On the nature of nitrate in coarse continental aerosols

In nonmarine environments, the nitrate (NO₃⁻) aerosol occurs in both the fine fraction (diameter < 2.5 μm) as NH₄NO₃ and in the coarse fraction (diameter ⩾ 2.5 μm). Our summertime studies in the eastern U.S. show that NO₃⁻ is predominantly in the coarse fraction. Strong correlations between coarse NO₃⁻ and the crustal elements suggest that the NO₃⁻ is associated with entrained soil dust. Various formation mechanisms, including artifact NO₃⁻ formation on filters, were examined and it appears that the most important mechanism is the reaction of HNO₃ with airborne crustal constituents.     

The chemical composition of tropospheric aerosols and their contributing sources to a continental background site in northern Zimbabwe from 1994 to 2000

Atmospheric aerosols were collected in separate coarse (2–10 μm diameter) and fine (diameter less than 2 μm) size fractions at Rukomechi Research Station (16.1°S, 29.4°E), Zimbabwe, in the central part of southern Africa, from September 1994 to January 2000. The samples were analysed for the particulate mass (PM), black carbon, and 47 elements. The overall data set and the separate wet and dry season data sets were examined with absolute principal component analysis (APCA). Natural and anthropogenic aerosol sources were identified in both seasons, but the sources and their contributions to the total PM were found to vary between seasons and between size fractions. Crustal matter, sea salt (SS), a mixed biogenic (BIO) emission/biomass burning (BB) component, and a copper component were identified for the coarse aerosols during the wet season. APCA attributed 29% of the total wet season coarse PM to the mixed BIO/BB component, and 32% to SS. The copper component is likely due to the copper smelters in the Zambian Copperbelt. The dry season coarse PM originated from crustal matter, BB, BIO, and SS sources, with the major contribution (32%) coming from BB. Four components (crustal matter, BB, non-ferrous smelters, and SS) were identified for the fine particles for both the wet and dry seasons. The BB component provided the major contribution to the total fine PM, accounting for 44% and 79% in the wet and dry seasons, respectively. The relative contributions to the total PM (both fine and coarse) for all sources were greater in the dry season than the wet season, except for SS.     

Size-differentiated composition of inorganic atmospheric aerosols of both marine and polluted continental origin

Atmospheric aerosols were sampled with a high volume impactor/diffusion battery system and the collected fractions analysed for their major water-soluble inorganic constituents. Sulphate, nitrate and chloride showed bimodal distributions; sulphate and nitrate were mainly associated with NH₄⁺, having approximately log-normal distributions with modes at 1.0 μm. In unpolluted maritime air, chlorides appeared as salts of sodium and magnesium with average modes at c. 5 μm, whilst in polluted air masses significant concentrations of ammonium chloride sub-μm aerosols were detected. Sodium nitrate and sodium sulphate aerosols having average modes of c. 3.5 μm were observed in mixed maritime/polluted air masses. The dimensions of these particles indicate formation from absorption of H₂SO₄ and HNO₃ at the surface of marine NaCl particles. The concentration of H⁺ was very low, but the possibility of its neutralization by atmospheric ammonia during sampling was ruled out by parallel air sampling using an ‘ammonia denuder’.     

Effect of enrichment in marine aerosols on estimated background concentration of sulphate in precipitation

A recent investigation (Garland, 1981) has been made of the relative concentration of sulphate in marine aerosols compared with its relative concentration in bulk seawater. This work indicated that a small enrichment may take place in the aerosol. This memorandum reports on the effect such an enrichment would have on the interpretation of sulphate measurements made in the OECD project on the long-range transport of air pollutants. It is shown that such an enrichment would not substantially change transfrontier mass balances between countries, but could explain part, though not all, of the background sulphate observed in precipitation at remote sites.     

