scholarly journals A Comprehensive Nontarget Analysis for the Molecular Reconstruction of Organic Aerosol Composition from Glacier Ice Cores

2019 ◽  
Vol 53 (21) ◽  
pp. 12565-12575
Author(s):  
Alexander L. Vogel ◽  
Anja Lauer ◽  
Ling Fang ◽  
Katarzyna Arturi ◽  
Franziska Bachmeier ◽  
...  
Keyword(s):  
Ice Cores ◽  
Organic Aerosol ◽  
Aerosol Composition ◽  
Glacier Ice ◽  
Nontarget Analysis

scholarly journals Towards a quasi-complete reconstruction of past atmospheric aerosol load and composition (organic and inorganic) over Europe since 1920 inferred from Alpine ice cores

2013 ◽  
Vol 9 (1) ◽  
pp. 1099-1134 ◽  
Author(s):  
S. Preunkert ◽  
M. Legrand
Keyword(s):  
World War Ii ◽  
Organic Carbon ◽  
Atmospheric Aerosol ◽  
Ice Core ◽  
Ice Cores ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Climate Forcing ◽  
World War ◽  
Aerosol Composition

Abstract. Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps) are here revisited in view to reconstruct past aerosol load of the free European troposphere from prior World War II to present. The extended array of inorganic (Na+, Ca2+, NH4+, Cl−, NO3−, and SO42−) and organic (carboxylates, HCHO, HUmic LIke Substances, dissolved organic carbon, water insoluble organic carbon, and black carbon) compounds and fractions already investigated permit to examine the overall aerosol composition and its change over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921–1951 to 1971–1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). It is shown that not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarii dealing with climate forcing by atmospheric aerosol.

scholarly journals Urban organic aerosol composition in Eastern China differs from North to South: Molecular insight from a liquid chromatography-Orbitrap mass spectrometry study

2019 ◽  
Author(s):  
Kai Wang ◽  
Ru-Jin Huang ◽  
Martin Brüggemann ◽  
Yun Zhang ◽  
Lu Yang ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Liquid Chromatography ◽  
Eastern China ◽  
Organic Aerosol ◽  
Photochemical Oxidation ◽  
Lower Latitude ◽  
Molecular Formula ◽  
Aerosol Composition ◽  
Orbitrap Mass Spectrometry ◽  
Low Degrees

Abstract. Particulate air pollution in China is influencing human health, ecosystem and climate. However, the chemical composition of particulate aerosol, especially of the organic fraction, is still not well understood. In this study, particulate aerosol samples with a diameter ≤ 2.5 μm (PM2.5) were collected in January 2014 in three cities located in Northeast, East and Southeast China, i.e., Changchun, Shanghai and Guangzhou, respectively. Organic aerosol (OA) in the PM2.5 samples was analyzed by ultrahigh performance liquid chromatography (UHPLC) coupled to high-resolution Orbitrap mass spectrometry in both negative mode (ESI−) and positive mode electrospray ionization (ESI+). After a non-target screening including molecular formula assignments, compounds were classified into five groups based on their elemental composition, i.e., CHO, CHON, CHN, CHOS and CHONS. The CHO, CHON and CHN compounds present the dominant signal abundances of 81–99.7 % in the mass spectra and the majority of these compounds were assigned to mono- and polyaromatics, suggesting that anthropogenic emissions are a large source of urban OA in all three cities. However, the chemical characteristics of these compounds varied among different cities. The degree of aromaticity and the number of polyaromatic compounds were significantly higher in samples from Changchun, which could be attributed to the large emissions from residential heating (i.e., coal combustion) during winter time in Northeast China. Moreover, the ESI− analysis showed higher H / C and O / C ratios for organic compounds in Shanghai and Guangzhou compared to samples from Changchun, indicating that OA in lower latitude regions of China experiences more intense photochemical oxidation processes. The majority of sulfur-containing compounds (CHOS and CHONS) in all cities were assigned to aliphatic compounds with low degrees of unsaturation and aromaticity. Again, samples from Shanghai and Guangzhou exhibit a larger chemical similarity but largely differ from those from Changchun.

scholarly journals Glacier ice archives nearly 15,000-year-old microbes and phages

