Formate, acetate and methanesulfonate measurements in antarctic ice: Some geochemical implications

doi:10.1016/0004-6981(88)90278-8

Atmospheric Environment (1967)

Volume 22, Issue 5, 1988, Pages 1011-1017

https://doi.org/10.1016/0004-6981(88)90278-8 Get rights and content

Abstract

Serious contamination problems are encountered when measuring organic acids in polar ice. Using an involved experimental protocol, methanesulfonate, formate and acetate have been investigated in ice core sections from Antarctica. With CH₃SO₃⁻ concentrations of a few ppb, HCOO⁻at a few tenths of ppb and CH₃COO⁻ around our detection limit, the organic acids represent only a small percentage of the total acidity in Antarctic ice.

Analysis of the various possible sources indicates that methane is probably the major atmospheric precursor (via formaldehyde) of formate present in the ice.

The significant presence of CH₃SO₃⁻ in Antarctic ice confirms the preponderant role played by marine biogenic emissions in the Antarctic sulfate budget. The CH₃SO₃⁻ ratio with respect to non-sea-salt sulfate is higher in Antarctic precipitation than in marine aerosol. Finally, CH₃SO₃⁻ in polar ice is suggested to be a more suitable parameter than excess sulfate for the study of marine biogenic emissions in the past.

