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.

scholarly journals The first UK measurements of nitryl chloride using a chemical ionization mass spectrometer in central London in the summer of 2012, and an investigation of the role of Cl atom oxidation

2015 ◽  
Vol 120 (11) ◽  
pp. 5638-5657 ◽  
Author(s):  
Thomas J. Bannan ◽  
A. Murray Booth ◽  
Asan Bacak ◽  
Jennifer B. A. Muller ◽  
Kimberley E. Leather ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ionization Mass ◽  
Nitryl Chloride ◽  
Cl Atom

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 The potential importance of frost flowers, recycling on snow, and open leads for Ozone Depletion Events

2007 ◽  
Vol 7 (2) ◽  
pp. 4521-4595 ◽  
Author(s):  
M. Piot ◽  
R. von Glasow
Keyword(s):  
Gas Phase ◽  
Ozone Depletion ◽  
Aerosol Deposition ◽  
Heterogeneous Reactions ◽  
The Arctic ◽  
Acid Uptake ◽  
Mixing Ratios ◽  
Haze Pollution ◽  
Frost Flowers

Abstract. We present model studies with the one-dimensional model MISTRA to investigate the potential role of frost flowers, recycling on snow, and open leads in the depletion of tropospheric ozone in the Arctic spring. In our model, we assumed frost flower aerosols to be the major source of bromine. We show that a major ozone depletion event can be satisfactorily reproduced only if the recycling on snow of deposited bromine into gas phase bromine is assumed. In the model, this cycling is more efficient than the bromine explosion process and maintains sufficiently high levels of bromine to deplete ozone down to few nmol mol−1 within four days. We assessed the influence of different surface combinations (open lead/frost flowers) on the chemistry in the model. Results showed noticeable modifications affecting the composition of aerosols and the deposition velocities. A model run with a series of coupled frost flower fields and open leads, separated by large areas of snow, showed results comparable with field observations. In addition, we studied the effects of modified temperature of either the frost flower field or the ambient airmass. A warmer frost flower field increases the relative humidity and the aerosol deposition rate. The deposition/re-emission process gains in importance, inducing more reactive bromine in the gas phase, and a stronger ozone depletion. A decrease of 1 K in airmass temperature shows in our model that the aerosol uptake capacities of all gas phase species substantially increases, leading to enhanced uptake of acids from the gas phase. Consequently, the so-called bromine explosion accelerated and O3 mixing ratios decreased. In our model representation, variations in wind speed affected the aerosol source function and influenced the amount of bromine in the atmosphere and thus the ozone depletion strength. Recent studies have suggested the important role of the precipitation of calcium carbonate (CaCO3) out of the brine layer for the possible acidification of the liquid phase by acid uptake. Our investigation showed that this precipitation is a crucial process for the timing of the bromine explosion in aerosols. Nevertheless, model runs with either 50% precipitation or complete precipitation displayed a relatively weak difference in ozone mixing ratios after four simulated days. By considering conditions typical for "Arctic Haze" pollution events at the start of the run we obtained a low pH in frost flower aerosols due to a greater mixing ratio of SO2, and a strong recycling efficiency via large aerosol number concentration. The aerosol acidification during a haze event most likely intensifies the ozone depletion strength and occurrence. The comparison between our modeled deposition on snow and sampled snow at Barrow (Alaska) shows that approximately 75% of deposited bromine may be re-emitted into the gas phase as Br2/BrCl. Among several non-halogen fluxes from the snow, model simulations showed that only HONO affects the chemistry. Finally, we investigated the release of Br2 potentially produced by heterogeneous reactions directly on frost flowers. In this case, we obtained unrealistic results of aerosol compositions and deposition rates on snow compared to observations in the Arctic.

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 The potential importance of frost flowers, recycling on snow, and open leads for ozone depletion events

2008 ◽  
Vol 8 (9) ◽  
pp. 2437-2467 ◽  
Author(s):  
M. Piot ◽  
R. von Glasow
Keyword(s):  
Gas Phase ◽  
Ozone Depletion ◽  
Aerosol Deposition ◽  
Heterogeneous Reactions ◽  
The Arctic ◽  
Acid Uptake ◽  
Mixing Ratios ◽  
Haze Pollution ◽  
Frost Flowers