Microbiome ◽  
2021 ◽  
Vol 9 (1) ◽  
Author(s):  
Zhi-Ping Zhong ◽  
Funing Tian ◽  
Simon Roux ◽  
M. Consuelo Gazitúa ◽  
Natalie E. Solonenko ◽  
...  
Keyword(s):  
Climate Change ◽  
Ice Core ◽  
Ice Cores ◽  
Single Species ◽  
Amplicon Sequencing ◽  
Future Climate Change ◽  
Climate Conditions ◽  
Glacier Ice ◽  
Sampling Procedures ◽  
Functional Genome

Abstract Background Glacier ice archives information, including microbiology, that helps reveal paleoclimate histories and predict future climate change. Though glacier-ice microbes are studied using culture or amplicon approaches, more challenging metagenomic approaches, which provide access to functional, genome-resolved information and viruses, are under-utilized, partly due to low biomass and potential contamination. Results We expand existing clean sampling procedures using controlled artificial ice-core experiments and adapted previously established low-biomass metagenomic approaches to study glacier-ice viruses. Controlled sampling experiments drastically reduced mock contaminants including bacteria, viruses, and free DNA to background levels. Amplicon sequencing from eight depths of two Tibetan Plateau ice cores revealed common glacier-ice lineages including Janthinobacterium, Polaromonas, Herminiimonas, Flavobacterium, Sphingomonas, and Methylobacterium as the dominant genera, while microbial communities were significantly different between two ice cores, associating with different climate conditions during deposition. Separately, ~355- and ~14,400-year-old ice were subject to viral enrichment and low-input quantitative sequencing, yielding genomic sequences for 33 vOTUs. These were virtually all unique to this study, representing 28 novel genera and not a single species shared with 225 environmentally diverse viromes. Further, 42.4% of the vOTUs were identifiable temperate, which is significantly higher than that in gut, soil, and marine viromes, and indicates that temperate phages are possibly favored in glacier-ice environments before being frozen. In silico host predictions linked 18 vOTUs to co-occurring abundant bacteria (Methylobacterium, Sphingomonas, and Janthinobacterium), indicating that these phages infected ice-abundant bacterial groups before being archived. Functional genome annotation revealed four virus-encoded auxiliary metabolic genes, particularly two motility genes suggest viruses potentially facilitate nutrient acquisition for their hosts. Finally, given their possible importance to methane cycling in ice, we focused on Methylobacterium viruses by contextualizing our ice-observed viruses against 123 viromes and prophages extracted from 131 Methylobacterium genomes, revealing that the archived viruses might originate from soil or plants. Conclusions Together, these efforts further microbial and viral sampling procedures for glacier ice and provide a first window into viral communities and functions in ancient glacier environments. Such methods and datasets can potentially enable researchers to contextualize new discoveries and begin to incorporate glacier-ice microbes and their viruses relative to past and present climate change in geographically diverse regions globally.

scholarly journals Characterization of Aerosol Composition, Aerosol Acidity and Organic Acid Partitioning at an Agriculture-Intensive Rural Southeastern U.S. Site

2018 ◽  
Author(s):  
Theodora Nah ◽  
Hongyu Guo ◽  
Amy P. Sullivan ◽  
Yunle Chen ◽  
David J. Tanner ◽  
...  
Keyword(s):  
Oxalic Acid ◽  
Organic Acids ◽  
Organic Acid ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Molar Concentration ◽  
Particle Phase ◽  
Aerosol Composition ◽  
Phase Water ◽  
Acetic Acids

Abstract. The implementation of stringent emission regulations has resulted in the decline of anthropogenic pollutants including sulfur dioxide (SO2), nitrogen oxides (NOx) and carbon monoxide (CO). In contrast, ammonia (NH3) emissions are largely unregulated, with emissions projected to increase in the future. We present real-time aerosol and gas measurements from a field study conducted in an agricultural-intensive region in the southeastern U.S. during the fall of 2016 to investigate how NH3 affects particle acidity and SOA formation via the gas-particle partitioning of semi-volatile organic acids. Particle water and pH were determined using the ISORROPIA-II thermodynamic model and validated by comparing predicted inorganic HNO3-NO3− and NH3-NH4+ gas-particle partitioning ratios with measured values. Our results showed that despite the high NH3 concentrations (study average 8.1 ± 5.2 ppb), PM1 were highly acidic with pH values ranging from 0.9 to 3.8, and a study-averaged pH of 2.2 ± 0.6. PM1 pH varied by approximately 1.4 units diurnally. Formic and acetic acids were the most abundant gas-phase organic acids, and oxalate was the most abundant particle-phase water-soluble organic acid anion. Measured particle-phase water-soluble organic acids were on average 6 % of the total non-refractory PM1 organic aerosol mass. The measured molar fraction of oxalic acid in the particle phase (i.e., particle-phase oxalic acid molar concentration divided by the total oxalic acid molar concentration) ranged between 47 and 90 % for PM1 pH 1.2 to 3.4. The measured oxalic acid gas-particle partitioning ratios were in good agreement with their corresponding thermodynamic predictions, calculated based on oxalic acid’s physicochemical properties, ambient temperature, particle water and pH. In contrast, gas-particle partitioning of formic and acetic acids were not well predicted for reasons currently unknown. For this study, higher NH3 concentrations relative to what has been measured in the region in previous studies had minor effects on PM1 organic acids and their influence on the overall organic aerosol and PM1 mass concentrations.

