scholarly journals Levels and Seasonal Trends of C1–C4 Perfluoroalkyl Acids and the Discovery of Trifluoromethane Sulfonic Acid in Surface Snow in the Arctic

Author(s):  
Maria K. Björnsdotter ◽  
William F. Hartz ◽  
Roland Kallenborn ◽  
Ingrid Ericson Jogsten ◽  
Jack D. Humby ◽  
...  
2015 ◽  
Vol 9 (1) ◽  
pp. 495-539
Author(s):  
M. Niwano ◽  
T. Aoki ◽  
S. Matoba ◽  
S. Yamaguchi ◽  
T. Tanikawa ◽  
...  

Abstract. The surface energy balance (SEB) from 30 June to 14 July 2012 at site SIGMA (Snow Impurity and Glacial Microbe effects on abrupt warming in the Arctic)-A, (78°03' N, 67°38' W; 1490 m a.s.l.) on the northwest Greenland Ice Sheet (GrIS) was investigated by using in situ atmospheric and snow measurements, as well as numerical modeling with a one-dimensional, multi-layered, physical snowpack model called SMAP (Snow Metamorphism and Albedo Process). At SIGMA-A, remarkable near-surface snowmelt and continuous heavy rainfall (accumulated precipitation between 10 and 14 July was estimated to be 100 mm) were observed after 10 July 2012. Application of the SMAP model to the GrIS snowpack was evaluated based on the snow temperature profile, snow surface temperature, surface snow grain size, and shortwave albedo, all of which the model simulated reasonably well. However, comparison of the SMAP-calculated surface snow grain size with in situ measurements during the period when surface hoar with small grain size was observed on-site revealed that it was necessary to input air temperature, relative humidity, and wind speed data from two heights to simulate the latent heat flux into the snow surface and subsequent surface hoar formation. The calculated latent heat flux was always directed away from the surface if data from only one height were input to the SMAP model, even if the value for roughness length of momentum was perturbed between the possible maximum and minimum values in numerical sensitivity tests. This result highlights the need to use two-level atmospheric profiles to obtain realistic latent heat flux. Using such profiles, we calculated the SEB at SIGMA-A from 30 June to 14 July 2012. Radiation-related fluxes were obtained from in situ measurements, whereas other fluxes were calculated with the SMAP model. By examining the components of the SEB, we determined that low-level clouds accompanied by a significant temperature increase played an important role in the melt event observed at SIGMA-A. These conditions induced a remarkable surface heating via cloud radiative forcing in the polar region.


Holzforschung ◽  
1999 ◽  
Vol 53 (1) ◽  
pp. 39-42 ◽  
Author(s):  
S. Li ◽  
K. Lundquist

Summary Refluxing of trans–2-(3,4-dimethoxyphenyl)-3-hydroxymethyl-7-methoxy-2,3-dihydrobenzo[b]furan with dioxane-water (9 : 1) in the presence of various acid catalysts led to the formation of 2-(3,4-dimethoxyphenyl)- 7-methoxy-3-methylbenzo[b]furan, the trans and cis forms of 2-hydroxy-3,3′4′-trimethoxystilbene and cis–2-(3,4-dimethoxyphenyl)-3-hydroxymethyl-7-methoxy-2,3-dihydrobenzo[b]furan. The proportions of the products were strongly dependent on the particular acid used as catalyst. HCl and to a greater extent HBr favored the formation of the 2-arylbenzofuran (phenylcoumarone) while the trans-stilbene derivative predominated in reaction products from the experiments with trifluoromethane sulfonic acid as the catalyst. Isomerization of the starting material occurred, regardless of the nature of the catalyst (small amounts of the cis-isomer formed). The number of phenylpropane units in spruce lignin attached to an adjacent unit by a β−5 linkage was estimated to be 6–9% on the basis of 1H NMR spectrometric measurements of the formation of phenylcoumarone structures on refluxing of milled wood lignin from spruce with 0.1M HBr in dioxane-water (9 : 1).


2011 ◽  
Vol 11 (8) ◽  
pp. 3949-3979 ◽  
Author(s):  
K. Toyota ◽  
J. C. McConnell ◽  
A. Lupu ◽  
L. Neary ◽  
C. A. McLinden ◽  
...  

Abstract. Episodes of high bromine levels and surface ozone depletion in the springtime Arctic are simulated by an online air-quality model, GEM-AQ, with gas-phase and heterogeneous reactions of inorganic bromine species and a simple scheme of air-snowpack chemical interactions implemented for this study. Snowpack on sea ice is assumed to be the only source of bromine to the atmosphere and to be capable of converting relatively stable bromine species to photolabile Br2 via air-snowpack interactions. A set of sensitivity model runs are performed for April 2001 at a horizontal resolution of approximately 100 km×100 km in the Arctic, to provide insights into the effects of temperature and the age (first-year, FY, versus multi-year, MY) of sea ice on the release of reactive bromine to the atmosphere. The model simulations capture much of the temporal variations in surface ozone mixing ratios as observed at stations in the high Arctic and the synoptic-scale evolution of areas with enhanced BrO column amount ("BrO clouds") as estimated from satellite observations. The simulated "BrO clouds" are in modestly better agreement with the satellite measurements when the FY sea ice is assumed to be more efficient at releasing reactive bromine to the atmosphere than on the MY sea ice. Surface ozone data from coastal stations used in this study are not sufficient to evaluate unambiguously the difference between the FY sea ice and the MY sea ice as a source of bromine. The results strongly suggest that reactive bromine is released ubiquitously from the snow on the sea ice during the Arctic spring while the timing and location of the bromine release are largely controlled by meteorological factors. It appears that a rapid advection and an enhanced turbulent diffusion associated with strong boundary-layer winds drive transport and dispersion of ozone to the near-surface air over the sea ice, increasing the oxidation rate of bromide (Br−) in the surface snow. Also, if indeed the surface snowpack does supply most of the reactive bromine in the Arctic boundary layer, it appears to be capable of releasing reactive bromine at temperatures as high as −10 °C, particularly on the sea ice in the central and eastern Arctic Ocean. Dynamically-induced BrO column variability in the lowermost stratosphere appears to interfere with the use of satellite BrO column measurements for interpreting BrO variability in the lower troposphere but probably not to the extent of totally obscuring "BrO clouds" that originate from the surface snow/ice source of bromine in the high Arctic. A budget analysis of the simulated air-surface exchange of bromine compounds suggests that a "bromine explosion" occurs in the interstitial air of the snowpack and/or is accelerated by heterogeneous reactions on the surface of wind-blown snow in ambient air, both of which are not represented explicitly in our simple model but could have been approximated by a parameter adjustment for the yield of Br2 from the trigger.


