Water Air Soil Pollut
DOI 10.1007/s11270-008-9826-5
The Odd–Even Behaviour of Dicarboxylic Acids Solubility
in the Atmospheric Aerosols
Mohd Zul Helmi Rozaini & Peter Brimblecombe
Received: 25 January 2008 / Accepted: 6 August 2008
# Springer Science + Business Media B.V. 2008
Abstract The solubility and the enthalpy of dicarbox-
ylic acids have been determined in water at intervals
between 278.5 and 543.5 K. At 298.15 K, the values
derived were: ΔsolHm (m=1.33 mol kg−1)=29.80 kJ
mol−1for oxalic acid; ΔsolHm (m=16.03 mol kg−1)=
12.82 kJ mol−1 for malonic acid; ΔsolHm (m=0.75
mol kg−1)=28.20 kJ mol−1 for succinic acid; ΔsolHm
(m=8.77 mol kg−1)=48.01 kJ mol−1 and ΔsolHm (m=
0.17 mol kg−1)=40.30 kJ mol−1 for glutaric and
adipic acid respectively. The solubility value exhibits
a prominent odd–even effect with respect to terms
with even number of carbon atoms with the odd
carbon numbers showing much higher solubility.
Observations made in the atmospheres suggest that
this odd–even effect may have implications for the
relative abundance of these acids in aerosols.
Keywords Oxalic acid . Malonic acid . Succinic acid .
Glutaric acid . Adipic acid . Solubility .
Water soluble aerosol
M. Z. H. Rozaini (*) : P. Brimblecombe
School of Environmental Science,
University of East Anglia,
Norwich, Norfolk NR4 7TJ, UK
e-mail: mohd.rozaini@uea.ac.uk
M. Z. H. Rozaini
Department of Chemical Sciences,
Faculty of Science and Technology,
University Malaysia Terengganu,
21030 Kuala Terengganu, Malaysia
1 Introduction
1.1 Dicarboxlic Acids Distributions
in the Atmosphere
Low molecular weight dicarboxylic acids (DCAs) are
ubiquitous and important components of the organic
fraction of atmospheric particles. They have been
detected in a variety of environments in many regions
in the world, including urban (Kawamura and Kaplan
1987; Kawamura and Watanabe 2004; Limbeck and
Puxbaum 1999; Rohrl and Lammel 2001; Sempere and
Kawamura 2003), rural (Kawamura and Kaplan 1987;
Khwaja et al. 1995; Narukawa et al. 1999; Yu et al.
2005) and remote marine atmospheres (Kawamura and
Sakagushi 1999).
Whatever the region; urban and continental, or
remote marine (see Table 1), oxalic acid (C2: HOOC-
COOH) is found to be the most abundant diacid
followed by succinic (C4: HOOC(CH2)2COOH) and/or
malonic (C3: HOOCCH2COOH) acid with concentra-
tions of several hundreds of nanograms per cubic meter
in urban and continental regions (Kawamura and
Ikushima 1993; Kawamura and Kaplan 1987) to a
few tens of nanograms per cubic meter in remote marine
boundary layer (Kawamura and Sakagushi 1999;
Sempere and Kawamura 2003). In Europe, the most
continuous study of diacids was conducted for over 1
year by Limbeck et al. (2005) at Vienna, Austria.
Although available data on diacids are more sparse at
mid-latitudes in Europe, they tend to show that oxalic
acid levels at nonurban or rural sites are not consider-
 Water Air Soil Pollut

Table 1 Summary of aerosol dicarboxylate concentration (ng m-3) in urban and continental (a); remote marine (b) locations

