Hydroxyl radicals (OH) are a key species in atmospheric photochemistry. In the lower atmosphere, up to ~30% of the primary OH radical production is attributed to the photolysis of nitrous acid (HONO), and field observations suggest a large missing source of HONO. We show that soil nitrite can release HONO and explain the reported strength and diurnal variation of the missing source. Fertilized soils with low pH appear to be particularly strong sources of HONO and OH. Thus, agricultural activities and land-use changes may strongly influence the oxidizing capacity of the atmosphere. Because of the widespread occurrence of nitrite-producing microbes, the release of HONO from soil may also be important in natural environments, including forests and boreal regions.
Abstract. Heterogeneous reactions of mineral dust aerosol with trace gases in the atmosphere could directly and indirectly affect tropospheric oxidation capacity, in addition to aerosol composition and physicochemical properties. In this article we provide a comprehensive and critical review of laboratory studies of heterogeneous uptake of OH, NO 3 , O 3 , and their directly related species as well (including HO 2 , H 2 O 2 , HCHO, HONO, and N 2 O 5 ) by mineral dust particles. The atmospheric importance of heterogeneous uptake as sinks for these species is assessed (i) by comparing their lifetimes with respect to heterogeneous reactions with mineral dust to lifetimes with respect to other major loss processes and (ii) by discussing relevant field and modeling studies. We have also outlined major open questions and challenges in laboratory studies of heterogeneous uptake by mineral dust and discussed research strategies to address them in order to better understand the effects of heterogeneous reactions with mineral dust on tropospheric oxidation capacity.
Submicron aerosol (PM1) species measured by aerosol mass spectrometers have been widely used to validate chemical transport models; however, the uncertainties due to chemical differences between PM1 and PM2.5 are poorly constrained. Here we characterized such differences in a highly polluted environment in north China in winter. Our results showed that the changes in PM1/PM2.5 ratios as a function of relative humidity (RH) were largely different for primary and secondary species. Secondary organic and inorganic aerosol (SOA and SIA) presented clear decreases in PM1/PM2.5 ratios at RH > 60% during periods with high SIA contributions (>50%), likely driven by the changes in aerosol hygroscopicity and phase states, while the traffic and coal combustion OA had limited dependence on RH. Thermodynamic modeling showed negligible impacts of PM differences on predictions of particle acidity, yet these impacts can cause a difference in aerosol water content by up to 50–70%.
Abstract. The hygroscopicity of organic aerosol (OA) is important for investigation of its climatic and environmental impacts. However, the hygroscopicity parameter κOA remains poorly characterized, especially in the relatively polluted environment on the North China Plain (NCP). Here we conducted simultaneous wintertime measurements of bulk aerosol chemical compositions of PM2.5 and PM1 and bulk aerosol hygroscopicity of PM10 and PM1 on the NCP using a capture-vaporizer time-of-flight aerosol chemical speciation monitor (CV-ToF-ACSM) and a humidified nephelometer system which measures the aerosol light-scattering enhancement factor f(RH). A method for calculating κOA based on f(RH) and bulk aerosol chemical-composition measurements was developed. We found that κOA varied in a wide range with significant diurnal variations. The derived κOA ranged from almost 0.0 to 0.25, with an average (±1σ) of 0.08 (±0.06) for the entire study. The derived κOA was highly correlated with f44 (fraction of m∕z 44 in OA measured by CV-ToF-ACSM), an indicator of the oxidation degree of OA (R=0.79), and the relationship can be parameterized as κOA=1.04×f44-0.02 (κOA=0.3×O:C-0.02, based on the relationship between the f44 and O∕C ratio for CV-ToF-ACSM). On average, κOA reached the minimum (0.02) in the morning near 07:30 local time (LT) and then increased rapidly, reaching the peak value of 0.16 near 14:30 LT. The diurnal variations in κOA were highly and positively correlated with those of mass fractions of oxygenated OA (R=0.95), indicating that photochemical processing played a dominant role in the increase in κOA in winter on the NCP. Results in this study demonstrate the potential wide applications of a humidified nephelometer system together with aerosol composition measurements for investigating the hygroscopicity of OA in various environments and highlight that the parameterization of κOA as a function of OA aging processes needs to be considered in chemical transport models for better evaluating the impacts of OA on cloud formation, atmospheric chemistry, and radiative forcing.
Abstract. Particulate amines play an important role for the particle acidity and hygroscopicity and also contribute to secondary organic aerosol mass. We investigated the sources and mixing states of particulate amines using a single-particle aerosol mass spectrometer (SPAMS) during summer and winter 2014 at a rural site in the Pearl River Delta, China. Amine-containing particles accounted for 11.1 and 9.4 % of the total detected individual particles in summer and winter, respectively. Although the increase in amine-containing particle counts mostly occurred at night, no obvious correlations between amine-containing particles and ambient relative humidity (RH) were found during the sampling period. Among the three markers we considered, the most abundant amine marker was 74(C2H5)2NH2+, which was detected in 90 and 86 % of amine-containing particles in summer and winter, followed by amine marker ions of 59(CH3)3N+, and 86(C2H5)2NCH2+ which were detected in less than 10 % of amine-containing particles during sampling period. The amine-containing particles were characterized by high fractions of carbonaceous marker ions, carbon–nitrogen fragments, sulfate, and nitrate in both summer and winter. More than 90 % of amine-containing particles were found to be internally mixed with sulfate throughout the sampling period, while the percentage of amine particles containing nitrate increased from 43 % in summer to 69 % in winter. Robust correlations between the peak intensities of amines, sulfate, and nitrate were observed, suggesting the possible formation of aminium sulfate and nitrate salts. Interestingly, only 8 % of amine particles contained ammonium in summer, while the percentage increased dramatically to 54 % in winter, indicating a relatively ammonium-poor state in summer and an ammonium-rich state in winter. The total ammonium-containing particles were investigated and showed a much lower abundance in ambient particles in summer (3.6 %) than that in winter (32.6 %), which suggests the ammonium-poor state of amine-containing particles in summer may be related to the lower abundance of ammonia/ammonium in gas and particle phases. In addition, higher abundance of amines in ammonium-containing particles than that of ammonium in amine-containing particles suggests a possible contribution of ammonium–amine exchange reactions to the low abundance of ammonium in amine-containing particles at high ambient RH (72 ± 13 %) in summer. The particle acidity of amine-containing particles is estimated via the relative acidity ratio (Ra), which is defined as the ratio of the sum of the sulfate and nitrate peak areas divided by the ammonium peak area. The Ra was 326 ± 326 in summer and 31 ± 13 in winter, indicating that the amine-containing particles were more acidic in summer than in winter. However, after including amines along with the ammonium in the acidity calculation, the new Ra′ values showed no seasonal change in summer (11 ± 4) and winter (10 ± 2), which suggests that amines could be a buffer for the particle acidity of ammonium-poor particles.
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