Abstract. We present model studies with the one-dimensional model MISTRA to investigate the potential role of frost flowers, recycling on snow, and open leads in the depletion of tropospheric ozone in the Arctic spring. In our model, we assumed frost flower aerosols to be the major source of bromine. We show that a major ozone depletion event can be satisfactorily reproduced only if the recycling on snow of deposited bromine into gas phase bromine is assumed. In the model, this cycling is more efficient than the bromine explosion process and maintains sufficiently high levels of bromine to deplete ozone down to few nmol mol−1 within four days. We assessed the influence of different surface combinations (open lead/frost flowers) on the chemistry in the model. Results showed noticeable modifications affecting the composition of aerosols and the deposition velocities. A model run with a series of coupled frost flower fields and open leads, separated by large areas of snow, showed results comparable with field observations. In addition, we studied the effects of modified temperature of either the frost flower field or the ambient airmass. A warmer frost flower field increases the relative humidity and the aerosol deposition rate. The deposition/re-emission process gains in importance, inducing more reactive bromine in the gas phase, and a stronger ozone depletion. A decrease of 1K in airmass temperature shows in our model that the aerosol uptake capacities of all gas phase species substantially increases, leading to enhanced uptake of acids from the gas phase. Consequently, the so-called bromine explosion accelerated and O3 mixing ratios decreased. In our model representation, variations in wind speed affected the aerosol source function and influenced the amount of bromine in the atmosphere and thus the ozone depletion strength. Recent studies have suggested the important role of the precipitation of calcium carbonate (CaCO3) out of the brine layer for the possible acidification of the liquid phase by acid uptake. Our investigation showed that this precipitation is a crucial process for the timing of the bromine explosion in aerosols. Nevertheless, model runs with either 50% precipitation or complete precipitation displayed a relatively weak difference in ozone mixing ratios after four simulated days. By considering conditions typical for "Arctic Haze" pollution events at the start of the run we obtained a low pH in frost flower aerosols due to a greater mixing ratio of SO2, and a strong recycling efficiency via large aerosol number concentration. The aerosol acidification during a haze event most likely intensifies the ozone depletion strength and occurrence. The comparison between our modeled deposition on snow and sampled snow at Barrow (Alaska) shows that approximately 75% of deposited bromine may be re-emitted into the gas phase as Br2/BrCl. Among several non-halogen fluxes from the snow, model simulations showed that only HONO affects the chemistry. Finally, we investigated the release of Br2 potentially produced by heterogeneous reactions directly on frost flowers. In this case, we obtained unrealistic results of aerosol compositions and deposition rates on snow compared to observations in the Arctic.

A novel spectroscopic approach for detection of chlorine reservoir species: HCl-TILDAS

2020 ◽  
Author(s):  
John Halfacre ◽  
Pete Edwards ◽  
Scott Herndon ◽  
Joseph Roscioli ◽  
Christoph Dyroff ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Chlorine Atom ◽  
Nitrogen Loss ◽  
Tunable Laser ◽  
Ozone Production ◽  
Specific Method ◽  
Nitryl Chloride ◽  
Reservoir Species ◽  
Chlorine Radicals ◽  
Observational Techniques

&lt;p&gt;Atomic chlorine radicals are known to affect atmospheric oxidation and pollutant lifetimes, but are challenging to detect due to their low ambient concentrations.&amp;#160; A lack of field observations limits useful assessments of the impacts of tropospheric chlorine oxidation on important atmospheric processes, such as regional ozone production, reactive nitrogen loss, and global methane removal.&amp;#160; In the last decade, instrumental innovations have enabled detection and speciation of much more stable chlorine atom reservoir species, such as nitryl chloride, through techniques such as cavity ring down spectroscopy and mass spectrometry.&amp;#160; HCl is the most abundant and long-lived tropospheric chlorine reservoir species, yet few observations exist.&amp;#160; Here, we present a specific method for detection of HCl via Tunable Laser Infrared Direct Absorption Spectrometer (TILDAS), which has been further extended for the detection of nitryl chloride.&amp;#160; This analytical method has several advantages over current observational techniques (e.g. chemical ionisation mass spectrometry), and will provide a much needed constraint on the tropospheric chlorine atom budget.&lt;/p&gt;

scholarly journals Influence of Land Use on Avian Diversity in North African Urban Environments

Land ◽  
2021 ◽  
Vol 10 (4) ◽  
pp. 434
Author(s):  
Hani Amir Aouissi ◽  
Alexandru-Ionuţ Petrişor ◽  
Mostefa Ababsa ◽  
Maria Boştenaru-Dan ◽  
Mahmoud Tourki ◽  
...  
Keyword(s):  
Green Infrastructure ◽  
Diversity Index ◽  
Research Question ◽  
Urban Environments ◽  
Ecological Group ◽  
Avian Diversity ◽  
North African ◽  
Index Method ◽  
Urban Green Spaces

Land cover and use changes are important to study for their impact on ecosystem services and ultimately on sustainability. In urban environments, a particularly important research question addresses the relationship between urbanization-related changes and biodiversity, subject to controversies in the literature. Birds are an important ecological group, and useful for answering this question. The present study builds upon the hypothesis according to which avian diversity decreases with urbanization. In order to answer it, a sample of 4245 observations from 650 sites in Annaba, Algeria, obtained through the point abundance index method, were investigated by computing Shannon-Wiener’s diversity index and the species richness, mapping them, and analyzing the results statistically. The findings confirm the study hypothesis and are relevant for planning, as they stress the role of urban green spaces as biodiversity hotspots, and plead for the need of connecting them. From a planning perspective, the results emphasize the need for interconnecting the green infrastructure through avian corridors. Moreover, the results fill in an important lack of data on the biodiversity of the region, and are relevant for other similar Mediterranean areas. Future studies could use the findings to compare with data from other countries and continents.

68 Examining the role of supportive adults in violence exposure among male youth in urban environments

2015 ◽  
Vol 21 (Suppl 2) ◽  
pp. A24.3-A25
Author(s):  
Alison Culyba ◽  
Kenneth Ginsburg ◽  
Joel Fein ◽  
Elizabeth Miller ◽  
Charles Branas ◽  
...  
Keyword(s):  
Violence Exposure ◽  
Urban Environments ◽  
Male Youth
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