Indoor and Outdoor Size-Resolved Particulate Matter in Urban Beijing: Chemical Compositions, Sources, and Health Risks

Ventilation may lead to a deterioration in indoor air quality in urban environments located close to roads. Understanding the differences in the chemical compositions of size-resolved particulate matter (PM) in indoor air and outdoor air could aid in assessing the health impacts of air in these settings and establishing relevant regulation policies. In this study, indoor and outdoor size-resolved PM was collected from an office in Beijing in summer (between 5 and 25 July 2020) and winter (between 5 and 31 January 2021). Its chemical components, including sulfate, nitrate, ammonium, chlorine, organic matter (OM), elemental carbon (EC), crustal materials (CM), and heavy metals (HM), were analyzed. The mean levels of indoor and outdoor PM2.1 and PM9 were found to be much higher than those in the guidelines for PM2.5 and PM10 outlined by the National Ambient Air Quality Standard. Moreover, the levels of PM2.1 and PM2.1–9 mass were higher outdoors than they were indoors. The size distributions of mass concentrations were shown to be bimodal, peaking at 0.43–0.65 μm and 4.7–5.8 μm, respectively. The most abundant chemicals were OM, nitrate, and sulfate for PM2.1 and OM, CM, and nitrate for PM2.1–9. We found higher percentages of sulfate, nitrate, ammonium, EC, and HM in smaller-size fractions of PM. Additionally, positive matrix factorization showed that biomass burning, secondary inorganic aerosol, coal combustion, dust, traffic, and industrial pollution were the main sources of PM during the study period. The greatest non-carcinogenic and carcinogenic hazards were found at 0.43–0.65 μm in summer and 2.1–3.3 μm in winter. Our results indicate that size-resolved PM of ambient origin may infiltrate buildings near roads to varying degrees, resulting in negative health effects.

Sources of Southern Hemisphere Marine Aerosols: Insights From Carbonaceous Fraction Concentration and Stable Carbon Isotope Analysis

AbstractMarine carbonaceous aerosols, originating from marine and continental sources, are significant global aerosol components. The understanding of marine carbonaceous aerosols is currently limited, especially in the Southern Hemisphere. Furthermore, there is an ongoing debate regarding the contributions of marine fresh and ancient carbon to marine aerosols. To address these gaps, we conducted an extensive investigation utilizing a long‐term data set of aerosol samples collected during six Antarctic cruises (28°N–78°S) from 2013 to 2020. Our analysis revealed an average organic carbon (OC) concentration of 1.29 ± 1.15 μg/m3 and an element carbon (EC) concentration of 0.13 ± 0.18 μg/m3 in the samples. These concentrations varied within a range spanning from background marine samples to those impacted by substantial continental transport. Fossil fuel combustion remained the primary source of continental influence in the marine environment, as evidenced by the OC/EC ratio. The δ13CTC value for all samples range from −22.3‰ to −28.4‰, with a mean value of −26.3 ‰. Using a three‐endmember isotopic source model, we find that continental carbonaceous aerosols make substantial contributions in the Eastern Indian Ocean (81 ± 4%), while their prevalence is lower in the Southern Ocean (SO) (44 ± 20%). In contrast to mid‐latitudes, primary marine aerosol of the SO exhibits a significantly higher contribution from the fresh carbon pool (52 ± 19%). Furthermore, our study suggests that SO sea ice may play a potential role in driving emissions from the fresh carbon pool. These findings contribute to a comprehensive understanding of the effects of carbonaceous aerosols on climate change and the ocean‐atmosphere carbon cycle.