Organic acids in springtime wisconsin precipitation samples

A short-term study on organic acids in precipitation was conducted from 15 March to 1 June 1984 at two sites on the Wisconsin Acid Deposition Monitoring Network. Aliquots of collected samples were fixed with tetrachloromercurate (TCM) and analyzed for low molecular weight organic anions via ion-exclusion chromatography (ICE). Unfixed aliquots were subjected to standard network inorganic analyses. Of the 31 samples collected, 30 contained detectable concentrations of formate and acetate ions, with concentrations ranging from < 0.43 to 56μmol ℓ⁻¹ for the former and < 0.83 to 33 μmol ℓ⁻¹ for the latter. Propionate, oxalate and malonate ions were also detected in a number of samples. Statistical analysis of the combined organic and inorganic data set indicated that no significant differences existed between the concentrations of organic ions at the two sites; however, samples containing visible sediments had significantly greater concentrations than samples without sediments. Maximum contributions of the organic acids to precipitation-free acidity, calculated by assuming that the only sources of the measured formate and acetate were their respective acid forms, averaged 18.6% for samples with a pH ⩽ 5.0. Formate and acetate concentrations were highly correlated. Correlations between organic and inorganic ions were weak; NH⁺₄ and Ca²⁺ generally exhibited the highest, though still weak, correlations. The study emphasizes the need for further, longer-term investigations to determine the role of low molecular weight organic compounds in precipitation chemistry.     

Free amino acids in marine aerosols over the western North Pacific Ocean

Atmospheric input of fixed nitrogen species to the ocean has attracted considerable attention from the viewpoint of the oceanic biogeochemical cycle of nitrogen, although few measurements of organic nitrogen compounds in atmospheric aerosols have been extensively conducted over remote ocean areas. In this study, we report the geographical distribution of dissolved free amino acids (DFAA) in the water-soluble fraction of two size-segregated marine aerosols over the western North Pacific. The concentrations of DFAA showed higher values over the region north of 30°N, whereas they clearly decreased south of 30°N. Approximately 59–96% of DFAA was found in fine-mode particles. Long-range transport from continental sources could largely contribute to DFAA in marine aerosols over the remote North Pacific.     

Direct quantification of organic acids in aerosols by desorption electrospray ionization mass spectrometry

Desorption electrospray ionization mass spectrometry (DESI-MS) is a novel analytical technique for direct surface analysis under ambient conditions. In this work, we report the first application of DESI-MS to the analysis of organic acids in atmospheric aerosols. We took oxalic and oleic acids as two typical representatives of the particulate organic acids. Experimental parameters for DESI-MS were optimized to enhance the signal intensity. Calibrations for both acids showed great linearity over a concentration range of 5 orders of magnitude with correlation coefficients R²>0.99. The relative standard deviation (RSD) was less than 10% for oxalic acid and within 15% for oleic acid measurement. The detection limits for oxalic acid and oleic acid are about 1 pg mm^?2 with 5–10 s sampling time. Mass concentrations of organic acids in both laboratory-generated biomass burning and ambient aerosols were measured by DESI-MS and the results agree well with the ion chromatography (IC) and GC–MS values. This work demonstrates that DESI-MS is a promising method for rapid quantitative analysis of organic acids in atmospheric aerosols.     

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

PM_2.5 (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 PM_2.5 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.     

Effect of biomass burning and regional background aerosols on CCN activity derived from airborne in-situ measurements

Airborne in-situ measurements were analyzed to investigate the effects of biomass burning and regional background aerosols on cloud condensation nuclei (CCN) activity in the Pacific Dust Experiment (PACDEX) during April and May 2007. Airmass trajectories with both horizontal and vertical motions were provided to identify the aerosol sources. In the biomass burning cases, the elevated aerosol layers were clearly observed at dry conditions because of the convection of airmass in the source region. The relative aging of aerosols was supported by the ratios of BC to particles with size ranging from 0.1 to 1.0 μm (N_0.1–1.0) and BC to carbon monoxide. Compared to aerosols in the precedent plume of biomass burning, aged particles in the latter plume were more activated to CCN at 0.4% (CCN_0.4%) than 0.1% supersaturation (CCN_0.1%) due to aerosols chemical modification during the aging process. On the other hand, significant difference of CCN_0.4% and CCN_0.1% at regional background aerosols over the Pacific Ocean was due to the activated particles below 1 μm in diameter. Although higher concentrations of aged particles were observed over the eastern Pacific Ocean, activated aerosols to cloud droplet was comparatively similar in the western Pacific Ocean because of the similar concentrations of N_0.1–1.0 in both cases.     

