Atmospheric Environment 35 (2001) 6231–6244
Role of organic and black carbon in the chemical composition
of atmospheric aerosol at European background sites
Z. Kriva! csya,*, A. Hofferb, Zs. Sa! rva! rib, D. Temesia,b, U. Baltenspergerc, S. Nyekic,
E. Weingartnerc, S. Kleefeldd, S.G. Jenningsd
a
! P.O. Box 158. 8201-Veszprem,
! Hungary
Air Chemistry Group of Hungarian Academy of Sciences, University of Veszprem,
b
! P.O. Box 158. 8201-Veszprem,
! Hungary
Department of Earth and Environmental Sciences, University of Veszprem,
c
Paul Scherrer Institute, CH-5232, Villigen, Switzerland
d
Atmospheric Research Group, Department of Physics, National University of Ireland, Galway, Ireland
Received 12 June 2001; accepted 7 September 2001
Abstract
The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black
carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch,
Switzerland (high-alpine, PM2.5 aerosol); (ii) K-puszta, Hungary (rural, PM1.0 aerosol); (iii) Mace Head, Ireland
(marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to
the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about
60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable
portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass
concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon
was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but
instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass.
These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical)
might be significant. r 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Background atmospheric aerosol; Organic carbon; Black carbon; Water solubility; Thermal behaviour; Carboxylic acids;
Humic-like substances
1. Introduction
Knowledge of the chemical composition of atmospheric aerosol is essential to assess its impact on the
environment, either by affecting the air quality in
populated areas, or by influencing the climate. The fine
mode of the aerosol (diameter do1 mm) is of particular
importance because fine particles are inhalable, they can
interact with the solar radiation and provide the
majority of cloud condensation nuclei. The main
*Corresponding author. Tel.: +36-88-422022/4490; fax:
+36-88-423203.
E-mail address: [email protected] (Z. Kriv!acsy).
constituents of fine atmospheric aerosol are inorganic
ions, organic compounds and to a lesser extent black
carbon (BC) otherwise known as elemental carbon (EC).
While inorganic ion species and their concentrations
have been determined at many locations around the
world, data for carbonaceous compounds are rather
limited, of which a significant portion are for urban
areas (e.g. Dod et al., 1986; Sloane et al., 1991; Nunes
and Pio, 1993; Chan et al., 1997; Hering et al., 1997;
Kuhlbusch et al., 1998; Didyk et al., 2000). These data
are primarily important in emission strength measurements and air quality studies. However, the more global
effects of aerosols can be better estimated at rural and
remote locations. Results obtained for organic carbon
1352-2310/01/$ - see front matter r 2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 2 - 2 3 1 0 ( 0 1 ) 0 0 4 6 7 - 8
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et al. / Atmospheric Environment 35 (2001) 6231–6244
(OC) and BC or EC during the last two decades in rural
environments are summarised in Table 1. (As regards
BC or EC the light-absorbing carbon determined by
optical methods is usually called BC, and refractory
carbon determined by thermal (or thermo-optical)
methods is usually called EC. This operative definition
is also used in this paper). Most data are from the USA,
while similar studies in Europe began only in the mid1990s. Data from remote sites are scarce and generally
available only for BC or EC (Table 2). Mace Head,
which is one of the sampling sites in our study, is listed
in both Tables 1 and 2. If the site is influenced by local
or continental air then conditions refer to a rural,
coastal environment, but if clean air masses arrive from
the Atlantic Ocean then Mace Head is representative of
a remote marine location. Further speciation of OC to
water-soluble organic carbon (WSOC) and waterinsoluble organic carbon (WINSOC) is also important
in assessing the effect of organic compounds on the
hygroscopic behaviour of aerosol particles. WSOC is not
commonly measured although results indicate that
about half of the OC is water soluble (e.g. Cadle and
Groblicki, 1982; Mueller et al., 1982; Sempere and
Kawamura, 1994; Zappoli et al., 1999).