Characterization of aerosol and its oxidative potential in a coastal semi-rural site of Southern Italy

Considering the scarce number of studies investigating the oxidative potential of PM2.5 in Italy, a measurement campaign was conducted from February 2020 to October 2020 in a coastal semi-rural site of Basilicata (Southern Italy) with the goal to characterize the fine fraction of ambient particulate matter (PM) and investigate its chemical and toxicological properties, by means of oxidative potential. Different instruments such as an automatic low-volume sampler, an aethalometer and an optical particle counter, were employed for the measurement of PM2.5 mass concentration, equivalent black carbon (eBC) concentration and absorption Ångström exponent (AAE), and particle number size distribution in 0.25–31 μm size range, respectively. 108 daily PM samples, collected on quartz fibre filters, were chemically analysed. Organic (OC) and elemental (EC) carbon content was estimated by thermo-optical transmittance technique (TOT), the concentrations of the main water-soluble ions and total elements were determined by ion chromatography and ED-XRF technique, while the oxidative potential of the water-soluble fraction was estimated through the dithiothreitol (DTT) assay. The mean value of PM2.5 mass concentration was 9.2 ± 2.5 μg/m3 and the average contribution of measured species on PM2.5 mass was 3.3% EC; 19.3% OC; 27.0% secondary inorganic aerosol (sum of SO42−, NH4+ and NO3−), and 10.2% of the other ions and elements. The OC and EC contributions to PM2.5 mass and their mean ratio (OC/EC = 6.6 ± 3.1) suggest that the site is affected by the combined contribution of traffic emissions and biomass combustion (domestic heating and agricultural activities), with the latter prevailing over the traffic, as supported by the mean AAE value of 1.3. The mean OP normalized by sampled volume, OPDTTV, was as high as 0.34 ± 0.22 nmol/min·m3, a value comparable to those recorded for PM2.5 in suburban areas of Italy. The correlation between OPDTTV and the chemical species observed in the PM2.5 samples showed a good agreement with the carbonaceous component OC (r = 0.62) and with some ions, K+ and SO42− (r = 0.60). These results identify combustion sources as the most responsible for the relatively high OPDTTV activity of PM2.5 recorded in this area.

Analysis of PM2.5, black carbon, and trace metals measurements from the Kansas City Transportation and Local-Scale Air Quality Study (KC-TRAQS)

ABSTRACT Communities near transportation sources can be impacted by higher concentrations of particulate matter (PM) and other air pollutants. Few studies have reported on air quality in complex urban environments with multiple transportation sources. To better understand these environments, the Kansas City Transportation and Local-Scale Air Quality Study (KC-TRAQS) was conducted in three neighborhoods in Southeast Kansas City, Kansas. This area has several emissions sources including transportation (railyards, vehicles, diesel trucks), light industry, commercial facilities, and residential areas. Stationary samples were collected for 1-year (October 24, 2017, to October 31, 2018) at six sites using traditional sampling methods and lower-cost air sensor packages. This work examines PM less than 2.5 μm in diameter (PM2.5), black carbon (BC), and trace metals data collected during KC-TRAQS. PM2.5 filter samples showed the highest 24-h mean concentrations (9.34 μg/m3) at the sites located within 20–50 m of the railyard. Mean 24-h PM2.5 concentrations, ranging from 7.96 to 9.34 μg/m3, at all sites were lower than that of the nearby regulatory site (9.83 μg/m3). Daily maximum PM2.5 concentrations were higher at the KC-TRAQS sites (ranging from 25.31 to 43.76 μg/m3) compared to the regulatory site (20.50 μg/m3), suggesting short-duration impacts of localized emissions sources. Across the KC-TRAQS sites, 24-h averaged PM2.5 concentrations from the sensor package (P-POD) ranged from 3.24 to 5.69 µg/m3 showing that, out-of-the-box, the PM sensor underestimated the reference concentrations. KC-TRAQS was supplemented by elemental and organic carbon (EC/OC) and trace metal analysis of filter samples. The EC/OC data suggested the presence of secondary organic aerosol formation, with the highest mean concentrations observed at the site within 20 m of the railyard. Trace metals data showed daily, monthly, and seasonal variations for iron, copper, zinc, chromium, and nickel, with elevated concentrations occurring during the summer at most of the sites. Implications: This work reports on findings from a year-long air quality study in Southeast Kansas City, Kansas to understand micro-scale air quality in neighborhoods impacted by multiple emissions sources such as transportation sources (including a large railyard operation), light industry, commercial facilities, and residential areas. While dozens of studies have reported on air quality near roadways, this work will provide more information on PM2.5, black carbon, and trace metals concentrations near other transportation sources in particular railyards. This work can also inform additional field studies near railyards.