References Location Oxalic Malonic Succinic Glutaric Adipic

(a)
(Grosjean et al. 1978) New York – 3.6 21.8 17.2 13.2
(Grosjean et al. 1978) New York – 3.9 24.9 23.2 11.6
(Kawamura and Kaplan 1987) West LA 6.38 1.58 1.96 0.6 2.22
(Kawamura and Kaplan 1987) West LA 2.12 0.4 0.66 0.22 0.94
(Kawamura and Kaplan 1987) West LA 8.13 0.72 2.34 0.66 3.31
(Kawamura and Kaplan 1987) West LA 8.65 1.45 2.37 0.74 0.49
(Kawamura and Kaplan 1987) Downtown LA 6.21 0.71 1.19 0.52 0.1
(Kawamura and Kaplan 1987) Downtown LA 6.6 0.76 1.84 0.52 0.2
(Kawamura and Kaplan 1987) Downtown LA 8.31 1.22 2.13 0.83 0.63
(Sempere and Kawamura 1994) Tokyo 29.65 6.69 13.18 3.72 6.66
(Sempere and Kawamura 1994) Tokyo 58.89 20.29 28.82 7.54 6.79
(Sempere and Kawamura 1994) Tokyo 330 141.3 161.1 4.15 2.91
(Limbeck and Puxbaum 1999) South Africa 193 142 58 8.8 7.9
(Limbeck and Puxbaum 1999) Sonblick observatory 153 22 14 2.7 4.4
(Limbeck and Puxbaum 1999) Vienna 340 244 117 26 117
(Kawamura and Watanabe 2004) Tokyo 357 71.4 73.4 23.1 25.8
(Kawamura and Watanabe 2004) Tokyo 157 44 41 11 13
(Kawamura and Watanabe 2004) Tokyo 186 40.5 47.4 18.2 14.2
(Rohrl and Lammel 2001) Helsinki – – – – –
(Ho et al. 2006) Hong Kong (road) 478 89.1 71.88 20 10.7
(Ho et al. 2006) Hong Kong (road) 268 47.6 33 6.95 12.7
(Hsieh et al. 2007) Tainan, Taiwan 574 65.8 101 43 13.2
(Hsieh et al. 2007) Tainan, Taiwan 432 34.2 87.9 10.3 8.8
(Limbeck et al. 2005) Vienna, Austria 99.6 34 37 7.7 3.3
(Limbeck et al. 2005) Vienna, Austria 66.2 38.6 30.8 6.6 3.2
(Limbeck et al. 2005) Vienna, Austria 63.1 21.5 31.2 5.6 2.5
(Limbeck et al. 2005) Mt Rax, Austria 34.5 9.1 16.4 2.3 0.8
(Limbeck et al. 2005) Mt Rax, Austria 26.4 6.9 14.9 2.3 4.3
(Limbeck et al. 2005) Mt Rax, Austria 32.6 16.4 22.4 3 1.7
(Decesari et al. 2006) Rondonia, Brazil 194.7 73.1 123.5 23.5 14.5
(Decesari et al. 2006) Rondonia, Brazil 793.3 56.8 210.2 32.1 12.6
(Decesari et al. 2006) Rondonia, Brazil 937.9 128.5 423.9 34.7 21.2
(Decesari et al. 2006) Rondonia, Brazil 1260 476.5 667.2 121.1 97.4
(Wang et al. 2006) Hong Kong (Tunnel) 505 69.4 85.2 20.9 26.4
(Wang et al. 2006) Hong Kong (Tunnel) 221 34.5 32.7 14.7 13.5
(Wang et al. 2006) Hong Kong (Tunnel) 234 42 51.4 17.1 24.7
(Wang et al. 2006) Hong Kong (Tunnel) 312 59.7 62.9 16.7 15.5
(Wang et al. 2006) Hong Kong (Tunnel) 633 59.3 95.1 30.3 25.9
(b)
(Kawamura and Kaplan 1987) Green House LA 1.31 0.3 0.29 0.04 0.1
(Kawamura and Kaplan 1987) Green House LA 2.83 0.14 0.86 0 0.22
(Kawamura and Sakagushi 1999) North Pacific 44.7 23.2 19.5 2.57 3.08
(Kawamura and Sakagushi 1999) North Pacific 8.73 2.18 2.16 0.61 1.26
(Kawamura and Sakagushi 1999) North Pacific 10.6 1.98 2.22 0.23 2.12
(Kawamura and Sakagushi 1999) North Pacific 28.6 12.8 13 1.84 1.34
(Kawamura and Sakagushi 1999) North Pacific 667 189 93 20.1 4.9
(Kawamura and Sakagushi 1999) North Pacific 190 38.6 16.7 10.2 2.76
(Kawamura and Sakagushi 1999) North Pacific 88.5 34.5 21.6 4.72 6.04
(Kawamura and Sakagushi 1999) North Pacific 24.9 5.66 10.1 1.87 1.67
(Kawamura and Sakagushi 1999) North Pacific 10 2.12 1.52 0.32 0.43
(Kawamura and Sakagushi 1999) North Pacific 18.3 3.45 4.02 0.62 0.46
Water Air Soil Pollut