The chemical composition of atmospheric aerosol
collected at three European background sitesFJungfraujoch (JFJ; Switzerland), K-puszta (Hungary) and
Mace Head (Ireland)Fis studied in this work. The JFJ
and K-puszta are typical of high-alpine and rural
continental environments, respectively. At Mace Head
our aim was to collect ‘‘pure’’ marine aerosol for
comparison to the continental samples. Therefore,
despite its European location Mace Head aerosol is
representative of the Atlantic Ocean and not European
aerosol in this study. Samples were taken during the
same period, July and August 1998 at each location.
Due to the different sampling instrumentation available,
the aerosol size range measured at JFJ and K-puszta was
PM2.5 (particulate matter with an aerodynamic diameter
d a o 2.5 mm) and PM1.0, respectively. Fractionation was
not available at Mace Head and total particulate
matter was therefore sampled. We are aware that this
is a drawback in this study, but we believe that
despite the inconsistent sampling procedures, results
presented here improve our knowledge on the OC,
WSOC and BC concentrations at European background
sites and may serve as potential input data for model
calculations.
The main objectives of the study were: (i) the
determination of the mass concentrations of major
inorganic ions as well as WSOC, WINSOC and BC in
order to measure their relative contribution to the
aerosol mass; (ii) the study the thermal behaviour of
carbonaceous compounds; (iii) obtaining information
about the chemical composition of the WSOC fraction
and (iv) a comparison of the chemical character of the
carbonaceous matter in continental and marine aerosol.
Concerning this last point comparison was made by
paying special attention to the different size-cuts of the
samples. As a result, we think that our conclusions are
valid independently of the different size ranges and
provide new findings about the chemical character of
continental and marine aerosol.
2. Experimental
2.1. Sampling sites and sampling parameters
Aerosol was collected at three European background
sites all of which belong to the Global Atmosphere
Watch (GAW) programme of the WMO.
(i) JFJ, Switzerland: Sampling was performed at the
Sphinx building (461330 N, 71590 E; 3580 m a.s.l.) of the
high-alpine research station. The station is situated on
the northern side of the main central European alpine
chain in Switzerland. During summer, the JFJ is often
influenced in the early afternoon by the planetary
boundary layer (PBL) through thermally driven aerosol
transport, while at other times and seasons free tropospheric conditions prevail (Lugauer et al., 1998). During
the period 9 July to 5 August 1998 eight samples were
collected on quartz filters (D ¼ 150 mm; QF20, Schleicher & Schuell) by using a HiVol PM2.5 sampling system
(Digitel DHA-80) with a heated inlet. The flow rate was
0.5 m3 min1, and the total sampled volume for each
filter varied in the range 947–4325 m3 (at ambient
conditions). Segregated samples were also collected at
this site by using a 12-stage small deposit area impactor
(Maenhaut et al., 1996). The cut-off values referring to
650 mbar pressure and 201C temperature were 0.029,
0.060, 0.120, 0.196, 0.313, 0.553, 0.758, 1.01, 1.64, 2.56,
4.06 and 8.50 mm. The flow rate was 10.2 l min1. The
sampling time was one week to have enough material for
carbon analysis.
(ii) K-puszta, Hungary: The sampling station is
situated in a mixed forest clearing on the Great
Hungarian Plain (461580 N, 191330 E; 136 m a.s.l.) about
80 km SE of Budapest. Because of the lack of nearby
anthropogenic pollution sources, the location is representative of a continental, rural background air.
Twenty-two samples were taken during the sampling
period 28 July to 12 August 1998 on quartz fibre filters
(Whatman QM, 47 mm in diameter) using a two-stage
multi-jet impactor on a day (16 h) and night (8 h) basis.
Measurements were performed at a height of 10 m above
ground and the impactor flow rate was 26 l min1 with a
cut-off value at da =1.0 mm (PM1.0).
