GC MS HRMS Itms Tof

Journal of Chromatography A, 1000 (2003) 125–151
www.elsevier.com / locate / chroma
Review
Modern developments in gas chromatography–mass spectrometry-

based environmental analysis
F.J. Santos, M.T. Galceran*
´
Departamento de Quımica ´ , Universitat de Barcelona, Diagonal 647, Barcelona 08028, Spain
Analıtica
Abstract
Gas chromatography coupled with mass spectrometry (GC–MS) continues to play an important role in the identification
and quantification of organic contaminants in environmental samples. GC–MS is one of the most attractive and powerful
techniques for routine analysis of some ubiquitous organic pollutants due to its good sensitivity and high selectivity and
versatility. This paper presents an overview of recent developments and applications of the GC–MS technique in relation to
the analysis in environmental samples of known persistent pollutants and some emerging contaminants. The use of different
mass analysers such as linear quadrupole, quadrupole ion-trap, double-focusing sectors and time-of-flight analysers is
examined. The advantages and limitations of GC–MS methods for selected applications in the field of environmental
analysis are discussed. Recent developments in field-portable GC–MS are also examined.
 2003 Elsevier Science B.V. All rights reserved.
Keywords: Reviews; Environmental analysis; Gas chromatography–mass spectrometry; Mass spectrometry
Contents
1. Introduction ............................................................................................................................................................................ 125

2. Gas chromatography–quadrupole mass spectrometry ................................................................................................................. 127
3. Gas chromatography–ion-trap mass spectrometry (GC–ITMS)................................................................................................... 131
4. Gas chromatography–high resolution mass spectrometry (GC–HRMS) ...................................................................................... 136
5. GC–time-of-flight mass spectrometry (GC–TOF-MS) ............................................................................................................... 140
5.1. Fast GC and GC3GC ..................................................................................................................................................... 141
5.2. Accurate mass instruments............................................................................................................................................... 144
5.3. Laser and plasma sources ................................................................................................................................................ 145
6. Portable GC–MS instruments................................................................................................................................................... 146
7. Conclusions and future perspectives ......................................................................................................................................... 148
References .................................................................................................................................................................................. 149
1. Introduction
*Corresponding author. Tel.: 134-93-402-1275; fax: 134-93- Gas chromatography coupled to mass spec-
402-1233. trometry (GC–MS) is the technique most commonly
E-mail address: galceran@apolo.qui.ub.es (M.T. Galceran). employed today for the analysis of volatile organic
0021-9673 / 03 / $ – see front matter  2003 Elsevier Science B.V. All rights reserved.
doi:10.1016 / S0021-9673(03)00305-4
126 F. J. Santos, M.T. Galceran / J. Chromatogr. A 1000 (2003) 125–151
pollutants in environmental samples. The very high ions and sample molecules. As a result, molecular
number of applications is the result of the efficiency ions, adduct ions and fragment ions can be gener-
of gas chromatography separation and the good ated. However, the degree of fragmentation is much
qualitative information and high sensitivity provided less than in EI and can be controlled by varying the
by mass spectrometry (MS). The MS fragmentation nature of the reagent gas. CI reagents vary from
pattern can often provide unambiguous component application to application, but the most popular are
identification by comparison with library spectra. methane, isobutane and ammonia. The major re-
When gas chromatography (GC) and MS are com- action in positive-ion chemical ionisation (PCI) is
bined, the GC separation usually provides isomer proton transfer, which takes place in sample mole-
selectivity, while the MS shows compound class and cules with a higher proton affinity (PA) than the
homologue specificity. GC–MS was born in 1959, reagent ions. Other reactions that can also occur
when Gohlke [1] first described the direct intro- include charge exchange, if the reagent gas does not
duction of GC effluent into a time-of-flight (TOF) contain available hydrogen, electrophilic addition
mass spectrometer equipped with an oscilloscope. In and anion abstraction. In CI, negative ions can also
the mid-1960s the analysis of different volatile be produced (NCI). These negative ions are formed
organic mixtures with the new technique was re- by ion–molecule reactions between sample and
ported [2,3]. These procedures mainly involved using reagent gas ions. Such reactions include proton
TOF and high-resolution mass spectrometers. Never- transfer, charge exchange, nucleophilic addition or
theless, to couple packed columns to MS, a reduction nucleophilic displacement. Moreover, the capture of
of pressure was needed to meet the vacuum require- the thermal electrons generated under CI conditions
ments of the mass spectrometer. At present, direct allows for the formation of molecular anions from
coupling of capillary columns to the ion source of compounds with a positive electron affinity (i.e.
the mass spectrometer is by far the most common electron-capturing compounds). Chemical ionisation
interfacing method in use. High-resolution GC di- provides better sensitivity and selectivity than EI,
rectly coupled to low cost bench-top MS instruments but, given the special requirements of CI work, the
has made GC–MS one of the most attractive tech- number of applications is relatively low compared to
niques for routine analysis of volatile organic pollu- EI. Nevertheless, CI is the technique of choice for
tants. the analysis of isomers in environmental samples,
Several ionisation techniques are used in GC–MS. because different isomers have different reactivities
Among them, electron ionisation (EI) is the most towards the reagent gas, resulting in different spec-
popular because it often produces both molecular and tra. In contrast, with EI, very similar spectra are
fragment ions. In EI, gas analyte molecules are obtained for different isomer compounds. Some
bombarded by energetic electrons (typically 70 eV), examples of the applicability of CI in the analysis of
which leads to the generation of a molecular radical isomers will be discussed in the next sections of this
ion (M 1? ) that can subsequently generate ionised paper.
fragments. This technique generally allows for the Compound identification is currently performed by
determination of both relative molecular mass and comparing an unknown electron ionisation MS spec-
the structure of the molecule. One important feature trum with collections of reference spectra. Huge
of electron ionisation spectra is that they are highly electron ionisation mass spectral libraries are com-
reproducible, which means that mass spectral li- mercially available, such as the NIST Library, which
braries can be used for identification of unknowns. contains 230 000 spectra, and the Wiley Library,
However, in some cases, EI does not provide the with 275 000 spectra. The identification process is
sensitivity required for the analysis of very small based on search algorithms that compare the ob-
amounts of compounds in environmental samples. tained spectra with those of a library, which are
This is mainly due to extensive fragmentation. To generally implemented in the GC–MS instrument. A
solve this problem, softer ionisation techniques such spectral match and fit factor defines the certainty of
as chemical ionisation (CI) are applied. In CI, ion– the identification. Although the library search is a
molecule reactions take place between reagent gas powerful tool for the identification of unknowns, for
F. J. Santos, M.T. Galceran / J. Chromatogr. A 1000 (2003) 125–151 127
identification a series of conditions must be satisfied: which can help in the identification of families of
the compound must be included in the library; the compounds.
MS conditions at which both spectra have been Instruments with different mass analysers, e.g.
obtained must be similar; and the GC separation magnetic sectors, linear quadrupoles, quadrupole ion
must be sufficiently efficient to obtain a clean mass traps and time-of-flight analysers have been used for
spectrum. In order to guarantee correct identification coupling to GC. The great majority of GC–MS
and prevent false positives, different strategies can applications utilise bench-top instruments with linear
be adopted. For instance, the U.S. Environmental quadrupoles and electron ionisation. There are, how-
Protection Agency (U.S. EPA) proposes the use of at ever, new and interesting applications using other
least two different m /z for each analyte, and the mass analysers and ionisation techniques. As the
relative abundance of both ions must be kept within number of GC–MS applications in environmental
the 15–20% range. Even if the spectrum is not in the analysis is very large, only some selected examples
library, the search procedure can yield valuable of recent research are included in the following
information that can be complemented with addition- sections. These sections are organised according to
al MS experiments. Such complementary procedures mass analyser type, the characteristics of which,
may include CI, to provide molecular mass, high- obtained from specifications of commercial instru-
resolution MS (HRMS), for accurate mass determi- ments, are summarised in Table 1.
nation, or tandem mass spectrometry (MS–MS), for
structure elucidation.
A large number of publications have resulted from 2. Gas chromatography–quadrupole mass
research on environmental applications of GC–MS. spectrometry
This technique is frequently used to study the
behavior of environmental pollutants and to monitor The popularity of quadrupole mass spectrometers
their presence in the environment. GC–MS is cur- arises from their relatively low cost, compactness,
rently a mature technique applied in the analysis of a the ease with which their resolution can be electroni-
significant number of pollutants in samples of differ- cally controlled and the simplicity of operation. The
ent origin, such as air, atmospheric aerosols, water, linear quadrupole mass analyser can be considered as
soils, sludges, biological samples and others. The a mass filter and it consists of four hyperbolic rods
compounds most commonly analysed include al- placed parallel in a radial array. An appropriate
kanes, polycyclic aromatic hydrocarbons (PAHs), combination of DC and RF electric field applied to
pesticides, off-flavor compounds, water disinfection the four rods induces an oscillatory motion in a beam
by-products, polychlorinated biphenyls (PCBs), poly- of ions injected approximately axially into the as-
chlorinated dibenzo-p-dioxins and furans (PCDD/ sembly by means of a low accelerating potential. The
Fs), as well as other endocrine disrupting chemicals oscillating trajectories are mass dependent and ions
such as phthalates and short ethoxy alkylphenol with one particular m /z can be transmitted toward
etoxilates. GC–MS is also the technique of choice the detector when a stable trajectory through the rods
for the analysis of emerging pollutants such as is obtained. Ions of different m /z can be consecutive-
polybrominated diphenyl ethers (PBDEs) or poly- ly transmitted by the linear quadrupole filter toward
chlorinated alkanes. In addition to the above-men- the detector when the DC and RF potentials are
tioned compounds, GC–MS has also been applied in swept at a constant ratio and oscillation frequencies.
the analysis of polar and non-thermal stable com- Linear quadrupoles are the mass analysers most
pounds after derivatisation. Derivatisation converts widely used for the analysis of environmental pollu-
the analyte into a product with greater stability and tants by GC–MS, mainly because they make it
superior chromatographic properties, such as im- possible to obtain high sensitivity, good qualitative
proved peak shape. Moreover, in MS, derivatisation information and adequate quantitative results with
may result in improved ionisation efficiency, en- relatively low maintenance. Moreover, the ready
hanced response and the production of fragmentation availability of reliable commercial instruments has
patterns related to the introduced organic group, promoted the widespread use of this type of equip-
128
F. J. Santos, M.T. Galceran / J. Chromatogr. A 1000 (2003) 125–151
Table 1
General specifications and features for linear quadrupole, ion-trap, double-focusing magnetic sector and TOF analysers
Criteria Linear quadrupole Ion-trap Double-focusing magnetic sector Time-of-flight
Mass range 2–1000 Da 10–1000 Da 2–4000 Da 5–1500 Da

Mass accuracy 60.1–0.2 m/z ,5 ppm (,2 mDa)) To within 5 ppm (610 mDa) for
GCT姠-Micromass
Speed 5200–10 000 a.m.u./s 5600–10 000 a.m.u./s 0.15 s/decade 5000–40 000 transients/s
Monitoring mode Full-scan, SIM and simultaneous Full-scan, SIM, full-scan of Full-scan, SIM Full range spectrum
full-scan/SIM product ions
Sensitivity EI full-scan: 1–10 pg OFN S/N 20:1, EI full-scan: 1–10 pg OFN 100 fg of 2,3,7,8-TCDD, 1–2 pg HCB S/N 10:1 for m/z 284
m/z 272 S/N 50:1 for m/z 272 S/N 125:1 m/z 321.8936 (SIM
EI-SIM: 20–100 fg OFN S/N 25:1, mode at 10 000 of resolution)
m/z 272
Dynamic range 4–7 Orders of magnitude 4–5 Orders of magnitude .5 Orders of magnitude 2.5–5 Orders of magnitude
Versatility EI, PCI, NCI EI, PCI, NCI (only PolarisQ) EI, PCI, NCI, field ionisation EI, PCI, NCI, Field ionisation
Mass resolution Unit mass resolution Unit mass resolution .10 000 (10% valley definition) 1000–10 000 FWHM (#7000,
10% valley definition)
MS–MS None a MS n , n55–10 Only with EBEqQ configuration None
Performance/cost Low Low Very high High
BzPh, benzophenone; DFBZ, decafluorobenzophenone; HCB, hexachlorobenzence; OFN, octafluoronaphthalene.