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A 6 × 6 cm section was cut from the center of the 10 cm diameter core in order to limit contamination present in the outer layers of the core. ~50% of the outer portion of the core was removed in order to obtain a contaminant free portion of the core (Saigne et al., 1987; Legrand et al., 1988; Legrand et al., 1993; Jauhiainen et al., 1999). The inner core was allowed to melt at room temperature in covered 4L beakers that had been baked at 450 °C in a muffle furnace for a minimum of 4.5 h to remove organics prior to use.
The first methanol and ethanol concentrations in a Greenland ice core are reported for 14 annual samples ranging from 1686 to 1947 AD. Concentrations ranged from 83 nM to 1666 nM and 16 nM–424 nM for methanol and ethanol, respectively. Low median methanol and ethanol concentrations from 1686 to 1745 result primarily from natural emissions during a cold climate period. These concentrations provide a baseline alcohol level in deposition before impacts from various sources (e.g. naturally recovering plant populations, anthropogenic sources, and changing atmospheric oxidation chemistry) increased alcohol concentrations in the atmosphere. Concentrations of both alcohols increased after 1745 possibly due to increased biogenic and anthropogenic sources. Because both of these alcohols react with hydroxyl radicals, this increase has important implications for changing atmospheric oxidation chemistry. Samples were also analyzed for various other ice core components (e.g. aldehydes, anions, H⁺, DOC) to investigate possible correlation with alcohol concentrations. These ice core data are significant because they can be used to determine the extent temporal trends in alcohol concentrations were due to changes in atmospheric chemistry and varying source type and magnitude.
Spatial variability and possible sources of acetate and formate in the surface snow of East Antarctica
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Since, these organic acids contribute to total acidity of precipitation (Kawamura et al., 1996; Keene et al., 1983) and can potentially play an important role in the cloud condensation nuclei activity and influence the radiation budget of the earth's atmosphere (Kanakidou et al., 2005), understanding the sources and fluxes of these organic acids is important. The study of carboxylic acids in Antarctic snow can also provide useful information on the sources and transport processes of atmospheric constituents related to biogeochemical cycling (Keene and Galloway, 1988; Legrand and Saigne, 1988). In addition, carboxylic acids are one of the important components of dissolved organic matter in the snowpack (Legrand et al., 2013) and are possible carbon sources for resident microorganisms (Amato et al., 2007), potentially playing an important role in biological processes within the snowpack.
Spatial trends of acetate (Ac⁻) and formate (Fo⁻) were determined in surface snow samples along a coastal-inland transect (180 km) in the ice cap region at Princess Elizabeth Land and along a coastal transect in the Amery Ice Shelf (130 km), East Antarctica. Variations in both Ac⁻ and Fo⁻ seem to be unrelated to the acidity of snow. Ionic balance determined for the snow samples indicate the availability of HNO₃ that could undergo photolysis to produce hydroxyl radical (OH), one of the major reactants involved in oxidation reactions with organic matter. The strong positive correlations between Ac⁻ and NO₃⁻ in snow from both regions indicate that NO₃⁻ mediated OH-oxidation of organic compounds in snow could be an important source of Ac⁻ within the snowpack. On the other hand, negative correlation between Fo⁻ and NO₃⁻ might indicate that sources other than OH-oxidation of organic matter may be dominant in the case of Fo⁻. Higher Ac⁻ concentrations in the ice cap compared to the ice shelf correspond with long-range transport of biomass burning emissions to the ice cap region. Interaction of Ac⁻ and Fo⁻ with alkaline minerals could lead to their stability in the snowpack and minimize their loss from the snow surface. Resident microbial communities could also influence the budget of the carboxylic acids in snow.
Antarctic Tropospheric Chemistry Investigation (ANTCI) 2003 overview
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The Antarctic Tropospheric Chemistry Investigation (ANTCI) was carried out from late November to December 2003 with both extended ground-based and tethered balloon studies at Amundsen Scott Station, South Pole. ANTCI 2003 was the first of two Antarctic field studies with the primary goal of further exploring the active photochemistry of the South Pole region that was first identified in the previous Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) program. Since ISCAT was fully ground-based, ANTCI 2003 goals included expanding chemical studies both vertically upward to investigate mixing and horizontally to better understand large-scale plateau NO_x production and transport. Thus, in addition to ground-based experiments at South Pole, Twin Otter aircraft sampling took place out to hundreds of kilometers in several directions from the South Pole. These were designed to specifically address the issue of how representative past South Pole chemical measurements are of the surrounding high plateau region. The Twin Otter was also used to make transects along the coast both north and south of McMurdo Station. The present paper summarizes the overall setting and results of this investigation and highlights the many new findings that were obtained.
Persistent organic pollutants in soils and sediments from James Ross Island, Antarctica
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Polar territories as the regions playing a very significant role in global environmental processes keep attracting an interest of environmental scientists. Increasing levels of persistent organic pollutants (POPs) in various environmental matrices in these pristine locations (Blais et al., 1998; Donald et al., 1999; Carrera et al., 2001) are the matter of a growing concern but they also enhance the understanding of atmospheric chemistry and transport (Legrand and Saigne, 1988). Organochlorine compounds (OCs) including polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs) continue to pervade global ecosystems despite of successful curtailing of most of their emissions (AMAP, 2003).
Soil and sediment samples from James Ross Island were analyzed for their PCB, OCP and PAH contents. Soil concentrations ranged between 0.51 and 1.82 ng g⁻¹ for seven indicator PCB congeners, between 0.49 and 1.34 ng g⁻¹ for HCH congeners, between 0.51 and 3.68 ng g⁻¹ for the sum of p,p′-DDT, DDE, and DDD, and between 34.9 and 171 ng g⁻¹ for the sum of 16 EPA PAHs. Sediment levels from 0.32 to 0.83 ng g⁻¹ were found for PCBs, from 0.14 to 0.76 ng g⁻¹ for HCHs, from 0.19 to 1.15 ng g⁻¹ for DDTs, and from 1.4 to 205 ng g⁻¹ for PAHs. A prevalence of low-mass PAHs, less chlorinated PCBs, and more volatile chemicals indicates that the long-range atmospheric transport from populated areas of Africa, South America, and Australia is the most probable contamination source for the solid matrices in James Ross Island.
An overview of ISCAT 2000
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Citation Excerpt :
As stated in a 1991 symposium on Antarctic Tropospheric Chemistry, “there are many unique features of Antarctica that make it a valuable laboratory for monitoring and understanding the state of our global environment” (Bodhaine et al., 1992). Clearly, one of the most unique features of this land of ice is that it represents a giant archive of atmospheric conditions dating back nearly 500,000 years bp (Legrand and Feniet-Saigne, 1988; Legrand et al., 1991, and references therein). Thus, all major global geophysical, biological, and/or climatological events that have had a measurable impact on atmospheric composition are recorded in some form in the vast ice accumulations on this continent.
The Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) took place over the timer period of 15 November to 31 December in the year 2000. The study location was the Amundsen Scott Station in Antarctica. ISCAT 2000 defines the second phase of a program designed to explore tropospheric chemistry in Antarctica. As in 1998, the 2000 ISCAT study revealed a strong oxidizing environment at South Pole (SP). During the 2000 investigation, however, the suite of measurements was greatly expanded. These new measurements established the recycling of reactive nitrogen as a critical component of this unique environment. This paper first presents the historical background leading up to the ISCAT 2000 observations; then it focuses on providing a summary of the year 2000 results and contrasts these with those recorded during 1998. Important developments made during the 2000 study included the recording of SP data for several species being emitted from the snowpack. These included NO, H₂O₂ and CH₂O. In this context, eddy-diffusion flux measurements provided the first quantitative estimates of the SP NO and NO_x snow-to-atmosphere fluxes. This study also revealed that HNO₃ and HO₂NO₂ were major sink species for HO_x and NO_x radicals. And, it identified the critical factors responsible for SP NO levels exceeding those at other polar sites by nearly an order of magnitude. Finally, it reports on the levels of gas phase sulfur species and provides evidence indicating that the absence of DMS at SP is most likely due to its greatly shorten chemical lifetime in the near vicinity of the plateau. It is proposed that this is due to the influence of NO on the distribution of OH in the lower free troposphere over a region that extends well beyond the plateau itself. Details related to each of the above findings plus others can be found in the 11 accompanying Special Issue papers.
Shouldn't snowpacks be sources of monocarboxylic acids?
2002, Atmospheric Environment
We report the first measurements of the mixing ratios of acetic (CH₃COOH) and formic (HCOOH) acids in the air filling the pore spaces of the snowpacks (firn air) at Summit, Greenland and South Pole. Both monocarboxylic acids were present at levels well above 1 ppbv throughout the upper 35 cm of the snowpack at Summit. Maximum mixing ratios in Summit firn air reached nearly 8 ppbv CH₃COOH and 6 ppbv HCOOH. At South Pole the mixing ratios of these acids in the top 35 cm of firn air were also generally >1 ppbv, though their maximums barely exceeded 2.5 ppbv of CH₃COOH and 2.0 ppbv of HCOOH. Mixing ratios of the monocarboxylic acids in firn air did not consistently respond to diel and experimental (fast) variations in light intensity, unlike the case for N oxides in the same experiments. Air-to-snow fluxes of CH₃COOH and HCOOH apparently support high mixing ratios (means of (CH₃COOH/HCOOH) 445/460 and 310/159 pptv at Summit and South Pole, respectively) in air just above the snow during the summer sampling seasons at these sites. We hypothesize that oxidation of carbonyls and alkenes (that are produced by photo- and OH-oxidation of ubiquitous organic compounds) within the snowpack is the source of the monocarboxylic acids.