(iii) Mace Head, Ireland: The Mace Head Atmospheric Research Station (531200 N, 91540 W; 20 m a.s.l.)
is located on the west coast of Ireland near Carna,
County Galway, offering westerly exposure to the North
Table 1
Mean concentrations (minimum and maximum values in parentheses) of OC and BC or EC at rural sites
Sampling time
OC (mg m3)
BC or EC (mg m3)
Reference
Continental
Southwestern USA
Abbeville, LA, USA
Luray, VA, USA
Waterbury, VT, USA
Cheboygan County, MI, USA
Tahoma Woods, WA, USA
K-puszta, Hungary
K-puszta, Hungary
San Pietro Capofiume, Italy
June, July 1979; PM2.5
August–September 1979
July–August 1980
January–March 1982
Winters 1984, 1985
June–September 1990; PM2.5
July–August 1996; PM2.5
July–August 1996; PM1.5
September–October 1996; PM1.5
(0.78–7.81)
10.8a
7.7a
9.8 (4.3–16.2)
2.0 (0.12–5.7)
2.55 (0.1–7.37)
7.1
5.0 (3.7–6.4)
6.2 (3.7–9.0)
(0.08–0.26)
1.7
1.7
4.1 (2.6–7.3)
0.6 (o0.04–3.5)
0.7 (0.05–2.24)
0.42
0.6
1.0 (0.50–1.50)
Macias et al. (1981)
Wolff et al. (1982)
Wolff et al. (1982)
Sexton et al. (1985)
Cadle and Dash (1988)
Malm and Gebhart (1996)
Moln!ar et al. (1999)
Zappoli et al. (1999)
Zappoli et al. (1999)
Coastal
Lewes, DE, USA
Mace Head, Ireland
Santa Barbara County, CA, USA
Tabua, Anadia, Are*ao, Portugal
Aspvreten, Sweden
February 1990–April 1991
October–December 1989; PM10
1994–1996
June, July 1996; PM1.5
3.1
ND
1.2
0.28
Wolff et al. (1986a)
Jennings et al. (1993)
Chow et al. (1996)
Castro et al. (1999)
Zappoli et al. (1999)
Marine
Hachijo-jima, Chichi-jima, Japan
San Nicolas Island, USA
Anacapa Island, USA
Kangwha and Kosan, Korea
Winter 1981
Summer 1987; PM2.5
October–December 1989; PM10
1994–1999; PM2.5
a
TC=2.1–3.4
(1.0–6.8)a
2.2 (1.5–2.6)
(0.3–1.7)
0.1 (0.05–0.17)
(0.8–3.1)
1.53
(0.4–1.4)
0.16
TC=3.1
(1.05–15.99)
(0.02–4.47)
Ohta and Okita (1984)
Chow et al. (1994)
Chow et al. (1996)
Kim et al. (2000)
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et al. / Atmospheric Environment 35 (2001) 6231–6244
Sampling site
OC calculated in this work as TCEC; TCFtotal carbon; NDFnot determined.
6233
6234
Table 2
Mean concentrations (minimum and maximum values in parentheses) of OC and BC or EC at remote sites
OC (mg m3)
BC or EC (mg m3)
Reference
April–May 1979
March 1981
July–September 1980
January
July
January
July
ND
0.068 (0.003–0.174)
Heintzenberg (1982)
ND
ND
ND
ND
ND
0.005
0.314
0.080
0.0015
0.3
Lannefors et al. (1983)
Rosen et al. (1984)
ND
0.67
(0.09–0.165)
0.5–2.5
o0.6
ND
0.4a
ND
0.2
(0.02–0.5)
0.03
(0.00–0.09)
(0–0.3)
o0.02
0.03870.011
0.04
0.03–0.3
o0.01
Andreae (1983)
Wolff et al. (1986b)
Pacific Ocean, Northern Hemisphere
Pacific Ocean, Southern Hemisphere
Mace Head, Ireland
Mace Head, Ireland
Pacific Ocean
Atlantic Ocean, Tenerife
August 1982
January–February 1983; PM2.5
May–July 1987
May–July 1987
February 1990–April 1991
September 1993
1993–1996; PM2
June–July 1997 (o1.26 mm)
High alpine
Mt. Sonnblick, Austria
Jungfraujoch, Switzerland
September 1995 (0.1–1 mm)
July 1995–June 1997
0.5b
0.32 (0.005–0.94)
0.16b
0.21 (0.02–0.61)
Hitzenberger et al. (1999)
Lavanchy et al. (1999)
Free troposphere
Atlantic Ocean, Tenerife
June–July 1997 (o1.26 mm)
0.17
0.004
Putaud et al. (2000)
Arctic
(
Ny Alesund,
Svalbard
Ice See
Barrow, Alaska, USA
South Pole
Marine
North Atlantic
Bermuda
a
b
OC calculated in this work as TCEC; NDFnot determined.