a
Only triple-step quadrupole MS.
ment. Generally, these instruments are characterised productive consequences [10]. In addition to volatile
by a bench-top configuration with mass unit res- chlorinated compounds such as trihalomethanes
olution and both electron and chemical ionisation (THMs), attention has been directed to other semi-
techniques (Table 1). A survey of the literature over volatile compounds such as haloacetic acids (HAAs),
the last 5 years shows that the number of papers haloacetonitriles, haloketones and haloaldehydes.
describing GC–MS applications using linear quad- Most of the methods used to determine these com-
rupole instruments is on the order of several pounds involve gas chromatography, with electron-
thousand and the ongoing trends indicate a constant capture detection, or coupled with EI low-resolution
and impressive improvement in sensitivity and de- mass spectrometry with quadrupole mass analysers
tection limits. Recently, some new developments [11,12]. Due to the regulation of HAAs in drinking
have been implemented in GC–MS instrumentation water [13], these compounds continue to be the
based on quadrupole technology and related to the subject of new analytical methods [14]. For their
stability of mass calibration and higher scan-speed analysis by GC, a prior derivatisation step is neces-
and sensitivity similar to ion-trap analyser (Table 1). sary because of their low volatility and high polarity.
This has led to a significant improvement in GC– For instance, recently, Xie developed a method for
linear quadrupole MS capabilities and it is now the analysis of HAAs using liquid–liquid micro-
possible to work simultaneously with full-scan and extraction, acidic methanol derivatisation and GC–
selected ion monitoring (SIM) modes in a single run EI-MS determination [15]. Limits of detection were
(Table 1). in the microgram per liter range, and in comparison
One of the main areas of interest to environmental to EPA Method 552.2 [16], which uses GC with
chemists is the identification and quantification of electron capture detection (GC–ECD), cleaner
polycyclic aromatic hydrocarbons and pesticides in baselines and fewer interfering peaks were evident.
water, air and sediments. These compounds represent Another problem of major concern for many water
an important class of hazardous organic chemicals utilities around the world is the presence of off-
that are ubiquitous in the environment due to their flavour compounds that produce an unpleasant taste
high persistence and bioaccumulation. Different ana- and odor in water. The most obvious taste and odor
lytical methods have been proposed in the literature compounds, such as hydrocarbons, solvents,
for their determination, but GC with selective detec- iodoforms and various chloro- and bromophenols,
tors and coupled to MS are the most widely used which have odor thresholds in the microgram per
techniques. GC–MS has proved to be an advantage- liter range, are currently analysed by GC–EI-MS
ous and powerful technique compared with other using linear quadrupole bench-top instruments. In
selective detection systems due to its good sensitivi- addition, the implementation of extraction and pre-
ty, high versatility and selectivity. Confirmation concentration techniques such as closed-loop-strip-
capabilities are an additional advantage. For this ping analysis (CLSA) and solid-phase microextrac-
reason, selective detectors have progressively been tion (SPME), coupled to GC–MS instruments, has
replaced by MS using both electron and chemical allowed for the identification and quantification of
ionisation modes. A large number of applications algal metabolites (geosmin and methylisoborneol),
related to the analysis of different families of pes- which, at their ng / l odor thresholds, are responsible
ticides in water, soil and sediment samples can be for most earthy-musty odor episodes around the
found in the literature [4–7]. Most applications are world [17–20].
based on the combination off-line or on-line sample Endocrine-disrupting chemicals (EDCs) have also
preparation techniques such as SPE and SPME with received special attention in recent years. In wildlife,
GC–MS in order to obtain less time- and labor- these compounds are suspected of being responsible
consuming procedures [5,6,8]. for the decline of certain species and change of sex
In recent years, a great deal of research has in fish and shellfish. Chemicals suspected of being
focused on disinfection by-products (DBPs) in drink- estrogenic include synthetic estrogens, steroids, pes-
ing water [9], following the finding that several ticides, phthalates, alkylphenol ethoxylate surfac-
DBPs are carcinogenic and may have adverse re- tants, dioxins, PCBs, PBDEs and natural estrogens
such as phytoestrogens [9]. GC–MS and LC–MS are 4–2100 ng / l [22] and 17 ng / g [23], respectively. For
the most commonly used techniques for the en- the analysis of nonylphenoxy carboxylic acids
vironmental analysis of EDCs. Generally, GC–MS is (NPnECs), a derivatisation step is required to over-
used for apolar (e.g. PCDD/ Fs, PCBs, PBDEs) or come the problem posed by their low volatility. Dıaz ´
moderate polar compounds (e.g. alkylphenols, phtha- et al. [24] recently proposed the use of dimethyl
lates), while for polar compounds such as alkyl- sulfate / NaOH for the derivatisation of NPnEOs and
phenol carboxylates, LC–MS is the preferred tech- NPnECs (n#2) to their corresponding methyl esters.
nique. Other compounds such as steroid sex hor- The analysis of these compounds was performed by
mones are analysed using both techniques. Among headspace solid-phase microextraction and GC–MS
these compounds, nonylphenol ethoxylates in SIM mode. As an example, Fig. 1 shows GC–EI-
(NPnEOs, n5number of ethoxy units) have recently MS single-ion chromatograms of derivatised NP,
been studied as a result of the fact that persistent NPnEOs and NPnECs for a water sample taken from
degradation products (nonylphenols and carboxylic a river where they had been detected. PCI-MS with
derivatives) generated during wastewater treatment ammonia as the reagent gas has also been used for
and in sewage treatment plants are regarded as the analysis of NPnECs in paper mill and municipal
endocrine-disrupting compounds [21]. Recently, sewage treatment plant effluents and river water. All
nonylphenol (NP) and NPnEOs (n#2) have been NPnECs produced molecular ion adducts with am-
analysed in water from a sewage treatment plant and monia to give base peaks corresponding to [M1
in fish by GC–EI-MS, and detection limits were NH 4 ] 1 . Using this ionisation mode, limits of de-
Fig. 1. Headspace-SPME–GC–MS single-ion chromatograms of derivatized compounds from river water entering water treatment plant.
NP, nonylphenol; NP1EO, nonylphenol monoethoxylate; NP2EO, nonylphenol diethoxylate; NP1EC, nonylphenoxyacetic acid; NP2EC,
nonylphenoxyethoxyacetic acid. Experimental conditions: GC column: DB-5MS, 30 m30.25 mm I.D., 0.25 mm film thickness. MS
analyser: quadrupole, operating in SIM mode. (Reprinted with permission from Ref. [24], Copyright 2002, American Chemical Society)
tection lower (4–8-fold) than those with EI-MS were and are used for congener-specific determination. In
achieved for NPnECs (n: 1–4) [25,26]. addition, the availability of various 13 C-labeled
Several papers have recently been published con- standards allows for quantification using the isotopic
cerning the analysis of phthalates, another estrogenic dilution method. GC–low-resolution MS with nega-
family of compounds. GC–MS with EI and CI, using tive chemical ionisation is commonly employed for
methane or isobutane as reagent gas, has been used the analysis of PBDEs in environmental samples,
for the analysis of these compounds in water, soil although in some cases GC–HRMS is preferred. The
and sewage sludge samples [27]. PCI with methane high selectivity of HRMS prevents interferences
was found to be very useful in obtaining molecular produced by other halogenated compounds, although
mass information, but EI-MS is the most sensitive it has not been demonstrated that in practice this
mode. The ion at m /z 149 is the most abundant in technique is superior to LRMS [39]. GC–NCI-
the EI mass spectra for all phthalates except di- LRMS offers higher sensitivity than EI-LRMS,
methylphthalate, which gives a base peak at m /z especially for compounds with more than four
163. These ions and other ions at higher mass range bromine atoms. Nevertheless, a drawback of the NCI
are currently selected for quantification purposes and technique is that for most PBDEs only the ions due
for the identification of isomeric mixtures. Using to bromine can be monitored (m /z 79 and 81),
GC–MS in EI mode, limits of detection of 2–30 although, occasionally, some higher mass fragments
ng / l in river and sea water, 125–250 ng / kg in can be used for quantification, such as m /z 487 and
sediments, and 10–600 ng / g in sewage sludge have 489 for BDE-209. EI-LRMS would offer higher
been reported [27–29]. The main problem to be selectivity and the capability of confirming the
solved when analysing phthalates is contamination identity of compounds from the full mass spectrum,
by laboratory materials during the different steps of but at the cost of lower sensitivity. Eljarrat et al.
the analysis. To solve the background contamination [40], who have compared the two ionisation meth-
problem, simple and rapid analytical procedures have ods, indicate that for EI-MS limits of detection were
been proposed, based on SPME. These involve 15 times higher than those for NCI-MS. In contrast,
applying both direct immersion and headspace tech- Covaci et al. [41], using large volume injection and
niques, and subsequent GC–MS analysis [29–31]. narrow bore columns, obtained comparable results
Another endocrine disrupting compound of recent with both ionisation modes. However, EI provides
interest is bisphenol A, which has also been analysed better structure information than NCI, and interfer-
by GC–MS, although its high polarity often requires ence problems between the penta-BDE-126 and
a derivatisation step prior GC analysis. Derivatisa- hexa-BDE-155 in NCI mode can be overcome when
tion to silyl bisphenol A [32,33] or pentafluoro- using EI mode by monitoring the molecular ions of
benzoylate ester [34] are the most commonly used each homologue group. In spite of these considera-
procedures for the analysis of this compound. GC– tions, as a result of its higher sensitivity, GC–NCI-
NCI-MS with methane as reagent gas allowed for a MS has been the most frequently used technique for
very high detectability of BPA in water (0.02 ng / l) the analysis of PBDEs in air [42], sediment [39,43]
after derivatisation to pentafluorobenzoylate [35], and biota samples [39,44–50]. As an example, Fig. 2
which is greater than that obtained using GC–EI-MS shows the chromatograms of a PBDE standard
for underivatised BPA (0.1 mg / l) [36,37]. solution containing 14 BDE congeners, and cormor-
Polybrominated diphenyl ethers (PBDEs), which ant liver and porpoise blubber samples where various
are used as flame retardants, are being determined in BDE congeners were detected by GC–NCI-MS in
a growing number of environmental samples around SIM mode [44].
the world because they have been shown to be
significant endocrine disrupting compounds [38]. Up
until recently, quantification of PBDEs had been 3. Gas chromatography–ion-trap mass
carried out using technical PBDE products due to the spectrometry (GC–ITMS)
lack of pure reference standards, but more than 30
individual congeners are now commercially available The ion-trap mass spectrometer is a member of the
Fig. 2. GC–NCI-MS chromatograms for the sum of two bromine ions monitoring (79 and 81 Da) for (a) a standard solution containing the
14 BDE congeners determined, (b) a cormorant liver sample, and (c) a porpoise blubber sample. Experimental conditions: GC column:
CP-Sil 8, 50 m30.21 mm I.D., 0.25 mm film thickness. MS analyser: quadrupole, operating in NCI mode, monitoring bromine at 79 and 81
Da. (Reprinted from Ref. [44], Copyright 2002, with permission from Elsevier Science)
quadrupole family of instruments, first described by use, an auxiliary oscillating potential of low am-
Paul and Steinwedel [51], who developed a method plitude is applied across the end-cap electrodes while
for mass analysis by trapping a range of ion masses a radio-frequency (RF) oscillating drive potential of
in the quadrupole ion trap and detecting and measur- |1 MHz is applied to the ring electrode. Ions are
ing the ions while stored. From 1960 to 1980, created within the ion trap by injection of electrons,
modifications in the operating system were made in or may be injected from an external source. A range
order to store only a single mass at a time, but the of m /z values can be held in stable orbits by virtue
impetus for the widespread implementation of the of the RF potential and become focused as a cloud at
ion trap in mass spectrometry was the invention in the ion trap center. As the amplitude of RF potential
the early 1980s of a mode of ion trap operation is increased, the motion of the ions becomes pro-
termed mass-selective ejection [52]. Using this tech- gressively more energetic and they develop unstable
nique, trapped ions are sequentially ejected from the trajectories. Ions then exit the ion trap to a detector
trapping volume towards an external detector in in order of increasing m /z value, generating a mass
increasing mass / charge order. Prior to this develop- spectrum. Usually, several such mass spectra, termed
ment, the acquisition of an entire mass spectrum micro-scans, are obtained in succession and summed
using an ion trap was a complex and time-consuming prior to being displayed as a scan.
process and the linear quadrupole, invented concur- An important breakthrough in GC–MS analysis
rently with the quadrupole ion trap, became the was achieved with the advent of the ion-trap detector
dominant bench-top mass spectrometer. At present, because of its capability of performing MS–MS by
the ion trap is challenging this position, with means of collision-induced dissociation (CID). The
thousands of GC–MS instruments installed in re- theoretical aspects of ion-trap tandem mass spec-
search and routine laboratories worldwide. trometry can be found in the comprehensive paper
Coupled to gas chromatography, quadrupole ion- published by Plomley et al. [53]. The most common
trap mass spectrometry offers good sensitivity, the way to perform CID is to apply a radio-frequency
ability to manipulate ions during storage, relatively (RF) voltage to the end-cap electrodes of the ion trap
high mass range, low cost and reduced size. Current- to isolate ions with a selected m /z value or a small
ly, two ion-trap instruments coupled to GC are range of m /z values. After isolation, an excitation
commercially available: ThermoFinnigan’s PolarisQ voltage, resonant or non-resonant, is applied over the
uses external source ionisation, and Varian’s Saturn trap, and collisions with helium buffer gas lead to the
2000, internal source ionisation. Both commercial formation of product ions. Compared with the triple-
instruments offer electron and positive chemical stage quadrupole, the ion trap offers some advan-
ionisation modes as well as an MS–MS option, but tages. First, it operates in a pulsed mode, so that ions
only PolarisQ can function in negative chemical are accumulated mass selectively over time. In this
ionisation mode. All these instruments offer unit way, a target ion number can be selected so as to
mass resolution, a mass range up to 1000 a.m.u. and ensure constant signal-to-noise ratio over a wide
high sensitivity (Table 1). Moreover, enhanced range of eluent concentrations. This results in an
selectivity can be obtained in MS–MS mode, with enhancement in sensitivity at low concentrations
the additional advantage of confirmation capabilities (Table 1). A second advantage is that collision-
as the full-scan spectra of product ions is collected. induced dissociation in the ion trap is produced by
A drawback of ion-trap instruments is that sensitivity several hundred collisions of a mass-selected ion
depends on the quantity of ions present in the trap, with helium buffer gas atoms. Under these con-
which affects the response in real samples. As a ditions, it is possible to dissociate the accumulated
consequence, additional requirements for either cali- mass-selected ions completely, and, moreover,
bration or clean-up procedures are needed. practically 90% of fragment ions are confined within
The quadrupole ion trap is the three-dimensional the ion trap in favorable cases. In such cases, the
analogue of the conventional quadrupole mass filter. efficiency of formation, storage and transmission of
It consists of three cylindrically symmetric electrodes product ions to the detector is high, and more
(two end-caps and a ring). In the normal mode of product ions are therefore obtained. An additional
advantage of ion-trap instruments is the capability of ions CH 3 CHF 1 and CH 3 CF 1

