Nighttime removal of NOx in the summer marine boundary layer

Brown, Steven S.; Dibb, Jack E.; Stark, Harald; Aldener, M.; Vozella, M.; Whitlow, Sallie I.; Williams, E. J.; Lerner, B. M.; Jakoubek, R.; Middlebrook, A. M.; Gouw, J. A. de; Warneke, C.; Goldan, P. D.; Kuster, W. C.; Angevine, W. M.; Sueper, D.; Quinn, Patricia K.; Bates, T. S.; Meagher, James F.; Fehsenfeld, F. C.; Ravishankara, A. R.

doi:10.1029/2004gl019412

Cited by 148 publications

(162 citation statements)

References 22 publications

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“…In addition; nighttime secondary NO 3 − formation involves the hydrolysis of dinitrogen-pentaoxide (N 2 O 5 ) through the heterogeneous reaction on aerosol surfaces and higher relative humidity enhances the heterogeneous hydrolysis of N 2 O 5 (Ravishankara et al, 1997;Jacob, 2000;Pathak et al, 2009). Brown et al (2004) have suggested that the conversion efficiency of NO x to HNO 3 during nighttime can be equivalent to the daytime photochemical conversion. Moreover, Vrekoussis et al (2006) have found that ~55-65% of the total production of nighttime HNO 3 and NO 3 − were through the heterogeneous reactions of NO 3 radical in an anthropogenically-influenced eastern Mediterranean marine boundary layer.…”

Section: Sulphur and Nitrogen Oxidation Ratios (Sor And Nor)mentioning

confidence: 99%

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the Indo-Gangetic Plain

Ram

Sarin

Sudheer

et al. 2012

Aerosol Air Qual. Res.

137

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The chemical composition of total suspended particulate (TSP) matter and secondary aerosol formation have been studied during wintertime fog and haze events from urban sites (Allahabad and Hisar) in the Indo-Gangetic Plain. The atmospheric abundances of elemental carbon (EC), organic carbon (OC), water-soluble OC (WSOC) suggest that organic matter is a major component of TSP, followed by concentrations of sulphate and nitrate under varying meteorological conditions. The concentrations of EC, OC, and WSOC show a nearly 30% increase during fog and haze events at Allahabad and a marginal increase at Hisar; whereas inorganic constituents (NH 4 + , NO 3 − and SO 4 2− ) are 2-3 times higher than those during clear days at both the locations. The sulphur and nitrogen oxidation ratios (SOR and NOR) also exhibit significant increases suggesting possible enhancement of secondary formation of SO 4 2− and NO 3 − during fog and haze events. The significant correlation between NH 4 + -SO 4 2− (R 2 = 0.66, n = 61) and an NH 4 + /SO 4 2− equivalent ratio ≥ 1 during fog-haze conditions suggest nearcomplete neutralization of sulphuric acid by ammonia. In contrast, NH 4 + /SO 4 2− equivalent ratios are less than 1 during normal days suggesting an NH 3 -deficient environment and the possible association of SO 4 2− with mineral dust for neutralization. Secondary inorganic aerosol formation and their hygroscopic growth can have significant impact on atmospheric chemistry, air-quality and visibility impairment during fog-haze events over northern India.

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Section: Sulphur and Nitrogen Oxidation Ratios (Sor And Nor)mentioning

confidence: 99%

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the Indo-Gangetic Plain

Ram

Sarin

Sudheer

et al. 2012

Aerosol Air Qual. Res.

137

View full text Add to dashboard Cite

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“…Measurements of NO 3 have been overestimated by model calculations in several studies (Mihelcic et al, 1993;Sommariva et al, , 2007, with those of nighttime OH and HO 2 radicals typically underestimated, indicating poor understanding of nighttime tropospheric oxidation processes (Kanaya et al, 1999(Kanaya et al, , 2002(Kanaya et al, , 2007aEmmerson and Carslaw, 2009;Geyer et al, 2003;Faloona et al, 2001;Martinez et al, 2003;Ren et al, 2006). While a number of nighttime studies at ground level close to local sources of NO have observed a limited role of NO 3 in nighttime radical production owing to surface losses of NO 3 and the rapid reaction between NO 3 and NO (Salisbury et al, 2001;Fleming et al, 2006;Sommariva et al, 2007;Kanaya et al, 1999Kanaya et al, , 2002Kanaya et al, , 2007aEmmerson and Carslaw, 2009;Faloona et al, 2001;Martinez et al, 2003;Ren et al, 2003Ren et al, , 2005Ren et al, , 2006Volkamer et al, 2010), several studies of NO 3 and N 2 O 5 above ground level and in more remote regions have indicated a more significant role for NO 3 in nighttime radical production and tropospheric oxidation (Platt et al, 1980;Povey et al, 1998;South et al, 1998;Aliwell et al, 1998;Allan et al, 2002;Stutz et al, 2004;Brown et al, 2003Brown et al, , 2004Brown et al, , 2006Brown et al, , 2007Brown et al, , 2009...…”

Section: Introductionmentioning

confidence: 99%

“…Measurements of NO 3 and N 2 O 5 were made downwind of New York City during the New England Air Quality Study (NEAQS) by cavity ringdown spectroscopy (CRDS) onboard the National Oceanic and Atmospheric Administration (NOAA) research vessel (R/V) Ronald H. Brown in summers 2002 Brown et al, 2004;Aldener et al, 2006) and 2004 . While measurements of nighttime composition in New York City led to the conclusion that O 3 -initiated oxidation processes were dominant at night (Ren et al, 2003(Ren et al, , 2006, those made during NEAQS indicated little influence of O 3 -initiated VOC oxidation at night, with oxidation of biogenic VOCs dominated by NO 3 .…”

