Formation of Amino Acids and Carboxylic Acids in Weakly Reducing Planetary Atmospheres by Solar Energetic Particles from the Young Sun.

Life most likely started during the Hadean Eon; however, the environmental conditions which contributed to the complexity of its chemistry are poorly known. A better understanding of various environmental conditions, including global (heliospheric) and local (atmospheric, surface, and oceanic), along with the internal dynamic conditions of the early Earth, are required to understand the onset of abiogenesis. Herein, we examine the contributions of galactic cosmic rays (GCRs) and solar energetic particles (SEPs) associated with superflares from the young Sun to the formation of amino acids and carboxylic acids in weakly reduced gas mixtures representing the early Earth's atmosphere. We also compare the products with those introduced by lightning events and solar ultraviolet light (UV). In a series of laboratory experiments, we detected and characterized the formation of amino acids and carboxylic acids via proton irradiation of a mixture of carbon dioxide, methane, nitrogen, and water in various mixing ratios. These experiments show the detection of amino acids after acid hydrolysis when 0.5% (v/v) of initial methane was introduced to the gas mixture. In the set of experiments with spark discharges (simulation of lightning flashes) performed for the same gas mixture, we found that at least 15% methane was required to detect the formation of amino acids, and no amino acids were detected in experiments via UV irradiation, even when 50% methane was used. Carboxylic acids were formed in non-reducing gas mixtures (0% methane) by proton irradiation and spark discharges. Hence, we suggest that GCRs and SEP events from the young Sun represent the most effective energy sources for the prebiotic formation of biologically important organic compounds from weakly reducing atmospheres. Since the energy flux of space weather, which generated frequent SEPs from the young Sun in the first 600 million years after the birth of the solar system, was expected to be much greater than that of GCRs, we conclude that SEP-driven energetic protons are the most promising energy sources for the prebiotic production of bioorganic compounds in the atmosphere of the Hadean Earth.

Physical and chemical properties of PM1 in Delhi: A comparison between clean and polluted days.

Considering the significance of PM1 aerosol in assessing health impacts of air pollution, an extensive analysis of PM1 samples collected at an urban site in Delhi is presented in this study. Overall, PM1 contributed to about 50 % of PM2.5 mass which is alarming especially in Delhi where particle mass loadings are usually higher than prescribed limits. Major portion of PM1 consisted of organic matter (OM) that formed nearly 47 % of PM1 mass. Elemental carbon (EC) contributed to about 13 % of PM1 mass, whereas SO42- (16 %), NH4+ (10 %), NO3- (4 %) and Cl- (3 %) were the major inorganic ions present. Sampling was performed in two distinctive campaign periods (in terms of meteorological conditions and heating (fire) activities), during the year 2019, each spanning two-week time, i.e. (i) September 3rd-16th (clean days), and (ii) November 22nd-December 5th (polluted days). Additionally, PM2.5 and black carbon (BC) were measured simultaneously for subsequent analysis. The 24-h averaged mean concentrations of PM2.5 and BC during clean days (polluted days) were 70.6 ± 26.9 and 3.9 ± 1.0 µg m-3 (196 ± 104 and 7.6 ± 4.1 µg m-3), respectively, which were systematically lower (higher) than that of the annual mean (taken from studies conducted at same site in 2019) of 142 and 5.7 µg m-3, respectively. Changes in characteristic ratios (i.e., organic carbon (OC)/elemental carbon (EC) and K+/EC) of chemical species detected in PM1 show an increase in biomass emissions during polluted days. Increase in biomass emission can be attributed to increase in heating practices (burning of biofuels such as wood logs, straw, and cow-dung cake) in- and around- Delhi because of fall in temperature during second campaign. Furthermore, a significant increase in NO3- fraction of PM1 is observed during second campaign which shows fog processing of NOX due to conducive meteorological conditions in winters. Also, comparatively stronger correlation of NO3- with K+ during second campaign (r = 0.98 as compared to r = 0.5 during first campaign) suggests the increased heating practices to be a contributing factor for increased fraction of NO3- in PM1. We observed that during polluted days, meteorological parameters such as dispersion rate also played a major role in intensifying the impact of increased local emissions due to heating activities. Apart from this, change in the direction of regional emission transport to study site and the topology of Delhi are the possible reasons for the elevated pollution level, especially PM1 during winter in Delhi. This study also suggests that black carbon measurement techniques used in current study (optical absorbance with heated inlet and evolved carbon techniques) can be used as reference techniques to determine the site-specific calibration constant of optical photometers for urban aerosol.