2 and PAHs. This meth-
performing MS n . Environmental applications have od allowed for the separation and determination of
exploited this advantage only to a limited extent, co-eluting isomers. Another example of chemical
despite its usefulness, as for instance for the identifi- ionisation and full-scan IT is the analysis of linear
cation of metabolites of environmental contaminants. alkylbenzenesulfonates (LAS) and their degradation
In comparison with triple-stage quadrupole or hybrid products, sulfophenylcarboxylic acids, in sewage
sector instruments, one limitation of the ion trap in effluents and river water [57]. Since the abundance
MS–MS mode is the fact that only helium can be of LAS molecular ions in EI mass spectra is low and
used as the collision gas. sometimes they are not detected, the use of positive
In recent years, some interesting applications of chemical ionisation has been proposed. This allows
GC–ion trap mass spectrometry in environmental for a 10- to 50-fold enhancement of sensitivity in
analysis have been published. These have focused relation to the EI mode. An interesting characteristic
mainly on the determination of halogenated com- of ion-trap mass spectrometry is the ability of the
pounds, such as PCDDs / Fs, PCBs, toxaphene and system to change the ionisation mode from positive
polybrominated diphenyl ethers, steroids, pesticides to negative during the analysis. Sequential positive
and PAHs and their derivatives. Generally, EI is the and negative chemical ionisation combined with
chosen ionisation technique, and full-scan acquisition GC–ITMS has been used as a selective and sensitive
mode is currently used because it provides quali- method for the analysis of organochlorine and or-
tative information for unequivocal identification. One ganophosphorus pesticides in vegetable samples [58]
of the advantages of ion-trap analysers compared to with good reproducibility, ,25%, and low detection
linear quadrupoles is their high sensitivity in full limits, 2–2000 times below EU regulatory levels
scan mode, which means reliable spectra can be (0.01 mg / kg).
produced at low concentration levels. Different au- Tandem mass spectrometry is the ITMS mode
thors have taken advantage of this capability to most widely used for the analysis of environmental
identify and quantify environment contaminants at contaminants because it provides very high selectivi-
ppt levels. Typical recent applications include the ty. The potential of ion-trap tandem mass spec-
use of full-scan ITMS for the analysis of PBDEs in trometry (ITMS–MS) using EI mode for the analysis
sediments and biota by Allchin et al. [54], and an of polychlorodibenzo-p-dioxins and dibenzofurans,
SPME–GC–ITMS method for the determination of dioxin-like PCBs, toxaphene and polybrominated
haloacetic acids in water, proposed by Sarrion ´ et al. diphenyl ethers has recently been evaluated. These
[55]. In contrast with what happens in linear quad- compounds are often analysed by GC–HRMS, but
rupole analysers, the selected ion monitoring mode is this technique involves high investment and mainte-
not frequently used in ion traps because no improve- nance costs. Alternative methods such as GC–
ment in sensitivity is obtained with respect to the ITMS–MS have been studied to replace the refer-
full-scan mode. Nevertheless, an enhancement of ence method (GC–HRMS), or at least decrease
selectivity is achieved, which can be used to prevent analysis costs by using such methods for preliminary
MS interferences. screening. Only suspect samples are then kept for
GC–ITMS combined with chemical ionisation analysis by the reference method. A recent estimate
(CI) and full-scan operation mode has not been of the total time required for instrumental analysis
frequently applied in the analysis of organic pollu- revealed that HRMS requires at least 50% more time
tants in the environment. Nevertheless, several paper sample than does ITMS–MS, considering the
pers that compare CI and EI modes have been analysis time as the time required for instrument
published. Methane is the most widely used chemical tuning, calibration, maintenance and repair [59].
ionisation reagent, although other compounds have Several papers related to the evaluation of the GC–
also been proposed. For instance, Mosi et al. [56] ITMS–MS technique for the analysis of these com-
utilised 1,1-difluoethane as a reagent gas to differen- pounds have recently been published. For instance,
tiate PAH isomers through the formation of specific the technique has been successfully applied to the
adducts by ion–molecule reaction between the cat- analysis of PCDD/ Fs in fly ash [60,61], soil extracts
[62], sewage effluents [63], foods [59,64], fish These values are slightly higher than those obtained
tissues [65] and waste mineral oils [66]. Non-ortho by GC–HRMS, but in all cases they are enough to
PCBs (77, 81, 126 and 169) and mono- and di-ortho obtain reliable results at low concentration levels.
substituted PCBs (105, 118, 128, 156 and 157), also One interesting approach to improve the sensitivity
known as dioxin-like PCBs, have also been de- of GC–ITMS for the analysis of these compounds is
termined using GC–ITMS–MS in EI mode [53,67– to replace the standard stainless steel electrodes of
69]. The predominant transitions [M12] 1? →[M1 the ion trap with fused-silica-coated electrodes
2–COCl ? ] 1 from tetra- to octa-chlorinated dioxins (silchrom electrodes) [59]. These electrodes have
and furans and [M12] 1? →[M12–Cl 2 ] 1 for each been found to produce a 30–50% increase in re-
chlorination degree of dioxin-like PCBs have been sponse for all PCDD/ Fs congeners. GC–ITMS–MS
commonly used in EI-MS–MS mode. High selectivi- has generally produced results comparable to those
ty and specificity have been obtained using these obtained with high-resolution mass spectrometry for
product ions for these families of compounds. As an PCDD and PCDFs in different environmental ma-
example, Fig. 3 shows the GC–ITMS–MS chro- trices. Nevertheless, the quality of the clean-up
matograms corresponding to tetrachlorodibenzo-p- procedures and the presence of interfering com-
dioxins (product ion m /z 259) from a ball clay pounds in the final extracts can significantly affect
containing chicken feed, a reference toxic fat and fly the sensitivity and reproducibility of the method. For
ash, where different elution profiles and abundance instance, Kemmochi et al. [62] indicate that low
of 2,3,7,8-TCDD were detected [70]. Generally, ionisation conditions (electron energy 30 eV and
GC–ITMS–MS provides good repeatability and emission current 150 A) are enough to obtain a
reproducibility (RSD% ,15%) with low limits of reproducible quantification, but if interfering ions are
detection. Typical LODs are 60–300 fg injected for present higher ionisation conditions (electron energy
non-ortho PCBs [67,68] and 150–500 fg for the 17 90 eV and emission current 350 A) must be used.
toxic PCDD/ Fs congeners [59], although values A further example of the applicability of GC–
from 1 to 3 pg have also been reported [60,65]. ITMS–MS with EI mode is the analysis of tox-
Fig. 3. GC–ITMS–MS product ion chromatograms (m /z 259) for tetrachlorodibenzo-p-dioxins from (a) a ball clay containing chicken feed,
(b) a reference toxic fat, and (c) a fly ash from a waste cogeneration incinerator. Experimental conditions: GC column: DB-5MS,
40 m30.18 mm I.D., MS analyser: ion-trap MS, working in MS–MS mode. (Reprinted from Ref. [70], Copyright 1999, with permission
from Elsevier Science)
aphene in biological samples. Currently, negative employed for many years and is still being used to
chemical ionisation mass spectrometry (NCI-MS) in solve some specific environmental problems in dif-
SIM mode has been used for quantification of total ferent GC–MS application areas. An example of
toxaphene and selected polychlorobornane congeners these applications is the analysis of polychlorinated
in environmental matrixes. However, differences of compounds such as polychlorodibenzo-p-dioxins and
at least 1 order of magnitude in the response factors furans. Highly sophisticated and dedicated equip-
between isomers have been obtained using NCI-MS. ment is used for this purpose, generally based on
Although EI shows more similar response factors for double-focusing sector instruments. The characteris-
toxaphene congeners, low-resolution MS with linear tics of this instrumentation are summarised in Table
quadrupole analysers is not sensitive enough for the 1.
analysis of these compounds in environmental sam- Environmental applications of HRMS in GC–MS
ples. The high sensitivity and selectivity of the EI- are based on enhancing the selectivity of the MS as a
ITMS–MS prompted some authors [71,72] to pro- detector by increasing resolution. There are two main
pose the use of this technique as an alternative to types of applications of HRMS in environmental
NCI-MS. For the analysis of these compounds, the analysis. The first is based on a very high capacity to
ion at m /z 125, which corresponds to a chlorinated remove the contribution of matrix interfering com-
monochlorotropolium structure, and the ions at m /z pounds in the determination of the analytes. This
303 / 305 were selected as precursor ions. As an capacity is exploited, for example, in the analysis of
example, Fig. 4 shows the GC–EI-ITMS and GC– polychlorinated dibenzo-p-dioxins (PCDDs) and
EI-ITMS–MS chromatograms (m /z 125→m /z 891 furans (PCDFs), dioxin-like PCBs and polybromi-
99) obtained from cod liver oil NIST SRM 1588 and nated diphenyl ethers. Using selected ion monitoring
beluga skin samples. As can be seen, the gain in (SIM) at a mass resolution of 10 000, the presence of
selectivity and sensitivity was considerable when matrix components in the extracts does not interfere
switching from EI-MS mode to EI-MS–MS mode and detection at a high level of mass accuracy can be
[72], and the chromatograms were virtually undis- performed. The second type of application is related
turbed by the sample matrix and other polychlori- to the determination of complex mixtures of con-
nated compounds. Instrumental detection limits of taminants such as polychlorinated terphenyls, tox-
1–2 pg for the individual congeners and 130 pg for aphene and polychlorinated alkanes, where, in addi-
the total toxaphene have been achieved [72]. These tion to the matrix interferences, some problems arise
detection limits are lower than those obtained by due to interferences between fragment ions of con-
NCI-MS or by EI-HRMS in SIM mode. geners with different degrees of chlorination. In
order to remove these specific interferences, HRMS
at a resolving power higher than 10 000 is required.
Polychlorinated dibenzo-p-dioxins (PCDDs), poly-
4. Gas chromatography–high resolution mass chlorinated dibenzofurans (PCDFs) and dioxin-like
spectrometry (GC–HRMS) PCBs (non-ortho and mono-ortho PCBs) are exam-
ples of polyhalogenated compounds whose determi-
For many years, a high level of concern about the nation is mainly performed by gas chromatography
presence of different pollutants at low levels (part coupled to high-resolution mass spectrometry (GC–
per trillion) in the environment has led scientists to HRMS) using the EI mode to provide the required
develop sensitive analytical methods. Although in sensitivity and selectivity for analysis. Negative
most applications of GC–MS a linear quadrupole or chemical ionisation with methane as reagent gas has
a quadrupole ion trap is used for mass analysis, also been used as an alternative technique to electron
higher mass resolution is sometimes needed in order ionisation, but lower sensitivities have been reported
to avoid some interferences detected in the environ- [73,74]. A complete picture of the state-of-the-art for
mental analysis. Due to its high specificity and PCDD and PCDF analysis was given by Liem [75].
sensitivity, gas chromatography coupled with high- Improvements in the sensitivity of mass spectrome-
resolution mass spectrometry (GC–HRMS) has been ters, the use of high-resolution capillary GC columns
Fig. 4. GC–EI-MS and GC–EI-MS–MS mass chromatograms of a NIST SRM 1588 (A and C) and a beluga ‘‘muktuk’’ (skin) sample (B
and D), respectively. Toxaphene congeners (Parlar and Andrews-Vetter nomenclature) and other chlorinated pesticides are assigned as well
as the time where the product ion was changed (dotted line). Signals exceeding the abundance scale are marked with a dashed line: c-CD,
cis-chlordane; chrys, chrysene-d12; HEP, heptachlorepoxide; OXY, oxychlordane; t-CD, trans-nonachlor; tx, probably unknown toxaphene
congeners; ?, unknown. Experimental conditions: GC column: DB-5MS, 30 m30.25 mm I.D., 0.25 mm film thickness. MS analyser:
