scholarly journals Diurnal cycle of iodine, bromine, and mercury concentrations in Svalbard surface snow

2019 ◽  
Vol 19 (20) ◽  
pp. 13325-13339 ◽  
Author(s):  
Andrea Spolaor ◽  
Elena Barbaro ◽  
David Cappelletti ◽  
Clara Turetta ◽  
Mauro Mazzola ◽  
...  
Keyword(s):  
Gas Phase ◽  
Diurnal Cycle ◽  
Field Experiments ◽  
Marine Boundary Layer ◽  
Ambient Air ◽  
Atmospheric Nucleation ◽  
Depositional Processes ◽  
Air Interface ◽  
Surface Snow ◽  
Different Seasons

Abstract. Sunlit snow is highly photochemically active and plays a key role in the exchange of gas phase species between the cryosphere and the atmosphere. Here, we investigate the behaviour of two selected species in surface snow: mercury (Hg) and iodine (I). Hg can deposit year-round and accumulate in the snowpack. However, photo-induced re-emission of gas phase Hg from the surface has been widely reported. Iodine is active in atmospheric new particle formation, especially in the marine boundary layer, and in the destruction of atmospheric ozone. It can also undergo photochemical re-emission. Although previous studies indicate possible post-depositional processes, little is known about the diurnal behaviour of these two species and their interaction in surface snow. The mechanisms are still poorly constrained, and no field experiments have been performed in different seasons to investigate the magnitude of re-emission processes Three sampling campaigns conducted at an hourly resolution for 3 d each were carried out near Ny-Ålesund (Svalbard) to study the behaviour of mercury and iodine in surface snow under different sunlight and environmental conditions (24 h darkness, 24 h sunlight and day–night cycles). Our results indicate a different behaviour of mercury and iodine in surface snow during the different campaigns. The day–night experiments demonstrate the existence of a diurnal cycle in surface snow for Hg and iodine, indicating that these species are indeed influenced by the daily solar radiation cycle. Differently, bromine did not show any diurnal cycle. The diurnal cycle also disappeared for Hg and iodine during the 24 h sunlight period and during 24 h darkness experiments supporting the idea of the occurrence (absence) of a continuous recycling or exchange at the snow–air interface. These results demonstrate that this surface snow recycling is seasonally dependent, through sunlight. They also highlight the non-negligible role that snowpack emissions have on ambient air concentrations and potentially on iodine-induced atmospheric nucleation processes.

scholarly journals Diurnal cycle of iodine and mercury concentrations in Svalbard surface snow

2019 ◽  
Author(s):  
Andrea Spolaor ◽  
Elena Barbaro ◽  
David Cappelletti ◽  
Clara Turetta ◽  
Mauro Mazzola ◽  
...  
Keyword(s):  
Gas Phase ◽  
Diurnal Cycle ◽  
Field Experiments ◽  
Marine Boundary Layer ◽  
Ambient Air ◽  
High Temporal Resolution ◽  
Atmospheric Nucleation ◽  
Depositional Processes ◽  
Sampling Campaign ◽  
Surface Snow

Abstract. Sunlit snow is highly photochemically active and plays an important role in the exchange of gas-phase species between the cryosphere to the atmosphere. Here, we investigate the behaviour of two selected species in surface snow: mercury (Hg) and iodine (I). Hg can deposit year-round and accumulate in the snowpack. However, photo-induced re-emission of gas phase Hg from the surface has been widely reported. Iodine is active in atmosphere new particle formation, especially in the marine boundary layer, and in the destruction of atmospheric ozone. It can also undergo photochemical re-emission. Although previous studies indicate possible post-depositional processes, little is known about the diurnal behaviour of these two species and their interaction in surface snow. The mechanisms are still poorly constrained and no field experiments have been performed in different seasons to investigate the magnitude of re-emission processes. Three high temporal resolution (hourly samples) 3 days long sampling campaign were carried out near Ny-Ålesund (Svalbard) to study the behaviour of mercury and iodine in surface snow under different sunlight and environmental conditions (24 h-darkness, 24 h-sunlight and day/night cycles). Our results indicate a clearly different behaviour of Hg and I in surface snow during the different campaign. The day/night experiments demonstrate the existence of a diurnal cycle in surface snow for Hg and iodine, indicating that these species are indeed influenced by the daily solar radiation cycle. Differently bromine did not show any diurnal cycle. The diurnal cycle disappeared also for Hg and iodine during the 24 h-sunlight period and during 24 h-darkness experiments supporting the idea of the occurrence (absence) of a continuous recycling/exchange at the snow-air interface. These results demonstrate that this surface snow recycling is seasonally dependent, through sunlight. They also highlight the non-negligible role that snowpack emissions have on ambient air concentrations and potentially on iodine-induced atmospheric nucleation processes.