Geochemical Characteristics of Mature to High-Maturity Shale Resources, Occurrence State of Shale Oil, and Sweet Spot Evaluation in the Qingshankou Formation, Gulong Sag, Songliao Basin

The exploration of continental shale oil in China has made a breakthrough in many basins, but the pure shale type has only been found in the Qingshankou Formation, Gulong Sag, Songliao Basin, and the evaluation of shale oil occurrence and sweet spot faces great challenges. Using information about the total organic carbon (TOC), Rock-Eval pyrolysis, vitrinite reflectance (Ro), kerogen elemental composition, carbon isotopes, gas chromatography (GC), bitumen extraction, and component separation, this paper systematically studies the organic geochemical characteristics and shale oil occurrence at the Qingshankou Formation. The G1 well, which was cored through the entire section of the Qingshankou Formation in the Gulong Sag, was the object of this study. On this basis, the favorable sweet spots for shale oil exploration are predicted. It is concluded that the shale of the Qingshankou Formation has high organic heterogeneity in terms of organic matter features. The TOC content of the source rocks in the Qingshankou Formation is enhanced with the increase in the burial depth, and the corresponding organic matter types gradually changed from Ⅱ2 and Ⅱ1 types to the Ⅰ type. The distribution of Ro ranges from 1.09% to 1.67%, and it is the mature to high-mature evolution stage that generates a large amount of normal crude oil and gas condensate. The high-quality source rocks of good to excellent grade are mainly distributed in the Qing 1 member and the lower part of the Qing 2 member. After the recovery of light hydrocarbons and the correction of pyrolytic heavy soluble hydrocarbons, it is concluded that the occurrence state of shale oil in the Qingshankou Formation is mainly the free-state form, with an average value of 6.9 mg/g, and there is four times as much free oil as adsorbed oil. The oil saturation index (OSI), mobile hydrocarbon content, Ro, and TOC were selected to establish the geochemical evaluation criteria for shale oil sweet spots in the Qingshankou Formation. The evaluation results show that interval 3 and interval 5 of the Qingshankou Formation in the G1 well are the most favorable sections for shale oil exploration.

Impacts of Fuel Stage Ratio on the Morphological and Nanostructural Characteristics of Soot Emissions from a Twin Annular Premixing Swirler Combustor.

Soot particles emitted from aircraft engines constitute a major anthropogenic source of pollution in the vicinity of airports and at cruising altitudes. This emission poses a significant threat to human health and may alter the global climate. Understanding the characteristics of soot particles, particularly those generated from Twin Annular Premixing Swirler (TAPS) combustors, a mainstream combustor in civil aviation engines, is crucial for aviation environmental protection. In this study, a comprehensive characterization of soot particles emitted from TAPS combustors was conducted using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The morphology and nanostructure of soot particles were examined across three distinct fuel stage ratios (FSR), at 10%, 15%, and 20%. The SEM analysis of soot particle morphology revealed that coated particles constitute over 90% of the total particle sample, with coating content increasing proportionally to the fuel stage ratio. The results obtained from HRTEM indicated that average primary particle sizes increase with the fuel stage ratio. The results of HRTEM and Raman spectroscopy suggest that the nanostructure of soot particles becomes more ordered and graphitized with an increasing fuel stage ratio, resulting in lower oxidation activity. Specifically, soot fringe length increased with the fuel stage ratio, while soot fringe tortuosity and separation distance decreased. In addition, there is a prevalent occurrence of defects in the graphitic lattice structure of soot particles, suggesting a high degree of elemental carbon disorder.

206 Measurements of diesel exhausts - Comparing elemental carbon and black carbon

206 Measurements of diesel exhausts - Comparing elemental carbon and black carbon

258 An evaluation of respirable and submicron elemental carbon measured using the NIOSH analytical method 5040 in low concentration diesel environments

258 An evaluation of respirable and submicron elemental carbon measured using the NIOSH analytical method 5040 in low concentration diesel environments

Relaxation of Spring Festival Firework Regulations Leads to a Deterioration in Air Quality.