ion-trap MS, working in full-scan mode and full-scan product mode. (Reprinted with permission from Ref. [72], Copyright 2002, American
Chemical Society)
and the availability of high-purity chemical standards sensitivity and selectivity can be achieved. Typically,
have allowed the quantification of all PCDD/ Fs in LODs ranging from 0.1 to 5 pg have been obtained.
the sub-ppt range. GC–HRMS with EI (electron GC–HRMS is also applied to the environmental
energy |38 eV) at a resolving power of 10 000 is the analysis of complex mixtures such as toxaphene
reference method for the analysis of PCDD/ Fs and (chlorobornanes), polychlorinated terphenyls (PCTs),
non-ortho PCBs. This method is described in U.S. and polychlorinated alkanes (PCAs). In these appli-
EPA Methods 1613 and 1668, and the European cations, the interferences produced by matrix com-
Standard EN1948-1 / 2 / 3 [76–78]. Quantification is ponents and between congeners with different de-
performed by selected ion monitoring (SIM) and grees of chlorination can be overcome by using
isotopic dilution using stable isotope-labelled 13 C 12 HRMS at a resolving power higher than 10 000. The
analogues of PCDD/ Fs and dioxin-like PCBs. Al- analysis of chlorobornanes (CHBs) in environmental
though the signal due to the polychlorinated com- and biological samples is difficult, mainly due to the
pounds decreases as a result of increasing mass substantial difference in peak profiles between sam-
spectral resolution, detection limits improve, because ples and industrial formulations and to the lack of
noise decreases even further. Limits of detection as individual isotopically labelled internal standards for
low as 10–200 fg have been obtained using GC– quantification. The use of GC–HRMS allows for
HRMS systems [79]. Over the last 2 years, a large higher selectivity than low-resolution mass spec-
number of papers (almost 200) have been published trometry, and unambiguous determination of the
describing GC–HRMS applications for routine anal- individual congeners in environmental samples has
ysis of PCDD/ Fs and dioxin-like PCBs in environ- been achieved. Three different approaches using
mental samples. These papers focus primarily on the GC–EI-HRMS have been applied. The first is based
analysis of soils [80], sediments [81–83], sludges on monitoring of the m /z 158.9768 and the isotope
[84], municipal solid wastes [85], incinerator emis- peaks at m /z 160.9739 and 162.9709, which corre-
sions [86] and biota [87,88]. Typical limits of spond to the dichlorotropylium ion structure
detection for PCDD/ Fs using GC–EI-HRMS are (C 7 H 5 Cl 21 ). The use of these characteristic ions in
0.05–0.3 ppt for animal tissues, ,0.02 ppt for feeds, combination with HRMS at a resolving power higher
and ,0.03 ppt for biota [89]. than 10 000 allows good selectivity, but only the
Another important example of the application of concentration of total toxaphene can be determined
GC–MS in environmental analysis is the determi- and the presence of the different homologue groups
nation of two families of brominated compounds, cannot be distinguished [94–96]. This method has
polybrominated biphenyls (PBBs) and polybromi- been successfully applied to the analysis of tox-
nated diphenyl ethers (PBDEs). Although GC–low aphene in biota samples [94,95], providing limits of
resolution MS in NCI mode provides sufficiently detection lower than 10 mg / g. The second approach
high sensitivity, magnetic-sector-based GC–MS sys- is based on the determination of homologue com-
tems operating at high resolution (10 000) are the position. Due to the interferences of homologues
ideal instruments for analysis of compounds of this with an additional chlorine atom over each homo-
type, because they remove the contribution of other logue group, GC–EI-HRMS at resolving power of
halogenated contaminants present in the matrix. 20 000 is needed. A scheme of the contribution of
Given the commercial availability of individual the nonachlorobornane [M–Cl–HCl] 1 ions on the
congeners, quantification based on congener-specific selected octachlorobornane [M–Cl] 1 ions is given in
method is currently a routine practice. In recent Fig. 5, as an example of the high resolution needed.
years, some applications of GC–HRMS to the analy- In practice, when using a resolution of 10 000, most
sis of these compounds in different environmental of the interferences can be eliminated [97]. Finally,
matrices such as biota [90,91], fish [92] and veget- the third approach is based on specific-congener
ables [93] have been reported. Using the two most analysis using GC–EI-HRMS in SIM mode [98].
abundant ions of the molecular cluster for mono-, Negative chemical ionisation-HRMS at resolving
di-, tri- and tetrabromo-DEs, and the [M–2Br] 1 for power higher than 10 000 has also been used for the
tetra- to hepta-bromosubstituted congeners, high analysis of CHBs in environmental samples [99,100].
Fig. 5. Interfering mass from nonachlorobornane [M–Cl–HCl] 1 fragment ion at the monitored [M–Cl] 1 fragment ions for octa-
chlorobornanes.
This technique provides good selectivity and very quantification purposes, homologue distributions of
high sensitivity, while avoiding interferences by some PCT standard mixtures and environmental
other organochlorine compounds such as polychlori- samples have been determined using HRMS
nated diphenyl ethers or organochlorine pesticides. [101,102], making it possible to determine the source
In all cases, methane has been used as the moderat- of PCT sample contamination. The analysis of PCAs
ing gas for NCI mode. Using this technique, low is very difficult because of the complexity of mix-
detection limits have been obtained for individual tures (more than 10 000 congeners), and only semi-
CHB congeners, ranging from 0.3 to 7 pg as amount quantitative analysis is currently performed [79].
injected. PCA chromatograms are characterised by a large
GC–EI-HRMS operating in SIM mode has also hump where all congeners coelute. The determi-
been used for the analysis of complex mixtures such nation of PCAs in environmental samples has mainly
as PCTs and polychlorinated alkanes (PCAs) in been performed by GC–ECD and GC–NCI-low
environmental samples. Analysis of PCTs has proven resolution MS, but some authors have proposed the
to be difficult because of the complexity of the use of GC–NCI-high resolution MS at a resolving
mixtures, the high boiling points of the heavily power of 10 000–12 000, because with this tech-
chlorinated congeners, and the co-elution of the nique it is possible to determine the contribution of
lower chlorinated PCTs with some PCBs. The analy- each homologue group in the samples and avoid
sis of these compounds using EI-LRMS presents interferences from other organochlorine compounds
some interferences due to the contribution of [M– [79,103–105]. This method, which involves using
Cl 2 ] 1 fragment ions of homologues with two addi- methane as moderating gas and selecting the [M–
tional chlorine atoms over the molecular ions of each Cl] 2 ions of each homologue group, has been
homologue group. In general, for the complete successfully used for the determination of PCA in
elimination of all internal interferences, a resolution sediments and biota [103,104]. As an example, Fig. 6
of 35 000 is recommended to avoid errors in quanti- shows the GC–NCI-HRMS elution profiles obtained
fication due to interfering fragments [79,101]. For for each degree of chlorination and carbon chain
Fig. 6. GC–NCI-HRMS elution profiles of monitoring ions in a commercial PCA mixture of C 10 –C 13 chain length and |60% chlorine by
mass (PCA-60). Experimental conditions: GC column: DB-5MS, 30 m30.25 mm I.D., 0.25 mm film thickness. MS analyser: double-
focusing magnetic sector (EBE, geometry), operating in NCI at a resolving power of 12 000 and SIM mode. (Reprinted with permission
from Ref. [103], Copyright 1997, American Chemical Society)
length of the commercial PCA product PCA-60 (TOF-MS) has gained considerable acceptance as a
(C 10 –C 13 carbon chain length and |60% chlorine). mass analyser for different applications. In fact, the
renaissance of TOF-MS, a technique that was estab-
lished more than 50 years ago, is largely due to
5. GC–time-of-flight mass spectrometry (GC– biological applications that require a large mass
TOF-MS) range (.10 5 a.m.u. / charge). Recently, however, the
advantages of the high speed of the technique (a few
In recent years, time-of-flight mass spectrometry milliseconds) are being exploited in other research
fields, and TOF-MS is being coupled to GC. From a voltage push and bunched in time. In most GC–
conceptual point of view, time-of-flight instruments TOF-MS instruments, an appropriate voltage pulse is
are very simple: ions are formed or sampled on applied to accelerate the ions in the direction ortho-
bushes, which are accelerated within a linear electric gonal to their initial flight direction. In orthogonal
field into a field-free flight tube. Ions travel some acceleration (oa-TOF-MS) a nearly parallel ion beam
distance in the field and gain kinetic energy which is ideally has no velocity spread, and the finite spatial
related to their velocity. Since velocity is inversely spread is corrected with a linear or reflecting instru-
proportional to the square root of m /z, the ions will ment geometry. In GC–TOF-MS, the predominant
separate so that lighter ions traverse the acceleration method of data collection is integrating transient
and drift regions before the heavier ones. A planar recording (ITR), in which the successive ion pulses
detector is used to convert the ion arrival event into that arrive at short time intervals (10 000 pulses per
an electrical signal whose time relative to the start second) are collected and stored in the consecutive
event is recorded. recording channels of a multichannel analyser. Rela-
The mass resolving power in TOF-MS instruments tively noise-free mass spectra can be obtained by the
is independent of ion mass but for a given uncertain- addition of several spectra. When signals are very
ty in time (Dt) it increases with (m /z)2 . Mass weak, the flight times of individual ions can be
resolving power can be improved by increasing the determined from their start and stop signals by using
flight time, which can be achieved by using lower a multistep time-to-digital (TDC) converter.
accelerating voltages or longer flight distances. The key strengths of TOF-MS are summarised in
Moreover, a decrease in the uncertainty in time will Table 1. In relation to the coupling to gas chroma-
also produce an improvement in mass resolving tography, the most important features are the capa-
power. In spite of the simplicity of the method, there bility of producing mass spectra of good quality
are a number of factors that can have a significant within a very short time (a few milliseconds) and
effect on flight time: differences in the initial posi- high sensitivity (higher efficiency than scanning
tion at which ions are formed (spatial spread), in the MS). High speed has made it possible to use TOF
times over which they are formed (temporal spread), mass analysers as detectors in high-speed GC. More-
in initial velocity (kinetic energy spread), and in over, the good mass accuracy (low ppm errors) of
direction of motion (angular spread). The dispersion the oa-TOF mass analyser has provided an alter-
in ion arrival time due to differences in initial native to accurate mass GC–MS with sector instru-
position of ionisation may be corrected by spatial ments. Different commercial TOF instruments have
focusing. The ions are generated in an electric field appeared offering high speed (Pegasus-LECO and
such that those formed further from the detector Tempus-ThermoQuest) or high mass accuracy
experience the force due to the field for longer and (GCT姠-Micromass) as their main feature. Some
reach a higher velocity. As a result, time-focusing of environmental applications of GC–TOF-MS are
ions of the same mass occurs at the detector. For described in the following sections.
velocity focusing, the best device is the reflectron,
which is placed at the end of the drift region and 5.1. Fast GC and GC 3 GC
consists of a series of lens plates with different
voltages that act as a retarding field. Ions with the Fast separations have represented a major trend in
same mass that have greater kinetic energy will gas chromatography in recent years. These tech-
penetrate more deeply into the retarding field and niques can dramatically reduce analysis time for the
take longer to emerge. So they will catch up with the determination of volatile and semi-volatile organic
ions with lower kinetic energy at the detector. compounds, and should result in increased sample
Additional refocusing is often achieved by lenses or throughput and reduced analysis costs for many