Table 1 (continued)

References Location Oxalic Malonic Succinic Glutaric Adipic

(Kawamura and Sakagushi 1999) North Pacific 25.5 5.93 2.99 0.65 0.4
Kawamura (1996) Antarctic 1.59 0.13 0.63 0.31 0.49
Kawamura (1996) Antarctic 3.12 0.38 5.77 0.58 0.85
Kawamura (1996) Antarctic 3.26 0.52 1.18 0.34 0.33
Kawamura (1996) Antarctic 10.29 2.69 61.53 2.26 1.81
Narukawa et al. (1999) Indonesia 2200 800.3 1090 310 350
Narukawa et al. (1999) Indonesia 225 18.4 123 30 40
Khwaja et al. (1995) Semi urban site NY 308 84 55 12 89
Khwaja et al. (1995) Semi urban site NY 245 92 106 16.3 101
Khwaja et al. (1995) Semi urban site NY 118 165 107 15 40
Khwaja et al. (1995) Semi urban site NY 58 81 129 20 21
Khwaja et al. (1995) Semi urban site NY 298 96 90 23 31
Khwaja et al. (1995) Semi urban site NY 1 43 0.5 39 20
Khwaja et al. (1995) Semi urban site NY 360 88 167 46 50
Sempere and Kawamura (2003) Western Pacific 428.5 78.6 33.4 7.6 7.2
Rohrl and Lammel (2001) Rural (I) – – 14 – –
Rohrl and Lammel (2001) Rural (II) – – 8.8 – –
Rohrl and Lammel (2001) Rural (III) – – 18 – –
Kawamura et al. 2007 Canadian arctic 9.89 2.74 2.16 0.54 0.51
Kawamura et al. 2007 Canadian arctic 8.3 2.87 1.44 0.37 0.26
Kawamura et al. 2007 Canadian arctic 5.26 1.67 1.08 0.22 0.27
Narukawa et al. 2002 Arctic, Alert 23.5 5.03 3.21 1.21 0.54
Narukawa et al. 2002 Arctic, Alert 40.09 11.6 15.67 2.16 0.55
Mochida et al. 2007 North Pacific, ACE 600 110 52 8.9 2

ably different from those at urban sites (Limbeck and
Puxbaum 1999; Rohrl and Lammel 2001).
Motor exhausts have been proposed to be primary
sources of oxalic, malonic, succinic, and glutaric (C5:
HOOC(CH2)3COOH) acids (Grosjean et al. 1978;
Kawamura and Kaplan 1987). Some of these diacids
are also emitted by wood burning, particularly malonic
acid (pine wood) and succinic acid (oak wood; Rogge
et al. 1991, 1993). Until now no direct source of malic
(hydroxysuccinic: hC4: HOOCCH2CHOHCOOH) and
tartaric (dihydroxysuccinic: dhC4: HOOC(CHOH)2-
COOH) acids has been identified for aerosols.
Glutaric, succinic, and adipic (C6: HOOC(CH2)4
COOH) acids have been identified in laboratory studies
(Hatakeyama et al. 1985) as secondary organic aerosol
products of the reaction of O3 with cyclohexene, a
symmetrical alkene molecule similar to monoterpenes
emitted by the biosphere. Hatakeyama et al. (1985)
also suggested that malonic and oxalic acids are also
produced in the cyclohexene-ozone system.
The DCAs have received much attention because
of their roles in affecting the global climate by
involving in the production of cloud condensation
nuclei (Kerminen et al. 2000) and may contribute to
the acidity of precipitation (Chebbi and Carlier 1996).
With a low vapour pressure and high water solubility,
diacids have an influence on the chemical and physical
properties of aerosol (Lightstone et al. 2000). Conse-
quently, they may have direct and indirect effects on
the earth’s radiation balance by scattering incoming
solar radiation, which counteracts the global warming
caused by the increase of greenhouse gasses.
As an initial step towards a better understanding on
the physical chemistry of these multiphase com-
pounds, laboratory studies into the solubility of the
acids have been undertaken. It is also particularly
noticeable that there is odd and even effect of carbon
atom number on dicarboxylic acid solubility, which
may have an influence on the phase and chemical
properties of atmospheric aerosols.
1.2 Solubility
The dissolution of compounds in aqueous aerosols
affects their water activity and thus the related to the
relative humidity at which the aerosol equilibrates