Identification of dicarboxylic acids and aldehydes of PM10 and PM2.5 aerosols in Nanjing,China

In this study aerosol samples of PM10 and PM2.5 collected from 18 February 2001 to 1 May 2001 in Nanjing, China were analyzed for their water-soluble organic compounds. A series of homologous dicarboxylic acids (C_2–10) and two kinds of aldehydes (methylglyoxal and 2-oxo-malonaldehyde) were detected by GC and GC/MS. Among the identified compounds, the concentration of oxalic acid was the highest at all the five sites, which ranged from 178 to 1423 ng/m³. The second highest concentration of dicarboxylic acids were malonic and succinic acids, which ranged from 26.9 to 243 ng/m³. Higher level of azelaic acid was also observed, of which the maximum was 301 ng/m³. As the highest fraction of dicarboxylic acids, oxalic acid comprised from 28% to 86% of total dicarboxylic acids in PM10 and from 41% to 65% of total dicarboxylic acids in PM2.5. The dicarboxylic acids (C₂, C₃, C₄) together accounted for 38–95% of total dicarboxylic acids in PM10 and 59–87% of dicarboxylic acids in PM2.5. In this study, the total dicarboxylic acids accounted for 2.8–7.9% of total organic carbon (TOC) of water-soluble matters for PM10 and 3.4–11.8% of TOC for PM2.5. All dicarboxylic acids detected in this study together accounted for about 1% of particle mass. The concentration of azelaic acid was higher at one site than others, which may be resulted from higher level of volatile fat used for cooking. The amounts of dicarboxyic acids (C_2,3,4,9) and 2-oxo-malonaldehyde of PM2.5 were higher in winter and lower in spring. Compared with other major metropolitans in the world, the level of oxalic acid concentration of Nanjing is much higher, which may be contributed to higher level of particle loadings, especially for fine particles.     

Determination of primary and secondary sources of organic acids and carbonaceous aerosols using stable carbon isotopes

Stable carbon isotope ratio (δ¹³C) data can provide important information regarding the sources and the processing of atmospheric organic carbon species. Formic, acetic and oxalic acid were collected from Zurich city in August–September 2002 and March 2003 in the gas and aerosol phase, and the corresponding δ¹³C analysis was performed using a wet oxidation method followed by isotope ratio mass spectrometry. In August, the δ¹³C values of gas phase formic acid showed a significant correlation with ozone (coefficient of determination (r²) = 0.63) due to the kinetic isotope effect (KIE). This indicates the presence of secondary sources (i.e. production of organic acids in the atmosphere) in addition to direct emission. In March, both gaseous formic and acetic acid exhibited similar δ¹³C values and did not show any correlation with ozone, indicating a predominantly primary origin. Even though oxalic acid is mainly produced by secondary processes, the δ¹³C value of particulate oxalic acid was not depleted and did not show any correlation with ozone, which may be due to the enrichment of ¹³C during the gas - aerosol partitioning.The concentrations and δ¹³C values of the different aerosol fractions (water soluble organic carbon, water insoluble organic carbon, carbonate and black carbon) collected during the same period were also determined. Water soluble organic carbon (WSOC) contributed about 60% to the total carbon and was enriched in ¹³C compared to other fractions indicating a possible effect of gas - aerosol partitioning on δ¹³C of carbonaceous aerosols. The carbonate fraction in general was very low (3% of the total carbon).     