by ion reflectors. environmental applications. In high-speed gas chro-
In TOF instruments, ions must be sampled in matography (HSGC) the timescale has shifted 1 to 2
bushes. If they are produced continuously, they can orders of magnitude and separations that required 20
be stored for a very short time, extracted using a min or longer by conventional capillary GC can be
obtained in 20 s by HSGC. Different terms such as the deconvoluted chromatogram of nine pesticides
fast GC, very fast GC and ultra fast GC are often eluting in a 3-s window obtained at a relatively low
used in the literature; separation is performed in the acquisition rate (40 spectra / s) [107]. This was
minute range in fast GC, and in seconds or sub- sufficient to separate nine of the ten compounds
seconds in very fast GC and in ultra fast GC, tested. As an example of the influence of acquisition
respectively. rate on peak resolution and deconvolution perform-
High-speed separations are currently obtained ance, Fig. 8 shows the chromatograms of a mixture
using capillary short columns (length ,10 m) oper- of hydrocarbons recorded at 500 and 50 spectra per
ated at higher than usual carrier gas flow rates. second, respectively [106]. At 500 spectra per sec-
Under these conditions peak widths are very small. ond, the first three peaks are baseline separated and
For instance, van Deursen el al. [106] have calcu- quantitation can be performed. In contrast, at 50
lated peak widths at half-height for a narrow bore spectra per second it is not possible to deconvolute
column (10 m350 mm I.D.) for fast GC, and two the overlapping peaks. The greater the peak overlap,
very short columns (1 m and 0.3 m350 mm I.D.) for the higher the spectral acquisition rate required to
very fast GC and ultra fast GC. The values obtained ensure a sufficient number of spectra (at least four)
were 0.2 s for the narrow bore column and 30 ms between peaks. However, an increase in spectral
and 10 ms, respectively, for the short columns. So, in acquisition rate results in a reduction in the intensity
order to couple high-speed GC to MS for the of the peaks (Fig. 8) so the optimum scan rate must
characterisation of complex environmental mixtures, be a compromise between sufficient resolution and
an extremely fast acquisition rate is needed. With high sensitivity.
TOF instruments complete mass spectra can be Currently, chromatographic separations obtained
obtained at rates as high as 500 spectra per second, in fast GC are sufficient for peak finding and for
which can allow for accurate treatment of the very applying deconvolution algorithms to recognise the
narrow chromatographic peaks produced by HSGC. presence of two or more components in a single
An additional advantage of TOF instruments with chromatographic feature and some applications to
time-array detection is the complete absence of environmental contaminants such as pesticides, her-
concentration biasing, given that all the ion frag- bicides, aromatic hydrocarbons, PCBs and pharma-
ments of the spectrum represent the same point on ceutical compounds in water and sediments, have
the chromatographic peak. This is not the case with been published [107–111]. The fragmentation pat-
scanning instruments, where, in addition to their terns of isomers, however, are often too similar for
relatively low scan rate (a few spectra per second), deconvolution and spectral identification based on
the concentration for each mass changes in the ion comparisons with library spectra. For instance, con-
source during a scan and the spectra would be gener-specific PCB identification is difficult because
distorted as ion currents are simply sampled with no the lack of separation in the short columns used in
regard for their intensity between points. very fast GC results in coelution of isomers that
An important consequence of the absence of cannot be differentiated on the basis of their mass
concentration biasing in TOF instruments is the spectra [107]. In these cases, greater peak separation
possibility of performing spectral deconvolution of is required. This can be achieved by a combination
partially overlapping chromatographic peaks if the of GC columns of different selectivity. Various
fragmentation patterns for the overlapping compo- approaches have been proposed to increase sepa-
nents are significantly different. Up to now, most of ration capacity in order to obtain sufficient resolution
the papers published in the literature related to to solve the coelution problem and allow for the use
environmental applications of HSGC–TOF-MS deal of the TOF-MS additional separation dimension to
with the compromise between the need for fast produce library-searchable mass spectra. One possi-
separation and the resolution requirements for the bility is the combination in series of two GC
identification of unknown peaks using spectral de- columns by means of an electronic pressure control
convolution. The acquisition rate of the TOF ana- at the junction point between the columns. Leonard
lyser is highly significant. For instance, Fig. 7 shows and Sacks [112] have proposed the use of this
Fig. 7. Chromatogram of pesticides using vacuum-outlet GC–TOF-MS at 40 spectra / s. Unique ions and TIC (dashed line) are plotted. A
faster acquisition rate allowed automatic peak location for nine of the ten compounds. Experimental conditions: GC column: CP-Sil 8 CB,
5 m30.53 mm I.D., 0.5 mm film thickness with a 3 m30.18 mm I.D. deactivated fused-silica column as retention gap. MS analyser: TOF,
operating at m /z range 120–520. (Reproduced from Ref. [107], Copyright 2002, by permission of Preston Publications)
procedure for the separation of a mixture of com- column. Since separation in the second column is
pounds with different polarities and a wide range of very fast and peaks are on the order of 200 ms wide
boiling points. Results show that pressure-tuneable at half width, only TOF-MS instruments have the
column ensembles can be useful for the high-speed rapid spectrum acquisition capability required for the
analysis of moderately complex mixtures. Another reconstruction of the chromatograms and for quanti-
highly promising possibility for the separation of fication. Data from GC3GC–TOF-MS shows
very complex mixtures is comprehensive two-dimen- groups of pulsed peaks with the same spectra,
sional gas chromatography. corresponding to the series of pulses of a single
Comprehensive two-dimensional gas chromatog- component. The pulsed peaks are separated by a time
raphy (GC3GC) involves the direct coupling of two interval depending on the modulation frequency. For
columns with different separation mechanisms in overlapping peaks eluted from the first column,
order to separate in the second column unresolved interleaved pulses of peaks appear if the compounds
compounds that eluted from the first. Thus GC3GC are resolved in the second dimension. The com-
can be considered a special case of multidimensional pounds can be identified by their retention time and
gas chromatography, where every component of the mass spectra and quantified by combining all the
mixture is subjected to an orthogonal two-dimension second-dimension peaks that belong to the same
separation. The instrumental design involves a analyte.
modulator interface that couples the two columns. Thus far, very few papers have been published
The first column generally is a conventional non- dealing with the use of GC3GC–TOF-MS for the
polar GC column, and the second one is a short polar analysis of contaminants in environmental samples.
Fig. 8. Comparison of chromatograms recorded at 500 and 50 spectra per second, respectively. Experimental conditions: capillary column:
OV-1, 0.3 m350 mm I.D, 0.17 mm film thickness. MS analyser: TOF, operating at m /z range 40–200. Compounds: (1) pentane, (2)
2,3-dimethylbutane, (3) hexane, (4) benzene, (5) heptane, (6) methylcyclohexane, (7) toluene and (8) octane. (Reprinted from Ref. [106],
Copyright 2000, with permission from Elsevier Science)
Nevertheless studies that demonstrate the power of cation at trace levels [117]. The decrease in mass
the method have been performed using phenols and accuracy at high signal intensities is due to the
PAHs [113], PCBs [114] and pesticides [115,116]. In time-to-digital converter (TDC) used for data collec-
¨
a recent publication, Dalluge et al. [115] give tion. TDC is only able to distinguish between events
interesting information about GC3GC–TOF-MS separated by sufficient time (dead time). At high ion
quality parameters, demonstrating that for pesticides currents, multiple ion arrivals cause counts to be
good linearity and repeatability of peak areas (RSD missed, resulting in mass spectral peaks with lower
5–11%) can be obtained. The paper includes a intensity than expected and inaccurate mass assign-
thorough discussion of data processing procedures to ment. A dead time correction algorithm and a device
obtain analytical information such as identification that reduces the transmission of the ion beam into the
and quantification of target analytes, screening for sample region are used to increase the dynamic range
unknowns and group type analysis. and exact mass capability. Very few papers have been
published concerning the application of these instru-
5.2. Accurate mass instruments ments to environmental problems [117,118], but
¨
Daluge et al. have demonstrated that very good
The very good mass accuracy of the oa-TOF mass detection limits can be obtained for PCBs and
analyser has provided an alternative to accurate GC– pesticides, at low pg range. In addition, the use of
MS with sector instruments. For peaks with suffi- narrow mass windows provides a good separation of
cient intensity and using internal reference mass, a coeluting compounds. As an example, Fig. 9 shows
mass accuracy of 0.001 Da can be obtained (5 ppm the GC–TOF-MS [117] chromatogram of a PCB
for measurements at m /z 200). Mass accuracy, congener (CB-118) in an eel extract using two
however, depends on signal intensity and decreases different mass windows, 1 Da (B) and 0.02 Da (C).
at both very low and very high signal intensities. In this case, the use of a mass window of 0.02 Da
Low mass accuracy at low mass intensities can result prevented a false-positive identification.
in an underestimation of the peak area. Consequent- An interesting development in GC–TOF-MS is the
ly, a broader mass window must be used for quantifi- use of the field ionisation ion source (FI). Many
Fig. 9. GC–TOF-MS chromatograms of the m /z 323.8834 ion traces of (A) a PCB standard (10 pg) and (B,C) an eel extract. (A,C)
Extracted using a window of 0.02 Da, and (B) using a mass window of 1 Da. Signal intensities are the same in all three frames.
Experimental conditions: GC column: DB-5, 40 m30.18 mm I.D., 0.18 mm film thickness. MS analyser: TOF equipped with 1-GHz
time-to-digital converter and operating at a pusher interval of 40 ms and at m /z range 50–500. (Reprinted from Ref. [117], Copyright 2002,
with permission from Elsevier Science)
compounds of interest do not provide good molecu- tion of a laser photon when the wavelength of the
lar weight information by electron impact methods, laser is in resonance with a UV transition. The
whereas FI yields simple spectra with intense molec- excited molecules are subsequently ionised by ab-
ular ions and very little or no fragmentation. The sorption of an additional laser photon. The method
mass and full spectrum sensitivity of oa-TOF-MS has been proposed for the determination of PAHs and
combines well with FI and the high mass accuracy chlorinated benzenes in environmental samples
obtained can greatly simplify the interpretation of [120,121].
chromatograms from complex mixtures such as coal- Plasma source mass spectrometry (PS-MS), which
based fuels [119]. employs plasma sources such as microwave induced
plasma (MIP), inductively coupled plasma (ICP),
5.3. Laser and plasma sources and glow discharge (GD), have been coupled to gas
chromatography for speciation analysis in environ-
Laser-induced resonance-enhanced multiphoton mental samples. Some recent publications in GC–
ionisation time-of-flight mass spectrometry ICP-TOF-MS have shown the potential of this
(REMPI–TOF) is a highly selective and sensitive technique for the separation and speciation of or-
technique that has been used as a detector for gas ganotin [122] and organolead compounds [123]. The
chromatography. This technique combines UV spec- important characteristics that make TOF-MS well
troscopy and mass spectrometry. Intermediate stages suited for coupling to ICP are the high sampling rate,
of target molecules are selectively excited by absorp- which prevents peak distortions, and the possibility
of simultaneously measuring different isotopes dur- 6. Portable GC–MS instruments

