Water-insoluble Organic Carbon Research Articles

Characterizing water solubility of fresh and aged secondary organic aerosol in PM2.5 with the stable carbon isotope technique

Abstract. The investigation of the water-soluble characteristics of secondary organic carbon (SOC) is essential for a more comprehensive understanding of its climate effects. However, due to the limitations of the existing source apportionment methods, the water solubility of different types of SOC remains uncertain. This study analyzed stable carbon isotope and mass spectral signatures of total carbon (TC) and water-soluble organic carbon (WSOC) in ambient PM2.5 samples for 1 year and established stable carbon isotope profiles of fresh and aged SOC. Furthermore, a Bayesian stable isotope mixing (BSIM) model was employed to reveal the water solubility characteristics of fresh and aged SOC in a coastal megacity of China. WSOC was dominated by secondary sources, with fresh and aged SOC contributing 28.1 % and 45.2 %, respectively. Water-insoluble organic carbon (WIOC) was dominated by primary sources, to which fresh and aged SOC contributed 23.2 % and 13.4 %. We also found that the aging degree of SOC has considerable impacts on its water solubility due to the much higher water-soluble fraction of aged SOC (76.5 %) compared to fresh SOC (54.2 %). Findings of this study may provide a new perspective for further investigation of the hygroscopicity effects of SOC with different aging degrees on light extinction and climate change.

The water-insoluble organic carbon in PM2.5 of typical Chinese urban areas: light-absorbing properties, potential sources, radiative forcing effects, and a possible light-absorbing continuum

Abstract. Water-insoluble organic carbon (WIOC) constitutes a substantial portion of organic carbon (OC) and contributes significantly to light absorption by brown carbon (BrC), playing pivotal roles in climate forcing. China is a hotspot region with high levels of OC and BrC, but information regarding the sources and light-absorbing properties of WIOC on a national scale remains scarce. Here, we investigated the light-absorbing properties and sources of WIOC in 10 representative urban cities in China. On average, WIOC made up 33.4 ± 7.66 % and 40.5 ± 9.73 % of concentrations and light absorption at 365 nm (Abs365) of extractable OC (EX-OC), which includes relatively hydrophobic OC (WIOC and humic-like substances, HULIS-C) and hydrophilic OC (non-humic-like substances, non-HULIS-C). The mass absorption efficiency of WIOC at 365 nm (MAE365) was (1.59 ± 0.55 m2 (g C)−1) comparable to that of HULIS (1.54 ± 0.57 m2 (g C)−1) but significantly higher than non-HULIS (0.71 ± 0.28 m2 (g C)−1), indicating that hydrophobic OC possesses a stronger light-absorbing capacity than hydrophilic OC. Biomass burning (31.0 %) and coal combustion (31.1 %) were the dominant sources of WIOC, with coal combustion sources exhibiting the strongest light-absorbing capacity. Moreover, employing the simple forcing efficiency (SFE300–700 nm) method, we observed that WIOC exhibited the highest SFE300–700 nm (6.57 ± 5.37 W g−1) among the EX-OC fractions. The radiative forcing of EX-OC was predominantly contributed by hydrophobic OC (WIOC – 39.4 ± 15.5 % and HULIS – 39.5 ± 12.1 %). Considering the aromaticity, sources, and atmospheric processes of different carbonaceous components, we propose a light-absorbing carbonaceous continuum, revealing that components enriched with fossil sources tend to possess stronger light-absorbing capacity, higher aromatic levels, increased molecular weights, and greater recalcitrance in the atmosphere. Reducing fossil fuel emissions emerges as an effective means of mitigating both gaseous (CO2) and particulate light-absorbing carbonaceous warming components.

Chemical composition, source characteristics, and hygroscopic properties of organic-enriched aerosols in the high Arctic during summer

