scholarly journals Significant concentrations of nitryl chloride sustained in the morning: Investigations of the causes and impacts on ozone production in a polluted region of northern China

2016 ◽  
Author(s):  
Yee Jun Tham ◽  
Zhe Wang ◽  
Qinyi Li ◽  
Hui Yun ◽  
Weihao Wang ◽  
...  
Keyword(s):  
Inversion Layer ◽  
Northern China ◽  
Residual Layer ◽  
Ozone Production ◽  
Rural Site ◽  
Ionization Mass ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Nocturnal Inversion

Abstract. Nitryl chloride (ClNO2) is a dominant source of chlorine radical in polluted environment and can significantly affect the atmospheric oxidative chemistry. However, the abundance of ClNO2 and its exact role are not fully understood under different environmental conditions. During the summer of 2014, we deployed a chemical ionization mass spectrometer to measure ClNO2 and dinitrogen pentoxide (N2O5) at a rural site in the polluted North China Plain. Elevated mixing ratios of ClNO2 (> 350 pptv) were observed at most of the nights with low levels of N2O5 (< 200 pptv). The highest ClNO2 mixing ratio of 2070 pptv (1-min average) was observed in a plume from megacity (Tianjin) and was characterized with faster N2O5 heterogeneous loss rate and ClNO2 production rate compared to average condition. The abundant ClNO2 concentration kept increasing even after sunrise and reached a peak 4 hours later. Such highly sustained ClNO2 peaks after sunrise are discrepant from the previously observed typical diurnal pattern. Meteorological and chemical analysis show that the sustained ClNO2 morning peaks are caused by significant ClNO2 production in the residual layer at night followed by downward mixing after break-up of the nocturnal inversion layer in the morning. We estimated that ~ 1.7–4.0 ppbv of ClNO2 would exist in the residual layer in order to maintain the observed morning ClNO2 peaks at the surface site. Observation-based box model analysis show that photolysis of ClNO2 produced chlorine radical with a rate up to 1.12 ppbv h−1, accounting for 10–30 % of primary ROx production in the morning hours. The perturbation in total radical production leads to an increase of integrated daytime net ozone production by 3 % (4.3 ppbv) on average, and with a larger increase of 13 % (11 ppbv) in megacity outflow that was characterized with higher ClNO2 and relatively lower OVOC to NMHC ratio.

scholarly journals Significant concentrations of nitryl chloride sustained in the morning: investigations of the causes and impacts on ozone production in a polluted region of northern China

2016 ◽  
Vol 16 (23) ◽  
pp. 14959-14977 ◽  
Author(s):  
Yee Jun Tham ◽  
Zhe Wang ◽  
Qinyi Li ◽  
Hui Yun ◽  
Weihao Wang ◽  
...  
Keyword(s):  
Inversion Layer ◽  
Northern China ◽  
Residual Layer ◽  
Ozone Production ◽  
Rural Site ◽  
Ionization Mass ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Nocturnal Inversion

Abstract. Nitryl chloride (ClNO2) is a dominant source of chlorine radical in polluted environment, and can significantly affect the atmospheric oxidative chemistry. However, the abundance of ClNO2 and its exact role are not fully understood under different environmental conditions. During the summer of 2014, we deployed a chemical ionization mass spectrometer to measure ClNO2 and dinitrogen pentoxide (N2O5) at a rural site in the polluted North China Plain. Elevated mixing ratios of ClNO2 (> 350 pptv) were observed at most of the nights with low levels of N2O5 (< 200 pptv). The highest ClNO2 mixing ratio of 2070 pptv (1 min average) was observed in a plume from a megacity (Tianjin), and was characterized with a faster N2O5 heterogeneous loss rate and ClNO2 production rate compared to average conditions. The abundant ClNO2 concentration kept increasing even after sunrise, and reached a peak 4 h later. Such highly sustained ClNO2 peaks after sunrise are discrepant from the previously observed typical diurnal pattern. Meteorological and chemical analysis shows that the sustained ClNO2 morning peaks are caused by significant ClNO2 production in the residual layer at night followed by downward mixing after breakup of the nocturnal inversion layer in the morning. We estimated that  ∼  1.7–4.0 ppbv of ClNO2 would exist in the residual layer in order to maintain the observed morning ClNO2 peaks at the surface site. Observation-based box model analysis show that photolysis of ClNO2 produced chlorine radical with a rate up to 1.12 ppbv h−1, accounting for 10–30 % of primary ROx production in the morning hours. The perturbation in total radical production leads to an increase of integrated daytime net ozone production by 3 % (4.3 ppbv) on average, and with a larger increase of 13 % (11 ppbv) in megacity outflow that was characterized with higher ClNO2 and a relatively lower oxygenated hydrocarbon (OVOC) to non-methane hydrocarbon (NMHC) ratio.

