Atmospheric Environment 33 (1999) 4953}4962

Collection and analysis of organic acids in exhaust gas.

Comparison of di!erent methods
E. Zervas*, X. Montagne, J. Lahaye
Institut Franc7 ais du Pe& trole (IFP), 1 et 4 avenue du Bois Pre& au, F-92852 Rueil-Malmaison cedex, France
Institut de Chimie des Surfaces et Interfaces, 15 rue Jean Starcky, F-68057 Mulhouse cedex, France
Received 1 August 1997; accepted 3 February 1999
Abstract
This paper reports the development of a speci"c method to identify organic acids in exhaust gases. The organic acids
are collected in two impingers containing liquids (pure water or Na
`
CO
`
1% aqueous solution) and four cartridges
containing solids (silica, #uorisil, alumina B and alumina N). Once collected, the acids are eluted of the solids by a hot
water stream. These traps performances, in terms of organic acids collection and elution e$ciency, are evaluated and
compared. Two sources are used to produce the gas #ow containing organic acids: one generates a #ow whose
concentration is known and stable, the other produces organic acids among other combustion products. For eluted
solutions analysis, two methods are used: isocratic ionic chromatography/conductivity detection and GC/FID. Their
e$ciency in separating 10 aliphatic acids are compared. Their characteristics such as detection limits, detection linearity,
repeatability and possible interferences with other components found in exhaust gases are determined. The stability of the
organic acids solutions is also studied. Lastly, the use of these methods is illustrated by the analysis of the gas-phase
organic acids exhausted by a spark ignition and by a diesel engine. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Organic acids; Ionic chromatography; Internal combustion engines; Gas chromatography; Propane
1. Introduction
The usual "elds of organic acids analysis are the
atmosphere control in urban or rural areas and vehicle
emission studies (Kawamura, 1985). Of late, due to the
possible toxicity and reactivity of these compounds, in-
creased attention has been paid to the vehicle emission
studies but, in literature there are not many papers deal-
ing with organic acids emissions. Although these pollu-
tants can be analysed by continuous methods, as FTIR
for formic acid analysis (Grosjean, 1990), the most com-
mon procedures involve their trapping in a liquid such as
water (Smith, 1985), or aqueous solutions of Na
`
CO
`
(Lopez, 1987), or KOH (Kawamura, 1985). The collec-
*Corresponding author.
Present address: Ecole des Mines de Nantes, 4 rue Alfred
Kastler, F-44070 Nantes cedex 03, France.
tion may also take place on a "lter (Kawamura, 1985;
Yokouchi, 1986), a solid cartridge (Hekmat, 1991;
Grosjean, 1990) or a denuder tube (Lawrence, 1992;
Slanina, 1992). When a cartridge is used, the acids need to
be eluted before analysis.
So far, the only continuous method, the FTIR, can
only analyse formic acid and cannot be used to measure
out the other organic acids. Liquid or solid traps are
needed. As organic acid concentrations in atmosphere or
in exhaust gases are very low (some ppbs or ppms), the
trap has to be extremely e$cient and independent of the
gas volume collected. Literature evokes traps with e$-
ciency rates up to 99% (Smith, 1985) (water), but no
details are provided on the way acids are collected. Fil-
ters are not as e$cient and are a too heavy a technique to
be used in a routine analysis. Denuder tubes do not resist
to high temperatures of exhaust gases. Further, the eluted
solution has to be compatible with the analytical method,
for example, Na
`
CO
`
solution is not compatible with
GC analysis.
1352-2310/99/$- see front matter 1999 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 2 - 2 3 1 0 ( 9 9 ) 0 0 2 7 8 - 2
The eluted solution analysis can be performed by
chromatographic methods such as ionic chromato-
graphy (Smith, 1985), ionic exclusion chromatography
(Tanaka, 1986), GC/FID or GC/MS (Yokouchi, 1986),
HPLC or capillary electrophoresis (Levi, 1993). A deriva-
tion of the captured acids is sometimes needed before
analysis (Kawamura, 1985; McCalley, 1984), but this
adds a supplementary step which is not always e$cient.