Arctic regions are extremely sensitive to global warming. Aerosols are one of the most important short-lived climate-forcing agents affecting the Arctic climate. The present study examines the summertime chemical characteristics and potential sources of various organic and inorganic aerosols at a Norwegian Arctic site, Ny-Ålesund (79°N). The results show that organic matter (OM) accounts for 60 % of the total PM10 mass, followed by sulfate (SO42−). Water-soluble organic carbon (WSOC) contributes 62 % of OC. Photochemical processes involving diverse anthropogenic and biogenic precursor compounds are identified as the major sources of WSOC, while water-insoluble organic carbon (WIOC) aerosols are predominantly linked to primary marine emissions. Despite being a remote pristine site, the aerosols show a sign of chemical aging, evidenced by a significant chloride depletion, which was about 82 % on average during the study period. Nitrogen-containing aerosols are likely stemming from migratory seabird colonies and local dust sources around the sampling site. While biogenic, crustal, and sea salt-derived SO42- account for 37%, 8%, and 5% respectively, the remaining 50% is attributed to anthropogenic SO42-. Through chemical tracers, Pearson correlation coefficient matrix, and Hierarchical Cluster Analysis (HCA), the present study identifies soil biota (terrestrial biogenic) and marine emissions, along with their photochemical oxidation processes, as potential sources of Arctic aerosols during summer, while biomass burning and combustion-related sources have a minor contribution. The chemical closure of hygroscopicity highlights that while organics predominantly control aerosol hygroscopicity in the Arctic summer, specific inorganic components like (NH4)2SO4 can significantly increase it on certain days, affecting aerosol-cloud interactions and climate processes over the Arctic during summer. The present study highlights the high abundance of organics and their vital role in the Arctic climate during summer when natural aerosols are conquered.

Comparison of water-soluble and water-insoluble organic compositions attributing to different light absorption efficiency between residential coal and biomass burning emissions

Abstract. There are growing concerns about the climate impacts of absorbing organic carbon (also known as brown carbon, BrC) in the environment, yet its chemical composition and association with the light absorption capabilities remain poorly understood. This study characterized water-soluble and water-insoluble organic carbon (WSOC and WIOC) from residential solid fuel combustion at the molecular level and evaluated their quantitative relationship with mass absorption efficiency (MAE). The MAE values at λ = 365 nm from biomass burning were significantly higher than those from coal combustion (p < 0.05). Thousands of peaks were identified in the m/z range of 150–800, with the most intense ion peaks occurring between m/z 200–500 for WSOC and m/z 600–800 for WIOC, respectively. The CHO group predominated in the WSOC extract from biomass burning emissions, while sulfur-containing compounds (SOCs) including CHOS and CHONS were more intense in the WIOC extract, particularly from coal emissions. Emissions of the CHON group were positively correlated with the fuel nitrogen content (r = 0.936; p < 0.05), explaining their higher abundance in coal emissions compared to biomass. The SOC emissions were more predominant during flaming phases, as indicated by a positive correlation with modified combustion efficiency (MCE) (r = 0.750; p < 0.05). The unique formulas of coal combustion aerosols were in the lower H/C and O/C regions, with higher unsaturated compounds in the van Krevelen (VK) diagram. In the WIOC extract, coal combustion emissions contained significantly higher fractions of condensed aromatics (32 %–59 %) compared to only 4.3 %–9.7 % in biomass burning emissions. In contrast, the CHOS group in biomass burning emissions was characterized by larger condensed aromatic compound fractions than those in coal combustion. Moreover, the CHOS aromatic compound fractions were positively correlated with MAE values in both WSOC (r = 0.714; p < 0.05) and WIOC extracts (r = 0.929; p < 0.001), suggesting that these compounds significantly contributed to MAE variabilities across different fuels.

Roles of water-soluble aerosol coatings for the enhanced radiative absorption of black carbon over south asia and the northern indian ocean

Black Carbon (BC), formed by incomplete combustion, absorbs solar radiation and heats the atmosphere. We investigated the enhancement in optical absorption of BC due to coatings of water-soluble (WS) species in the polluted South Asian atmosphere. The BC Mass Absorption Cross-section (MAC; 678 nm) was estimated before and after removal of the WS components. Wintertime samples were collected from three South Asian receptor observatories intercepting large-footprint outflow: Bangladesh Climate Observatory Bhola (BCOB; integrating outflow of the Indo-Gangetic Plain), Maldives Climate Observatories at Hanimaadhoo (MCOH) and at Gan (MCOG), both reflecting outflow from the South Asian region. The ambient MAC observed at BCOB, MCOH and MCOG were 4.2 ± 1.4, 7.9 ± 1.9 and 7.1 ± 1.5 m2 g−1, respectively.The average enhancement of the BC MAC due to WS coatings (i.e., ws-EMAC) was identical at all three sites (1.6 ± 0.5) indicating that the anthropogenic aerosols had already evolved to a fully coated morphology at BCOB and/or that subsequent aging involved two compensating evolution processes of the coating. Inspecting the key coating component sulfate; the sulfate-to-BC ratio increased threefold when transitioning from BCOB to MCOH and by about 1.5 times from BCOB to MCOG. Conversely, both WS organic carbon (WSOC)/BC and water-insoluble OC (WIOC)/BC ratios declined with distance: WSOC/BC diminished by 84 % from BCOB to MCOH and by 80 % from BCOB to MCOG, while WIOC/BC dropped by about 63 % and 59 %, respectively. Such declines in WSOC and WIOC reflect a combination of photochemical oxidation and more efficient washout of OC compared to BC. The observed changes in the SO42−/BC and WSOC/BC ratios across South Asia highlight the significant impact of aerosol composition on the optical properties of Black Carbon (BC). These findings emphasize the need for detailed studies on aerosol composition to improve climate models and develop effective strategies for reducing the impact of anthropogenic aerosols on the climate.