Section: Introductionmentioning

confidence: 99%

Radical chemistry at night: comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project

et al. 2014

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Abstract. The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO 2 , NO 3 , N 2 O 5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO 2 by ∼ 200 % and overpredicts NO 3 and N 2 O 5 by around 80 and 50 %, respectively. Cycling between NO 3 and N 2 O 5 is fast and thus we define the NO 3x (NO 3x = NO 3 + N 2 O 5 ) family. Production of NO 3x is overwhelmingly dominated by the reaction of NO 2 with O 3 , whereas its loss is dominated by aerosol uptake of N 2 O 5 , with NO 3 + VOCs (volatile organic compounds) and NO 3 + RO 2 playing smaller roles. The production of HO x and RO x radicals is mainly due to the reaction of NO 3 with VOCs. The loss of these radicals occurs through a combination of HO 2 + RO 2 reactions, heterogeneous processes and production of HNO 3 from OH + NO 2 , with radical propagation primarily achieved through reactions of NO 3 with peroxy radicals. Thus NO 3 at night plays a similar role to both OH and NO during the day in that it both initiates RO x radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N 2 O 5 aerosol uptake coefficient (γ N 2 O 5 ) is discussed and we find that a value of γ N 2 O 5 = 0.05 improves model simulations for NO 3 and N 2 O 5 , but that these improvements are at the expense of model success for HO 2 . Improvements to model simulations for HO 2 , NO 3 and N 2 O 5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

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“…The concentration of NO x varies from > 100 ppb (parts per billion) next to roads (Carslaw, 2005;Pandey et al, 2008) to low ppt (parts per trillion) in the remote atmosphere . Direct transport of NO x from polluted to remote regions is not efficient, because NO x is removed from the atmosphere on a timescale of around a day by the reaction of NO 2 with OH and the hydrolysis of N 2 O 5 on aerosol surfaces (Brown et al, 2004;Dentener and Crutzen, 1993;Riemer et al, 2003). Instead, reservoir species such as peroxyacetyl nitrate are made in polluted regions (where concentrations in both NO x and peroxyacetyl precursors such as acetaldehyde are elevated) and are subsequently transported to remote regions, where they thermally break down to release NO x (Fischer et al, 2014;Moxim et al, 1996;Roberts et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

Interferences in photolytic NO2 measurements: explanation for an apparent missing oxidant?

et al. 2016

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Abstract. Measurement of NO 2 at low concentrations (tens of ppts) is non-trivial. A variety of techniques exist, with the conversion of NO 2 into NO followed by chemiluminescent detection of NO being prevalent. Historically this conversion has used a catalytic approach (molybdenum); however, this has been plagued with interferences. More recently, photolytic conversion based on UV-LED irradiation of a reaction cell has been used. Although this appears to be robust there have been a range of observations in low-NO x environments which have measured higher NO 2 concentrations than might be expected from steady-state analysis of simultaneously measured NO, O 3 , j NO 2 , etc. A range of explanations exist in the literature, most of which focus on an unknown and unmeasured "compound X" that is able to convert NO to NO 2 selectively. Here we explore in the laboratory the interference on the photolytic NO 2 measurements from the thermal decomposition of peroxyacetyl nitrate (PAN) within the photolysis cell. We find that approximately 5 % of the PAN decomposes within the instrument, providing a potentially significant interference. We parameterize the decomposition in terms of the temperature of the light source, the ambient temperature, and a mixing timescale (∼ 0.4 s for our instrument) and expand the parametric analysis to other atmospheric compounds that decompose readily to NO 2 (HO 2 NO 2 , N 2 O 5 , CH 3 O 2 NO 2 , IONO 2 , BrONO 2 , higher PANs). We apply these parameters to the output of a global atmospheric model (GEOS-Chem) to investigate the global impact of this interference on (1) the NO 2 measurements and (2) the NO 2 : NO ratio, i.e. the Leighton relationship. We find that there are significant interferences in cold regions with low NO x concentrations such as the Antarctic, the remote Southern Hemisphere, and the upper troposphere. Although this interference is likely instrument-specific, the thermal decomposition to NO 2 within the instrument's photolysis cell could give an at least partial explanation for the anomalously high NO 2 that has been reported in remote regions. The interference can be minimized by better instrument characterization, coupled to instrumental designs which reduce the heating within the cell, thus simplifying interpretation of data from remote locations.

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Nighttime removal of NO_x in the summer marine boundary layer

Cited by 148 publications

References 22 publications

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the Indo-Gangetic Plain

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the Indo-Gangetic Plain

Radical chemistry at night: comparisons between observed and modelled HO<sub>x</sub>, NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> during the RONOCO project

Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?

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Nighttime removal of NOx in the summer marine boundary layer

Cited by 148 publications

References 22 publications

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the Indo-Gangetic Plain

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the Indo-Gangetic Plain

Radical chemistry at night: comparisons between observed and modelled HO&lt;sub&gt;x&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt; and N&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; during the RONOCO project

Interferences in photolytic NO&lt;sub&gt;2&lt;/sub&gt; measurements: explanation for an apparent missing oxidant?

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Nighttime removal of NO_x in the summer marine boundary layer

Radical chemistry at night: comparisons between observed and modelled HO<sub>x</sub>, NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> during the RONOCO project

Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?