Sensitive determination of glyoxal, methylglyoxal and hydroxyacetaldehyde in environmental water samples by using dansylacetamidooxyamine derivatization and liquid chromatography/fluorescence

Abstract

In this study we improved the dansylacetamidooxyamine (DNSAOA)-LC-fluorescence method for the determination of aqueous-phase glyoxal (GL), methylglyoxal (MG) and hydroxyacetaldehyde (HA). As derivatization of dicarbonyls can potentially lead to complex mixtures, a thorough study of the reaction patterns of GL and MG with DNSAOA was carried out. Derivatization of GL and MG was shown to follow the kinetics of successive reactions, yielding predominantly doubly derivatized compounds. We verified that the bis-DNSAOA structure of these adducts exerted only minor influence on their fluorescence properties. Contrary to observations made with formaldehyde, derivatization of GL, MG and, to a lesser extent of HA, was shown to be faster in acidic (H(2)SO(4)) medium with a maximum of efficiency for acid concentrations of ca. 2.5 mM. Concomitant separation of GL, MG, HA and of single carbonyls was achieved within 20 min by using C(18) chromatography and a gradient of CH(3)CN in water. Detection limits of 0.27, 0.17 and 0.12 nM were determined for GL, MG and HA, respectively. Consequently, low sample volumes are sufficient and, unlike numerous published methods, neither preconcentration nor large injection volumes are necessary to monitor trace-level samples. The method shows relative measurement uncertainties better than ±15% at the 95% level of confidence and good dynamic ranges (R(2)>0.99) from 0.01 to 1.5 μM for all carbonyls. GL, MG and HA were identified for the first time in polar snow samples, but also in saline frost flowers for which unexpected levels of 0.1-0.6 μM were measured. Concentrations in the 0.02-2.3 μM range were also measured in cloud water. In most samples, a predominance of HA over GL and MG was observed.

Formaldehyde in the Alaskan Arctic snowpack: Partitioning and physical processes involved in air-snow exchanges

“…The analytical procedure followed is described by Houdier et al [2000] with subsequent improvements detailed by Houdier et al [2011]. Briefly, HCHO was analyzed by using DNSAOA derivatization followed by HPLC separation and fluorescence detection.…”

Frost flowers growing in the Arctic ocean‐atmosphere–sea ice–snow interface: 1. Chemical composition

“…All samples were thawed at room temperature before chemical analysis by dansylacetamidooxyamine (DNSAOA) derivatization followed by HPLC separation and fluorescence detection as described by Houdier et al [2000] with improvements detailed by Houdier et al [2011]. Elevated salinity in samples was shown to reduce the reactivity of the DNSAOA reagent with the aldehydes studied here (M. Barret and S. Houdier, unpublished results, 2009).…”

Glyoxal and methylglyoxal in Atlantic seawater and marine aerosol particles: method development and first application during the Polarstern cruise ANT XXVII/4

“…Zhou and Mopper (1997) found lower LODs for GLY and MGLY of 3-4 ng L −1 after enrichment via SPE and DNPH-LC-UV analysis probably due to the very high injection volumes of 2000 µL into the LC system. Using highly fluorescence derivatization agents and LC-FLD analysis, LODs of 16 ng L −1 (GLY) and 12 ng L −1 (MGLY) can be achieved without preconcentration (Houdier et al, 2011). However due to the high matrix content of real samples, mostly sample preparation steps for a combination of clean up and analyte enrichment are applied.…”

“…However, especially for seawater samples problems in SPE due to clogging of the cartridge due to matrix compounds are reported (Mbukwa et al, 2012). Recently a very sensitive HPLC method with fluorescence detection using dansylacetamidooxyamine as derivatization agent was presented for carbonyls in environmental water (Houdier et al, 2011). Kawamura and Ikushima (1993) developed a method for alpha dicarbonyls and atmospheric acids using BF3/butanol derivatization and gas chromatography-mass spectrometry (GC-MS).…”