Metrological traceable calibration of organic carbon and elemental carbon based on laboratory-generated reference materials

Carbonaceous aerosol, including organic carbon (OC) and elemental carbon (EC), has significant influence on human health, air quality and climate change. Accurate measurement of carbonaceous aerosol is essential to reduce the uncertainty of radiative forcing estimation and source apportionment. The accurate separation of OC and EC is controversial due to the charring of OC. Therefore, the development of reference materials (RM) for the validation of OC/EC separation is an important basis for further study. Previous RMs were mainly based on ambient air sampling, which could not provide traceability of OC and EC concentration. To develop traceable RMs with known OC/EC contents, our study applied an improved aerosol generation and mixing technique, providing uniform deposition of particles on quartz filters. To generate OC aerosol with similar pyrolytic property of ambient aerosol, both water soluble organic carbon (WSOC) and water insoluble organic carbon (WIOC) were used, and amorphous carbon was selected for EC surrogate. The RMs were analyzed using different protocols. The homogeneity within the filter was validated, reaching below 2%. The long-term stability of RMs has been validated with RSD ranged from 1.7%–3.2%. Good correlation was observed between nominal concentration of RMs with measured concentration by two protocols, while the difference of EC concentration was within 20%. The results indicated that the newly developed RMs were acceptable for the calibration of OC and EC, which could improve the accuracy of carbonaceous aerosol measurement. Moreover, the laboratory-generated EC-RMs could be suitable for the calibration of equivalent BC concentration by Aethalometers.

Dust dominates glacier darkening across majority of the Tibetan Plateau based on new measurements

Rapid retreat and darkening of most glaciers in the Tibetan Plateau (TP) are enhanced by the deposition of light-absorbing particles (LAPs). Here, we provided new knowledge on the estimation of albedo reduction caused by black carbon (BC), water-insoluble organic carbon (WIOC), and mineral dust (MD), based on a comprehensive study of snowpit samples from ten glaciers across the TP collected in the spring of 2020. According to the albedo reductions caused by the three LAPs, the TP was divided into three sub-regions: the eastern and northern margins, Himalayas and southeastern TP, and western to inner TP. Our findings indicated that MD had a dominant role in causing snow albedo reductions across the western to inner TP, with comparable effects to WIOC but stronger effects than BC in the Himalayas and southeastern TP. BC played a more important role in the eastern and northern margins of the TP. In conclusion, the findings of this study emphasize not only the important role of MD in glacier darkening across majority of the TP but also the influence of the WIOC in enhancing glacier melting which indicates the dominant contribution of non-BC components in the LAP-related glacier melting of the TP.

Design, optimization, and evaluation of a wet electrostatic precipitator (ESP) for aerosol collection

In this study, we developed, optimized, and evaluated in lab and field experiments a wet electrostatic precipitator (ESP) for the collection of ambient PM2.5 (particulate matter with aerodynamic diameter <2.5 μm) into ultrapure water by applying an electrostatic charge to the particles. We operated the wet ESP at different flow rates and voltages to identify the optimal operating conditions. According to our experimental measurements, a flow rate of 125 lpm and an applied positive voltage of 11 kV resulted in a lower ozone generation of 133 ppb and a particle collection efficiency exceeding 80–90% in all size ranges. For the field tests, the wet ESP was compared with the versatile aerosol concentration enrichment system (VACES) connected to a BioSampler, a PTFE filter sampler, and an OC/EC analyzer (Sunset Laboratory Inc., USA) as a reference. The chemical analysis results indicated the wet ESP concentrations of metal and trace elements were in very good agreement with those measured by the VACES/BioSampler and PTFE filter sampler. Moreover, our results showed comparable total organic carbon (TOC) concentrations measured by the wet ESP, BioSampler, and OC/EC analyzer, while somewhat lower TOC concentrations were measured by the PTFE filter sampler, possibly due to the limitations of extracting water-insoluble organic carbon (WIOC) from a dry substrate in the latter sampler. The comparable TOC content in the wet ESP and BioSampler samples differs from previous findings that showed higher TOC content in BioSampler samples compared to those collected by dry ESP. The results of the Dithiothreitol (DTT) assay showed comparable DTT activity in the VACES/BioSampler and wet ESP PM samples while slightly lower in the PTFE filter samples. Overall, our results suggest that the wet ESP could be a promising alternative to other conventional sampling methods.