scholarly journals Towards a quasi-complete reconstruction of past atmospheric aerosol load and composition (organic and inorganic) over Europe since 1920 inferred from Alpine ice cores

2013 ◽  
Vol 9 (4) ◽  
pp. 1403-1416 ◽  
Author(s):  
S. Preunkert ◽  
M. Legrand
Keyword(s):  
World War Ii ◽  
Organic Carbon ◽  
Atmospheric Aerosol ◽  
Ice Core ◽  
Ice Cores ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Climate Forcing ◽  
World War ◽  
Ice Core Records

Abstract. Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps), are here used to reconstruct past aerosol load and composition of the free European troposphere from before World War II to present. Available ice core records include inorganic (Na+, Ca2+, NH4+, Cl−, NO3−, and SO42−) and organic (carboxylates, HCHO, humic-like substances, dissolved organic carbon, water-insoluble organic carbon, and black carbon) compounds and fractions that permit reconstructing the key aerosol components and their changes over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921–1951 to 1971–1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). Thus, not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water-soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarios dealing with climate forcing by atmospheric aerosol.

scholarly journals Technical Note: Relating functional group measurements to carbon types for improved model-measurement comparisons of organic aerosol composition

2016 ◽  
Author(s):  
Satoshi Takahama ◽  
Giulia Ruggeri
Keyword(s):  
Organic Carbon ◽  
Functional Group ◽  
Organic Aerosol ◽  
Chem Phys ◽  
Technical Note ◽  
Molecular Structures ◽  
Organic Carbon Content ◽  
Aerosol Composition ◽  
Ft Ir ◽  
Model Measurement

Abstract. Functional group (FG) analysis provides a means by which functionalization in organic aerosol can be attributed to the abundances of its underlying molecular structures. However, performing this attribution requires additional, unobserved details about the molecular mixture to provide constraints in the estimation process. To address this issue, we present an approach for conceptualizing FG measurements of organic aerosol in terms of its functionalized carbon atoms. This reformulation facilitates estimation of mass recovery and biases in popular carbon-centric metrics that describe the extent of functionalization (such as oxygen to carbon ratio, organic mass to organic carbon mass ratio, and mean carbon oxidation state) for any given set of molecules and FGs analyzed. Furthermore, this approach allows development of parameterizations to more precisely estimate the organic carbon content from measured FG abundance. We use simulated photooxidation products of α-pinene secondary organic aerosol previously reported by Ruggeri et al. (Atmos. Chem. Phys., 16, 4401–4422, 2016) and FG measurements by Fourier Transform Infrared (FT-IR) spectroscopy in chamber experiments by Sax et al. (Aerosol Sci. Tech., 39, 822–830, 2005) to infer the relationships among molecular composition, FG composition, and metrics of organic aerosol functionalization. We find that for this simulated system, ~ 80 % of the carbon atoms should be detected by FGs for which calibration models are commonly developed, and ~ 7 % of the carbon atoms are undetectable by FT-IR analysis because they are not associated with vibrational modes in the infrared. Estimated biases due to undetected carbon fraction for these simulations are used to make adjustments in these carbon-centric metrics such that model-measurement differences are framed in terms of unmeasured heteroatoms (e.g., in hydroperoxide and nitrate groups for the case studied in this demonstration). The formality of this method provides framework for extending FG analysis to not only model-measurement but also instrument intercomparisons in other chemical systems.