ing a single chromatographic run. Limits of detection
in the fg level and reproducibilities lower than 10% Field-portable GC–MS instruments and applica-
have been obtained. As an example, Fig. 10 shows tions have evolved and grown considerably over the
the chromatogram obtained from an alpine snow last decade. The concept of mobile GC–MS began to
sample where dimethyllead (DML) and trimethyllead be developed more than 30 years ago for use on
(TML) were identified [123]. The coupling of TOF- board planetary and interplanetary space probes, and
MS to a helium microwave plasma torch and gas its possibilities prompted researchers to consider
chromatography has been explored for the element- other applications. Several instruments have been
selective detection of halogens [124]. Recently, gas developed and successfully used for environmental
chromatography has been coupled to a helium-sup- applications including in situ analysis and remedia-
ported gas sampling glow discharge (GSGD) ionisation, emissions monitoring and control, site charac-
tion source for mass spectrometry with a TOF terisation, emergency response, chemical weapons
instrument [122,125]. Both atomic and molecular detection and mapping of air pollutants. Other field
spectra can be generated sequentially in the helium- analytical techniques are also used to provide in-
supported plasma. Thus far, experiments have been formation about environmental problems, but many
conducted with chlorinated hydrocarbons and results lack the high level of certainty provided by GC–MS
show that low detection limits (1–5 pg / s in the analysis. Field-portable GC–MS systems are widely
atomic mode and 10–20 pg / s at the molecular mode) used in situations that require rapid identification of
can be obtained. Moreover, elemental ratios, for the analytes and a high degree of certainty in data.
instance, 35 Cl 1 / 12 C 1 can be used to differentiate Current environmental sampling and analysis meth-
chlorinated compounds. Additional work needs to be ods are time-consuming, costly and present potential
done in order to determine how this source can be exposure hazards to the personnel involved. In situ
used in environmental applications. measurements of environmental contaminants are
Fig. 10. GC–ICP-TOF-MS chromatogram obtained from an alpine snow sample. Compounds: DML, dimethyllead; I.S., internal standard,
trimethylethyllead; Pb i , tetrapropyllead originated from inorganic lead; TML, trimethyllead. Experimental conditions: GC column: HP-1,
2530.32 mm I.D., 0.17 mm film thickness. (Reprinted from Ref. [123], Copyright 2001, with permission from Springer-Verlag)
preferable to laboratory analysis, but they must meet for monitoring of air pollutants. For instance, this
data quality objectives and be cost competitive. sample system coupled to a GC-MS instrument has
Commercial transportable GC–MS instruments been used in a roving instrument for the analysis of
have been used for several years, although limita- benzene, toluene and xylenes (BTX) in urban out-
tions are imposed by power, weight and analytical door environments. As an example, Fig. 11 shows
capability issues. Nevertheless, recent advances in the temporal fluctuations of toluene and benzene in a
design and miniaturisation of components have led to street near a gas station [128].
reductions in size, weight and power consumption. The mass analyser most frequently used in GC–
The essential features of these instruments are sam- MS field instruments is the linear quadrupole be-
ple capabilities, robust detection, autonomy for suffi- cause of its inherent simplicity, small size, durability
ciently long periods of time, and flexible and easy- and compactness. Most of the commercial transport-
to-use software systems. In environmental applica- able GC–MS instruments incorporate this type of
tions, different types of field-portable GC–MS in- mass analyser. For instance, the mobile Bruker EM
struments are used, which can be grouped in two 640 consists of a quadrupole mass spectrometer
main categories: vehicle-portable and man-portable (mass range m /z 1–640) with a membrane separator
systems [126]. Vehicle-portable instruments involve inlet, a 70-eV electron ionisation ion source, a
the use of a car, a boat or a helicopter to transport the membrane pump and a turbomolecular pump (70
mobile GC–MS instrument to the location where the l / s). This instrument features several sampling acces-
system performs the analysis. The latest generation sories that allow a wide range of applications, and
of these systems are the so-called roving GC–MS, has been used for the analysis of gaseous samples,
which are capable of taking measurements on the fly, volatiles and semivolatiles in water and soils [129].
and are used for monitoring and mapping trends and The Agilent 5973 mass selective detector, which also
gradients in space and time. Man-portable GC–MS belongs to the linear quadrupole family, has been
systems require miniaturised fast capillary GC, sim- incorporated in the products of Viking Instruments,
ple and compact small mass spectrometers, small recently acquired by Bruker. The last instrument of
vacuum pumps and battery-operated instrumentation. the series, the Viking 573, is a small, compact, robust
One of the advantages of using field-portable GC– and lightweight portable instrument (39 kg) that also
MS systems is that analysis can be performed at or provides a multifunction inlet system, including
near the sampling point. Sampling must, however, be purge and trap, thermal desorption, direct air sam-
representative and sample integrity must be main- pling and direct injection. These instruments have
tained. The sampling system in a field-portable GC– been used for different applications, such as on-site
MS unit should be compact, stable, capable of analysis and remediation [130], and identification of
remote operation and versatile for use with multiple hazardous compounds after chemical accidents or
media sampling. Direct injection, thermal desorption, fires [131,132]. Quality control through inter-labora-
gas sampling / thermal desorption and membrane tory comparisons shows good results and demon-
inlets are currently used. For instance, Eckenrode strates the good quality of the data obtained with this
[127] has demonstrated the capability of a valving instrumentation [130]. The HAPSITE (Inficon) GC–
and control system using absorbing tubes to success- MS system is a man-portable instrument (16 kg)
fully trap and desorb volatile organic compounds especially designed for on-site analysis of volatile
(VOCs) in air, with low detection limits (reaching organic compounds. The U.S. Environmental Protec-
single-digit ppb levels) and good reproducibilities. In tion Agency has recently evaluated this instrument
situ analysis of these highly volatile compounds in for the measurement of VOC levels in ground water,
air is a good option because it can solve the and results show that it can provide useful and
problems related with sampling, evaporative loss and cost-effective data for on-site and real-time moni-
transport. Direct vapor sampling that introduces the toring. Moreover, accurate and precise analytical
sample to the head of the GC column without valves results directly comparable with those from an off-
or seals and reduces the potential sites for analyte site laboratory were obtained [133].
condensation and sample loss has also been applied Given its relative simplicity and performance
Fig. 11. Roving GC–MS data showing temporal fluctuations in ambient BTX concentration with the selected ion chromatograms for: (A)
benzene (m /z 78) and (B) toluene and xylene (m /z 91) obtained while standing |10 m downwind from a gas station. Experimental
conditions: GC column: DB-5 1.85 m30.1 mm I.D., 0.1 mm film thickness. MS analyser: quadrupole, operating in SIM mode. (Reprinted
from Ref. [128], Copyright 1996, by permission of John Wiley and Sons, Inc.)
characteristics, TOF-MS has considerable potential that the limiting factor for cost, power, size and mass
to address the needs of field-portable GC–MS instru- of miniature mass spectrometers is not the mass
mentation. Although various field-portable TOF-MS analyser itself but the associated vacuum and elec-
instruments have been designed, very few papers tronic components. The trend to miniaturisation is
have been published about the coupling of these now being applied to sector analysers [136], linear
instruments to GC. Syage, for example, has de- quadrupoles [137], ion traps and TOF mass spec-
veloped a GC–TOF-MS for man-portable field-use trometers [135], and it is likely that in a few years
[134], which uses a photoionisation source and a these instruments will be coupled to GC for in situ
quadrupole ion trap-TOF mass analyser. The princi- analysis.
pal purpose of the ion trap is to accumulate ions that
are continuously generated from the source and
inject them to the TOF-MS. Preliminary results show 7. Conclusions and future perspectives
that fast chromatography with reasonable separation
and responses can be obtained. GC combined with MS provides reliable and
Miniature instrumentation and field portability is conclusive analytical information for the identifica-
an area of increasing interest in mass spectrometry. tion and quantification of a wide range of organic
The commercial introduction of small vacuum contaminants in environmental samples. The GC–
pumps, battery power supplies, and other off-the- MS instruments used range from simple linear
shelf components makes it possible to build small quadrupoles to multi-sector analysers with EI and
and hand-portable GC–MS instruments for environ- positive / negative CI capabilities that allow for the
mental applications. In a recent review on miniature achievement of low detection limits. At present, the
mass analysers, Badman and Cooks [135] indicated linear quadrupole is still the most widely used MS
analyser for GC–MS analysis of environmental generation of time-of-flight analysers is expected to

