Beruflich Dokumente
Kultur Dokumente
Department of Chemistry, Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
Received 29 July 2005; received in revised form 15 December 2005; accepted 19 December 2005
Available online 6 January 2006
Abstract
We here report a method for the determination of sugar compounds of known presence in atmospheric aerosols using liquid chromatography (LC)
combined with positive electrospray ionization mass spectrometry (MS). The target analytes include C
3
C
6
monosaccharide alcohols (glycerol,
erythritol, xylitol, mannitol), C
5
C
6
monosaccharides (xylose, glucose, andlevoglucosan), a disaccharide (sucrose), anda trisaccharide (melezitose).
A mobile phase consisting of 20% 10 mM aqueous ammonium acetate, 8% methanol, and 72% water was found to provide abundant [M+NH
4
]
+
adduct ions when coupled with electrospray ionization. Use of a polymer-based amino analytical column resolved the target compounds from the
bulk solvent and provided limited separation among the target compounds. The target analytes were quantied using their [M+NH
4
]
+
ions. Sample
pretreatment was greatly simplied in comparison with the more commonly used gas chromatographic methods. It involved extraction of aerosol
lters in methanol, evaporation of the solvent, and reconstitution with 5 mM ammonium acetate in water prior to the LCMS analysis. The analyte
recoveries were measured at the levels of 100, 500 and 1000 g/Lto be in the range of 78102%, 94112%, and 92110%, respectively. The detection
limits were lower than 10 pmol/injection for the tested target compounds except for xylose. Xylose had a detection limit of 95 pmol/injection. The
method was applied to analyze 30 atmospheric aerosol samples to demonstrate its feasibility. The LCMS method made possible the detection of
trisaccharides as aerosol constituents for the rst time.
2005 Elsevier B.V. All rights reserved.
Keywords: LCMS analysis of aerosol organics; Levoglucosan; Disacchrides; Trisacchrides; Sugar alcohols
1. Introduction
Organic carbon (OC) accounts for a signicant fraction
of ne aerosol mass, typically ranging from 10% in the
rural atmosphere to 30% in the urban environment [1].
Chemical characterization of the OC fraction at a molecu-
lar level has mainly focused during the past few decades
on the organicsolvent extractable portion that is amenable
to gas chromatographymass spectrometry (GCMS) analysis
[24]. These relatively non-polar compounds only accounted
for 1030% of OC mass [3,5,6]. Recent studies have indicated
that water-soluble organic compounds can be a dominant frac-
tion of OC, especially in rural and remote atmospheres [7].
Despite the abundance of water-soluble organic carbon (WSOC)
Corresponding author. Tel.: +852 2358 7389; fax: +852 2358 1594.
E-mail address: chjianyu@ust.hk (J.Z. Yu).
in atmospheric aerosols, its molecular composition is less stud-
ied due to the diverse nature of its constituents [8], which require
diverse analytical techniques for their determination. A number
of sugar compounds, such as levoglucosan, glucose, glycerol,
and sucrose, are known to be present in atmospheric aerosols as
a result of biomass combustion and soil resuspension [6,913].
The analysis of these sugar compounds is important for aerosol
source apportioning [5,14] and for the understanding of the
impact of biomass burning aerosols on local and regional air
quality as well as on the global climate.
The existing analytical methods for sugar compounds
fall into four categories: GC-based methods, high per-
formance liquid chromatography (HPLC)-based methods,
direct MS methods, and LCMS methods [15]. The GC-
based methods require derivatization of the hydroxyl groups.
The most-used derivatization technique is silylation using
bis(trimethylsilyl)triuoroacetamide (BSTFA), which causes
multiple derivatives for sugar compounds with both aldehyde
0021-9673/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2005.12.062
176 E.C.H. Wan, J.Z. Yu / J. Chromatogr. A 1107 (2006) 175181
Fig. 1. Structures of the target sugar analytes.
and OH groups as a result of unwanted silylation of the alde-
hyde group [9]. The derivatization step also adds extra sam-
ple handling and chemical manipulation, therefore becoming
more labor-intensive and prone to contamination. The HPLC
methods utilize a suitable column for separation and a vari-
ety of detection methods, including electrochemical detection
[16], refractive index (RI) detection, and evaporative light-
scattering detection (ELSD) [17]. In general, sugar compounds
lack chromophoric and uorophoric moieties required for UV
and uorescence detection. As a result, less sensitive HPLC
detection methods such as RI and ELSD are used. These detec-
tion methods typically provide detection limits in the range
of 0.051.2 g/injection [18], rendering them not practical for
measuring the trace levels in atmospheric aerosols. The direct
MS methods inject the sample extracts into a LC-MS system
with the LC column removed [11]. The coexistence of sam-
ple matrix components could adversely affect sensitivity in the
direct MS methods [19,20]. An LCMS method in the negative
ion mode was reported by Niwa et al. [21] for monosaccharides
andpolyols inuremic serumsamples. The applicationof LCMS
to study sugar compounds in atmospheric aerosols is so far very
limited. The study by Dye and Yttri [22] was the only study
we found in the literature that reported an LCMS method for
the determination of three monosaccharide anhydrides in atmo-
spheric aerosols.
In this work, we present an LCMS method for the deter-
mination of the atmospherically relevant sugar compounds and
demonstrate its use with real aerosol samples. Fig. 1 shows the
chemical structures of nine target analytes selected for this study.
With the exception of melezitose, the presence of other sugar
compounds has been reported in ambient aerosols or biomass
burning aerosols [6,9,1113,23]. The detection of any trisac-
chrides in atmospheric aerosols has not been reported in the
literature. This may well be due to the inability of GC based
methods for their detection. Melezitose is included as a trisac-
chride example in our list of target compounds to check their
presence since our LCMS method does not have the limita-
tions of the previous GC methods.
2. Experimental
2.1. Reagents and standards
All the organic solvents were LC grade. UV-irradiation
treated high purity water (18 M, supplied by a Milli-Q water-
purication system, Millipore, Bedford, MA, USA) was used
wherever water was needed. The sugar standards were from
Acros Organics (Geel, Belgium) and used as purchased without
further purication. Ammonium acetate (NH
4
Ac) of analytical
grade was purchased fromBDH(Poole, UK). Levoglucosan-
13
C
isotope was purchased from Cambridge Isotope (Andover, MA,
USA) and used as an internal standard (IS). Individual standard
stocks were made at the level of 500 mg/L in water and subse-
quently used to make a composite standard of 4.00 mg/L. The
individual and the composite standard solutions were stored at
4
C under
a gentle nitrogen stream. The residue was reconstituted with a
250 L aqueous solution of 5 mM ammonium acetate and thor-
oughly vortex-mixed for 30 s. The samples were analyzed within
30 days.
2.3. LCMS analysis
The samples or the standard solutions were injected into an
LCMSsystemfor quantication. The LCMSsystemconsisted
of a Waters 2695 HPLC and a Waters ZQ micromass quadru-
ple MS, equipped with an electrospray ionization (ESI) source
and a nitrogen solvent sparging unit. An injection volume of
100 L was used. The column for separation was a Prevail car-
bohydrate ES column (250 mm4.6 mm) packed with 5 m
spherical polymer beads coated with amino-based proprietary
bonding material (Alltech, Deereld, IL, USA). Isocratic elu-
tion was carried out in a mobile phase consisting of 20% 10 mM
NH
4
Ac, 8% methanol and 72% water. The column was kept at
a temperature of 25 1
C; desolvation tempera-
ture, 450