scholarly journals Mercury dynamics in the Rocky Mountain, Colorado, snowpack

2013 ◽  
Vol 10 (6) ◽  
pp. 3793-3807 ◽  
Author(s):  
X. Faïn ◽  
D. Helmig ◽  
J. Hueber ◽  
D. Obrist ◽  
M. W. Williams
Keyword(s):  
Rocky Mountain ◽  
Co2 Flux ◽  
Elemental Mercury ◽  
Ambient Air ◽  
Transport Processes ◽  
Gaseous Elemental Mercury ◽  
Air Interface ◽  
Surface Snow ◽  
Long Term Ecological Research ◽  
Interstitial Air

Abstract. Gaseous elemental mercury (GEM) was monitored at the Niwot Ridge (NWT) Long-Term Ecological Research (LTER) site (Colorado, USA, 40° N) from interstitial air extracted from the snowpack at depths ranging from the snow surface to 10 cm above the soil. A highly dynamic cycling of mercury (Hg) in this mid-latitude snowpack was observed. Patterns were driven by both GEM production in surface snow and GEM destruction in the deeper snowpack layers. Thorough mixing and vertical transport processes were observed through the snowpack. GEM was photochemically produced near the snow-air interface throughout the entire winter, leading to enhanced GEM levels in interstitial air of surface snow of up to 8 ng m−3. During low-wind periods, GEM in surface snow layers remained significantly above ambient air levels at night as well, which may indicate a potential weak GEM production overnight. Analyses of vertical GEM gradients in the snowpack show that surface GEM enhancements efficiently propagated down the snowpack, with a temporal lag in peak GEM levels observed with increasing depth. Downward diffusion was responsible for much of these patterns, although vertical advection also contributed to vertical redistribution. Destruction of GEM in the lower snowpack layers was attributed to dark oxidation of GEM. Analysis of vertical GEM / CO2 flux ratios indicated that this GEM destruction occurred in the snow and not in the underlying soil. The strong, diurnal patterns of photochemical GEM production at the surface ultimately lead to re-emission losses of deposited Hg back to the atmosphere. The NWT data show that highest GEM surface production and re-emissions occur shortly after fresh snowfall, which possibly resupplies photoreducible Hg to the snowpack, and that photochemical GEM reduction is not radiation-limited as it is strong even on cloudy days.

scholarly journals Mercury dynamics in the Rocky Mountain, Colorado, Snowpack

2012 ◽  
Vol 9 (11) ◽  
pp. 15423-15458
Author(s):  
X. Faïn ◽  
D. Helmig ◽  
J. Hueber ◽  
D. Obrist ◽  
M. M. Williams
Keyword(s):  
Rocky Mountain ◽  
Co2 Flux ◽  
Elemental Mercury ◽  
Ambient Air ◽  
Transport Processes ◽  
Gaseous Elemental Mercury ◽  
Air Interface ◽  
Surface Snow ◽  
Long Term Ecological Research ◽  
Interstitial Air

Abstract. Gaseous Elemental Mercury (GEM) was monitored at the Niwot Ridge (NWT) long-term ecological research (LTER) site (Colorado, USA, 40° N) from interstitial air extracted from the snowpack at depths ranging from the snow surface to 10 cm above the soil. A highly dynamic cycling of mercury (Hg) in this mid-latitude snowpack was observed. Patterns were driven by both GEM production in surface snow and GEM destruction in the deeper snowpack layers. Thorough mixing and vertical transport processes were observed through the snowpack. GEM was photochemically produced near the snow-air interface leading to enhanced GEM levels in interstitial air of surface snow of up to 8 ng m−3. During low wind periods, GEM in surface snow layers remained significantly above ambient air levels at night as well, which may indicate a potential weak GEM production over night. Analysis of vertical GEM gradients in the snowpack show that surface GEM enhancements efficiently propagated down the snowpack, with a temporal lag in peak GEM levels observed with increasing depth. Downward diffusion was responsible for much of these patterns, although vertical advection also contributed to vertical redistribution. Destruction of GEM in the lower snowpack layers was attributed to dark oxidation of GEM. Analysis of vertical GEM/CO2 flux ratios indicated that this GEM destruction occurred in the snow and not in the underlying soil. The strong, diurnal patterns of photochemical GEM production at the surface ultimately lead to re-emission losses of deposited Hg back to the atmosphere. The NWT data show that highest of GEM production and emission occur shortly after fresh snowfall, indicating that fresh snow possibly resupplies photoreducible Hg to the snowpack.