Values calculated in this work from the size distribution of total carbon and contributions of OC and BC to the total mass.
Hansen et al. (1988)
Rau and Khalil (1993)
Rau and Khalil (1993)
Jennings et al. (1993)
Castro et al. (1999)
Kaneyasu and Murayama (2000)
Putaud et al. (2000)
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et al. / Atmospheric Environment 35 (2001) 6231–6244
Sampling time
Sampling site
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Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
Atlantic Ocean. At this site total aerosol samples were
taken on pre-fired (4501C) quartz fibre filters (Whatman
QM, 47 mm in diameter) at a flow rate of about
20 l min1 using a low-volume sampler. The sampling
time was about one week for each sample. Five-day back
trajectories were used to rigorously select the samples
which were not affected by continental air masses and
were representative of marine background air. Five
samples were found to fulfil this requirement. These
samples were collected during the period from 8 July to
26 August 1998.
The filters exposed at all sites were stored in a freezer
until analysis took place.
2.2. Chemical analysis
Determination of total carbon (TC) and WSOC was
carried out by catalytic combustion in oxygen at 6801C
by using an Astrolab TOC 2100 carbon analyser
(Zellweger Analytics). TC was measured by burning
filter spots from the original samples. For the determination of WSOC other filter spots were soaked overnight in high-purity (MilliQ) water after which the
remaining carbon (water-insoluble carbon=WINSOC+
BC) was measured. Repeatability of the method at the
typical carbon level of 5–10 mg a run was better than 5%.
Further details of the analysis can be found elsewhere
(Gelencs!er et al., 2000a). Here we would like to mention
that during the measurement the sample is placed to a
quartz boat which is moved with a constant velocity in
the reactor tube from a position which is at about 401C
to the position where the catalysator is found at 6801C.
The temperature along the tube is not controlled, so the
detector signal can only be recorded as a function of the
time instead of temperature, and the obtained curve is
called thermal profile instead of thermogram.
The concentration of BC (soot) was determined by
light absorption measurements in which the optical
attenuation (ATN) is linearly related to the mass of BC
deposited on the active surface of a filter through the
mass absorption efficiency aa (m2 g1). The uncertainty
of this type of measurement is that aa can vary with the
chemical composition and state-of-mixing of the sootcontaining particles to a great extent, and this can lead
to an over- or underestimation of the true BC
concentration (Liousse et al., 1993). Thermal methods
measuring EC are usually used to check the accuracy of
BC measurements assuming that EC is equal to BC.