with the atmosphere. Highly soluble compounds can
form very concentrated solutions and can remain so
even at low relative humidity. It is also possible for
aerosol droplets to persist as supersaturated systems.
The low molecular weight DCAs and dicarboxylates
have a strong affinity for moisture so will absorb
relatively large amounts of water from the atmosphere
to form a liquid solution The relative humidity at
which such deliquescence takes place is also depen-
dent on the solubility of the compound. There are
surprisingly few measurements of the solubility of
DCAs especially in electrolytes of relevance to the
atmosphere (such as sodium chloride and ammonium
sulphate solutions), so we have undertaken a range of
solubility measurements for low molecular weight
DCAs.
Solubility describes the composition of solutions
and in the case of aqueous solutions of soluble
organic materials it represents the amount material
that will dissolve in a liquid. The aqueous solubility
of a solute is often expressed as the number of moles
of solid dissolved in a certain amount of water, here a.
kilogram, such that the units are referred as molality,
m (mol kg−1). Although volumetric measurements are
popular in the laboratory for ease of preparation (i.e.
molar units, or moles of solute per litre of solution),
they are inconvenient in terms of physical representa-
tions. The concentration changes with temperature
and at high concentrations the solute solvent ratio is
not proportional to the expressed concentration. Here
we report the variation of aqueous solubility with
temperature for the 2–6 carbon acids.
2 Experimental
2.1 Reagents
The reagents were used throughout this work stated
by the molecular weight, Mw were: oxalic acid, Mw =
90.636 g mol−1; malonic acid, Mw =104.06 g mol−1;
succinic acid, Mw =118.19 g mol−1; glutaric acid, Mw =
132.11 g mol−1; adipic acid, Mw =146.14 g mol−1;
sodium chloride; Mw =58.44 g mol−1; ammonium
nitrate, Mw =80.04 g mol−1; ammonium sulphate, Mw =
132.14 g mol−1 and water, Mw =18.0153 g mol−1. There
were obtained from Aldrich with analytical grade
reagents purities >99% (with the exception of glutaric
and adipic acid with the purity ~98 and >97%
Water Air Soil Pollut
respectively) and the substances were used without
further purification.
2.2 Solubility Determination
The simple apparatus used to determine solubility is
shown in Fig. 1. A two-hole rubber stopper fitted
snugly into a test tube (25×150 mm) of borosilicate
glass. The thermometer was inserted carefully through
one hole of the rubber stopper so that the thermometer
tip was near the bottom of the test tube. A glass rod
was inserted through other hole, so that the solution
could be agitated. The large borosilicate beaker (2 L)
contained water and sat on a hot plate. The solid acids
and were weighed accurately into the test tube and
distilled water (initially about 2.00 mL) was dis-
pensed from the burette into the test tube and
recorded to 0.01 mL.
The solution in the tube was heated (to about 80°C)
and once the acid dissolved was allowed to cool, while
being agitated, to determine at which temperature the
acid begins to crystallize. The temperature was noted
and a small amount of water was added from the burette
and recorded. The solution was heated again until the
acid dissolved and cooled once more to record a new
point of crystal formation. This was repeated many
times such that the solubility (ever decreasing) at
various temperatures could be determined and it is these
that appear as our data tabulated within Figs. 2, 3, 4, 5
and 6. Solubility is plotted as the logarithm of the
solubility (ln m vs 1/T) as this is preferable from a
physical chemistry perspective as slope of the curve is
related to the molar enthalpy of dissolution.
3 Results and Discussions
3.1 Solubility of Dicarboxylic Acids
Solubility is a quantitative means of describing the
composition of solutions. Solutions may be formed by
mixing various combinations of liquids, gases, and
solids. In these experiments only the dissolution of a
solid in a liquid will be considered. Thus, solubility as
used to describe a solid dissolved in a liquid refers to
the quantitative composition of the solution. Solid
acids were dissolved and concentration at various
saturation temperatures expressed as mol per kg of
water. A solubility curve was drawn by plotting the
Water Air Soil Pollut
Fig. 1 The apparatus used
to determine solubility
mole per kilogram water on y-axis against saturation
temperature on x axis. The dependence of solubility
as function of temperature T can be expressed at
constant pressure, by the relation:
fd ln m=d ð1=T Þgð1 þ d ln g=d ln mÞ ¼
Δsol Hm =R ð1Þ
Where ΔsolHm is the molar enthalpy of solution, R
is the gas constant and m and γ is the solute and its
activity coefficient.
The solubility values of oxalic acid (1.33 mol kg−1)
from this study were similar to those of Apelblat
(1989) and Marcoli et al. (2004) at 298.15 K; with
almost same slope over the range of 293.15–338.15 K.
The results Stephen and Stephen found a slightly
lower solubility of 1.10 mol kg−1at 298.15. Experi-
mental conditions could explain this small disagree-
ment, but it is clear that saturated oxalic acid forms
approximately molal solutions in the atmosphere. At
348.15 K, the solubility of oxalic acid we determined
the solubility as 7.23 mol kg−1 and there are no
solubility measurements beyond this temperature.
Using the equation above for oxalic acid the molar
enthalpy (i.e. neglecting non-ideality) of solution at
298.15 K is ΔsolHm(m=1.33 mol kg−1)=29.8 kJ mol−1
(see Fig. 2).
The solubility of malonic acid (Fig. 3) was in
reasonable agreement with literature values from
278.15–323.15 K, but at higher temperatures (up to
343.15 K) there is a slight difference. As a compar-
ison, at 298.15 K, our solubility measurement for
 Water Air Soil Pollut
Fig. 2 Solubility of oxalic
acid in the water. Key: This
study (square), Apelblat
(1986) (circle), Stephens and
Stephens (1986) (triangle)
and Marcolli et al. (2004)
(diamond).m=mol kg−1

