Inland Concentrations of Cl2 and ClNO2 in Southeast Texas Suggest Chlorine Chemistry Significantly Contributes to Atmospheric Reactivity

被引：62

作者：

Faxon, Cameron B. ^{[1
]}

Bean, Jeffrey K. ^{[1
]}

Hildebrandt Ruiz, Lea ^{[1
]}

机构：

[1] Univ Texas Austin, Ctr Energy & Environm Resources, Austin, TX 78758 USA

来源：

ATMOSPHERE | 2015年 / 6卷 / 10期

关键词：

ambient observations; air quality; photochemistry; atomic chlorine; molecular chlorine; nitryl chloride; IONIZATION MASS-SPECTROMETER; URBAN OZONE FORMATION; GAS-PHASE REACTIONS; SEA-SALT AEROSOL; MOLECULAR CHLORINE; NITRYL CHLORIDE; HETEROGENEOUS REACTION; RATE CONSTANTS; ATOMS; N2O5;

D O I：

10.3390/atmos6101487

中图分类号：

X [环境科学、安全科学];

学科分类号：

08 ; 0830 ;

摘要：

Measurements of molecular chlorine (Cl-2), nitryl chloride (ClNO2), and dinitrogen pentoxide (N2O5) were taken as part of the DISCOVER-AQ Texas 2013 campaign with a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) using iodide (I-) as a reagent ion. ClNO2 concentrations exceeding 50 ppt were regularly detected with peak concentrations typically occurring between 7:00 a.m. and 10:00 am. Hourly averaged Cl-2 concentrations peaked daily between 3:00 p.m. and 4:00 p.m., with a 29-day average of 0.9 +/- 0.3 (1 sigma) ppt. A day-time Cl-2 source of up to 35 ppt.h(-1) is required to explain these observations, corresponding to a maximum chlorine radical (Cl-center dot) production rate of 70 ppt.h(-1). Modeling of the Cl-2 source suggests that it can enhance daily maximum O-3 and RO2 center dot concentrations by 8%-10% and 28%-50%, respectively. Modeling of observed ClNO2 assuming a well-mixed nocturnal boundary layer indicates O-3 and RO2 center dot enhancements of up to 2.1% and 38%, respectively, with a maximum impact in the early morning. These enhancements affect the formation of secondary organic aerosol and compliance with air quality standards for ozone and particulate matter.

引用

页码：1487 / 1506

页数：20

共 76 条

[41] Formation of molecular chlorine from the photolysis of ozone and aqueous sea-salt particles [J].

Oum, KW ;

Lakin, MJ ;

DeHaan, DO ;

Brauers, T ;

Finlayson-Pitts, BJ .

SCIENCE, 1998, 279 (5347) :74-77

[42] Significant concentrations of nitryl chloride observed in rural continental Europe associated with the influence of sea salt chloride and anthropogenic emissions [J].

Phillips, G. J. ;

Tang, M. J. ;

Thieser, J. ;

Brickwedde, B. ;

Schuster, G. ;

Bohn, B. ;

Lelieveld, J. ;

Crowley, J. N. .

GEOPHYSICAL RESEARCH LETTERS, 2012, 39

[43] Observation of playa salts as nuclei in orographic wave clouds [J].

Pratt, Kerri A. ;

Twohy, Cynthia H. ;

Murphy, Shane M. ;

Moffet, Ryan C. ;

Heymsfield, Andrew J. ;

Gaston, Cassandra J. ;

DeMott, Paul J. ;

Field, Paul R. ;

Henn, Tobias R. ;

Rogers, David C. ;

Gilles, Mary K. ;

Seinfeld, John H. ;

Prather, Kimberly A. .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 2010, 115

[44] EVIDENCE OF INORGANIC CHLORINE GASES OTHER THAN HYDROGEN-CHLORIDE IN MARINE SURFACE AIR [J].

PSZENNY, AAP ;

KEENE, WC ;

JACOB, DJ ;

FAN, S ;

MABEN, JR ;

ZETWO, MP ;

SPRINGERYOUNG, M ;

GALLOWAY, JN .

GEOPHYSICAL RESEARCH LETTERS, 1993, 20 (08) :699-702

[45] Kinetics and mechanism of the reaction of Cl atoms with 2-methyl-1,3-butadiene (isoprene) at 298 K [J].

Ragains, ML ;

FinlaysonPitts, BJ .

JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (08) :1509-1517

[46] Chlorine activation within urban or power plant plumes: Vertically resolved ClNO2 and Cl2 measurements from a tall tower in a polluted continental setting [J].

Riedel, Theran P. ;

Wagner, Nicholas L. ;

Dube, William P. ;

Middlebrook, Ann M. ;

Young, Cora J. ;

Ozturk, Fatma ;

Bahreini, Roya ;

VandenBoer, Trevor C. ;

Wolfe, Daniel E. ;

Williams, Eric J. ;

Roberts, James M. ;

Brown, Steven S. ;

Thornton, Joel A. .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 2013, 118 (15) :8702-8715

[47] Nitryl Chloride and Molecular Chlorine in the Coastal Marine Boundary Layer [J].

Riedel, Theran P. ;

Bertram, Timothy H. ;

Crisp, Timia A. ;

Williams, Eric J. ;

Lerner, Brian M. ;

Vlasenko, Alexander ;

Li, Shao-Meng ;

Gilman, Jessica ;

de Gouw, Joost ;

Bon, Daniel M. ;

Wagner, Nicholas L. ;

Brown, Steven S. ;

Thornton, Joel A. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2012, 46 (19) :10463-10470

[48] N2O5 oxidizes chloride to Cl2 in acidic atmospheric aerosol [J].

Roberts, James M. ;

Osthoff, Hans D. ;

Brown, Steven S. ;

Ravishankara, A. R. .

SCIENCE, 2008, 321 (5892) :1059-1059

[49] Laboratory studies of products of N2O5 uptake on Cl- containing substrates [J].

Roberts, James M. ;

Osthoff, Hans D. ;

Brown, Steven S. ;

Ravishankara, A. R. ;

Coffman, Derek ;

Quinn, Patricia ;

Bates, Timothy .

GEOPHYSICAL RESEARCH LETTERS, 2009, 36

[50] Formation of molecular chlorine in dark condition: Heterogeneous reaction of ozone with sea salt in the presence of ferric ion [J].

Sadanaga, Y ;

Hirokawa, J ;

Akimoto, H .

GEOPHYSICAL RESEARCH LETTERS, 2001, 28 (23) :4433-4436

← 1 2 3 4 5 6 7 8 →