Most of these methods cannot completely discriminate
between all the organic acids, or su!er from interferences
with other atmospheric compounds or combustion prod-
ucts, or need several intermediate steps which induce
a loss in e$ciency or make them too heavy to be applied
in routine analysis.
This article proposes a method for organic acids deter-
mination and compares di!erent ways of trapping gas-
phase organic acids. The performances of two liquid
traps are determined and compared: deionised water and
Na
`
CO
`
solution, and four solid ones: silica, #uorisil,
alumina B and alumina N. The elution e$ciency is also
compared. To generate a gas stream with a well-known
concentration in organic acids, two special sources have
been used, a quantitative one, which generates a gas
stream with stable and constant acid concentrations, and
a qualitative one, which generates organic acids within
other products. To avoid very complicated con"gura-
tions, the "nal analysis is performed by two common
analytical methods, isocratic ionic chromatography and
gas chromatography. The performances of these analyti-
cal methods are determined and compared. Also, the
performances of the global method is presented. Then,
these methods are applied to the determination of the
organic acids emitted either by a spark ignition engine or
by a Diesel engine fed with special synthetic fuels.
2. Experimental
2.1. Organic acids sources
One of the major problems encountered during the
development of a pollutant trap is the availability of a gas
stream containing a known and stable concentration of
the pollutant. Atmospheric pollutant concentrations are
usually very low and very disperse while vehicle exhaust
gas pollutant concentrations depend on the engine, on
the running conditions and on the fuel. In this work, two
sources have been used to obtain a gas stream containing
organic acids. The "rst one is a system which evaporates
an aqueous solution of the selected acids. A vapour
stream with known and stable concentration of organic
acids is then obtained. The second system is a combus-
tion reactor where organic acids are obtained together
with other combustion products.
The evaporation system involves a peristaltic pump
that brings the aqueous solution (organic acid concentra-
tion well known) to a furnace, where evaporation takes
place leading to an homogeneous gas-phase #ow. A ni-
trogen #ow can also be added to the furnace to dilute the
gas-phase and obtain lower concentrations. The aqueous
solution contains the "rst three acids: formic, acetic and
propionic, which are the main acids found in vehicle
emissions (Kawamura, 1985). Two furnace temperatures
are used: 423 and 473 K. These tests permitted deter-
mination of the thermal stability of organic acids at these
temperatures and veri"cation of the concentrations of the
gas stream obtained by this source. To achieve it, the
vapour is passed through two glass impingers containing
water, at two furnace temperatures, using di!erent time
periods. The analysis of the "nal solution showed a good
agreement between the acids theoretical emitted and
captured quantity; in such conditions the di!erences re-
main under 3%. As organic acid concentrations in ex-
haust gases reported in literature are very low, (ppm or
even ppb, Kawamura, 1985), the aqueous solution con-
centration and the nitrogen #ow have to be adjusted to
reach similar gas-phase concentrations. For these rea-
sons, the gas-phase concentration in organic acids varies
from 0.2 to 12 ppm.
The second system is a combustion reactor where
propane is used as a fuel. Propane is mixed with air in an
homogenisation chamber and then burned on a #at
burner. A speci"c probe, cooled by internal oil circula-
tion at 383 K and connected to a pump, takes out the
burned gases at di!erent distances from the burner. This
systemis used as a qualitative source of organic acids and
also to study the interferences with other combustion
products.
In all the cases, the gases are transferred from the
source to the capture device through a 383 K heated line.
2.2. Collection
Two liquid and four solid traps are tested for organic
acids collection. The "rst ones are either deionised water
or a Na
`
CO
`
1% aqueous solution. The others are
cartridges containing either silica or #uorisil or alumina
N or alumina B (purchased from water).
In the case of the liquid traps, 20 ml of liquid is placed
in each of the two glass impingers connected in a
line. The gas #ow speed through the liquid is 3.33;
10` m` s (2 L min). To minimise evaporation
losses, these impingers are placed in icy water.
When cartridges are used, they are directly connected
to the heated line. The gas containing the acids #ows at
the same speed as that of liquid solutions. As these gases
are hot ('378 K) and as the cartridges do not with-
stand such temperatures, gases are cooled by an external
cold water #ow in a speci"c glass shell. To determine the
cartridge e$ciency, they are connected to impingers con-
taining 2;10` m` (20 mL) pure water. Before the test,
the cartridges are cleaned by placing them under a hot
4954 E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962
water stream (363 K) all night long, under ultrasounds.
