Technical NoteCarboxylic acids measurements with ionic chromatography
Introduction
Low molecular weight carboxylic acids are ubiquitous in the troposphere and are found both in the gas phase, in liquid phases (cloud, precipitation or fog), and in aerosol particles (Chebbi and Carlier, 1996). They contribute to the acidity of precipitation and are end products of the oxidation of many primary compounds resulting from natural or anthropogenic emissions. There is a large body of data on the concentrations of these species in the environment, particularly for formic and acetic acids, with less information available for other organic acids (Meng et al., 1995).
Atmospheric sampling of the gaseous fraction of these acids generally takes place with denuders or mist chamber systems (Keene et al., 1989), with the particulate phase being collected by aerosol filtration. Precipitation samples are collected with various devices and analyzed directly. Several techniques are used for the analytical determination of their concentration in liquid samples, including gas chromatography (Kawamura et al., 1995) and ion-exclusion chromatography (Keene et al., 1983; Andreae et al., 1990; Khwaja, 1995), with ion-exchange chromatography using Dionex AS4A or AS4A-SC columns being most common (Keene et al., 1989; Lefer et al., 1994). Interferences have been noted for this last method, particularly for the determination of acetate, with co-elution of other organics (Andreae et al., 1990; Talbot et al., 1990) that are not currently identified, and some authors underline the need to confirm results with ion exclusion chromatography, much less susceptible to interferences from co-eluting species (Andreae et al., 1990).
In this paper, we confirm that interferences exist for ion-exchange chromatography with AS4A, we identify some species that can potentially interfere, show that they can be present at significant levels in environmental samples, and propose an analytical development to overcome this problem.
Section snippets
Method
We tested interferences for acetate measurement using a Dionex AS4A-SC column. Run conditions are as follow: system Dionex DX-500, conductimetric detector, column AS4A-SC (4 mm) with guard AG4A-SC, regeneration with AMMS-1 with 12 mM H2SO4 at 2 ml min-1. The eluant is 0.5 mM of NaHCO3 at 2 ml min-1 (isocratic). This is a lower concentration than recommended with this column, leading to slightly longer retention times. Background conductivity is about 7.5 μS, with a total pressure about 1400 psi.
Implications
Fig. 3 presents a chromatogram of an actual sample collected at Summit (Greenland, 72°40N, 38°45W; 3240 masl) on 1 July, 1995 (Dibb and Jaffrezo, 1997). It is a sample of surface snow, from a precipitation event that took place during the advection of a biomass burning plume over the site, most probably of Canadian origin (Jaffrezo et al., in prep). This type of situation is not rare at Summit (Dibb et al., 1996; Jaffrezo et al., 1998) and is recorded in ice core layers (Legrand and De Angelis,
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