Global S&T Development Trend Analysis Platform of Resources and Environment
DOI | 10.5194/acp-17-5107-2017 |
Inconsistency of ammonium-sulfate aerosol ratios with thermodynamic models in the eastern US: a possible role of organic aerosol | |
Silvern, Rachel F.1; Jacob, Daniel J.1,2; Kim, Patrick S.1; Marais, Eloise A.2,6; Turner, Jay R.3; Campuzano-Jost, Pedro4,5; Jimenez, Jose L.4,5 | |
2017-04-19 | |
发表期刊 | ATMOSPHERIC CHEMISTRY AND PHYSICS
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ISSN | 1680-7316 |
EISSN | 1680-7324 |
出版年 | 2017 |
卷号 | 17期号:8 |
文章类型 | Article |
语种 | 英语 |
国家 | USA; England |
英文摘要 | Thermodynamic models predict that sulfate aerosol (S(VI) + H2SO4(aq) + HSO4- + SO42-) should take up available ammonia (NH3) quantitatively as ammonium (NH4+) until the ammonium sulfate stoichiometry (NH4)(2)SO4 is close to being reached. This uptake of ammonia has important implications for aerosol mass, hygroscopicity, and acidity. When ammonia is in excess, the ammonium-sulfate aerosol ratio R =[NH4+] /[S(VI)] should approach 2, with excess ammonia remaining in the gas phase. When ammonia is in deficit, it should be fully taken up by the aerosol as ammonium and no significant ammonia should remain in the gas phase. Here we report that sulfate aerosol in the eastern US in summer has a low ammonium-sulfate ratio despite excess ammonia, and we show that this is at odds with thermodynamic models. The ammonium-sulfate ratio averages only 1.04 +/- 0.21 mol mol(-1) in the Southeast, even though ammonia is in large excess, as shown by the ammonium-sulfate ratio in wet deposition and by the presence of gas-phase ammonia. It further appears that the ammonium-sulfate aerosol ratio is insensitive to the supply of ammonia, remaining low even as the wet deposition ratio exceeds 6 mol mol(-1). While the ammonium-sulfate ratio in wet deposition has increased by 5.8% yr(-1) from 2003 to 2013 in the Southeast, consistent with SO2 emission controls, the ammonium-sulfate aerosol ratio decreased by 1.4-3.0% yr(-1). Thus, the aerosol is becoming more acidic even as SO2 emissions decrease and ammonia emissions stay constant; this is incompatible with simple sulfate-ammonium thermodynamics. A tentative explanation is that sulfate particles are increasingly coated by organic material, retarding the uptake of ammonia. Indeed, the ratio of organic aerosol (OA) to sulfate in the Southeast increased from 1.1 to 2.4 g g(-1) over the 2003-2013 period as sulfate decreased. We implement a simple kinetic mass transfer limitation for ammonia uptake to sulfate aerosols in the GEOS-Chem chemical transport model and find that we can reproduce both the observed ammonium-sulfate aerosol ratios and the concurrent presence of gas-phase ammonia. If sulfate aerosol becomes more acidic as OA / sulfate ratios increase, then controlling SO2 emissions to decrease sulfate aerosol will not have the co-benefit of suppressing acidcatalyzed secondary organic aerosol (SOA) formation. |
领域 | 地球科学 |
收录类别 | SCI-E |
WOS记录号 | WOS:000403958200005 |
WOS关键词 | SOUTHEASTERN UNITED-STATES ; LIQUID PHASE-SEPARATION ; 2013 SOUTHERN OXIDANT ; ATMOSPHERIC PARTICLES ; ANTHROPOGENIC EMISSIONS ; SATELLITE-OBSERVATIONS ; ELEMENTAL RATIO ; GROUND SITE ; MASS ; TRENDS |
WOS类目 | Environmental Sciences ; Meteorology & Atmospheric Sciences |
WOS研究方向 | Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/28345 |
专题 | 地球科学 |
作者单位 | 1.Harvard Univ, Dept Earth & Planetary Sci, 20 Oxford St, Cambridge, MA 02138 USA; 2.Harvard Univ, John A Paulson Sch Engn & Appl Sci, Cambridge, MA 02138 USA; 3.Washington Univ, Dept Energy Environm & Chem Engn, St Louis, MO USA; 4.Univ Colorado Boulder, Cooperat Inst Res Environm Sci, Boulder, CO USA; 5.Univ Colorado Boulder, Dept Chem & Biochem, Boulder, CO USA; 6.Univ Birmingham, Sch Geog Earth & Environm Sci, Edgbaston, England |
推荐引用方式 GB/T 7714 | Silvern, Rachel F.,Jacob, Daniel J.,Kim, Patrick S.,et al. Inconsistency of ammonium-sulfate aerosol ratios with thermodynamic models in the eastern US: a possible role of organic aerosol[J]. ATMOSPHERIC CHEMISTRY AND PHYSICS,2017,17(8). |
APA | Silvern, Rachel F..,Jacob, Daniel J..,Kim, Patrick S..,Marais, Eloise A..,Turner, Jay R..,...&Jimenez, Jose L..(2017).Inconsistency of ammonium-sulfate aerosol ratios with thermodynamic models in the eastern US: a possible role of organic aerosol.ATMOSPHERIC CHEMISTRY AND PHYSICS,17(8). |
MLA | Silvern, Rachel F.,et al."Inconsistency of ammonium-sulfate aerosol ratios with thermodynamic models in the eastern US: a possible role of organic aerosol".ATMOSPHERIC CHEMISTRY AND PHYSICS 17.8(2017). |
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