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Short communicationFormate, acetate and methanesulfonate measurements in antarctic ice: Some geochemical implications

Abstract

Geochim. cosmochim. Acta

Atmospheric Environment

Atmospheric Environment

Analvt. Chim. Acta

Atmospheric Environment

Dimethyl sulfide in the surface ocean and marine atmosphere: a global view

Science

Sulfate enrichment in marine aerosols owing to biogenic gaseous sulfur compounds

J. geophys. Res.

Aqueous-phase source of formic acid in clouds

Nature

The solubility of methanesulphonic acid and its implications for atmospheric chemistry

Environ. Tech. Lett.

Formic and acetic acids in the atmosphere of the southwest U.S.A.

Geophys. Res. Lett.

Background precipitation acidity

Organic material in the global troposphere

Rev. Geophys. Space Phys.

Atmospheric Chemistry: Fundamentals and Experimental Techniques

The composition of precipitation in remote areas of the world

J. geophys. Res.

Formaldehyde and other carbonyls in Los Angeles ambient air

Environment Technol.

Photo-oxidation of methylsulfide, ethyl-sulfide and methanethiol

Environ. Sci. Technol.

Formation of sulfur dioxide and methane sulfonic acid in the photo-oxidation of dimethylsulfide in the air

Geophys. Res. Lett.

Impurities sources of F−, Cl−, NO3− and SO42− in Greenland and Antarctic precipitation

J geophys. Res.

The Chemistry of the Atmosphere and Oceans

Short communication
Formate, acetate and methanesulfonate measurements in antarctic ice: Some geochemical implications

Impurities sources of F⁻, Cl⁻, NO₃⁻ and SO₄²⁻ in Greenland and Antarctic precipitation