Organic aerosols in the Miami area, USA: temporal variability of atmospheric particles and wet/dry deposition

Atmospheric particulate matter and both wet and dry deposition was collected over a period of nine months at one location in the metropolitan area of Miami, Florida. Molecular distributions and concentrations of n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAHs) and hopanes were determined using weekly composite samples over this time period in order to determine temporal variability, and their possible dependence on climatic parameters such as temperature, rainfall and wind direction and frequency. Based on molecular distributions of the compounds studied, potential emission sources for the atmospheric particles were assessed and suggested to be mainly derived from automobile exhaust and natural sources. Although wet and dry deposition processes were observed to remove about equal amounts of organic aerosols from the Miami atmosphere, dry deposition was dominant in the removal of anthropogenically derived compounds such as PAHs and hopanes. Only very limited seasonal trends were observed, while wind direction and frequency was found to be the most important meteorological parameter controlling the temporal variability of the organic aerosols. This is the first detailed report of this nature for the Miami area.     

Water-soluble sulphur compounds in aerosols

Sampling of particles and analysis of their water-soluble part for H⁺, NH₄⁺, SO₄²⁻ and NO₃⁻ were carried out in a remote and an urban area on the Swedish west coast. For the determination of H⁺ a special procedure based on Gran's plot was used. High concentrations of sulphate were found in two types of particles of apparently different genetic origin. In fine particles the following solid sulphate phases were identified: (NH₄)₂SO₄, (NH₄)₃H(SO₄)₂ and NH₄HSO₄. Conditions for the formation and range of existence of these phases are discussed. The observed sulphate maxima are divided according to genetic and to some extent geographic origin of the particles into black and white episodes. Black episodes are associated with Continental air. They are accompanied by increased concentrations of nitrate, dark components and metals e.g. Mn. Particles characteristic of white episodes seem to occur in air masses of varying origin. The sulphate maxima in this category are usually accompanied by hydrogen ion maxima, and minima for nitrate, dark components and metals. The formation of particle-borne ions in an urban area (Gothenburg, population 500,000) was also studied. For sulphate, this local contribution was found to be 16% of the mean concentration. Processes which might lead to black and white episodes are discussed.     

Contribution of carbonaceous material to cloud condensation nuclei concentrations in European background (Mt. Sonnblick) and urban (Vienna) aerosols

During four intensive measurement campaigns (two on Mt. Sonnblick, European background aerosol, and two in Vienna, urban aerosol), cloud condensation nuclei (CCN) were measured at supersaturations of 0.5%. Impactor measurements of the mass size distribution in the size range 0.1–10 μm were performed and later analyzed for Cl^-, NO^-₃, SO^2-₄, Na⁺, NH⁺₄, K⁺, Ca²⁺ and Mg²⁺ by ion chromatography, for total carbon (TC) using a combustion method, and for black carbon (BC) by an optical method (integrating sphere). Organic carbon (OC) was defined as the difference between TC (minus carbonate carbon) and BC. At all sites, the mass fraction of BC in the submicron aerosol was comparable (4–5%). CCN concentrations on Mt. Sonnblick were found to be 10–30% of those measured in Vienna, although high Mt. Sonnblick concentrations were comparable to low Vienna concentrations (around 800 cm^-3). The contribution of organic material was estimated from the mass concentrations of the chemical species sampled on the impactor stage with the lowest cut point (0.1–0.215 μm aerodynamic equivalent diameter). On Mt. Sonnblick, TC material contributed 11% to the total mass in fall 1995, and 67% in summer 1996, while the OC fraction was 6 and 61%. The combined electrolytes and mineral material contributed 18 and 16% in fall and summer. During the Vienna spring campaign, the contributions of OC and electrolytes to the total mass concentration in this size range were 48 and 36%, respectively.     