scholarly journals Influence of Water on the Gas-Phase Reaction of Dimethyl Sulfide with BrO in the Marine Boundary Layer

ACS Omega ◽  
2021 ◽  
Vol 6 (3) ◽  
pp. 2410-2419
Author(s):  
Junyao Li ◽  
Narcisse T. Tsona ◽  
Shanshan Tang ◽  
Xiuhui Zhang ◽  
Lin Du
Keyword(s):  
Boundary Layer ◽  
Gas Phase ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Influence Of Water

scholarly journals Pseudo steady states of HONO measured in the nocturnal marine boundary layer: a conceptual model for HONO formation on aqueous surfaces

2011 ◽  
Vol 11 (7) ◽  
pp. 3243-3261 ◽  
Author(s):  
P. Wojtal ◽  
J. D. Halla ◽  
R. McLaren
Keyword(s):  
Conceptual Model ◽  
Gas Phase ◽  
Formation Mechanism ◽  
Marine Boundary Layer ◽  
Steady States ◽  
Optical Absorption Spectroscopy ◽  
Aqueous Environment ◽  
Ambient Atmosphere ◽  
Mass Source ◽  
Aqueous Surfaces

Abstract. A complete understanding of the formation mechanism of nitrous acid (HONO) in the ambient atmosphere is complicated by a lack of understanding of processes occurring when aqueous water is present. We report nocturnal measurements of HONO, SO2 and NO2 by differential optical absorption spectroscopy over the ocean surface in a polluted marine environment. In this aqueous environment, we observed reproducible pseudo steady states (PSS) of HONO every night, that are fully formed shortly after sunset, much faster than seen in urban environments. During the PSS period, HONO is constant with time, independent of air mass source and independent of the concentration of NO2. The independence of HONO on the concentration of NO2 implies a 0° order formation process, likely on a saturated surface, with reversible partitioning of HONO to the gas phase, through vaporization and deposition to the surface. We observed median HONO/NO2 ratios starting at 0.13 at the beginning of the PSS period (with an apparent lower bound of 0.03), rising to median levels of ~0.30 at the end of the PSS period (with an upper bound >1.0). The implication of these numbers is that they suggest a common surface mechanism of HONO formation on terrestrial and aqueous surfaces, with an increase in the HONO/NO2 ratio with the amount of water available at the surface. The levels of HONO during the nocturnal PSS period are positively correlated with temperature, consistent with a partitioning of HONO from the surface to the gas phase with an apparent enthalpy of vaporization of ΔHSNL (HONO)=55.5±5.4 kJ mol−1. The formation mechanism on aqueous surfaces is independent of relative humidity (RH), despite observation of a negative HONO-RH correlation. A conceptual model for HONO formation on ambient aqueous surfaces is presented, with the main elements being the presence of a surface nanolayer (SNL), highly acidic and saturated with N(IV) precursors, production of HNO3, that diffuses to underlying water layers, and HONO, which partitions reversibly between the SNL and the gas phase. Implications of the conceptual model are discussed.

scholarly journals A method for detecting the presence of organic fraction in nucleation mode sized particles

2005 ◽  
Vol 5 (12) ◽  
pp. 3277-3287 ◽  
Author(s):  
P. Vaattovaara ◽  
M. Räsänen ◽  
T. Kühn ◽  
J. Joutsensaari ◽  
A. Laaksonen
Keyword(s):  
Sulfuric Acid ◽  
Field Experiments ◽  
Inorganic Compounds ◽  
Particle Diameter ◽  
Ethanol Vapor ◽  
Organic Fraction ◽  
Saturation Ratio ◽  
Nucleation Mode ◽  
Atmospheric Nucleation ◽  
20 Nm

Abstract. New particle formation and growth has a very important role in many climate processes. However, the overall knowlegde of the chemical composition of atmospheric nucleation mode (particle diameter, d<20 nm) and the lower end of Aitken mode particles (d≤50 nm) is still insufficient. In this work, we have applied the UFO-TDMA (ultrafine organic tandem differential mobility analyzer) method to shed light on the presence of an organic fraction in the nucleation mode size class in different atmospheric environments. The basic principle of the organic fraction detection is based on our laboratory UFO-TDMA measurements with organic and inorganic compounds. Our laboratory measurements indicate that the usefulness of the UFO-TDMA in the field experiments would arise especially from the fact that atmospherically the most relevant inorganic compounds do not grow in subsaturated ethanol vapor, when particle size is 10 nm in diameter and saturation ratio is about 86% or below it. Furthermore, internally mixed particles composed of ammonium bisulfate and sulfuric acid with sulfuric acid mass fraction ≤33% show no growth at 85% saturation ratio. In contrast, 10 nm particles composed of various oxidized organic compounds of atmospheric relevance are able to grow in those conditions. These discoveries indicate that it is possible to detect the presence of organics in atmospheric nucleation mode sized particles using the UFO-TDMA method. In the future, the UFO-TDMA is expected to be an important aid to describe the composition of atmospheric newly-formed particles.