(Theoretically this requirement is not always fulfilled
since organic compounds (e.g. humic-like substances)
can also absorb in the visible range (Zappoli et al.,1999;
Kriva! csy et al., 2001).) In this way, site-specific values
for aa can be determined. This is necessary because aa
has been observed to vary from site to site but is
generally constant at a given location for a specific air
mass (Liousse et al., 1993). At Mace Head, BC was
6235
measured by using a model AE-9 aethalometer (Magee
Scientific, Hansen et al., 1984). Since long-term measurements to determine the site-specific value of aa have
not been carried out yet, a mass absorption efficiency of
19 m2 g1 (instrumentation value) was used to calculate
BC mass concentrations. A model AE-10 aethalometer
was used at the JFJ where a seasonally independent
value of aa ¼ 9:3 m2 g1 (Lavanchy et al., 1999) was
previously found during a year-long comparison of BC
and EC concentrations. A continuous light absorption
photometer (Model PSAP; l ¼ 565 nm) was used at Kpuszta operating at a 0.5 l min1 flow rate. Although the
instrument is calibrated to measure the aerosol absorption coefficient, a previous study at this site revealed that
a value a ¼ 10 m2 g1 is a reasonable conversion factor
to determine the BC concentration (Gelencse! r et al.,
2000a).
Concentrations of inorganic ions and low molecular
weight carboxylic acids were measured by capillary
electrophoresis after extracting a portion of the filters
in high-purity (MilliQ) water in an ultrasonic bath
(Kriv!acsy et al., 1997). Repeatability of these measurements was better than 3%. Humic-like substances were
also studied by capillary electrophoresis (Kriv!acsy et al.,
2000).
3. Results and discussion
3.1. Thermal behaviour of carbonaceous compounds
Characteristic thermal profiles for the JFJ, K-puszta
and Mace Head aerosol are plotted in Fig. 1. All three
traces are composed of two broad overlapping peaks
indicating a continuous distribution of carbonaceous
compounds of different volatility and/or thermal stability. The peaks are better resolved and at the same
position in the thermal profiles of the JFJ and K-puszta
aerosol. The first peak is thought to be representative of
the more volatile and/or easily oxidisable carbon
fraction (volC), while the second peak is thought to be
representative of the less volatile and/or refractory
carbon fraction (nonvolC), which includes both refractory OC and EC. At the JFJ the average ratio of volC
and nonvolC was found to be 36% and 64%,
respectively. At K-puszta the contribution of the
nonvolC fraction was even higher, it exceeded 80%. It
is interesting to note that the standard deviation (SD)
values were pretty low (5–7%) at both sites. This might
indicate that the history of the aerosol (e.g. source types,
chemical transformation during long-range transport)
did not vary too much during the sampling time. It
should also be mentioned that EC is usually only the
minor component of the nonvolC fraction which has
previously been proved for the K-puszta aerosol
(Gelencs!er et al., 2000a), and is shown in this study, as
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Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
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0.3
signal (in arbitrary units)
0.25
A
0.2
B
0.15
C
0.1
0.05
0
50
100
150
200
250
300
integration time [s]
Fig. 1. Typical thermal profiles of carbonaceous compounds: (A) Jungfraujoch; (B) K-puszta; (C) Mace Head.
well (see Section 3.2). This means that in the continental
aerosol besides BC or EC, the major fraction of OC is
also refractory. In the thermal profile of the Mace Head
aerosol, peak maxima are shifted towards a later time
(i.e. higher temperature). The shift of the first peak is
large and results in a less resolved thermal profile
compared to the continental samples, which prevented
us from quantitatively distinguishing the volC and
nonvolC fractions in the marine samples. Qualitatively,
the different thermal characteristics mean that the
chemical composition of the organic matter is also
different. Low-volatility compounds found at continental sites are almost absent, the amount of the
most refractory carbon is relatively low, and the
majority of the carbon is of intermediate volatility
and/or oxidation-resistant. As the aerosol collected
at Mace Head had no upper size cut-off it cannot
be excluded that for instance primary biological particles may be partly responsible for the different thermal
profile. A similar phenomenon was observed for the Kpuszta aerosol when analysing the da > 1 mm fraction
(Gelencs!er et al., 2000a).
3.2. Carbon balance
One of the main goals of this study was to establish
the carbon balance for each site. As the amount of
inorganic carbon, measured directly by capillary electrophoresis or calculated indirectly from the concentrations of calcium and magnesium ions, was found to be
negligible in all samples the carbon balance was assumed
to be made up from WSOC, WINSOC and BC.