Seasonal characteristics of biogenic secondary organic aerosol tracers in a deciduous broadleaf forest in northern Japan.

We collected total suspended particulate (TSP) samples from January 2010 to December 2010 at Sapporo deciduous forest to understand the oxidation processes of biogenic volatile organic compounds (BVOCs). The gas chromatography-mass spectrometric technique was applied to determine biogenic secondary organic aerosols (BSOAs) in the TSP samples. We found the predominance of the isoprene SOA (iSOA) tracers (20.6 ng m-3) followed by α/ß-pinene SOA (pSOA) tracers (8.25 ng m-3) and ß-caryophyllene SOA (cSOA) tracer (1.53 ng m-3) in the forest aerosols. The results showed large isoprene fluxes and relatively high levels of oxidants in the forest atmosphere. The iSOA and pSOA tracers showed a clear seasonal trend with summer and autumn maxima and winter and spring minima. Their seasonal trends were mainly controlled by BVOCs emission from the local broadleaf deciduous forest. Additionally, the regional level of isoprene emissions from the oceanic sources may also be contributed during summertime aerosols. cSOA tracer showed high concentrations in the winter and spring, possibly due to an additional contribution of biomass burning (BB) aerosols from the local or regional BB activities. The biogenic secondary organic carbon (BSOC) was contributed mainly by the oxidation products of isoprene (136 ngC m-3) followed by ß-caryophyllene (63.0 ngC m-3) and α/ß-pinene (35.9 ngC m-3). The mass concentration ratio (0.92) of pinonic acid + pinic acid and 3-methyl-1,2,3-butanetricarboxylic acid ((PNA + PA)/3-MBTCA) indicates the photochemical transformation of first-generation oxidation products to the higher generation oxidation products. The average ratios of isoprene to α/ß-pinene (1.64) and ß-caryophyllene (18.6) oxidation products suggested a large difference in the emissions of isoprene and α/ß-pinene compared to ß-caryophyllene. The cSOA tracers in the forest aerosols are also contributed by BB during the winter and spring. Positive matrix factorization analyses of the BSOA tracers confirmed that organic aerosols of deciduous forests are mostly related to isoprene emissions. This study suggests that isoprene is a more significant precursor for the BSOA than α/ß-pinene and ß-caryophyllene in a broadleaf deciduous forest.

Large contribution of fossil-derived components to aqueous secondary organic aerosols in China.

Incomplete understanding of the sources of secondary organic aerosol (SOA) leads to large uncertainty in both air quality management and in climate change assessment. Chemical reactions occurring in the atmospheric aqueous phase represent an important source of SOA mass, yet, the effects of anthropogenic emissions on the aqueous SOA (aqSOA) are not well constrained. Here we use compound-specific dual-carbon isotopic fingerprints (δ13C and Δ14C) of dominant aqSOA molecules, such as oxalic acid, to track the precursor sources and formation mechanisms of aqSOA. Substantial stable carbon isotope fractionation of aqSOA molecules provides robust evidence for extensive aqueous-phase processing. Contrary to the paradigm that these aqSOA compounds are largely biogenic, radiocarbon-based source apportionments show that fossil precursors produced over one-half of the aqSOA molecules. Large fractions of fossil-derived aqSOA contribute substantially to the total water-soluble organic aerosol load and hence impact projections of both air quality and anthropogenic radiative forcing. Our findings reveal the importance of fossil emissions for aqSOA with effects on climate and air quality.

Aerosol Proteinaceous Matter in Coastal Okinawa, Japan: Influence of Long-Range Transport and Photochemical Degradation.

