Gaseous HCl at a remote tropical continental site

Sanhueza, Eugenio; Garaboto, A.

doi:10.3402/tellusb.v54i4.16675

Cited by 5 publications

(8 citation statements)

References 18 publications

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“…Most HCl measurements have been obtained in polluted coastal or continental regions at the surface, where HCl mixing ratios can exhibit extremely large variability and often exceed several parts per billion [e.g., Bari et al ., ; Keene et al ., ; Crisp et al ., ]. At remote and semi‐remote sites, HCl levels are generally lower and of the order of several tens to several hundred parts per trillion [e.g., Sanhueza and Garaboto , ; Sander et al ., ].…”

Section: Resultsmentioning

confidence: 99%

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A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

et al. 2016

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Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by ~2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea‐salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub‐ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1–5 × 104 atoms cm−3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to ~4320 Gg Cl/yr, sustaining a background surface [Cl] of <0.1 to 0.5 × 103 atoms cm−3 over large areas. Globally, we estimate a tropospheric methane sink of ~12–13 Tg CH4/yr due the CH4 + Cl reaction (~2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for ~10 to >20% of total boundary layer CH4 oxidation in some locations.

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Section: Resultsmentioning

confidence: 99%

“…Same as in Figure but for remote and semi‐remote locations. Measurement data: Lawler et al [], Sander et al [], Sanhueza and Garaboto [], Jourdain and Legrand [], Kim et al [], Pszenny et al [, ], Keene and Savoie [] and Keene et al [].…”

Section: Resultsmentioning

confidence: 99%

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

et al. 2016

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“…We do not include the anthropogenic Cl − source from fugitive dust, although it might be important in contributing to chloride levels in continental surface air (Sarwar et al, 2012). The global source of anthropogenic fugitive dust is estimated to be less than 13 Tg a −1 (Philip et al, 2017), of which 0.3 % by mass is estimated to be chloride (Reff et al, 2009).…”

Section: Sources Of Chlorinementioning

confidence: 99%

“…Only a small fraction is mobilized to the gas phase as HCl or other species. Additional minor sources of tropospheric chlorine include open fires, coal combustion, waste incineration, industry, road salt application, fugitive dust, and ocean emission of organochlorine compounds (Lobert et al, 1999;McCulloch et al, 1999;Sarwar et al, 2012;WMO, 2014;Kolesar et al, 2018). It is useful to define Cl y as total gas-phase inorganic chlorine, excluding particle-phase Cl − .…”

Section: Introductionmentioning

confidence: 99%

The role of chlorine in global tropospheric chemistry

et al. 2019

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Abstract. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant–aerosol–halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional small sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are also included. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl+OH reaction and by heterogeneous conversion of sea salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model successfully simulates the observed mixing ratios of HCl in marine air (highest at northern midlatitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night and attributes the chlorine to HCl volatilized from sea salt aerosol and transported inland following uptake by fine aerosol. The model successfully simulates the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be largely explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night, which could be due to uncertainty in the rate of the ClNO2+Cl- reaction, but we have no explanation for the high observed Cl2 in daytime. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr+Cl- reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

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“…Wet-effluent diffusion denuder NH 3 , HNO 3 , HONO, HCl and SO 2 Simon et al, 1991;Taira and Kanda, 1993;Buhr et al, 1995;Zellweger et al, 1999 Parallel-plate denuder NH 3 , HNO 3 , HONO, HCl and SO 2 Simon and Dasgupta, 1993;Boring et al, 1999;Genfa et al, 2003 Thermodenuder NH 3 , HNO 3 Keuken et al, 1989;Klockow et al, 1989 Wet-annular denuder NH 3 , HNO 3 , HONO, HCl and SO 2 Keuken et al, 1988;Wyers et al, 1993;Allegrini et al, 1994;Slanina and Wyers, 1994;Oms et al, 1996;Jongejan et al, 1997AiRRmonia NH 3 Erisman et al, 2001 Diffusion scrubber Diffusion scrubber and NH 3 , HNO 3 , HONO, Matusca et al, 1984;Cofer et al, 1985;mist chamber HCl and SO 2 Philips and Dasgupta, 1987;Lindgren, 1992;Lefer et al, 1999;Sanhueza and Garaboto, 2002 Fluorescence Laser-photolysis fragment-fluorescence HONO, HNO 3 Rodgers and Davis, 1989;Papenbrock and Stuhl, 1990;(LPFF) and laser-fluorescence NH 3 , aerosol NH + 4 Papenbrock and Stuhl, 1991;Abbas and Tanner, 1981; derivatization Rapsomanikis et al, 1988 Spectroscopy Differential optical absorption HNO 3 , HONO Perner and Platt, 1979;Plane and Nien, 1992; spectroscopy (DOAS) Winer and Biermann, 1994;Febo et al, 1996;Stutz et al, 2002 Chemical ionization mass HNO 3 , SO 2 Huey et al, 1998;Mauldin et al, 1998;spectrometer (CIMS) Furutani and…”

Section: Introductionmentioning

confidence: 99%

Real-time measurements of ammonia, acidic trace gases and water-soluble inorganic aerosol species at a rural site in the Amazon Basin

Trebs¹,

Meixner²,

Slanina³

et al. 2004

Preprint

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Abstract. We measured the mixing ratios of ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), hydrochloric acid (HCl), sulfur dioxide (SO2) and the corresponding water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3−), nitrite (NO2−), chloride (Cl−) and sulfate (SO42−), and their diel and seasonal variations at a pasture site in the Amazon Basin (Rondônia, Brazil). This study was conducted within the framework of LBA-SMOCC (Large Scale Biosphere Atmosphere Experiment in Amazonia Smoke Aerosols, Clouds, Rainfall and Climate). Sampling was performed from 12 September to 14 November 2002, extending from the dry season (extensive biomass burning activity), through the transition period to the wet season (background conditions). Measurements were made continuously using a wet-annular denuder in combination with a Steam-Jet Aerosol Collector (SJAC) followed by suitable on-line analysis. A detailed description and verification of the inlet system for simultaneous sampling of soluble gases and aerosol compounds is presented. Overall measurement uncertainties of the ambient mixing ratios usually remained below 15%. The limit of detection (LOD) was determined for each single data point measured during the field experiment. Median LOD values (3σ-definition) were ≤0.015 ppb for acidic trace gases and aerosol anions and ≤0.118 ppb for NH3 and aerosol NH4+. Mixing ratios of acidic trace gases remained below 1ppb throughout the measurement period, while NH3 levels were an order of magnitude higher. Accordingly, mixing ratios of NH4+ exceeded those of other inorganic aerosol contributors by a factor of 4 to 10. During the wet season, mixing ratios decreased by nearly a factor of 3 for all compounds compared to those observed when intensive biomass burning took place. Additionally, N-containing gas and aerosol species featured pronounced diel variations. This is attributed to strong relative humidity and temperature variations between day and night as well as to changing photochemistry and stability conditions of the planetary boundary layer. HONO exhibited a characteristic diel cycle with high mixing ratios at nighttime and was not completely depleted by photolysis during daylight hours.

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Gaseous HCl at a remote tropical continental site

Cited by 5 publications

References 18 publications

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

The role of chlorine in global tropospheric chemistry

Real-time measurements of ammonia, acidic trace gases and water-soluble inorganic aerosol species at a rural site in the Amazon Basin

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