Distributions of these three carbon fractions at the
three sites are presented in Fig. 2. In continental aerosols
the predominant carbon fraction is WSOC, while in
marine aerosol it is WINSOC. The average ratio of
WSOC to total organic carbon (TOC) is 0.60 and 0.63 at
JFJ and K-puszta, respectively, whereas at Mace Head it
is 0.41. The comparatively low value at Mace Head
might partially be attributed to the study of fine and
coarse particles together. Primary biological particles
which are ubiquitous in the atmosphere are mostly
present in the da > 2 mm size range (Heber, 1995), and
these particles are definitely water insoluble. In order to
estimate to what extent the carbon balance could be
affected by the different cut-off values, at the continental
sites information about the carbon content of the coarse
particles was also involved in the study. At the JFJ
impactor samples were concurrently collected, and the
size distribution of carbon can be seen in Fig. 3. It can
be calculated that 90–95% of TC is present in particles
with da o2:5 mm, and if it is assumed that all carbon in
particles with da > 2:5 mm is water insoluble the ratio of
WSOC would only decrease to 55–58%. The situation is
similar at K-puszta. A previous, long-term study has
shown that 87% of TC is in the d ao1 mm particles
(Gelencs!er et al., 2000a). This means that the different
size range cannot solely, and not even primarily be
responsible for the different water solubility of continental and marine aerosol. Another explanation might
be that the atmosphere is less oxidative over the oceans
than continents, furthermore, due to the higher
frequency of cloud formation the residence time of the
water-soluble compounds is lower under marine than
continental environments. To give a more comprehensive answer to this question we definitely need to
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Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
Table 3
Mean BC and OC concentrations (minimum and maximum
values in parentheses), and BC/OC ratios for all sampling sites
Jungfraujoch
TC=1.34 (0.37) µg/m3
BC
22 (10)%
WINSOC
31 (16)%
WSOC
47 (10)%
Sampling site BC (mg m3)
OC (mg m3)
Jungfraujoch
K-puszta
Mace Head
1.05 (0.79–1.32) 0.28
7.60 (4.77–12.51) 0.10
0.61 (0.51–0.85) 0.04
0.29 (0.08–0.72)
0.75 (0.12–1.89)
0.026 (0.017–0.034)
BC/
OC
improve our knowledge on the chemical composition of
the marine organic aerosol.
It is always interesting to compare the new data to
those obtained in previous studies. The mean OC and
BC concentrations are listed in Table 3. However, it
should be noted that in this case a comparison is to be
made with caution since it is known that the different
analytical approaches in OC–EC or OC–BC separation
can lead to significantly different results (e.g. Schmid
et al., 2001). Nevertheless, at the JFJ both OC and BC
concentrations were comparable with those at Mt.
Sonnblick (Hitzenberger et al., 1999), although it should
be mentioned that these results refer to summer and fall
campaigns, respectively, where concentrations may vary
widely due to strong variations in seasonal factors (see,
e.g. Lugauer et al., 1998). At K-puszta, the mean
concentrations of both OC and BC are similar to those
at rural sites in USA (see references in Table 1). At Mace
Head, the concentrations were considerably lower than
at other coastal and marine sites (see references in Table
1), but were similar to previous studies (Jennings et al.,
1993; Castro et al., 1999; see Table 2) at the same site
during clean marine conditions.
The BC/OC ratio (see Table 3) can give information
on sources of the aerosol. The relatively high value
obtained at the JFJ might probably be caused by the
convection of PBL airmasses in the afternoon in
summer. The same phenomenon was observed at
K-puszta
TC=8.354 (2.23) µg/m3
BC
9 (5)%
WINSOC
31 (16)%
6237
WSOC
57 (9)%
Mace Head
TC=0.63 (0.15) µg/m3
BC
3 (2)%
WSOC
40 (5)%
WINSOC
57 (6)%
Fig. 2. Contribution of WSOC, WINSOC and BC to the
carbon balance at the three sampling sites (standard deviations
referring to the natural variation of the chemical components
are shown in parantheses).