The characteristics, sources, and atmospheric oxidation processes of marine aerosol proteinaceous matter (APM), including total proteins and free amino acids (FAAs), were investigated using a set of 1 year total suspended particulate (TSP) samples collected in the coastal area of Okinawa Island in the western North Pacific rim. The concentrations of APM at this site (total proteins: 0.16 ± 0.10 µg m-3 and total FAAs: 9.7 ± 5.6 ng m-3, annual average) are comparable to those of marine APM. The major FAA species of APM are also similar to previously reported marine APM with glycine as the dominant species (31%). Based on the different seasonal trends and weak correlations of total proteins and FAAs, we found that they were contributed by different sources, especially with the influence of long-range transport from the Asian continent of northern China and Mongolia and the oceanic area of the Bohai Sea, Yellow Sea, and East China Sea. The photochemical oxidation processes of high-molecular-weight proteins releasing FAAs (especially glycine) were also considered as an important factor influencing the characteristics of APM at this site. In addition, we propose a degradation process based on the correlation with ozone and ultraviolet radiation, emphasizing their roles in the degradation of proteins. Our findings help to deepen the understanding of atmospheric photochemical reaction processes of organic aerosols.

Seasonal and temporal variations of ambient aerosols in a deciduous broadleaf forest from northern Japan: Contributions of biomass burning and biological particles.

Total suspended particulate (TSP) samples were collected in a deciduous broadleaf forest in Sapporo, Hokkaido, Japan, from January to December 2010 to understand the molecular composition and abundance of sugar compounds (SCs) in atmospheric aerosols. We analyzed the samples for anhydrosugars, primary sugars, and sugar alcohols using a gas chromatograph-mass spectrometer. The annual mean concentrations of total SCs ranged from 16.1 to 1748 ng m-3 (avg. 311 ng m-3) with maxima in spring (avg. 484 ng m-3) and minima in winter (avg. 28.2 ng m-3). Primary sugars and sugar alcohols followed the seasonal pattern of total SCs. High levels of anhydrosugars in winter (avg. 22.9 ng m-3) suggest a contribution of biomass burning from domestic heating due to lower ambient temperature. The high levels of arabitol and mannitol in spring followed by summer and autumn denote the contribution from multiple sources, i.e., growing vegetation and fungal spores in Sapporo forest. We observed an enhanced contribution of bioaerosols emitted from plant blossoms in spring and leaf decomposition in autumn. The identical seasonal trends of glucose and trehalose implied their similar sources in forest aerosols. Conversely, the highest concentration of sucrose in spring was due to the pollen emissions by blooming plants. Positive matrix factorization (PMF) analyses of the SCs suggested that organic aerosols in the deciduous forest are associated with the emissions from multiple sources, including vegetation, microbes, pollens, and wintertime biomass burning. The PMF analysis also suggested that vegetation is the primary carbon source in the forest atmosphere. The diagnostic mass ratios of levoglucosan to mannosan demonstrated the dominance of softwood burning. We noted that the meteorological parameters substantially affect the emission sources and seasonal concentrations of SCs in the deciduous forest.

Dicarboxylic acids and related compounds in fine particulate matter aerosols in Huangshi, central China.

PM2.5 (particulate matter with an aerodynamic diameter <2.5 µm) samples were collected in Huangshi, central China, from March 2012 to February 2013 and were analyzed for dicarboxylic acids (diacids) and related compounds (DARCs). Oxalic acid (C2; 416 ng m-3) was the most abundant species, followed by phthalic (Ph; 122 ng m-3), terephthalic (tPh; 116 ng m-3), succinic (C4; 70.4 ng m-3), azelaic (C9; 67.9 ng m-3), and adipic (C6; 57.8 ng m-3) acids. Relatively high abundances of Ph and tPh differed from the distribution in urban and marine aerosols, indicating contributions from nearby anthropogenic sources. Glyoxylic acid (ωC2; 41.4 ng m-3) was the dominant oxoacid, followed by 9-oxononanoic (ωC9; 40.8 ng m-3) and pyruvic (Pyr; 24.1 ng m-3) acids. Glyoxal (Gly; 35.5 ng m-3) was the dominant α-dicarbonyl. Highest average concentrations were found for C2, ωC2, and C9 in autumn, for C4, for Pyr and C6 in spring, for Ph, ωC9, and Gly in summer, whereas the lowest values were observed in winter. Seasonal variations and correlation coefficients of DARCs demonstrate that both primary emissions and secondary production are important sources. Principal component analysis of selected DARCs species suggests that a mixing of air masses from anthropogenic and biogenic sources contribute to the Huangshi aerosols. Implications: Both primary emissions and secondary production are important sources of diacids and related compounds in PM2.5 from Huangshi, central China. Principal component analysis of selected diacids in Huangshi aerosols suggests that mixing of air masses from anthropogenic and biogenic sources contribute to ambient aerosols in central China.