scholarly journals Production of N<sub>2</sub>O<sub>5</sub> and ClNO<sub>2</sub> in summer in urban Beijing, China

2018 ◽  
Vol 18 (16) ◽  
pp. 11581-11597 ◽  
Author(s):  
Wei Zhou ◽  
Jian Zhao ◽  
Bin Ouyang ◽  
Archit Mehra ◽  
Weiqi Xu ◽  
...  
Keyword(s):  
Urban Areas ◽  
Product Formation ◽  
High Reactivity ◽  
Ionization Mass ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Volatile Organic ◽  
Beijing China ◽  
Hydrolysis Of

Abstract. The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) has a significant impact on both nocturnal particulate nitrate formation and photochemistry on the following day through the photolysis of nitryl chloride (ClNO2), yet these processes in highly polluted urban areas remain poorly understood. Here we present measurements of gas-phase N2O5 and ClNO2 by high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) during summer in urban Beijing, China as part of the Air Pollution and Human Health (APHH) campaign. N2O5 and ClNO2 show large day-to-day variations with average (±1σ) mixing ratios of 79.2±157.1 and 174.3±262.0 pptv, respectively. High reactivity of N2O5, with τ (N2O5)−1 ranging from 0.20 × 10−2 to 1.46 × 10−2 s−1, suggests active nocturnal chemistry and a large nocturnal nitrate formation potential via N2O5 heterogeneous uptake. The lifetime of N2O5, τ (N2O5), decreases rapidly with the increase in aerosol surface area, yet it varies differently as a function of relative humidity with the highest value peaking at ∼ 40 %. The N2O5 uptake coefficients estimated from the product formation rates of ClNO2 and particulate nitrate are in the range of 0.017–0.19, corresponding to direct N2O5 loss rates of 0.00044–0.0034 s−1. Further analysis indicates that the fast N2O5 loss in the nocturnal boundary layer in urban Beijing is mainly attributed to its indirect loss via NO3, for example through the reactions with volatile organic compounds and NO, while the contribution of the heterogeneous uptake of N2O5 is comparably small (7–33 %). High ClNO2 yields ranging from 0.10 to 0.35 were also observed, which might have important implications for air quality by affecting nitrate and ozone formation.

scholarly journals Speciated mercury at marine, coastal, and inland sites in New England – Part 1: Temporal variability

2011 ◽  
Vol 11 (12) ◽  
pp. 32301-32336 ◽  
Author(s):  
H. Mao ◽  
R. Talbot
Keyword(s):  
New England ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Inversion Layer ◽  
Warm Season ◽  
Elemental Mercury ◽  
Rural Site ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
Nocturnal Inversion

Abstract. A comprehensive analysis was conducted using long-term continuous measurements of gaseous elemental mercury (Hgo), reactive mercury (RGM), and particulate phase mercury (HgP) at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland (Pac Monadnock, denoted as PM) sites from the AIRMAP Observatories. Decreasing trends in background Hgo were identified in the 7- and 5-yr records at TF and PM with decline rates of 3.3 parts per quadrillion by volume (ppqv) yr−1 and 6.3 ppqv yr−1, respectively. Common characteristics at these sites were the reproducible annual cycle of Hgo with its maximum in winter-spring and minimum in fall as well as a decline/increase trend in the warm/cool season. The coastal site TF differed from the other two sites with its exceptionally low levels (as low as below 50 ppqv) in the nocturnal inversion layer probably due to dissolution in dew water. Year-to-year variability was observed in the warm season decline in Hgo at TF varying from a minimum total seasonal loss of 20 ppqv in 2010 to a maximum of 92 ppqv in 2005, whereas variability remained small at AI and PM. Measurements of Hgo at PM, an elevated inland rural site, exhibited the smallest diurnal to annual variability among the three environments, where peak levels rarely exceeded 250 ppqv and the minimum was typically 100 ppqv. It should be noted that summertime diurnal patterns at TF and AI are opposite in phase indicating strong sink(s) for Hgo during the day in the marine boundary layer, which is consistent with the hypothesis of Hgo oxidation by halogen radicals there. Mixing ratios of RGM in the coastal and marine boundary layers reached annual maximum in spring and minimum in fall, whereas at PM levels were generally below the limit of detection (LOD) except in spring. RGM levels at AI were higher than at TF and PM indicating a stronger source strength(s) in the marine environment. Mixing ratios of HgP at AI and TF were close in magnitude to RGM levels and were mostly below 1 ppqv. Diurnal variation in HgP was barely discernible at TF and AI in spring and summer with higher levels during the day and smaller but above the LOD at night.