An optimised organic carbon ∕ elemental carbon (OC ∕ EC) fraction separation method for radiocarbon source apportionment applied to low-loaded Arctic aerosol filters

Abstract. Radiocarbon (14C) analysis of carbonaceous aerosols is used for source apportionment, separating the carbon content into fossil vs. non-fossil origin, and is particularly useful when applied to subfractions of total carbon (TC), i.e. elemental carbon (EC), organic carbon (OC), water-soluble OC (WSOC), and water-insoluble OC (WINSOC). However, this requires an unbiased physical separation of these fractions, which is difficult to achieve. Separation of EC from OC using thermal–optical analysis (TOA) can cause EC loss during the OC removal step and form artificial EC from pyrolysis of OC (i.e. so-called charring), both distorting the 14C analysis of EC. Previous work has shown that water extraction reduces charring. Here, we apply a new combination of a WSOC extraction and 14C analysis method with an optimised OC/EC separation that is coupled with a novel approach of thermal-desorption modelling for compensation of EC losses. As water-soluble components promote the formation of pyrolytic carbon, water extraction was used to minimise the charring artefact of EC and the eluate subjected to chemical wet oxidation to CO2 before direct 14C analysis in a gas-accepting accelerator mass spectrometer (AMS). This approach was applied to 13 aerosol filter samples collected at the Arctic Zeppelin Observatory (Svalbard) in 2017 and 2018, covering all seasons, which bear challenges for a simplified 14C source apportionment due to their low loading and the large portion of pyrolysable species. Our approach provided a mean EC yield of 0.87±0.07 and reduced the charring to 6.5 % of the recovered EC amounts. The mean fraction modern (F14C) over all seasons was 0.85±0.17 for TC; 0.61±0.17 and 0.66±0.16 for EC before and after correction with the thermal-desorption model, respectively; and 0.81±0.20 for WSOC.

Concentrations, sources, fluxes, and absorption properties of carbonaceous matter in a central Tibetan Plateau river basin

Carbonaceous matter (CM) (such as water-insoluble organic carbon (WIOC), black carbon (BC), and water-soluble organic carbon (WSOC)) has a significant impact on the carbon cycle and radiative forcing (RF) of glacier. Precipitation samples and glacier's snow/ice samples (snowpit, surface snow, and granular ice) (Xiao dongkemadi Glacier) were collected at the Dongkemadi River Basin (DRB) in the central Tibetan Plateau (TP) between May and October 2016 to investigate the characteristics and roles of CM in the TP River Basin. WIOC, BC, and WSOC concentrations in precipitation were relatively higher than that in snowpit, but lower than that in surface snow/ice, with the wet deposition fluxes of 0.10 ± 0.002, 0.04 ± 0.001, and 0.12 ± 0.002 g C m−2 yr−1 at DRB, respectively. The positive matrix factorization model identified four major sources (biomass burning source, secondary precursors, secondary aerosol, and dust source) of CM in precipitation at DRB. Two source areas (South Asia and the interior of TP) contributing to the pollution at DRB were identified using a potential source contribution function model, a concentration-weighted trajectory method, and the back-trajectory model. Moreover, the light-absorption by WSOC in the ultraviolet region was 23.0%, 12.1%, and 3.4% relative to the estimated total light-absorption in precipitation, snowpit, and surface snow/ice, respectively. Optical indices analysis revealed that WSOC in snowpit samples presented higher molecular weight, while presented higher aromatic and higher molecule sizes in surface snow/ice and precipitation samples, respectively. RF by WSOC relative to that of BC was estimated to be 17.6 ± 17.6% for precipitation, 10.9 ± 5.8% for snowpit, and 10.7 ± 11.6% for surface snow/ice, respectively, during the melt season in the central TP River Basin. These results help us understand how CM affects glaciers, and they can be utilized to create policies and recommendations that efficiently reduce emissions.