samples because it offers high sensitivity and good add to the capabilities and performance features of
qualitative information at low cost. However, HRMS field-portable GC–MS instrumentation over the next
is recommended when an enhancement of the selec- few years.
tivity of MS detection is required, because this
technique has the capacity to remove the contribution
of matrix-interfering compounds. In recent years, the
References
use of MS instruments with quadrupole ion-trap or
time-of-flight mass analysers has come to play an
[1] R.S. Gohlke, Anal. Chem. 31 (1959) 535.
important role in environmental analysis. The use of ´ L. Jenckel, K. Kronenberger, Z. Anal. Chem. 197
[2] C. Brunee,
these instruments is bound to increase in coming (1963) 42.
years due to their ease of operation, selectivity and [3] R. Ryhage, Anal. Chem. 36 (1964) 759.
detection limits down to parts per trillion (ppt). ˘
[4] I. Liska, ´ J. Chromatogr. A 733 (1996) 235.
J. Slobodnık,
GC–ion trap tandem mass spectrometry (GC– [5] G.R. van der Hoff, P. van Zoonen, J. Chromatogr. A 843
(1999) 301.
ITMS–MS) has proved to be an attractive method ´
[6] J. Beltran, F.J. Lopez, ´
F. Hernandez, J. Chromatogr. A 885
for the analysis of some persistent organic con- (2000) 389.
taminants, e.g. PCDDs and PCDFs, allowing high [7] F.E. Ahmed, Trends Anal. Chem. 20 (2001) 649.
selectivity and low analyte detectability. Recent GC– [8] B.A. Tomkins, R.H. Ilgner, J. Chromatogr. A 972 (2002)
ITMS–MS applications have shown that this tech- 183.
[9] S.D. Richardson, Anal. Chem. 74 (2002) 2719.
nique can successfully be used as an alternative to [10] F. Bove, Y. Shim, P. Zeitz, Environ. Health Perspect. 110
GC–HRMS for the analysis of complex environmen- (2002) 61.
tal samples, but further studies need to be carried out [11] C.P. Weisel, E.-K. Jo, Environ. Health Perspect. 104 (1996)
in order to determine the reliability of quantitative 48.
results and to ensure sufficient selectivity to prevent [12] B. Cancho, F. Ventura, M.T. Galceran, A. Dıaz, ´ S. Ricart,
Water Res. 34 (2000) 3380.
matrix interferences.
[13] Environmental Protection Agency, National primary drink-
The new generation of fast-scanning time-of-flight ing water regulations: disinfectants and disinfection byprod-
mass spectrometers are capable of working at high ucts: Final Rule, Fed. Reg. 63 (241) (1998) 69390.
scan rates (500 scan / s). These are sensitive detection [14] E.T. Urbanski, J. Environ. Monit. 2 (2000) 817.
instruments that are ideal for combining with high- [15] Y.F. Xie, Water Res. 35 (2001) 1599.
[16] U.S. EPA Method 552.2. Methods for the Determination of
speed GC or comprehensive two-dimensional gas
Organic Compounds in Drinking Water. Supplement III.
chromatography (GC3GC), the two most promising Determination of Organic Compounds in Drinking Water by
recent developments in GC. This coupling will Liquid–Liquid Extraction. Derivatization and Gas Chroma-
provide a powerful technique for the identification tography with Electron Capture Detection, U.S. Environmen-
and quantification of complex environmental samples tal Protection Agency, Environmental Monitoring Systems
Laboratory, Cincinnati, OH, 1995, EPA / 600 / R-95 / 131.
which require an extremely fast acquisition rate.
[17] L. Malleret, A. Bruchet, M.C. Hennion, Anal. Chem. 73
Moreover, the capability of TOF-MS to increase MS (2001) 1485.
resolving power and perform accurate mass measure- [18] S. Nakmura, N. Nakamura, S. Ito, J. Sep. Sci. 24 (2001) 674.
ments using a relatively high resolution makes this [19] N. Ochiai, K. Sasamoto, M. Takino, S. Yamashita, S.
technique attractive to solve some analytical prob- Daishima, A. Heiden, A. Hoffman, Analyst 126 (2001) 1652.
[20] T.-F. Lin, J.-Y. Wong, H.-P. Kao, Sci. Total Environ. 289
lems in environmental analysis. It is expected that in
(2002) 225.
the near future some GC–TOF-MS instruments will [21] S. Jobling, D. Sheahan, J.A. Osborne, P. Matthiessen, J.P.
replace GC–HRMS instruments given that the Sumpter, Environ. Toxicol. Chem. 15 (1996) 194.
former are easier to operate and less costly. [22] C. Planas, J.M. Guadayol, M. Droguet, A. Escalas, J. Rivera,
The use of portable GC–MS is increasing in J. Caixach, Water Res. 36 (2002) 982.
situations where an incident has occurred and rapid [23] T.L. Keith, S.A. Snyder, C.G. Naylor, C.A. Staples, C.
Summer, K. Kannan, J.P. Giesy, Environ. Sci. Technol. 35
identification of chemicals with a high degree of (2001) 10.
certainty is required. As a consequence, portable ´ F. Ventura, M.T. Galceran, Anal. Chem. 74 (2002)
[24] A. Dıaz,
GC–MS based on linear quadrupoles and on the new 3869.
[25] J.A. Field, R.L. Reed, Environ. Sci. Technol. 30 (1996) [56] A.A. Mosi, W.R. Cullen, G.K. Eigendorf, J. Mass Spectrom.
3544. 33 (1998) 250.
[26] H.B. Lee, Water Qual. Res. J. Can. 34 (1999) 3. [57] W.-H. Ding, J.-H. Lo, S.-H. Tzing, J. Chromatogr. A 818
[27] D. Berset, R. Etter-Holzer, J. AOAC Int. 84 (2001) 383. (1998) 270.
[28] M. Vitali, M. Guidotii, G. Macilenti, C. Cremisini, Environ. ¨
[58] M.D. Hernando, A. Aguera, ´
A.R. Fernandez-Alba, L. Piedra,
Int. 23 (1997) 337. M. Contreras, Analyst 126 (2001) 46.
˜
[29] A. Penalver, E. Pocurull, F. Borull, R.M. Marce, ´ J. Chroma- [59] D.G. Hayward, J. Holcomb, R. Glidden, P. Wilson, M.
togr. A 922 (2001) 377. Harris, V. Spencer, Chemosphere 43 (2001) 407.
[30] M. Guidotti, G. Ravioli, Ann. Chim. 89 (1999) 919. [60] J.-F. Focant, G. Eppe, E. De Pauw, Chemosphere 43 (2001)
[31] A. Saba, S. Pucci, A. Raffaelli, P. Salvadori, Rapid Commun. 417.
Mass Spectrom. 13 (1999) 966. [61] Y. Kemmochi, K. Tsutsumi, Chemosphere 43 (2001) 433.
[32] R.A. Rudel, S.J. Melly, P.W. Geno, G. Sun, J.G. Brody,
[62] Y. Kemmochi, K. Tsutsumi, K. Futami, Chemosphere 46
Environ. Sci. Technol. 32 (1998) 861.
(2002) 1451.
¨
[33] P. Spengler, W. Korner, J.W. Merzger, Environ. Toxicol.
[63] T. Kuchler, H. Brzeninski, Chemosphere 40 (2000) 213.
Chem. 20 (2001) 2133.
[64] D.G. Hayward, K. Hooper, D. Andrzejewski, Anal. Chem. 71
[34] H.M. Kuch, K. Ballschmiter, Environ. Sci. Technol. 35
(2001) 3201. (1999) 212.
´ E. Eljarrat, M.J. Lopez
[35] M. Petrovic, ´ ´ J.
de Alda, D. Barcelo, ´ V. Pacakova,
[65] R. Grabic, J. Novak, ´ ´ J. High Resolut. Chroma-
Chromatogr. A 974 (2002) 23. togr. 23 (2000) 595.
[36] M. Del Olmo, A. Gonzalez-Casado, N.A. Navas, J.L. [66] D.P. Samsonov, K.Yu. Evdokimov, N.P. Zhiryukhina, V.P.
Vilchez, Anal. Chim. Acta 346 (1997) 87. Kiryukhin, J. Anal. Chem. 53 (1998) 663.
[37] D.A. Markham, D.A. Menett, J.H. Birk, G.M. Klecka, M.J. [67] P.E.G. Leonards, U.A.Th. Brinkman, W.P. Cofino, Chemo-
Bartels, C.A. Staples, Int. J. Environ. Anal. Chem. 69 (1998) sphere 32 (1996) 2381.
565. [68] M. Mandalakis, M. Tsapakis, E.G. Stephanou, J. Chroma-
[38] C.A. de Wit, Chemosphere 46 (2002) 583. togr. A 925 (2001) 183.
[39] J. de Boer, C. Allchin, R. Law, B. Zegers, J.P. Boon, Trends [69] E.Y. Zeng, C.C. Chou, C. Yu, Anal. Chem. 74 (2002) 4513.
Anal. Chem. 20 (2001) 591. [70] D.G. Hayward, D. Nortrup, A. Gardner, M. Clower Jr.,
[40] E. Eljarrat, S. Lacorte, D. Barcelo, ´ J. Mass Spectrom. 37 Environ. Res. 81 (1999) 248.
(2002) 76. [71] H.M. Chan, J. Zhu, F. Yeboah, Chemosphere 36 (1998)
[41] A. Covaci, J. de Boer, J.J. Ryan, S. Voorspoels, P. Schepens, 2135.
Anal. Chem. 74 (2002) 790. [72] S. Skopp, M. Oehme, F.L. Chu, F. Yeboah, H.M. Chan,
[42] B. Strandberg, N.G. Dodder, I. Basu, R.A. Hites, Environ. Environ. Sci. Technol. 36 (2002) 2729.
Sci. Technol. 35 (2001) 1078. [73] H.-R. Buser, C. Rappe, P.-A. Bergquist, Environ. Health
[43] M. Petrovic,´ E. Eljarrat, M.J. Lopez
´ de Alda, D. Barcelo, ´ Perspect. 60 (1985) 293.
Trends Anal. Chem. 20 (2001) 637. [74] C. Rappe, M. Nygren, H.R. Buser, Applications of New
[44] R.J. Law, C.R. Allchin, M.E. Bennett, S. Morris, E. Rogan, Mass Spectrometry Techniques in Pesticide Chemistry, Vol.
Chemosphere 46 (2002) 673. 91, Wiley, New York, 1987.
[45] W. Vetter, Anal. Chem. 73 (2001) 4951. [75] A.K.D. Liem, R.M.C. Theelen, Dioxins: Chemical Analysis,