malonic acid is 16.02 mol kg−1 in satisfactory
agreement with Apelblat (1986) and also from the
older ones from Cahn (1899) cited by Seidell and
Linke (1952) of 15.99 and 15.92 mol kg−1 respec-
tively. However, there is a slight disagreement with
the measurements of Marcolli et al. (2004) and
(Stephens and Stephens 1986), which are almost
half the value at 8.15 and 6.71 mol kg−1 respectively.
Studies of bulk solutions by Peng and Chan (2001)
suggest solubility that is reasonably consistent with
our measurement, so we have discarded the lower
values. The molar enthalpy of solution for malonic
acid at 298.15 K is ΔsolHm (m=16.02 mol kg−1)=
12.82 kJ mol −1 . This value is slightly higher
than that based on the calorimetric values from the
molar enthalpy of solution at infinite dilution by
Apelblat (1986) which is (m=15.99 mol kg−1)=
11.20 kJ mol−1.
Results of our solubility determination for succinic
acid were compared with the values measured over the
period 1874 to 1919 as compiled by Seidell and Linke
(1952). This acid is notably less soluble than oxalic
and malonic acid. In fact, bulk solution measurements
are restricted to molalities of less than 0.7 mol kg−1. At
298.15 K, the solubility of succinic acid in our study
shows almost the same values with others in the
literature at 0.748 mol kg−1. There was apparent
problem in the data of Apelblat and Manzurola (1990)
where we can see an obvious decrease in solubility at
333.15 K which seems rather unusual (see Fig. 4). We

Fig. 3 Solubility of malonic

acid in the water. Key: This
study (square), Apelblat
(1986) (circle), Stephens and
Stephens (1986) (triangle)
and Marcolli et al. (2004)
(diamond). m=mol kg−1
Water Air Soil Pollut
Fig. 4 Solubility of succinic
acid in the water. Key: This
study (square), Apelblat
(1986) (circle), Stephens and
Stephens (1986) (triangle)
and Marcolli et al. (2004)
(diamond). m=mol kg−1