Chemical characteristics and deposition amounts of carbonaceous species and inorganic ions in precipitation in the Bangkok Metropolitan Region

A comprehensive study on the chemical characteristics and deposition fluxes of precipitation components, including water-insoluble organic carbon (WIOC), water-soluble organic carbon (WSOC), and elemental carbon (EC), including Char-EC and Soot-EC, and major inorganic ions, was conducted from September 2015 to March 2017 at suburban (AIT) and urban (PCD) sites in the Bangkok Metropolitan Region (BMR), Thailand. This is the first study of this kind conducted in tropical areas. To study the scavenging effect of atmospheric particles by wet deposition, atmospheric particulate carbonaceous components were simultaneously measured. The average concentrations of carbonaceous components in precipitation were higher at AIT than at PCD (Bangkok City Center). The contribution of WIOC to total organic carbon (OC) in precipitation was more important at AIT than at PCD sites, whereas the opposite was observed for the contribution of EC. The concentrations of all components in precipitation during the dry season were higher than those during the wet season. The washout processes efficiently removed atmospheric carbonaceous components in the study area, a tropical urban region with a high atmospheric particle concentration. The scavenging ratios (SRs) followed the order of main anthropogenic ions (NO3− and SO42−) > OC > Soot-EC > Char-EC. The annual mean SRs of NO3−, SO42−, OC, Soot-EC, and Char-EC were 1.61, 1.13, 0.75, 0.09, and 0.03 at AIT and 0.96, 1.04, 0.63, 0.08, and 0.03 at PCD, respectively. The washout process was dominant for water-insoluble components (EC and WIOC), whereas the rain-out process was relatively more prominent for water-soluble components (WSOC, SO42− and NO3−). The wet deposition amounts of carbonaceous and main inorganic anions ranked in the order of NO3−> WSOC> SO42− >WIOC>EC, suggesting that the influence of secondary particles was more significant than that of the primary particles. The volume-weighted average pH values of rainwater at suburban and urban sites were 6.25 and 6.04, respectively. NO3− was observed to play a relatively more important role than SO42− in the acidity of rainwater in the BMR. The acidity in the precipitation was almost neutralized by the alkalinity.

Measurement of light-absorbing particles in surface snow of central and western Himalayan glaciers: spatial variability, radiative impacts, and potential source regions

Abstract. We collected surface snow samples from three different glaciers – Yala, Thana, and Sachin – in the central and western Himalayas to understand the spatial variability and radiative impacts of light-absorbing particles. The Yala and Thana glaciers in Nepal and Bhutan, respectively, were selected to represent the central Himalayas. The Sachin glacier in Pakistan was selected to represent the western Himalayas. The samples were collected during the pre- and post-monsoon seasons of the year 2016. The samples were analyzed for black carbon (BC) and water-insoluble organic carbon (OC) through the thermal optical method. The average mass concentrations (BC 2381 ng g−1; OC 3896 ng g−1; dust 101 µg g−1) in the western Himalayas (Sachin glacier) were quite high compared to the mass concentrations (BC 358 ng g−1, OC 904 ng g−1, dust 22 µg g−1) in the central Himalayas (Yala glacier). The difference in mass concentration may be due to the difference in elevation, snow age, local pollution sources, and meteorological conditions. BC in surface snow was also estimated through Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) simulations at the three glacier sites during the sampling periods. Simulations reasonably capture the spatial and seasonal patterns of the observed BC in snow but with a relatively smaller magnitude. Absolute snow albedo was estimated through the Snow, Ice, and Aerosol Radiative (SNICAR) model. The absolute snow albedo reduction ranged from 0.48 % (Thana glacier during September) to 24 % (Sachin glacier during May) due to BC and 0.13 % (Yala glacier during September) to 5 % (Sachin glacier during May) due to dust. The instantaneous radiative forcing due to BC and dust was estimated in the range of 0 to 96.48 and 0 to 25 W m−2, respectively. The lowest and highest albedo reduction and radiative forcing were observed in central and western Himalayan glaciers, respectively. The potential source regions of the deposited pollutants were inferred using WRF-Chem tagged-tracer simulations. Selected glaciers in the western Himalayas were mostly affected by long-range transport from the Middle East and central Asia; however, the central Himalayan glaciers were mainly affected by local and south Asia emissions (from Nepal, India, and China) especially during the pre-monsoon season. Overall, south Asia and west Asia were the main contributing source regions of pollutants.

Soot biodegradation by psychrotolerant bacterial consortia.

To probe the bioavailability of soot released into the atmosphere is pivotal to understanding their environmental impacts. Soot aerosol absorbs organic matter, creating a hot spot for biogeochemical transformation and the global carbon cycle. Soot primarily contains condensed aromatics chemically recalcitrant; however, oligotrophic microorganisms might use it as a nutritional source. This study investigated the influence of psychrotolerant bacterial consortia on soot. Significant increase in the bacterial biomass, reduction in water-insoluble organic carbon (OC) and elemental carbon (EC) in soot residues and increase in water-soluble OC in the filtrate signifies the use of soot as a carbon and nutritional source. The influence on morphology and composition of soot was reported using Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy, and Energy Dispersive X-Ray analysis (EDX). The FTIR analysis showed significant variations in the pattern of soot spectra, suggesting degradation. Elemental analysis and EDX showed a reduction in carbon percentage. Besides, the reduction of optical density with incubation time signifies the OC and EC consumption. This study shows that soot can be a substrate and pivotal factor in the microbial food web. Nowadays, soot emission to the environment is growing; therefore, soot involvement in microbe-mediated processes should be closely focused.