scholarly journals Urban inland wintertime N<sub>2</sub>O<sub>5</sub> and ClNO<sub>2</sub> influenced by snow-covered ground, air turbulence, and precipitation

2021 ◽  
Author(s):  
Kathryn D. Kulju ◽  
Stephen M. McNamara ◽  
Qianjie Chen ◽  
Jacinta Edebeli ◽  
Jose D. Fuentes ◽  
...  
Keyword(s):  
Ground Cover ◽  
Atmospheric Particulate Matter ◽  
Ionization Mass ◽  
Bare Ground ◽  
Near Surface ◽  
Dinitrogen Pentoxide ◽  
Nitryl Chloride ◽  
Air Turbulence ◽  
Chlorine Radicals ◽  
Wet Scavenging

Abstract. The atmospheric multiphase reaction of dinitrogen pentoxide (N2O5) with chloride-containing aerosol particles produces nitryl chloride (ClNO2), which has been observed across the globe. The photolysis of ClNO2 produces chlorine radicals and nitrogen dioxide (NO2), which alter pollutant fates and air quality. However, the effects of local meteorology on near-surface ClNO2 production are not yet well understood, as most observational and modeling studies focus on periods of clear conditions. During a field campaign in Kalamazoo, Michigan from January–February 2018, N2O5 and ClNO2 were measured using chemical ionization mass spectrometry, with simultaneous measurements of atmospheric particulate matter and meteorological parameters. We examine the impacts of atmospheric turbulence, precipitation (snow, rain) and fog, and ground cover (snow-covered and bare ground) on the abundances of ClNO2 and N2O5. N2O5 mole ratios were lowest during periods of lower turbulence and were not statistically significantly different between snow-covered and bare ground. In contrast, ClNO2 mole ratios were highest, on average, over snow-covered ground, due to saline snowpack ClNO2 production. Both N2O5 and ClNO2 mole ratios were lowest, on average, during rainfall and fog because of scavenging, with N2O5 scavenging by fog droplets likely contributing to observed increased particulate nitrate concentrations. These observations, specifically those during active precipitation and with snow-covered ground, highlight important processes, including N2O5 and ClNO2 wet scavenging, fog nitrate production, and snowpack ClNO2 production, that govern the variability in observed atmospheric chlorine and nitrogen chemistry and are missed when considering only clear conditions.

scholarly journals High concentrations of N<sub>2</sub>O<sub>5</sub> and NO<sub>3</sub> observed in daytime with a TD-CIMS: chemical interference or a real atmospheric phenomenon?

2013 ◽  
Vol 6 (4) ◽  
pp. 7473-7504
Author(s):  
X. Wang ◽  
T. Wang ◽  
C. Yan ◽  
Y. J. Tham ◽  
L. Xue ◽  
...  
Keyword(s):  
Hong Kong ◽  
Atmospheric Chemistry ◽  
Thermal Dissociation ◽  
Measurement Techniques ◽  
Urban Site ◽  
Ionization Mass ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
High Concentrations ◽  
Interference Tests