After the capture tests, 1;10" m` (1 mL) of 363 K hot
water is injected for elution.
The gas volume passing through the impingers or
cartridges is kept constant at 0.01 m` (10 L) during all the
collection tests (except the tests of the sources validation
and those of the gas volume in#uence on the e$ciency,
where di!erent gas volumes used ).
2.3. Analysis
For the eluted solution analysis, two methods were used:
isocratic ionic chromatography and gas chromatography.
The "rst method enables to measure formic acid. The
apparatus used is a DIONEX Series 2000i isocratic ionic
chromatograph equipped with an IonPac AS4 column.
The elution solution is an aqueous solution of 0.5;
10` M of Na
`
B
"
O
`
whose #ow speed is 3.33;
10` m` s (2 mL min); the regeneration is obtained
with a H
`
SO
"
0.013 M aqueous solution. The detection
is conductimetric.
The second method, used to measure acetic, heavier
aliphatic acids and benzoic acid, requires a gas chromato-
graph equipped with a FID detector. The apparatus is
a VARIAN 3300 gas chromatography equipped with
a capillary column HP Megabore Innowax 30 m;
0.53 mm. Helium is the carrier gas with a speed of
4;10` m` s. The temperature of the furnace is pro-
grammed: initial temperature at 393 K during 120 s
(2 min) and "nal temperature at 473 K with a heating
speed of 0.066 K s (4 K min). The injector and the
detector temperatures are settled at 523 K.
As Na
`
CO
`
solutions are incompatible with this ana-
lytical method, when such a trap was used, the ionic
chromatography analysis alone was carried out and
propionic acid analysis was omitted.
3. Results and discussion
3.1. Analysis
(a) Ionic chromatography, in the described operating
conditions, can separate formic acid from acetic acid, but
not acetic acid from propionic acid. Our attempts to
separate these two acids by changing either the elution
#ow or the Na
`
B
"
O
`
concentration did not succeed.
Isobutyric acid is also poorly separated from acetic acid
and heavier organic acids cannot be completely separ-
ated from one another. A gradient of Na
`
B
"
O
`
concen-
trations has also been tested, but the acids could still not
be separated. Heavier acids can probably be separated
under other conditions, for example, using another col-
umn and gradient of concentration for the elution solu-
tion. Fig. 1 presents a typical analysis of the "rst two
acids with this method.
Fig. 1. Analysis of formic and acetic acid by ionic chromatogra-
phy/suppressed conductivity detection. Aqueous solution of 10
ppm. Apparatus used: DIONEX Series 2000i, column IonPac
AS4, isocratic elution with 0.5;10` M of Na
`
B
"
O
`
at a #ow
rate of 3.33;10` m` s (2 ml min), regenerate solution:
aqueous solution of H
`
SO
"
0.013 M.
The response of the conductivity detector is linear
within the range from 0 to 100 ppm (Fig. 2). Fig. 3 pres-
ents the relative standard deviation (r.s.d.) for formic acid
analysis for the same range of concentrations of a stan-
dard solution. The repeatability of this method is high, its
r.s.d. being 5% for a 1 ppm formic acid solution. The
detection limit of this method is quite low: some ppbs of
acid (less than 10). The incertitude of preparing a stan-
dard solution at this concentration level does not allow
a closer determination of the detection limits.
The possible interferences with other compounds of
propane combustion or of exhaust gases have been exam-
ined. That for, solutions containing other likely ions were
prepared and analysed. The formate ion does not inter-
fere with the Cl, F, NO
`
, PO`
"
, SO`
"
ions nor with
the other aliphatic acids.
(b) In the described operating conditions, gas chromato-
graphy separates completely the heavier aliphatic acids
from benzoic acid. Fig. 4 shows a typical chromatogram
of these acids.
The response of the FID detector for acetic and
propionic acids is linear from 0 to 100 ppm (Fig. 5). Fig. 6
presents the r.s.d. for acetic and propionic acids for
di!erent concentrations of a standard solution. Gas
chromatography is less repetitive than ionic chromato-
graphy, the r.s.d. of solutions containing 4.6 ppm acetic
E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962 4955
Fig. 2. Conductimetric detector response for formic acid analy-
sis as a function of the solution concentration.