The relaxation of restrictions on Chinese Spring Festival (SF) firework displays in certain regions has raised concerns due to intensive emissions exacerbating air quality deterioration. To evaluate the impacts of fireworks on air quality, a comparative investigation was conducted in a city between 2022 (restricted fireworks) and 2023 SF (unrestricted), utilizing high time-resolution field observations of particle chemical components and air quality model simulations. We observed two severe PM2.5 pollution episodes primarily triggered by firework emissions and exacerbated by static meteorology (contributing approximately 30%) during 2023 SF, contrasting with its absence in 2022. During firework displays, freshly emitted particles containing more primary inorganics (such as chloride and metals like Al, Mg, and Ba), elemental carbon, and organic compounds (including polycyclic aromatic hydrocarbons) were predominant; subsequently, aged particles with more secondary components became prevalent and continued to worsen air quality. The primary emissions from fireworks constituted 54% of the observed high PM2.5 during the displays, contributing a peak hourly PM2.5 concentration of 188 μg/m3 and representing over 70% of the ambient PM2.5. This study underscores that caution should be exercised when igniting substantial fireworks under stable meteorological conditions, considering both the primary and potential secondary effects.

Differences and similarities in optical properties of coated fractal soot and its surrogates

Atmospheric soot (or black carbon, BC) affects climate through solar light absorption and scattering, which depend strongly on the particle morphology and composition. Initially, soot particles are fractal aggregates of spherules made of elemental carbon (EC), but condensation of atmospheric trace vapors adds non-EC materials and often results in particle compaction. The optical properties of such processed soot differ from those of fractal soot, and the changes are caused both by particle volume increase from coating addition and by restructuring of the EC backbone. In laboratory studies of soot optics, surrogates such as carbon black (CB) and nigrosin are often used in place of flame-generated soot. Our goal was to investigate if compositional and morphological differences between these surrogates and soot may produce different processing rates and optical responses. In our experiments, we generated fractal soot, compact CB, agglomerated CB (via coagulation of compact CB), and spherical nigrosin aerosol particles, subjected them to supersaturated vapor of dioctyl sebacate (DOS) to form a coating layer, and investigated the morphological response of these four particle types to coating addition and removal. Using coated and coated-denuded aerosol particles with known composition and morphology, we quantified the contributions of volume increase and restructuring to light scattering and absorption enhancements. By comparing experimental measurements against different particle optics models we show that it is crucial to account for larger, multiply charged particles present in the mobility-classified aerosol. Producing a disproportionately high contribution to absolute values of optical cross sections, such larger particles also result in lesser optical enhancements due to slower growth by vapor condensation. Scattering increases for all particle types due to the addition of a coating layer, and also due to restructuring for fractal soot (strongly) and agglomerated CB (weakly). Absorption increases only due to coating addition caused by the coating layer for all particle types. We find that simple optical models, such as Mie, are often sufficient to provide reasonable closure with experimental results for bare and coated aerosols, but only after accounting for the contributions from multiply charged particles, both in terms of their stronger optical cross sections and slower condensational growth. We conclude that CB is an appropriate surrogate for soot in aerosol aging studies where the effects of restructuring do not need to be considered and that nigrosin can be used as a general model for light-absorbing aerosols but is not representative of optical properties of soot.

Stable Carbon Isotope Signatures of Carbonaceous Aerosol Endmembers in the Tibetan Plateau.