have discarded this anomalous value and determined
the enthalpy from their data (28.29 kJ mol−1) which is
similar to our own 28.20 kJ mol−1. Our measured solu-
bility for succinic acid at 298.15 K is 0.748 mol kg−1,
much in agreement with 0.747 from Apelblat and
Manzurola (1990) as well.
Measurements of glutaric acid solubility are
available from Attane and Doumani (1949) along
with determinations perform by Apelblat (1989). As
can be seen at Fig. 5, the agreement is satisfactory
only for temperatures up to 308.15 K. Above this
point and up to 343.15 K there is an unexpected
scatter of experimental points. However at 298.15 K,
we have a significant solubility values which ours is
8.768 and 8.956 mol kg−1 by Apelblat (1989). Our
molar enthalpy of glutaric acid at 298.15 K is ΔsolHm
(m=8.768 mol kg−1)=48.01 kJ mol−1 can be com-
pared with the calometric result of Apelblat (1989):
ΔsolHm (m=8.956 mol kg−1)=51.01 kJ mol−1.
Results of our solubility determination for adipic
acid is 0.171 mol kg−1 were comparable with other
measured values: 0.169 mol kg−1 (Apelblat 1986),
0.173 mol kg−1 (Attane and Doumani 1949) and
0.172 mol kg−1 (Marcolli et al. 2004) as in Fig. 6.
However, a measurement performed for adipic acid is
expressed as concentrations (Davies and Griffiths
1953) but without knowledge of the densities of
saturated solution cannot be used for comparison,
nonetheless, from estimated the values of 0.180, it is
still in a good agreement with those presented here.
Our value for the molar enthalpy of adipic acid is
ΔsolHm (m=0.171 mol kg−1)=40.30 kJ mol−1 and can

Fig. 5 Solubility of glutaric

acid in the water. Key: This
study (square), Apelblat
(1989) (circle), Stephens and
Stephens (1986) (triangle)
and Marcolli et al. (2004)
(diamond). m=mol kg−1
 Water Air Soil Pollut
Fig. 6 Solubility of adipic
acid in the water. Key: This
study (square), Apelblat
(1986) (circle), Stephens and
Stephens (1986) (triangle)
and Marcolli et al. (2004)
(diamond). m=mol kg−1