Abstract. Dinitrogen pentoxide (N2O5) and the nitrate radical (NO3) play important roles in atmospheric chemistry, yet accurate measurements of their concentrations remain challenging. A thermal dissociation chemical ionization mass spectrometer (TD-CIMS) was deployed to an urban site in Hong Kong to measure the sum of N2O5 and NO3 in autumn 2010. To our surprise, very high concentrations of N2O5 + NO3 were frequently observed in daytime, with mixing ratios in the range of 200–1000 pptv. To investigate this unusual phenomenon, various interference tests and measurements with different instrument configuration were conducted. It was found that peroxy acetyl nitrate (PAN) contributed to measurable signals at 62 amu, and more importantly, this interference increased significantly with co-existence of NO2. Nitric acid (HNO3), on the other hand, had little interference to the detection of N2O5/NO3 via the NO3− ion in our TD-CIMS. According to the test results, the interference from PAN and NO2 could have contributed to 30–50% of the average daytime (12:00–16:00 LT) N2O5 + NO3 signal at our site. However, evidence exists for the presence of elevated daytime N2O5, in addition to the daytime signal at 62 amu. This includes: (1) daytime N2O5 measured via the I(N2O5)− cluster ion with an unheated inlet, which subjects to minimum interferences, and (2) observation of elevated daytime ClNO2 (a product of N2O5 hydrolysis) during a follow-up study. In view of the difficulty in accurately quantifying the contribution from the interferences of PAN and NO2 and un-tested potential interfering chemicals in the real atmosphere, we caution the use of 62 amu in the TD-CIMS for measuring ambient N2O5 in a high NOx environment like Hong Kong. Additional studies are needed to re-examine the daytime issue using other measurement techniques.

scholarly journals Speciated mercury at marine, coastal, and inland sites in New England – Part 1: Temporal variability

2012 ◽  
Vol 12 (11) ◽  
pp. 5099-5112 ◽  
Author(s):  
H. Mao ◽  
R. Talbot
Keyword(s):  
New England ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Inversion Layer ◽  
Warm Season ◽  
Elemental Mercury ◽  
Positive Trend ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
Nocturnal Inversion

Abstract. A comprehensive analysis was conducted using long-term continuous measurements of gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate phase mercury (HgP) at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland (Pac Monadnock, denoted as PM) sites from the AIRMAP Observatories in southern New Hampshire, USA. Decreasing trends in background Hg0 were identified in the 7.5- and 5.5-yr records at TF and PM with decline rates of 3.3 parts per quadrillion by volume (ppqv) yr−1 and 6.3 ppqv yr−1, respectively. Common characteristics at these sites were the reproducible annual cycle of Hg0 with its maximum in winter-spring and minimum in fall, comprised of a positive trend in the warm season (spring – early fall) and a negative one in the cool season (late fall – winter). Year-to-year variability was observed in the warm season decline in Hg0 at TF varying from a minimum total (complete) seasonal loss of 43 ppqv in 2009 to a maximum of 92 ppqv in 2005, whereas variability remained small at AI and PM. The coastal site TF differed from the other two sites with its exceptionally low levels (as low as below 50 ppqv) in the nocturnal inversion layer possibly due to dissolution in dew water. Measurements of Hg0 at PM exhibited the smallest diurnal to annual variability among the three environments, where peak levels rarely exceeded 250 ppqv and the minimum was typically 100 ppqv. It should be noted that summertime diurnal patterns at TF and AI were opposite in phase indicating strong sink(s) for Hg0 during the day in the marine boundary layer, which was consistent with the hypothesis of Hg0 oxidation by halogen radicals there. Mixing ratios of RGM in the coastal and marine boundary layers reached annual maxima in spring and minima in fall, whereas at PM levels were generally below the limit of detection (LOD) except in spring. RGM levels at AI were higher than at TF and PM indicating a stronger source strength in the marine environment. Mixing ratios of HgP at AI and TF were close in magnitude to RGM levels and were mostly below 1 ppqv. Diurnal variation in HgP was barely discernible at TF and AI in spring and summer. Higher levels of HgP were observed during the day, while values that were smaller, but above the LOD, occurred at night.

scholarly journals An MCM modeling study of nitryl chloride (ClNO<sub>2</sub>) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

2014 ◽  
Vol 14 (8) ◽  
pp. 3789-3800 ◽  
Author(s):  
T. P. Riedel ◽  
G. M. Wolfe ◽  
K. T. Danas ◽  
J. B. Gilman ◽  
W. C. Kuster ◽  
...  
Keyword(s):  
Nitrogen Oxide ◽  
Organic Compounds ◽  
Field Measurements ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Model Framework ◽  
Dinitrogen Pentoxide ◽  
Nitryl Chloride ◽  
Hydrogen Oxide