Fig. 3. Relative standard deviation of formic acid analysis by
ionic chromatography as a function of the solution concentra-
tion.
acid or 7.6 ppm propionic acid are, respectively, 10.1 and
10.5%.
The detection limits of this method are below 0.5 ppm
for the two acids.
The possible interference with other compounds of
propane combustion or of exhaust gas has been exam-
ined using the technique described above. No interfer-
ence has been observed with C

}C
"
alcohols, C

}C
`
aldehydes and C

}C
`
hydrocarbons (para$ns, ole"ns,
aromatics).
This method cannot be used for the analysis of
formic acid which has a very low response in FID
(Dietz, 1967), but is convenient for the analysis of heavier
acids.
3.2. Organic acid sources
In the combustion reactor used as the organic acids
source, the acids can be found only very close to the
burner: within the "rst 5 mm around it. In the "rst 3 mm,
concentrations are high. Reaching the fourth and the "fth
millimetre, they decrease sharply down. No acids are
found from the sixth millimetre and above. Propane
combustion generates only formic, acetic and propionic
acids (Zervas, 1996). It is not clear whether the acids are
formed in the #ame or are products from other com-
pounds through some cooling reactions in the probe.
Figs. 7}9 show the organic acid concentrations obtained
depending on the distance of the burner and on the
equivalence ratio. These concentrations range from
0.09 to 10.6 ppm for formic acid, from 0.11 to 8.3 ppm
for acetic acid and from 0.05 to 0.069 ppm for propionic
acid.
3.3. Collection ezciency
The collection e$ciency of the di!erent traps was
characterised as the percentage collected in the "rst im-
pinger (or cartridge) of the total one.
The e$ciency of water and Na
`
CO
`
solutions for the
"rst two acids is presented in Fig. 10. In the test condi-
tions, it is above 90% for both liquids. It is always 1 or 2
units higher with formic than with acetic acid. Na
`
CO
`
solution traps the acids better than water; the corre-
sponding values are 4 or 5 units higher. Literature re-
ports values reach 99% with water (Smith, 1985) and
92% with Na
`
CO
`
solutions (Bodek, 1980), but e$ciency
values are in#uenced by the gas-phase concentration and
by the #ow rate of the gas passing through the impingers
(Zervas, 1996). The higher these parameters values, the
lower the e$ciency values.
Fig. 11 shows the in#uence of gas volumes, ranging
from 0.038 to 0.095 m`, on e$ciency when concentra-
tions of formic, acetic and propionic acid are, respectively,
9, 8.5 and 0.45 ppm. The gas volume passing through the
impingers does not in#uence the e$ciency for such gas-
phase concentrations. The decrease is 1% for acetic and
propionic acid and 0.4% for formic acid.
The e$ciency of the four cartridges used is presented in
Fig. 12. For formic acid, the four types have an e$ciency
of 100%. For acetic and propionic acids, the two
aluminas have an e$ciency of 100%, but silica and
#uorisil e$ciencies are lower (45}90%), silica being bet-
ter (about ten units) than #uorisil.
4956 E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962
Fig. 4. Analysis of nine aliphatic acids and of benzoic acid by gas chromatography/FID detection. Aqueous solution of 6}8 ppm.
Column used: HP Megabore Innowax 30 m;0.53 mm, carrier gas #ow: 4;10` m` s, injector and detector temperatures: 523 K,
initial column temperature: 393 K, initial time: 120 s, "nal temperature: 473 K, heating rate: 0.066 K s.
Fig. 5. FID response for acetic and propionic acid analysis as
a function of the solution concentration.
3.4. Elution ezciency
The e$ciency of the cartridge elution is presented in
Fig. 13. This item is de"ned as the percentage eluted the
"rst time over the total quantity eluted ("rst and second
Fig. 6. Relative standard deviation of acetic and propionic acid
analysis by gas chromatography as a function of the solution
concentration.
time). The elution of silica and of #uorisil is about the
same: 100% for formic acid, 80}85% for acetic acid and
90% for propionic acid. Alumina B leads to lower values,
from 50 to 85%. Last, alumina N has no e$ciency in
E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962 4957
Fig. 7. Combustion of propane. Formic acid concentration in
the gas-phase as a function of the equivalence ratio and the
distance probe-burner. Total (propane#air) #ow"3.33;
10" m` s, inspiration #ow"3.33;10` m` s.