[46] K. Booij, B.N. Zegers, J.P. Boon, Chemosphere 46 (2002) Exposure and Risk Assessment, Ph.D. Thesis, University of
683. Utrecht, Utrecht, 1997.
[47] J. She, M. Petreas, J. Winkler, P. Visita, M. McKinney, D. [76] U.S. EPA Method 1613. Tetra- Through Octa-Chrorinated
Kopec, Chemosphere 46 (2002) 697. Dioxin and Furan by Isotope Dilution HRGC / HRMS. Revi-
´
[48] J.H. Christensen, M. Glasius, M. Pecseli, J. Platz, G. Pritzl, sion A, United States Environmental Protection Agency,
Chemosphere 47 (2002) 631. Washington, DC, 1990.
[49] N.G. Dodder, B. Strandberg, R.A. Hites, Environ. Sci. [77] U.S. EPA Method 1668. Toxic Polychlorinated Biphenyls by
Technol. 36 (2002) 146. Isotope Dilution High Resolution Gas Chromatography / High
[50] K. Akutsu, H. Obana, M. Okihashi, M. Kitagawa, H. Resolution Mass Spectrometry, United States Environmental
Nakazawa, Y. Matsuki, T. Makino, H. Oda, S. Hori, Chemo- Protection Agency, Washington, DC, 1997.
sphere 44 (2001) 1325. [78] European Standard EN1948-1 / 2 / 3. Stationary Source Emis-
[51] W. Paul, H. Steinwedel, U.S. Patent 2,939,952 (1960). sions-Determination of the Mass Concentration of PCDDs /
[52] G.C. Stafford, P.E. Kelley, J.E.P. Syka, W.E. Reynolds, J.F.J. Fs, European Committee for Standardization, Brussels, 1996.
Todd, Int. J. Mass Spectrom. Ion Proc. 60 (1984) 85. [79] J. de Boer, J. Chromatogr. A 843 (1999) 179.
[53] J.B. Plomley, M. Lausevic, R.E. March, Mass Spectrom. [80] M. Schuhmacher, A. Bocio, M.C. Agramunt, J.L. Domingo,
Rev. 19 (2000) 305. H.A.M. Dekok, Chemosphere 48 (2002) 209.
[54] C.R. Allchin, R.J. Law, S. Morris, Environ. Pollut. 105 [81] J.A. Prange, C. Gaus, O. Papke, J.F. Muller, Chemosphere
(1999) 197. 46 (2002) 1335.
´ F.J. Santos, M.T. Galceran, Anal. Chem. 72
[55] M.N. Sarrion, [82] S.H. Im, K. Kannan, M. Matsuda, J.P. Giesy, T. Wakimoto,
(2000) 4865. Environ. Toxicol. Chem. 21 (2002) 245.
[83] S. Painter, C. Marvin, F. Rosa, T.B. Reynoldson, M.N. [111] R. Hirsch, Th.A. Ternes, I. Bobeldjik, R.A. Weck, Chimia
Charlton, M. Fox, L. Thiessen, J.F. Estenik, J. Great Lakes 55 (2001) 19.
Res. 27 (2001) 434. [112] C. Leonard, R. Sacks, Anal. Chem. 71 (1999) 5177.
[84] E. Eljarrat, J. Caixach, J. Rivera, Water Res. 35 (2001) 2799. [113] J. Grainger, V. Green, Z. Liu, J. Barr, C. McClure, G.G.
[85] E. Abad, M.A. Adrados, J. Caixach, J. Rivera, Environ. Sci. Patterson Jr., Organohalogen Comp. 27 (1996) 354.
Technol. 36 (2002) 92. [114] J. Dimandja, J. Grainger, D.G. Patterson Jr., Organohalogen
[86] J.E. Oh, Y.S. Chang, M.G. Ikonomou, J. Air Waste Manage. Comp. 40 (1999) 23.
Assoc. 52 (2002) 69. ¨
[115] J. Dalluge, R.J.J. Vreuls, J. Beens, U.A.Th. Brinkman, J.
[87] M. Jacobs, J. Ferrario, C. Byrne, Chemosphere 47 (2002) Sep. Sci. 25 (2002) 201.
183. ¨
[116] J. Dalluge, M. van Rijn, J. Beens, R.J.J. Vreuls, U.A.Th.
[88] W.Z. Wu, K.W. Schramm, Y. Xu, A. Kettrup, Chemosphere Brinkman, J. Chromatogr. A 965 (2002) 207.
43 (2001) 633. ¨
[117] J. Dalluge, P. Roose, U.A.Th. Brinkman, J. Chromatogr. A
[89] J.K. Huwe, J. Agric. Food Chem. 50 (2002) 1739. 970 (2002) 213.
[90] J.M. Luross, M. Alaee, D.B. Sergeant, C.M. Cannon, D.M. [118] N. Newton, R. Rao, Int. Lab. 32 (2002) 6.
Whittle, K.R. Solomon, D.C.G. Muir, Chemosphere 46 [119] P. Hancock, A. Newton, M. Green, M. Badger, Application
(2002) 665. Note 267, Micromass, Manchester, UK, 2002.
[91] M.G. Ikonomou, S. Rayne, M. Fischer, M.P. Fernadez, W. [120] R. Zimmermann, U. Boesl, H.-J. Heger, E.K. Rohwer, E.W.
Cretney, Chemosphere 46 (2002) 649. Schlag, A. Kettrup, J. High Resolut. Chromatogr. 20 (1997)
[92] M. Alaee, D.B. Sergeant, M.G. Ikonomou, J.M. Luross, 461.
Chemosphere 44 (2001) 1489. [121] R. Zimmermann, E.K. Rohwer, H.-J. Heger, Anal. Chem.
[93] S. Ohta, D. Ishizuja, H. Nishimura, T. Nakao, O. Aozasa, Y. 71 (1999) 4148.
Shimidzu, F. Ochiai, T. Kida, M. Nishi, H. Miyata, Chemos- [122] N.H. Bings, J.M. Costa-Fernandez, ´ J.P. Guzowski Jr., A.M.
phere 46 (2002) 689. Leach, G.M. Hieftje, Spectrochim. Acta B 55 (2000) 767.
[94] T.L. Wade, L. Chambers, P.R. Gardinali, J.L. Sericano, T.J. [123] M. Heisterkamp, F.C. Adams, Fresenius J. Anal. Chem. 370
Jackson, R.J. Tarpley, R. Snydam, Chemosphere 34 (1997) (2001) 597.
1351. [124] B.W. Pack, J.A. Broekaert, J.P. Guzowski, J. Poehlman,
[95] W.H. Newsome, J.J. Ryan, Chemosphere 39 (1999) 519. G.M. Hieftje, Anal. Chem. 70 (1998) 3557.
[96] F.I. Onuska, J.A. Terry, J. Chromatogr. 471 (1989) 161. [125] J.P. Guzowski Jr., G.M. Hieftje, Anal. Chem. 72 (2000)
[97] F.J. Santos, M.T. Galceran, J. Caixach, J. Rivera, X. Huguet, 3812.
Rapid Commun. Mass Spectrom. 11 (1997) 341. [126] H.L.C. Meuzelaar, J.P. Dworzanski, N.S. Arnold, Field
[98] A. Fromberg, T. Cederberg, G. Hilbert, Organohalogen Anal. Chem. Technol. 4 (2000) 3.
Comp. 35 (1998) 259. [127] B.A. Eckenrode, Field Anal. Chem. Technol. 2 (1998) 3.
[99] E. Braekevelt, G.T. Tomy, G.A. Stern, Environ. Sci. Tech- [128] W.H. McClennen, C.L. Vaughn, P.A. Cole, S.N. Sheya, D.J.
nol. 35 (2001) 3513. Wager, T.J. Mott, J.P. Dworzanski, N.S. Arnold, H.L.C.
[100] D.B. Donald, G.A. Stern, D.C.G. Muir, B.R. Fowler, B.M. Meuzelaar, Field Anal. Chem. Technol. 1 (1996) 109.
Miskimmin, R. Bailey, Environ. Sci. Technol. 32 (1998) [129] W.C. McDonald, M.D. Erickson, B.M. Abraham, A. Robbat
1391. Jr., Environ. Sci. Technol. 28 (1994) 336A.
[101] J. Caixach, J. Rivera, M.T. Galceran, F.J. Santos, J. [130] G. Matz, W. Schoder, ¨ Field Anal. Chem. Technol. 1 (1996)
Chromatogr. A 675 (1994) 205. 77.
´
[102] M.A. Fernandez, ´
L.M. Hernandez, ´
M.J. Gonzalez, E. [131] B.A. Eckenrode, J. Am. Soc. Mass Spectrom. 12 (2001)
Eljarrat, J. Caixach, J. Rivera, Chemosphere 36 (1998) 683.
2941. [132] G. Matz, W. Schoder, ¨ A. Harder, A. Schillings, P. Re-
[103] G.T. Tomy, G.A. Stern, D.C.G. Muir, A.T. Fisk, C.D. chenbach, Field Anal. Chem. Technol. 1 (1997) 181.
Cymbalisty, J.B. Westmore, Anal. Chem. 69 (1997) 2762. [133] U.S. Environmental Protection Agency, Innovations in Site
[104] G.T. Tomy, J.B. Westmore, G.A. Stern, D.C.G. Muir, A.T. Characterization Technology Evaluation: Real Time VOC
Fisk, Anal. Chem. 71 (1999) 446. Analysis Using A Field Portable GC / MS, EPA 542-R-01-
[105] G.T. Tomy, B. Billeck, G.A. Stern, Chemosphere 40 (2000) 011, National Service Center for Environmental Publi-
679. cations, Cincinnati, OH, August 2001, available on-line at:
[106] M.M. van Deursen, J. Beens, H.G. Janssen, P.A. Leclercq, http: / / cluin.org.
C.A. Cramers, J. Chromatogr. A 878 (2000) 205. [134] J.A. Syage, B.J. Nies, M.D. Evans, K.A. Hanold, J. Am.
[107] J.W. Cochran, J. Chromatogr. Sci. 40 (2002) 254. Soc. Mass Spectrom. 12 (2001) 648.
[108] B.D. Gardner, J.F. Holland, Organohalogen Comp. 31 [135] E.R. Badman, R.G. Cooks, J. Mass Spectrom. 35 (2000)
(1997) 208. 659.
[109] B. van Bavel, J. Hughes, S. Davis, H. Wingfors, G. [136] J.A. Diaz, C.F. Giese, W.R. Gentry, Field Anal. Chem.
¨ Organohalogen Comp. 40 (1999) 293.
Lindstrom, Technol. 5 (2001) 156.
[110] R.J.J. Vreuls, J. Dalluge, U.A.Th. Brinkman, J. Microcol. [137] S. Boumsellek, R.J. Ferran, J. Am. Soc. Mass Spectrom. 12
Sep. 11 (1999) 663. (2001) 633.

GC MS HRMS Itms Tof

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Journal of Chromatography A, 1000 (2003) 125–151

www.elsevier.com / locate / chroma

Modern developments in gas chromatography–mass spectrometry-

Keywords: Reviews; Environmental analysis; Gas chromatography–mass spectrometry; Mass spectrometry

1. Introduction ............................................................................................................................................................................ 125

Mass range 2–1000 Da 10–1000 Da 2–4000 Da 5–1500 Da

BzPh, benzophenone; DFBZ, decafluorobenzophenone; HCB, hexachlorobenzence; OFN, octafluoronaphthalene.

advantage of ion-trap instruments is the capability of ions CH 3 CHF 1 and CH 3 CF 1

of simultaneously measuring different isotopes dur- 6. Portable GC–MS instruments

analyser for GC–MS analysis of environmental generation of time-of-flight analysers is expected to

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