Abstract. Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm−3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl· addition to alkenes, which may be useful in identifying times of active Cl· chemistry.

scholarly journals Production of N<sub>2</sub>O<sub>5</sub> and ClNO<sub>2</sub> in summer in urban Beijing, China

2018 ◽  
Author(s):  
Wei Zhou ◽  
Jian Zhao ◽  
Bin Ouyang ◽  
Archit Mehra ◽  
Weiqi Xu ◽  
...  
Keyword(s):  
Urban Areas ◽  
Life Time ◽  
Product Formation ◽  
High Reactivity ◽  
Ionization Mass ◽  
Mass Spectrometers ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
Beijing China ◽  
Hydrolysis Of

Abstract. The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) has a significant impact on both nocturnal particulate nitrate formation and photochemistry the following day through photolysis of nitryl chloride (ClNO2), yet these processes in highly polluted urban areas remain poorly understood. Here we present measurements of gas-phase N2O5 and ClNO2 by high-resolution time-of-flight chemical ionization mass spectrometers (ToF-CIMS) during summer in urban Beijing, China as part of the Air Pollution and Human Health (APHH) campaign. N2O5 and ClNO2 show large day-to-day variations with average (±1σ) mixing ratios of 79.2 ± 157.1 and 174.3 ± 262.0 pptv, respectively. High reactivity of N2O5, with τ (N2O5)−1 ranging from 0.20 × 10−2 to 1.46 × 10−2 s−1, suggests active nocturnal chemistry and a large nocturnal nitrate formation potential via N2O5 heterogeneous uptake. The life time of N2O5, τ(N2O5), decreases rapidly as the increase of aerosol surface area, yet it varies differently as a function of relative humidity with the highest value peaking at ~ 40 %. The N2O5 uptake coefficients estimated from the product formation rates of ClNO2 and particulate nitrate are in the range of 0.017–0.19, corresponding to direct N2O5 loss rates of 0.00044–0.0034 s−1. Further analysis indicates that the fast N2O5 loss in the nocturnal boundary layer in urban Beijing is mainly attributed to its indirect loss via NO3, for example through the reactions with volatile organic compounds and NO, while the contribution of heterogeneous uptake of N2O5 is comparably small (7–33 %). High ClNO2 yields ranging from 0.10 to 0.35 were also observed which might have important implications for air quality by affecting nitrate and ozone formation.

Ubiquity of ClNO2 in the urban boundary layer of Calgary, Alberta, Canada

2016 ◽  
Vol 94 (4) ◽  
pp. 414-423 ◽  
Author(s):  
Levi H. Mielke ◽  
Amanda Furgeson ◽  
Charles A. Odame-Ankrah ◽  
Hans D. Osthoff
Keyword(s):  
Chlorine Atom ◽  
Urban Environments ◽  
Heterogeneous Reactions ◽  
Ionization Mass ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Reservoir Species ◽  
Intermittent Measurements ◽  
Oxidation Of No

The role of nitryl chloride (ClNO2) as a nocturnal nitrogen oxide reservoir species and chlorine atom precursor is well established for polluted coastal areas, but its role at midcontinental locations is less clear. In this paper, intermittent measurements over the course of several seasons of ClNO2 mixing ratios by iodide ion chemical ionization mass spectrometry in Calgary, Alberta, Canada, are presented. Mixing ratios were highly variable between nights and seasons and depended on the abundances of precursors and meteorological conditions. The lowest ClNO2 mixing ratios (nocturnal maximum of 30 parts per trillion by volume (pptv)) were observed in the summer, rationalized by losses of the nitrate radical (NO3) that were more efficient than in the other months. Higher ClNO2 mixing ratios (up to 330 pptv) were observed in the winter and spring months but varied between nights. In the fall, ClNO2 mixing ratios increased from night to night following the application of salt to roads. The ClNO2 yield relative to the amount of NO3 produced from oxidation of NO2 by O3 ranged from 0.1% to 4.5% (10th and 90th percentiles, median 1.0%). The ClNO2 yield relative to N2O5 consumed by heterogeneous reactions was estimated using a time-integrated box model and ranged from 0.5% to 12.1% (10th and 90th percentiles, median 3.4%). The ubiquity of ClNO2 implies that the chlorine atom needs to be considered as an oxidant in high-latitude urban environments in winter.

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