Fig. 8. Combustion of propane. Acetic acid concentration in the
gas-phase as a function of the equivalence ratio and the distance
probe-burner. Total (propane#air) #ow"3.33;10" m` s,
inspiration #ow"3.33;10` m` s.
elution. Acids are adsorbed so strongly that hot water
cannot elute them.
The yield of the collection, de"ned as the product ez-
ciency of the collection x ezciency of the elution, reaches
100% in the cases of formic acid collected on silica or on
Fig. 9. Combustion of propane. Propionic acid concentration in
the gas-phase as a function of the equivalence ratio and the
distance probe-burner. Total (propane#air) #ow"3.33;
10" m` s, inspiration #ow"3.33;10` m` s.
Fig. 10. E$ciency of formic and acetic acid collection in
2.0;10` m` of a 1% Na
`
CO
`
aqueous solution or in de-
ionised water. Gas #ow rate"3.33;10` m` s, gas vol-
ume"0.01 m`, gas-phase concentration"formic acid: 1 to
6 ppm, acetic acid: 1}5 ppm.
#uorisil. It is nil in the case of alumina N. Therefore, solid
cartridges cannot be used to capture all the organic acids.
It was decided to collect organic acids in pure water and
to analyse the solution by the combination of the two
methods described above: ionic and gas chromatography.
4958 E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962
Fig. 11. In#uence of the gas volume passing through the
deionised water impinger on its e$ciency. Volume of the
solution"2.0;10` m`, gas #ow rate"3.33;10` m` s,
gas-phase concentration: formic acid 9 ppm, acetic acid 8.5 ppm,
propionic acid 0.45 ppm.
Fig. 12. E$ciency of the four types of cartridges on acid collec-
tion. Gas-phase concentrations: formic acid 1}6 ppm, acetic acid
0.5}5 ppm, propionic acid 0.5}5 ppm, gas volume: 0.01 m`, gas
#ow rate: 3.33;10` m` s.
3.5. Stability of the eluted solutions
The stability of organic acid solutions has to be con-
trolled. Six aqueous solutions of organic acids issued
Fig. 13. E$ciency of elution on the four types of cartridges.
Elution by deionised water, volume"1;10" m`, temperature
363 K.
frompropane combustion were analysed, at weekly inter-
vals, during six weeks. In the intermediate period, they
were refrigerated at 243 K and preserved from light.
During the "rst two weeks, the di!erences in concen-
tration remained under 15%. Later, acetic acid concen-
tration increased in all solutions and reached 150% of
the initial value on week six. Formic and propionic acid
concentrations decreased and reached 10% of the initial
values after six weeks. Obviously, other compounds,
issued from propane combustion and collected in the
impingers were oxidised into acetic acid. Formic and
propionic acid were oxidised to simplest compounds.
3.6. Linearity, repeatability and detection limits of the
method
This method includes three steps: evaporation, collec-
tion and analysis of organic acids. The evaporation of an
aqueous solution of these acids is used as source. The
collection is performed in two impingers each containing
20 mL of deionised water and the analysis of the "nal
solution by two methods: ionic chromatography for the
analysis of the formic acid and gas chromatography for
the analysis of the heavier aliphatic acids. Linearity,
repeatability and detection limits of the global method
are presented here.
Figs. 14 and 15 present the area, as given by the
chromatograms, as a function of the collection time, for
two gas-phase concentrations obtained by the evapor-
ation system: 1 and 10 ppm of each of the three acids:
formic, acetic and propionic acid, using the same condi-
tions of collection and analysis as presented before. The
E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962 4959
Fig. 14. Linearity of the global method as a function of the
collection time. Gas-phase concentrations: 1 ppm of each acid,
gas #ow rate: 3.33;10` m` s, volume of the collection solu-
tion: 2.0;10` m` of deionised water.