scholarly journals Amines in boreal forest air at SMEAR II station in Finland

2018 ◽  
Vol 18 (9) ◽  
pp. 6367-6380 ◽  
Author(s):  
Marja Hemmilä ◽  
Heidi Hellén ◽  
Aki Virkkula ◽  
Ulla Makkonen ◽  
Arnaud P. Praplan ◽  
...  
Keyword(s):  
Boreal Forest ◽  
Gas Phase ◽  
Particle Number ◽  
Detection Limits ◽  
Ambient Air ◽  
Monthly Means ◽  
Ammonium Ions ◽  
Quadrupole Mass ◽  
Concentration Data ◽  
Diurnal Variability

Abstract. We measured amines in boreal forest air in Finland both in gas and particle phases with 1 h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air – MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2–3.1 ng m−3), the accuracy of IC-MS analysis was 11–37 %, and the precision 10–15 %. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were < 2.4 and 6.8 ± 9.1 ng m−3 in gas and aerosol phases, respectively, and for NH3 and NH4+ these were 52 ± 16 and 425 ± 371 ng m−3, respectively. Monthly medians in March for MMA(tot), NH3, and NH4+ were < 2.4, 19 and 90 ng m−3, respectively. DMA(tot) and TMA(tot) had summer maxima indicating biogenic sources. We observed diurnal variation for DMA(tot) but not for TMA(tot). The highest concentrations of these compounds were measured in July. Then, monthly means for DMA were < 3.1 and 8.4 ± 3.1 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 ± 0.1 and 1.8 ± 0.5 ng m−3. Monthly medians in July for DMA were below the detection limit (DL) and 4.9 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 and 1.4 ng m−3. When relative humidity of air was > 90 %, gas-phase DMA correlated well with 1.1–2 nm particle number concentration (R2=0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were < 0.36 and 0.4 ± 0.4 ng m−3 in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.

Pollution Level and Distribution of PCDD/PCDF Congeners between Gas Phase and Particulate Phase in early Spring Air of Dalian, China

2011 ◽  
Vol 71-78 ◽  
pp. 2679-2682
Author(s):  
Xiu Hua Zhu ◽  
Song Tao Qin ◽  
Qian Xu ◽  
Yu Wen Ni ◽  
Ji Ping Chen ◽  
...  
Keyword(s):  
Gas Phase ◽  
Gaseous Phase ◽  
High Volume ◽  
Ambient Air ◽  
Early Spring ◽  
Pollution Level ◽  
Particulate Phase ◽  
Spring Season ◽  
International Standard

Ambient air of Dalian was sampled with active high-volume air samplers in early spring time. The concentrations and the congeners between gas phase and particulate phase of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs) in the air were measured. Samples analysis results showed that the concentration of PCDD/Fs in particulate phase was higher than that in gas phase. The ratio of PCDD to PCDF in gaseous phase and particulate phase was lower than 0.4. The main sources of atmospheric PCDD/Fs in Dalian early spring season were coal-related source. The total I-TEQ in gaseous phase and particulate phase was 30.3 and 143.6 fg m-3, respectively. The I-TEQ of Dalian early spring atmosphere was lower than international standard, the atmospheric quality in Dalian was better.

scholarly journals Polyfluoroalkyl compounds in the Canadian Arctic atmosphere

2011 ◽  
Vol 8 (4) ◽  
pp. 399 ◽  
Author(s):  
Lutz Ahrens ◽  
Mahiba Shoeib ◽  
Sabino Del Vento ◽  
Garry Codling ◽  
Crispin Halsall
Keyword(s):  
Gas Phase ◽  
Environmental Concern ◽  
Canadian Arctic ◽  
High Volume ◽  
Ambient Air ◽  
Coast Guard ◽  
The Arctic ◽  
Particle Phase ◽  
Method Performance ◽  
Arctic Atmosphere