Deconvolving light absorption properties and influencing factors of carbonaceous aerosol in Shanghai

Black carbon (BC) and brown carbon (BrC) have intensive impacts on atmospheric visibility and global climate change. In this study, PM2.5 samples were collected at Pudong (PD) and Qingpu (QP) of Shanghai in 2017, and characterized typical organic molecular tracers by gas chromatography-mass spectrometer. The light absorption (Abs) of carbonaceous aerosol and water-soluble organic matter was analyzed by a multi-wavelength thermal/optical carbon analyzer and a long-range ultraviolet-visible spectrophotometer. An improved two-component model integrated with both optical and chemical fingerprints of carbonaceous aerosol was applied to analyze the Abs of BC, water-soluble organic carbon (WSOC) and water-insoluble organic carbon (WISOC), with which the potential influencing factors including emission source and atmospheric aging were investigated. Results indicated that BrC contributed 19% at PD and 16% at QP of the total light absorption of the carbonaceous aerosol at 405 nm wavelength. Meanwhile, AbsWSOC(405)/AbsBrC(405) showed significant seasonal variations (27–50%) at both sites. Positive matrix factorization (PMF) analysis showed that vehicle emissions (60–61%) and biomass combustion (38–39%) were the major contributors to AbsBC(405), while biomass burning (34–40%), nitrate-relevant secondary processes (22–23%), vehicle emissions (18–19%) and biogenic SOA (13–19%) were major contributors to AbsWSOC(405). Hybrid combustion source (94–96%) had a predominant contribution to AbsWISOC(405). Statistical analysis showed that biomass burning had a great impact on the enhancement of AbsWISOC. Absorption Ångström exponent (AAE) and mass absorption efficiency (MAE) of each factor (source) using PMF analysis indicated that WSOC from combustion sources had higher AAEWSOC(350–550) values (8.11 and 8.29 for coal and biomass burning, respectively) and MAEWSOC(365) values (0.63–0.99) compared to other sources. Atmospheric aging process can lower the MAEWSOC(365) value (0.24–0.52). Overall, our study facilitates a better understanding of the relationships among source, optical properties, and atmospheric transformation processes of the carbonaceous aerosols in Shanghai.

14C characteristics of organic carbon in the atmosphere and at glacier region of the Tibetan Plateau

As an important component of carbonaceous aerosols (CA), organic carbon (OC) exerts a strong, yet insufficiently constrained perturbation of the climate. In this study, we reported sources of OC based on its natural abundance radiocarbon (14C) fingerprinting in aerosols and water-insoluble organic carbon (WIOC) in snowpits across the Tibetan Plateau (TP) – one of the remote regions in the world and a freshwater reservoir for billions of people. Overall, the proportions from 14C-based non-fossil fuel contribution (fnon-fossil) for OC in aerosols was 74 ± 10%, while for WIOC in snowpits was 81 ± 10%, both of which were significantly higher than that of elemental carbon (EC). These indicated sources of OC (WIOC) and EC were different at remote TP. Spatially, high fnon-fossil of WIOC of snowpit samples appeared at the inner part of the TP, indicating the important contribution of local non-fossil sources. Therefore, local non-fossil sources rather than long-range transportation OC dominants its total amount of the TP. In addition, the contribution of local non-fossil sourced WIOC increased during the monsoon period because heavy precipitation removed a high ratio of long-range transportation WIOC. The results of this study showed that not only OC and EC but also their different fuel sources should be treated separately in models to investigate their sources and atmospheric transportation.