scholarly journals Seasonal variations in the high time-resolved aerosol composition, sources, and chemical process of background submicron particles in North China Plain

2020 ◽  
Author(s):  
Jiayun Li ◽  
Liming Cao ◽  
Wenkang Gao ◽  
Lingyan He ◽  
Yingchao Yan ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Seasonal Variations ◽  
North China Plain ◽  
North China ◽  
Organic Aerosol ◽  
Submicron Particles ◽  
Western China ◽  
Aerosol Composition ◽  
Oxidation Degree ◽  
Four Seasons

Abstract. For the first time in the North China Plain (NCP), we investigated the seasonal variations of submicron particles (NR-PM1) and its chemical composition at a background mountain station using Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS). The averaged NR-PM1 were highest in autumn (15.1 μg m−3) and lowest in summer (12.4 μg m−3), with the abundance of more nitrate in spring (34 %), winter (31 %), and autumn (34 %), and elevated organics (40 %) and sulfate (38 %) proportion in summer. The submicron particles were almost neutralized by excess ammonium in all four seasons except summer, when the aerosol particles appeared to be slightly acidic. The size distribution of all PM1 species showed a consistent accumulation mode peaked at approximately 600–800 nm (dva), indicating the highly aged and internally mixed nature of the background aerosols, which further supported by the source appointment using multilinear engine (ME-2) and significant contributions of aged secondary organic aerosol (SOA) in organic aerosol (OA) were resolved in all seasons (> 77 %), especially in summer (95 %). The oxidation degree and evolution process of OAs in the four seasons were further investigated, and enhanced carbon oxidation state (−0.45–0.10), O / C (0.54–0.75) and OM / OC (1.86–2.13) ratios compared with urban studies were observed, with the highest oxidation degree of which appeared in summer, likely due to the relatively stronger photochemical processing which dominated the processes of both less oxidized OA (LO-OOA) and more oxidized OA (MO-OOA) formations. Aqueous-phase processing also contributed to the SOA formation but prevailed in autumn and winter and the role of which to MO-OOA and LO-OOA also varied in different seasons. In addition, compared with the urban atmosphere, LO-OOA formation in the background atmosphere exhibited more regional characteristics, as photochemical and aqueous-phase processing enhanced during the transport in summer and autumn, respectively. Furthermore, the backward trajectories analysis showed that higher submicron particles were associated with air mass for short distance transported from the southern regions in four seasons, while the long-range transport from Inner Mongolia (west and north regions) also contributed to the summer particle pollutions in the background areas of NCP. Our results illustrate the background particles in NCP are influenced significantly by aging processing and transport, and the more neutralized state of submicron particles with the abundance of nitrate compared with those in the background atmosphere in southern and western China, highlighting the regional reductions in emissions of nitrogen oxide and ammonia are critical for remedying the increased occurrence of nitrate-dominated haze event in the NCP.

scholarly journals Chemical and physical characteristics of aerosol particles at a remote coastal location, Mace Head, Ireland, during NAMBLEX

2006 ◽  
Vol 6 (11) ◽  
pp. 3289-3301 ◽  
Author(s):  
H. Coe ◽  
J. D. Allan ◽  
M. R. Alfarra ◽  
K. N. Bower ◽  
M. J. Flynn ◽  
...  
Keyword(s):  
Surf Zone ◽  
Organic Aerosol ◽  
Sea Salt ◽  
Research Station ◽  
Aerosol Composition ◽  
Gaseous Species ◽  
Accumulation Mode ◽  
Coarse Mode ◽  
Wide Range ◽  
Loss Rates