Environmental contextPerfluoroalkyl compounds are of rising environmental concern because of their ubiquitous distribution in remote regions like the Arctic. The present study quantifies these contaminants in the gas and particle phases of the Canadian Arctic atmosphere. The results demonstrate the important role played by gas–particle partitioning in the transport and fate of perfluoroalkyl compounds in the atmosphere. AbstractPolyfluoroalkyl compounds (PFCs) were determined in high-volume air samples during a ship cruise onboard the Canadian Coast Guard Ship Amundsen crossing the Labrador Sea, Hudson Bay and the Beaufort Sea of the Canadian Arctic. Five PFC classes (i.e. perfluoroalkyl carboxylates (PFCAs), polyfluoroalkyl sulfonates (PFSAs), fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs)) were analysed separately in the gas phase collected on PUF/XAD-2 sandwiches and in the particle phase on glass-fibre filters (GFFs). The method performance of sampling, extraction and instrumental analysis were compared between two research groups. The FTOHs were the dominant PFCs in the gas phase (20–138 pg m–3), followed by the FOSEs (0.4–23 pg m–3) and FOSAs (0.5–4.7 pg m–3). The PFCAs could only be quantified in the particle phase with low levels (<0.04–0.18 pg m–3). In the particle phase, the dominant PFC class was the FOSEs (0.3–8.6 pg m–3). The particle-associated fraction followed the general trend of: FOSEs (~25 %) > FOSAs (~9 %) > FTOHs (~1 %). Significant positive correlation between ∑FOSA concentrations in the gas phase and ambient air temperature indicate that cold Arctic surfaces, such as the sea-ice snowpack and surface seawater could be influencing FOSAs in the atmosphere.

scholarly journals Inorganic bromine in the marine boundary layer: a critical review

2003 ◽  
Vol 3 (3) ◽  
pp. 2963-3050 ◽  
Author(s):  
R. Sander ◽  
W. C. Keene ◽  
A. A. P. Pszenny ◽  
R. Arimoto ◽  
G. P. Ayers ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Gas Phase ◽  
Marine Boundary Layer ◽  
Sea Water ◽  
Ocean Surface ◽  
Sea Salt ◽  
Future Research ◽  
Laboratory Studies ◽  
Model Calculations ◽  
Sea Salt Aerosol

Abstract. The cycling of inorganic bromine in the marine boundary layer (mbl) has received increased attention in recent years. Bromide, a constituent of sea water, is injected into the atmosphere in association with sea-salt aerosol by breaking waves on the ocean surface. Measurements reveal that supermicrometer sea-salt aerosol is depleted in bromine by about 50% relative to conservative tracers, whereas marine submicrometer aerosol is often enriched in bromine. Model calculations, laboratory studies, and field observations strongly suggest that these depletions reflect the chemical transformation of particulate bromide to reactive inorganic gases that influence the processing of ozone and other important constituents of marine air. However, currently available techniques cannot reliably quantify many \\chem{Br}-containing compounds at ambient concentrations and, consequently, our understanding of inorganic Br cycling over the oceans and its global significance are uncertain. To provide a more coherent framework for future research, we have reviewed measurements in marine aerosol, the gas phase, and in rain. We also summarize sources and sinks, as well as model and laboratory studies of chemical transformations. The focus is on inorganic bromine over the open oceans, excluding the polar regions. The generation of sea-salt aerosol at the ocean surface is the major tropospheric source producing about 6.2 Tg/a of bromide. The transport of  Br from continents (as mineral aerosol, and as products from biomass-burning and fossil-fuel combustion) can be of local importance. Transport of degradation products of long-lived Br-containing compounds from the stratosphere and other sources contribute lesser amounts. Available evidence suggests that, following aerosol acidification, sea-salt bromide reacts to form Br2 and BrCl that volatilize to the gas phase and photolyze in daylight to produce atomic Br and Cl. Subsequent transformations can destroy tropospheric ozone, oxidize dimethylsulfide (DMS) and hydrocarbons in the gas phase and S(IV) in aerosol solutions, and thereby potentially influence climate. The diurnal cycle of gas-phase \\Br and the corresponding particulate Br deficits are correlated. Higher values of Br in the gas phase during daytime are consistent with expectations based on photochemistry. Mechanisms that explain the widely reported accumulation of particulate Br in submicrometer aerosols are not yet understood. We expect that the importance of inorganic Br cycling will vary in the future as a function of both increasing acidification of the atmosphere (through anthropogenic emissions) and climate changes. The latter affects bromine cycling via meteorological factors including global wind fields (and the associated production of sea-salt aerosol), temperature, and relative humidity.

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