Photochemical production and loss of organic acids in high Arctic aerosols during long-range transport and polar sunrise ozone depletion events

Unique daily measurements of water-soluble organics in fine (<2 μm) and coarse (>2 μm) aerosols were conducted at Alert in the Canadian Arctic in winter to spring of 1992. They yield insight into photochemical production and loss of organics during long-range transport and ozone depletion events following polar sunrise. Comprehensive analyses of α, ω-dicarboxylic acids (C₂–C₁₂), ω-oxocarboxylic acids (C₂–C₉) and α-dicarbonyls (C₂, C₃) as well as pyruvic acid and aromatic (phthalic) diacid were conducted using GC and GC/MS techniques. Oxalic (C₂) acid was generally the dominant diacid species in both fine and coarse fractions, followed by malonic (C₃) and succinic (C₄) acids. Concentrations of total diacids in the fine aerosol fraction (0.2–64 ng m⁻³) were 5–60 times higher than those in the coarse fraction (0.01–3 ng m⁻³). After polar sunrise in early-March, the total concentration of fine aerosol diacids increased by a factor of 3–5 while the coarse mode did not change significantly. From dark winter to sunlit spring, temporal changes in correlations and ratios of these water-soluble organics to vanadium and sulfate measured simultaneously suggest that atmospheric diacids and related organic compounds are largely controlled by long-range atmospheric transport of polluted air during winter, but they are significantly affected by photochemical production. The latter can occur in sunlight either during transport to the Arctic or during photochemical events associated with surface ozone depletion and bromine chemistry near Alert in spring. Conversion of gaseous precursors to particulate matter via photochemical oxidation was intensified at polar sunrise, resulting in a peak in the ratio of total diacids to V. During ozone depletion events, complex patterns are indicated in photochemical production and loss depending on the diacid compound. Unsaturated (maleic and phthalic) diacids were inversely correlated with particulate Br whereas saturated diacids (C₂–C₄) positively correlated with particulate Br. These results suggest that Br chemistry associated with ozone depletion leads to degradation of unsaturated diacids and to the production of smaller saturated diacids.     

Measurement of hydroxymethanesulfonate in atmospheric aerosols

Hydroxymethanesulfonate (HMS), a product of the heterogeneous reaction between S(IV) and HCHO, was measured in atmospheric aerosol samples collected at two locations indicating it can exist outside of clouds. Sampling was performed through collection with filters and analysis using ion chromatography with a treatment step to distinguish between HMS and uncomplexed S(IV). Concentrations of HMS were found to range from below the detection limit to 6.5 ng m^-3 for samples collected in central New Mexico in the summer and around 30 ng m^-3 for two samples collected in Seattle, Washington in the spring. Higher concentrations were associated with greater occurrence of clouds, which is the presumed source of the HMS. In the samples collected in Seattle, about half of the HMS was found associated with fine particles. In the central New Mexico samples, molar ratios of HMS to sulfate in particulate matter were found to be less than 0.002 indicating that HMS was a minor contributor of aerosol sulfur under the conditions of the measurements.     

Organic and inorganic components of aerosols over the central Himalayas: winter and summer variations in stable carbon and nitrogen isotopic composition

The aerosol samples were collected from a high elevation mountain site, Nainital, in India (1958 m asl) during September 2006 to June 2007 and were analyzed for water-soluble inorganic species, total carbon, nitrogen, and their isotopic composition (δ¹³C and δ¹⁵N, respectively). The chemical and isotopic composition of aerosols revealed significant anthropogenic influence over this remote free-troposphere site. The amount of total carbon and nitrogen and their isotopic composition suggest a considerable contribution of biomass burning to the aerosols during winter. On the other hand, fossil fuel combustion sources are found to be dominant during summer. The carbon aerosol in winter is characterized by greater isotope ratios (av. ?24.0?‰), mostly originated from biomass burning of C₄ plants. On the contrary, the aerosols in summer showed smaller δ¹³C values (?26.0?‰), indicating that they are originated from vascular plants (mostly of C₃ plants). The secondary ions (i.e., SO₄ ^2?, NH₄ ⁺, and NO₃ ^?) were abundant due to the atmospheric reactions during long-range transport in both seasons. The water-soluble organic and inorganic compositions revealed that they are aged in winter but comparatively fresh in summer. This study validates that the pollutants generated from far distant sources could reach high altitudes over the Himalayan region under favorable meteorological conditions.