Black carbon and organic carbon dataset over the Third Pole

Abstract. The Tibetan Plateau and its surroundings, also known as the Third Pole, play an important role in the global and regional climate and hydrological cycle. Carbonaceous aerosols (CAs), including black carbon (BC) and organic carbon (OC), can directly or indirectly absorb and scatter solar radiation and change the energy balance on the Earth. CAs, along with the other atmospheric pollutants (e.g., mercury), can be frequently transported over long distances into the inland Tibetan Plateau. During the last decades, a coordinated monitoring network and research program named “Atmospheric Pollution and Cryospheric Changes” (APCC) has been gradually set up and continuously operated within the Third Pole regions to investigate the linkage between atmospheric pollutants and cryospheric changes. This paper presents a systematic dataset of BC, OC, water-soluble organic carbon (WSOC), and water-insoluble organic carbon (WIOC) from aerosols (20 stations), glaciers (17 glaciers, including samples from surface snow and ice, snow pits, and 2 ice cores), snow cover (2 stations continuously observed and 138 locations surveyed once), precipitation (6 stations), and lake sediment cores (7 lakes) collected across the Third Pole, based on the APCC program. These data were created based on online (in situ) and laboratory measurements. High-resolution (daily scale) atmospheric-equivalent BC concentrations were obtained by using an Aethalometer (AE-33) in the Mt. Everest (Qomolangma) region, which can provide new insight into the mechanism of BC transportation over the Himalayas. Spatial distributions of BC, OC, WSOC, and WIOC from aerosols, glaciers, snow cover, and precipitation indicated different features among the different regions of the Third Pole, which were mostly influenced by emission sources, transport pathways, and deposition processes. Historical records of BC from ice cores and lake sediment cores revealed the strength of the impacts of human activity since the Industrial Revolution. BC isotopes from glaciers and aerosols identified the relative contributions of biomass and fossil fuel combustion to BC deposition on the Third Pole. Mass absorption cross sections of BC and WSOC from aerosol, glaciers, snow cover, and precipitation samples were also provided. This updated dataset is released to the scientific communities focusing on atmospheric science, cryospheric science, hydrology, climatology, and environmental science. The related datasets are presented in the form of excel files. BC and OC datasets over the Third Pole are available to download from the National Cryosphere Desert Data Center (https://doi.org/10.12072/ncdc.NIEER.db0114.2021; Kang and Zhang, 2021).

Characteristics and source apportionment of particulate carbon in precipitation based on dual-carbon isotopes (13C and 14C) in Xi'an, China

Wet deposition is a dominant removal pathway of carbonaceous particles from the atmosphere, but few studies have assessed the particulate carbon in precipitation in Chinese cities. To assess the characteristics and sources of particulate carbon, we measured the concentrations, fluxes, stable carbon isotopes, and radiocarbon of particulate carbon, and some cations concentrations in precipitation in Xi'an, China, in 2019. In contrast to rainfall samples, particulate carbon in snowfall samples in Xi'an showed extremely high concentrations and wet deposition fluxes. The concentrations as well as wet deposition fluxes showed no significant (p > 0.05) differences between urban and suburban sites, and they also exhibited low seasonality in rainfall samples. Water-insoluble organic carbon (WIOC) accounted for the majority (∼90%) of the concentrations and wet deposition fluxes of water-insoluble total carbon (WITC) in precipitation. The best estimates of source apportionment of WITC in precipitation showed that biological sources were the main contributor (80.0% ± 10.5%) in summer, and their contributions decreased to 47.3% ± 12.8% in winter. The contribution of vehicle exhaust emissions accounted for 11.7% ± 3.5% in summer and 39.0% ± 4.3% in winter, while the contributions of coal combustion were relatively small in summer (8.3% ± 7.0%) and winter (13.8% ± 8.5%). Biomass burning accounted for 25.7% ± 9.3% and 89.9% ± 0.7% of the biological sources in summer and winter, respectively, with the remainder comprising other sources of contemporary carbon. These results highlight the nonnegligible contributions of biogenic emissions and biomass burning to particulate carbon in precipitation in this city in summer and winter, respectively.

The oxidative potential of fresh and aged elemental carbon-containing airborne particles: a review.

Elemental carbon is often found in ambient particulate matter (PM), and it contributes to the PM's oxidative potential (OP) and thus poses great health concerns. Previous review articles mainly focused on the methodologies in evaluating OP in PM and its relationship with selected chemical constituents, including metal ions, PAHs, and inorganic species. In recent years, growing attention has been paid to the effect of atmospheric aging processes on the OP of EC-containing airborne particles (ECCAPs). This review investigates more than 150 studies concerning the OP measurements and physico-chemical properties of both fresh and aged ECCAPs such as laboratory-generated elemental carbon (LGEC), carbon black (CB), soot (black carbon), and engineered carbon-containing nanomaterials (ECCBNs). Specifically, we summarize the characteristics of water-soluble and insoluble organic species, PAHs, quinone, and oxygen-containing functional groups (OFGs), and EC crystallinity. Both water-soluble organic carbon (WSOC) and water-insoluble organic carbon (WIOC) contribute to the OP. Low molecular weight (MW) PAHs show a higher correlation with OP than high MW PAHs. Furthermore, oxidative aging processes introduce OFGs, where quinone (CO) and epoxide (O-C-O) increase the OP of ECCAPs. In contrast, carboxyl (-COOH) and hydroxyl (-OH) slightly change the OP. The low crystallinity of EC favors the oxygen addition and forms active OFG quinone, thus increasing the OP. More detailed analyses for the EC microstructures and the organic coatings are needed to predict the OP of ECCAPs.