2020 ◽  
Vol 20 (13) ◽  
pp. 8139-8156
Author(s):  
Tobias Donth ◽  
Evelyn Jäkel ◽  
André Ehrlich ◽  
Bernd Heinold ◽  
Jacob Schacht ◽  
...  

Abstract. The magnitude of solar radiative effects (cooling or warming) of black carbon (BC) particles embedded in the Arctic atmosphere and surface snow layer was explored on the basis of case studies. For this purpose, combined atmospheric and snow radiative transfer simulations were performed for cloudless and cloudy conditions on the basis of BC mass concentrations measured in pristine early summer and more polluted early spring conditions. The area of interest is the remote sea-ice-covered Arctic Ocean in the vicinity of Spitsbergen, northern Greenland, and northern Alaska typically not affected by local pollution. To account for the radiative interactions between the black-carbon-containing snow surface layer and the atmosphere, an atmospheric and snow radiative transfer model were coupled iteratively. For pristine summer conditions (no atmospheric BC, minimum solar zenith angles of 55∘) and a representative BC particle mass concentration of 5 ng g−1 in the surface snow layer, a positive daily mean solar radiative forcing of +0.2 W m−2 was calculated for the surface radiative budget. A higher load of atmospheric BC representing early springtime conditions results in a slightly negative mean radiative forcing at the surface of about −0.05 W m−2, even when the low BC mass concentration measured in the pristine early summer conditions was embedded in the surface snow layer. The total net surface radiative forcing combining the effects of BC embedded in the atmosphere and in the snow layer strongly depends on the snow optical properties (snow specific surface area and snow density). For the conditions over the Arctic Ocean analyzed in the simulations, it was found that the atmospheric heating rate by water vapor or clouds is 1 to 2 orders of magnitude larger than that by atmospheric BC. Similarly, the daily mean total heating rate (6 K d−1) within a snowpack due to absorption by the ice was more than 1 order of magnitude larger than that of atmospheric BC (0.2 K d−1). Also, it was shown that the cooling by atmospheric BC of the near-surface air and the warming effect by BC embedded in snow are reduced in the presence of clouds.


2020 ◽  
Author(s):  
Michele Bertò ◽  
David Cappelletti ◽  
Elena Barbaro ◽  
Cristiano Varin ◽  
Jean-Charles Gallet ◽  
...  

Abstract. Black Carbon (BC) is a major forcing agent in the Arctic but substantial uncertainty remains to quantify its climate effects due to the complexity of mechanisms involved. In this study, we provide unique information on processes driving the variability of BC mass concentration in surface snow in the Arctic. Two different snow-sampling strategies were adopted during spring 2014 and 2015, focusing on the refractory BC (rBC) mass Ny-Ålesund concentration daily/hourly variability on a seasonal/daily time scale (referred to as 80-days and 3-days experiments). Despite the low rBC mass concentrations (never exceeding 22 ng g−1), a daily variability of up to 4.5 ng g−1 was observed. Atmospheric, meteorological and snow-related physico-chemical parameters were considered in multiple statistical models to understand the factors behind the observed variation of rBC mass concentrations. Results indicate that the main drivers of the variation of rBC are the precipitations events, snow metamorphism (melting-refreezing cycles, surface hoar formation and sublimation) and the activation of local sources (wind resuspension) during the snow melting periods. The rBC in the snow seems de-coupled with the atmospheric BC load. Our results highlighted a common association of snow rBC with coarse mode particles number concentration and with snow precipitation events.


2020 ◽  
Vol 20 (12) ◽  
pp. 7335-7358 ◽  
Author(s):  
Jiayue Huang ◽  
Lyatt Jaeglé ◽  
Qianjie Chen ◽  
Becky Alexander ◽  
Tomás Sherwen ◽  
...  

Abstract. We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowing-snow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCDtropo) from the GOME-2 (second Global Ozone Monitoring Experiment) and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007–2009), as well as against surface observations of O3. We conduct a simulation with blowing-snow SSA emissions from first-year sea ice (FYI; with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March–April GOME-2 and OMI VCDtropo to within 17 %, as well as their spatiotemporal variability (r=0.76–0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu), some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ∼5 in September–February to 10–60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment in deposition could enable blowing-snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCDtropo. We estimate that the atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing-snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4–8 ppbv (15 %–30 %) in March and 8–14 ppbv (30 %–40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40∘ N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures 25 %–40 % of the ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of many of these events and entirely misses 60 %–75 % of ODEs. This difficulty in reproducing observed surface ODEs could be related to the coarse horizontal resolution of the model, the known biases in simulating Arctic boundary layer exchange processes, the lack of detailed chlorine chemistry, and/or the fact that we did not include direct halogen activation by snowpack chemistry.


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