Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer

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Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer. / Kasibhatla, Prasad; Sherwen, Tomás; Evans, Mathew J.; Carpenter, Lucy J.; Reed, Chris; Alexander, Becky; Chen, Qianjie; Sulprizio, Melissa P.; Lee, James D.; Read, Katie A.; Bloss, William; Crilley, Leigh R.; Keene, William C.; Pszenny, Alexander A.P.; Hodzic, Alma.

In: Atmospheric Chemistry and Physics, Vol. 18, No. 15, 10.08.2018, p. 11185-11203.

Research output: Contribution to journalArticle

Harvard

Kasibhatla, P, Sherwen, T, Evans, MJ, Carpenter, LJ, Reed, C, Alexander, B, Chen, Q, Sulprizio, MP, Lee, JD, Read, KA, Bloss, W, Crilley, LR, Keene, WC, Pszenny, AAP & Hodzic, A 2018, 'Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer', Atmospheric Chemistry and Physics, vol. 18, no. 15, pp. 11185-11203. https://doi.org/10.5194/acp-18-11185-2018

APA

Kasibhatla, P., Sherwen, T., Evans, M. J., Carpenter, L. J., Reed, C., Alexander, B., ... Hodzic, A. (2018). Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer. Atmospheric Chemistry and Physics, 18(15), 11185-11203. https://doi.org/10.5194/acp-18-11185-2018

Vancouver

Author

Kasibhatla, Prasad ; Sherwen, Tomás ; Evans, Mathew J. ; Carpenter, Lucy J. ; Reed, Chris ; Alexander, Becky ; Chen, Qianjie ; Sulprizio, Melissa P. ; Lee, James D. ; Read, Katie A. ; Bloss, William ; Crilley, Leigh R. ; Keene, William C. ; Pszenny, Alexander A.P. ; Hodzic, Alma. / Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer. In: Atmospheric Chemistry and Physics. 2018 ; Vol. 18, No. 15. pp. 11185-11203.

Bibtex

@article{9da07a73412743a5bbc4463de16b26b4,
title = "Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer",
abstract = "Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer (MBL) using the GEOS-Chem model, after first updating the model to better simulate observed gas-particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25-50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurements of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5 to 20 for NOx, 1.2 to 1.6 for OH, and 1.1 to 1.3 for ozone. Since the spatial extent of the sea-salt aerosol (SSA) impact is limited, global impacts on NOx, ozone, and OH mass burdens are small ( ∼ 1-3 {\%}). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry.",
author = "Prasad Kasibhatla and Tom{\'a}s Sherwen and Evans, {Mathew J.} and Carpenter, {Lucy J.} and Chris Reed and Becky Alexander and Qianjie Chen and Sulprizio, {Melissa P.} and Lee, {James D.} and Read, {Katie A.} and William Bloss and Crilley, {Leigh R.} and Keene, {William C.} and Pszenny, {Alexander A.P.} and Alma Hodzic",
year = "2018",
month = "8",
day = "10",
doi = "10.5194/acp-18-11185-2018",
language = "English",
volume = "18",
pages = "11185--11203",
journal = "Atmospheric Chemistry and Physics",
issn = "1680-7316",
publisher = "Copernicus Publications",
number = "15",

}

RIS

TY - JOUR

T1 - Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer

AU - Kasibhatla, Prasad

AU - Sherwen, Tomás

AU - Evans, Mathew J.

AU - Carpenter, Lucy J.

AU - Reed, Chris

AU - Alexander, Becky

AU - Chen, Qianjie

AU - Sulprizio, Melissa P.

AU - Lee, James D.

AU - Read, Katie A.

AU - Bloss, William

AU - Crilley, Leigh R.

AU - Keene, William C.

AU - Pszenny, Alexander A.P.

AU - Hodzic, Alma

PY - 2018/8/10

Y1 - 2018/8/10

N2 - Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer (MBL) using the GEOS-Chem model, after first updating the model to better simulate observed gas-particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25-50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurements of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5 to 20 for NOx, 1.2 to 1.6 for OH, and 1.1 to 1.3 for ozone. Since the spatial extent of the sea-salt aerosol (SSA) impact is limited, global impacts on NOx, ozone, and OH mass burdens are small ( ∼ 1-3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry.

AB - Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer (MBL) using the GEOS-Chem model, after first updating the model to better simulate observed gas-particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25-50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurements of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5 to 20 for NOx, 1.2 to 1.6 for OH, and 1.1 to 1.3 for ozone. Since the spatial extent of the sea-salt aerosol (SSA) impact is limited, global impacts on NOx, ozone, and OH mass burdens are small ( ∼ 1-3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry.

UR - http://www.scopus.com/inward/record.url?scp=85051437066&partnerID=8YFLogxK

U2 - 10.5194/acp-18-11185-2018

DO - 10.5194/acp-18-11185-2018

M3 - Article

AN - SCOPUS:85051437066

VL - 18

SP - 11185

EP - 11203

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

SN - 1680-7316

IS - 15

ER -