Atmospheric deposition fluxes and processes of the water-soluble and water-insoluble organic carbon in central Japan

In order to investigate the wet and dry deposition fluxes of the water-soluble organic carbon (WSOC) and water-insoluble organic carbon (WIOC) and to clarify the factors influencing them, a simultaneous observation of the WSOC and WIOC in both the wet and dry deposition and in the aerosols was conducted for 2 years at an urban site in central Japan. The average deposition fluxes of the WSOC and WIOC by the wet process were 3.514 and 1.719 mgC m−2 day−1, respectively, and those by the dry process were 0.346 and 0.822 mgC m−2 day−1, respectively. About 82% of the organic carbon (OC) that is the sum of the WSOC and WIOC was deposited by the wet process. A large contribution of the wet process to the atmospheric deposition was found not only for the WSOC but also for the WIOC; the contribution of the wet process to the atmospheric deposition was about 91% for the WSOC and about 68% for the WIOC. About 67% of the OC in the wet deposition was explained by the WSOC, whereas about 70% of the OC in the dry deposition was by the WIOC. The WSOC in the coarse aerosols (d = 2.0–10 μm) in the surface atmosphere had a significant impact on the wet deposition flux of the WSOC. In addition, the length of the rainy period also strongly influenced the wet deposition flux of the WSOC. On the other hand, the WIOC in the wet deposition would be influenced by its concentration not only in the ground surface aerosols but also in the upper atmospheric aerosols. The dry deposition fluxes of the WSOC and WIOC were significantly affected by their concentrations in the aerosols with the diameters larger than 10 μm (PM>10). The dry deposition of the PM>10 aerosols in the surface atmosphere had a significant impact on the OC deposition by the dry process.

Organic aerosol formation and aging processes in Beijing constrained by size-resolved measurements of radiocarbon and stable isotopic 13C

This study investigates the sources and atmospheric processes of size-resolved carbonaceous aerosols in winter 2018 in urban Beijing, based on analysis of dual-carbon isotopes (i.e., radiocarbon and the stable isotope 13C). We found a size dependence of fossil source contributions to elemental carbon (EC), but no clear size dependence for organic carbon (OC). Comparable fossil source contributions to water-insoluble OC (WIOC; 55 ± 3%) and to water-soluble OC (WSOC; 54 ± 4%) highlight the importance of secondary aerosol formation, considering that fossil sources emit only small amounts of primary WSOC. OC concentrations increased during high PM2.5 pollution events, with increased fossil and non-fossil WSOC concentrating at larger particles (0.44–2.5 µm) than WIOC (0.25–2.5 µm), highlighting the aqueous-phase chemistry as an important pathway for OC production. The ratio of 13C/12C (expressed as δ13C) of total carbon (−27.0‰ to −23.3‰) fell in the range of anthropogenic aerosol, reflecting small biogenic influence. δ13C of OC increased with desorption temperature steps (200 °C, 350 °C and 650 °C). The strongly enriched δ13COC,650 (−26.9‰ to −20.3‰) and large mass fraction of OC650°C in total desorbed OC, both increasing with the increase of particle sizes, were caused by photochemical aging, especially during low and moderate PM2.5 pollution events, when regional, aged aerosol played an important role. During low pollution events, higher δ13COC,650 and WSOC/OC ratios reflect a larger contribution and more extensive chemical processing of aged aerosol. In contrast, relatively low δ13COC,200 (−27.2‰ to −25.7‰) suggests the influence of secondary OC formation on the more volatile OC desorbed at 200 °C. δ13COC,200 was similar for all particle sizes and for different pollution events, pointing to an internal mixture of local and aged regional OC. Our results show that the organic aerosol in Beijing arises from a mixture of various sources and complex formation processes, spanning local to regional scales. Particle sizes < 250 nm show strong contribution from local secondary OC formation, whereas refractory OC in particles around 1 µm shows strong evidence for regional aging processes. In summary, primary emission, secondary and aqueous-phase formation, and (photo-)chemical aging all need to be considered to understand organic aerosol in this region and their importance varies with particle size.