Carbonaceous aerosols play an important role in radiative forcing in the remote and climate-sensitive Tibetan Plateau (TP). However, the sources of carbonaceous aerosols to the TP remain poorly defined, in part due to the lack of regionally relevant data about the sources of carbonaceous aerosols. To address this knowledge gap, we present the first comprehensive analysis of the δ13C signatures of carbonaceous aerosol endmembers local to the TP, encompassing total carbon, water-insoluble particle carbon, and elemental carbon originating from fossil fuel combustion, biomass combustion, and topsoil. The δ13C signatures of these local carbonaceous endmembers differ from components collected in other regions of the world. For instance, fossil fuel-derived aerosols from the TP were 13C-depleted relative to fossil fuel-derived aerosols reported in other regions, while biomass fuel-derived aerosols from the TP were 13C-enriched relative to biomass fuel-derived aerosols reported in other regions. The δ13C values of fine-particle topsoil in the TP were related to regional variations in vegetation type. These findings enhance our understanding of the unique features of carbonaceous aerosols in the TP and aid in accurate source apportionment and environmental assessments of carbonaceous aerosols in this climate-sensitive region.

Diesel Particulate Matter Permeation into Normal Human Skin and Intervention Using a Topical Ceramide Formulation

Introduction: Diesel particulate matter (DPM) emitted from diesel engines is a major source of air pollutants. DPM is composed of elemental carbon, which adsorbs organic compounds including toxic polycyclic aromatic hydrocarbons (PAHs). The skin, as well as airways, is directly exposed to DPM, and association of atopic dermatitis, psoriasis flares, and premature skin aging with air pollutant levels has been documented. In skin, the permeation of DPM and DPM-adsorbed compounds is primarily blocked by the epidermal permeability barrier deployed in the stratum corneum. Depending upon the integrity of this barrier, certain amounts of DPM and DPM-adsorbed compounds can permeate into the skin. However, this permeation into human skin has not been completely elucidated. Methods: We assessed the permeation of PAHs (adsorbed to DPM) into skin using ex vivo normal (barrier-competent) organ-cultured human skin after application of DPM. Two major PAHs, 2-methylnaphthalene and triphenylene, and a carcinogenic PAH, benzo(a)pyrene, all found in DPM, were measured in the epidermis and dermis using liquid chromatography electrospray ionization tandem mass spectrometry. In addition, we investigated whether a topical formulation can attenuate the permeation of DPM into skin. Results: 2-Methylnaphthalene, triphenylene, and benzo(a)pyrene were recovered from the epidermis. Although these PAHs were also detected in the dermis after DPM application, these PAH levels were significantly lower than those found in the epidermis. We also demonstrated that a topical formulation that has the ability to form more uniform membrane structures can significantly suppress the permeation of PAHs adsorbed to DPM into the skin. Conclusion: Toxic compounds adsorbed by DPM can permeate even barrier-competent skin. Hence, barrier-compromised skin, such as in atopic dermatitis, psoriasis, and xerosis, is even more vulnerable to air pollutants. A properly formulated topical mixture that forms certain membrane structures on the skin surface can effectively prevent permeation of exogenous substances, including DPM, into skin.

Mitigation of zinc and organic carbon leached from end-of-life tire rubber in cementitious composites

End-of-life tire (ELT) rubber has been widely researched to replace fine or coarse aggregates in cementitious composites. While most studies paid attention to its effect on the engineering properties, very few considered chemical reactions with pore solution and the potential for environmental leachate. Recently the authors developed a methodology to remove zinc from the ELT rubber, since zinc can be toxic if it is leached into the environment. In this study, the authors utilized ELT rubber before and after the zinc extraction process to partially replace fine aggregate in a mortar. Flowability, compressive strength, flexural strength, and ultrasonic pulse velocity were measured for the engineering properties of rubberized mortars. Simultaneously, isothermal calorimetry was also employed to investigate the effects of ELT rubber on the hydration process of the rubberized mortars. In addition, the pore solution and leaching solutions were taken at different curing ages and then analyzed for elemental and total organic carbon (TOC) contents. The results showed a remarkable loss in engineering properties of rubberized mortar when ELT rubber was utilized, and the decrease in performance was more pronounced in the samples with zinc-extracted ELT rubber. The pore solution was found to contain significant quantities of zinc and TOC. However, the authors also found that using silica fume to partially replace cement could effectively recover the loss in strength and could reduce the leachability of zinc and TOC.