Fig. 15. Linearity of the global method as a function of the
collection time. Gas-phase concentrations: 10 ppm of each acid,
gas #ow rate: 3.33;10` m` s, volume of the collection solu-
tion: 2.0;10` m` of deionised water.
linearity is high, the r` of these lines are always better
than 0.98.
The relative standard deviation of the global method,
as a function of the solution concentration for a gas-
phase concentration of 1 ppm for the three acids, is
Fig. 16. Relative standard deviation of the global method as
a function of the solution concentration. Gas-phase concentra-
tions: 1 ppm, gas #ow rate: 3.33;10` m` s, volume of the
collection solution: 2.0;10` m` of deionised water, analysis of
the formic acid by ionic chromatography and of the acetic and
propionic acid by gas chromatography.
Fig. 17. Analysis by ionic chromatography of the organic acids
in spark ignition engine exhaust gas. Collection in two impingers
each containing 20 mL deionised water each, gas #ow:
3.33;10` m` s, gas volume: 0.01 m`, equivalent ratio: 1.0.
presented in Fig. 16. The r.s.d. values are lower than 10
for the concentrations of more than 1, 8 and 12 ppm in
the solution for the formic, acetic and propionic acid
respectively. These values are between 3 and 25% higher
4960 E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962
Fig. 18. Analysis by gas chromatography of the organic acids in spark ignition engine exhaust gas. Collection in two impingers each
containing 20 mL of deionised water each, gas #ow: 3.33;10` m` s, gas volume: 0.01 m`, equivalent ratio: 1.0.
than the rsd analysis alone (the most important di!erence
is observed in diluted solutions).
The detection limits of the method is under 10 ppb for
the formic acid and below 0.5 ppm for the heavier
aliphatic acids.
3.7. Practical use with engine exhaust gases
In the exhaust gases of a spark ignition engine fed with
several commercial fuels and within a large range of
tuning, formic, acetic, propionic, acrylic, butyric and
isovaleric acids can be detected, in concentrations of
0.1}15, 2}40, 0.5}80, 0}7, 0.8}3.5 and 0}5 ppm, respec-
tively. These concentrations depend on the fuel and the
equivalence ratio used. The other acid's concentrations
are below the detection limits. A Diesel engine, fed with
two di!erent commercial fuels, produces detectable con-
centrations of the "rst three acids (formic 2}6, acetic 4}8
and propionic 0.4}3 ppm).
The other compounds of the exhaust gases do not
interfere with the analysis of these acids. Figs. 17 and 18
are two chromatograms, corresponding to the analysis,
by ionic and by gas chromatography respectively, of
the acids produced by the spark ignition engine at
stoichiometry.
4. Conclusion
The evaporation of an aqueous solution containing
organic acids can be successfully used to generate a gas
#ow with a known and stable concentration in these
acids. Propane combustion on a #at burner can also
generate the "rst three acids in the "rst "ve mil-
limetres of the burner. It is not clear whether the organic
acids are formed in the #ame or in the probe, but this
method can be used as a stable source of these com-
pounds.
Organic acid trapping can be performed in deionised
water or in Na
`
CO
`
aqueous solution. The e$ciency of
these liquid traps is over 92% for the "rst two acids,
under the conditions we used. All four solid traps are
e$cient in collecting formic acid but only the two
aluminas can collect quantitatively acetic and propionic
acids. The elution e$ciency using hot water reaches
100% in the case of formic acid adsorbed on silica or
#uorisil; the other acids have lower elution rates
(80}90%) of these solids. Alumina B has a very low and
alumina N no e$ciency in elution; only silica could be
used for formic acid collection.
The analysis of the collected acids can be performed by
two methods, isocratic ionic chromatography for formic
acid and gas chromatography for the other acids. Or-
ganic acids have no interference with other compounds
of the exhaust gases and the detection limits are low,
some ppb in the case of formic acid and under 0.5 ppm in
the case of the other acids.
This method is applied to the analysis of the organic
acids produced by two internal combustion engines, a SI
and a Diesel one, using commercial fuels. Six acids are
detected in the exhaust gases of the "rst engine emissions
and three in the second.
E. Zervas et al. / Atmospheric Environment 33 (1999) 4953}4962 4961
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