be compared with the calorimetric result of Apelblat negative charges on carbon atoms (Falk and Nelson
(1986): ΔsolHm (m=0.169 mol kg−1)=42.58 kJ mol−1. 1910). Although these ideas now seem discordant with
our views on covalent bonding (Burrows 1992), they
3.2 Odd–Even Effect perhaps relate to resonance within covalence bonding
(Muller and Carl 2006). Larsson (1966) suggested that
A series of organic compounds with a chain of carbon packing in the planes containing the end groups
atoms often show an affect of physical property explained the effect. An increase in packing density
dependent on whether there is an odd or even number will increases the intermolecular interactions, notably
of carbon atoms. The aqueous solubility of DCAs is Van der Waals’s forces. These will stabilize the solid
highly dependent on the number of carbon atoms with phase and the particular alternation of the properties is
acids with odd numbers of carbon atoms being much
more soluble than those with even numbers.
Oxalic, adipic and succinic (even carbon numbers)
have much lower solubility than malonic and glutaric
acids, which are exceptionally soluble. The solubility (in
mole per kilogram) of the dicarboxylic acids is
presented as function of carbon chain length up to C8
in Fig. 7. A number of previous authors have observed
this particularly noticeable odd–even effect with
dicarboxylic acid solubility (e.g. Burrows 1992).
Cappa et al. (2007) and Larsson (1966) approached
this from an atmospheric science perspective in relation
the vapour pressure of (C4–C10) dicarboxylic acids.
The odd–even effect is often observed with longer
chain compounds particularly in terms of the triple
point of the mono-carboxylic acids and the Kraft
temperature which relates to surfactant properties. Fig. 7 Solubility of the dicarboxylic acids in the water at
Early theoretical explanations suggested that odd– 298.15 K. Also included are data for pimelic (square), suberic
(triangle) and azelaic acid (diamond) from Apelblat (1989) and
even differences arose from altering strong and weak
Apelblat and Manzurola (1990). Inset (i) shows the water
bonds along the carbon chain and others modified this activity of the saturated dicarboxylic acids from the thermody-
by introducing the idea of alternating positive and namic model of Pitzer (1991)
Water Air Soil Pollut
driven by differences at the interfaces between the
chain ends for even and odd members.
The large differences in solubility between subse-
quent homologues means that atmospheric aerosols of
malonic and glutaric acid would remain liquid to
rather low relative humidity (~60% and 85% respec-
tively), while oxalic, succinic and adipic would
readily crystallize.
3.3 Atmospheric Implications
Measurements of aerosol concentrations of DCAs
from the literature are listed in Table 1 including
information on the nature of the site. We chose to
divide the data into two groups: (1) urban and
continental measurements and (2) remote marine
measurements in Fig. 8. Not unexpectedly, the
reported urban concentrations are higher than those
from the remote marine sites. The distributions of
dicarboxylic acids with respect to carbon chain
length, shows the predominance of oxalic acid (see
Fig. 8). This is typically reported from urban areas
such as Tokyo, Los Angeles, Johannesburg, Christ-
church and Vienna and even in non-urban locations.
In urban locations the primary emission from vehicles
(incomplete combustion products of fuel or fuel
additives) are a potential source of oxalic acid, but
we have to imagine other sources for the non-urban
location as here oxalic acid still predominates.
Succinic acid is usually at the second highest
concentrations in both locations followed by malonic,
adipic and glutaric acid.
Fig. 8 Comparison of average dicarboxylic acids concentra-
tions in urban and continental and remote marine locations
In some cases succinic acid proved to be dominant
among the DCAs detected, for example in the South-
eastern Aerosol and Visibility Study (SEAVS). Here it is
argued that high humidity allowed succinic acid to be
present in the aerosol and thus protected from photo-
oxidation (Yu et al. 2005). The SEAVS also gave
importance to the C6 adipic acid reinforcing a view
that DCAs with even carbon number predominate.
It remote continental areas it is possible that primary
emissions from forest fires, soil or vegetation contributed
to the production of oxalic acid. Oxalic acid is also
formed in plants through incomplete oxidation of
carbohydrates, e.g., by fungi (Aspergillus niger) or
bacteria (acetobacter) and in the animal kingdom
through carbohydrate metabolism via tricarboxylic acid
cycle (Clarke 1986). Mammalian urine also contains a
small amount of oxalate. Moreover, some of the authors
believe that oxalic acid can also be produced from the
photo-oxidation of unsaturated fatty acids emitted from
seawater (Kawamura and Sakagushi 1999).
The odd–even pattern in composition is known from
petroleum geology as the carbon preference index
(CPI). This index is related to Σ (odd homologues)/Σ
(even homologues) for high molecular weight n-alkanes
traces their biological origin. This has also been used in
the atmosphere where a CPI in the order of 3 (i.e. odd
carbon numbers dominate) shows recent biological
origin of alkanes and oxygenated organic compounds
from leaf waxes etc. (Simoneit et al. 1990). The signal is
not always clear for carboxylic acids.
It may well be that the dominance of even carbon
numbers among the smaller DCAs found in aerosols
reflects a physical process driven by the large solubility
differences over the series rather than an initial biological
signature. An odd–even dependence with respect to total
carbon number is observed in the vapour pressure of 4–
12 carbon DCAs, with higher pressures fund in the odd
members (Cappa et al. 2007). However, this implies that
larger DCAs with an even number of carbon atoms
would partition more effectively onto aerosol particles.
The reason for the predominance of even carbon
numbers among the low molecular weight DCAs in
aerosol is not clear. It could also be affected by the
presence of aqueous electrolytes and other aerosol
components. Nevertheless, the strong variation in
their solubility has to be considered as a potential
driver of this variation and reminds us of potential
importance a relatively simple physical interaction in
moderating aerosol composition.

4 Conclusion
The smaller dicarboxylic acids (2–6 carbon atoms) are
soluble compounds commonly found in the atmo-
spheric aerosol. Measurements show that the acids
with odd numbers of carbon atoms (malonic and
glutaric) have much higher solubility than those even
with even numbers (oxalic, succinic and adipic).
Although odd–even effects on physical properties
have been observed before, they are typically small.
The extraordinarily large variations in solubility from
one DCA homologue to the next may well leave its
imprint on aerosols. Observations from aerosol
composition illustrate an odd even pattern in DCA
abundance give some support to this possibility.
Acknowledgement The corresponding author would like to
thank the Malaysian Government for financially supporting this
research under a scholarship.
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