Abstract. A suite of aerosol physical and chemical measurements were made at the Mace Head Atmospheric Research Station, Co. Galway, Ireland, a coastal site on the eastern seaboard of the north Atlantic Ocean during NAMBLEX. The data have been used in this paper to show that over a wide range of aerosol sizes there is no impact of the inter-tidal zone or the surf zone on measurements made at 7 m above ground level or higher. During the measurement period a range of air mass types were observed. During anticyclonic periods and conditions of continental outflow Aitken and accumulation mode were enhanced by a factor of 5 compared to the marine sector, whilst coarse mode particles were enhanced during westerly conditions. Baseline marine conditions were rarely met at Mace Head during NAMBLEX and high wind speeds were observed for brief periods only. The NAMBLEX experiment focussed on a detailed assessment of photochemistry in the marine environment, investigating the linkage between the HOx and the halogen radical cycles. Heterogeneous losses are important in both these cycles. In this paper loss rates of gaseous species to aerosol surfaces were calculated for a range of uptake coefficients. Even when the accommodation coefficient is unity, lifetimes due to heterogeneous loss of less than 10 s were never observed and rarely were they less than 500 s. Diffusional limitation to mass transfer is important in most conditions as the coarse mode is always significant. We calculate a minimum overestimate of 50% in the loss rate if this is neglected and so it should always be considered when calculating loss rates of gaseous species to particle surfaces. HO2 and HOI have accommodation coefficients of around 0.03 and hence we calculate lifetimes due to loss to particle surfaces of 2000 s or greater under the conditions experienced during NAMBLEX. Aerosol composition data collected during this experiment provide representative information on the input aerosol characteristics to western Europe. During NAMBLEX the submicron aerosol was predominately acidified sulphate and organic material, which was most likely internally mixed. The remaining accumulation mode aerosol was sea salt. The organic and sulphate fractions were approximately equally important, though the mass ratio varies considerably between air masses. Mass spectral fingerprints of the organic fraction in polluted conditions are similar to those observed at other locations that are characterised by aged continental aerosol. In marine conditions, the background input of both sulphate and organic aerosol into Europe was observed to be between 0.5 and 1 µg m−3. Key differences in the mass spectra were observed during the few clean periods but were insufficient to ascertain whether these changes reflect differences in the source fingerprint of the organic aerosol. The coarse mode was composed of sea salt and showed significant displacement of chloride by nitrate and to a lesser extent sulphate in polluted conditions.

scholarly journals Urban organic aerosol composition in eastern China differs from north to south: molecular insight from a liquid chromatography–mass spectrometry (Orbitrap) study

2021 ◽  
Vol 21 (11) ◽  
pp. 9089-9104
Author(s):  
Kai Wang ◽  
Ru-Jin Huang ◽  
Martin Brüggemann ◽  
Yun Zhang ◽  
Lu Yang ◽  
...  
Keyword(s):  
Eastern China ◽  
Organic Aerosol ◽  
Photochemical Oxidation ◽  
Lower Latitude ◽  
Aerosol Composition ◽  
Liquid Chromatograph ◽  
Positive Mode ◽  
Target Screening ◽  
Peak Abundance ◽  
Low Degrees

Abstract. Air pollution by particulate matter in China affects human health, the ecosystem and the climate. However, the chemical composition of particulate aerosol, especially of the organic fraction, is still not well understood. In this study, particulate aerosol samples with a diameter of ≤2.5 µm (PM2.5) were collected in January 2014 in three cities located in northeast, east and southeast China, namely Changchun, Shanghai and Guangzhou. Organic aerosol (OA) in the PM2.5 samples was analyzed by an ultrahigh-performance liquid chromatograph (UHPLC) coupled to a high-resolution Orbitrap mass spectrometer in both negative mode (ESI-) and positive mode electrospray ionization (ESI+). After non-target screening including the assignment of molecular formulas, the compounds were classified into five groups based on their elemental composition, i.e., CHO, CHON, CHN, CHOS and CHONS. The CHO, CHON and CHN groups present the dominant signal abundances of 81 %–99.7 % in the mass spectra and the majority of these compounds were assigned to mono- and polyaromatics, suggesting that anthropogenic emissions are a major source of urban OA in all three cities. However, the chemical characteristics of these compounds varied between the different cities. The degree of aromaticity and the number of polyaromatic compounds were substantially higher in samples from Changchun, which could be attributed to the large emissions from residential heating (i.e., coal combustion) during wintertime in northeast China. Moreover, the ESI- analysis showed higher H/C and O/C ratios for organic compounds in Shanghai and Guangzhou compared to samples from Changchun, indicating that OA undergoes more intense photochemical oxidation processes in lower-latitude regions of China and/or is affected to a larger degree by biogenic sources. The majority of sulfur-containing compounds (CHOS and CHONS) in all cities were assigned to aliphatic compounds with low degrees of unsaturation and aromaticity. Here again, samples from Shanghai and Guangzhou show a greater chemical similarity but differ largely from those from Changchun. It should be noted that the conclusions drawn in this study are mainly based on comparison of molecular formulas weighted by peak abundance and thus are associated with inherent uncertainties due to different ionization efficiencies for different organic species.

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