∆c/∆ log d ( µ gm-3µ m-1)
1.2
1
0.8
A
A
0.6
0.4
B
0.2
0
0.01
0.1
1
10
Aerodynamic diameter (µm)
Fig. 3. Size distribution of carbon at the Jungfraujoch. Sampling periods: (A) 15–21 July 1998; (B) 21–28 July 1998. (The y-axis is
normalised according to the difference in size-cuts at the neighbouring impactor stages).
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Mt. Sonnblick, Austria (3104 m a.s.l.) where the
concentration of BC in summer was about the same as
that found in Vienna (Hitzenberger et al., 1999). At Kpuszta, the relatively low BC/OC ratio is likely due to
the high input of local biogenic organic aerosol
(Gelencse! r et al., 2000b). In Mace Head, the low BC/
OC ratio and BC mass concentrations below 75 ng m3
are characteristic of air masses arriving from the
Atlantic Ocean (Cooke et al., 1997).
3.3. Mass concentration of carbonaceous vs. inorganic
compounds
If the relative contribution of the inorganic ions and
organic substances to the aerosol mass is to be
determined the masses of WSOC and WINSOC have
to be converted to those of water-soluble organic
substances (WSOS) and water-insoluble organic substances (WINSOS). So far, the uncertainty in this
calculation was that only estimated carbon-to-mass
conversion factors have been applied (Gray et al.,
1986; Molna! r et al., 1999; Zappoli et al., 1999).
Recently, a solid phase extraction procedure has been
worked out by means of which a conversion factor for
the WSOS fraction could experimentally be determined
(Varga et al., 2001). The value of 1.9 was found for both
the JFJ (Kriv!acsy et al., 2001) and the K-puszta aerosol
(Kiss et al., 2001). This value is significantly higher than
the estimated values used previously, and is in agreement
with the value which has recently been recommended by
Turpin et al. (2000). For calculation of the WINSOS
mass fraction the estimated value of 1.2 (Gray
et al.,1986; Zappoli et al., 1999) was used, but our preliminary results have shown that this value may also be
higher at rural and remote locations (Kiss et al., 2001).
The relative contribution of inorganic ions, BC,
WSOS and WINSOS (determined by the conversion
factors mentioned above) to the aerosol mass is shown
in Fig. 4, and the mass ratios of carbonaceous compounds vs. inorganic ions and WSOS vs. inorganic ions
are given in Table 4. It can be concluded that in the
continental fine aerosol, the mass concentration of
carbonaceous matter is significantly higher than that
of inorganic ions. Even WSOS dominate over inorganic
components at K-puszta, while both concentrations are
comparable at the JFJ. In the total aerosol collected at
Mace Head sea-salt is of course the prevailing component in the aerosol mass and the ratios of the
carbonaceous fractions are much lower. However, by
taking the mass size distributions of the chemical
components in the marine background aerosol into
account the approximate chemical composition of the
fine particles at Mace Head can be estimated. It is well
characterised that sea salt and nitrate can practically
all be found in the coarse mode (da > 1 mm), and
nss-sulphate in the fine mode (da o1 mm) (Fitzgerald,
Jungfraujoch
total=3.76 (1.62) µg/m3
WINSOS
16 (11)%
BC
8 (2)% nitrate
8 (3)%
ammonium
8 (3)%
WSOS
33 (9)%
other
inorganics
2 (1)%
sulphate
25 (11)%
K-puszta
total=20.55 (6.07) µg/m3
WINSOS
17 (8)%
BC
4 (2)% ammonium
8 (2)%
sulphate
22(7)%
WSOS
45 (7)%
other
inorganics
4 (2)%
Mace Head
total=10.92 (1.66) µg/m3
nns-ions
WSOS
4 (1)%
5 (1)%
WINSOS
4 (1)%
sea salt
86 (1)%
Fig. 4. Share of the mass concentrations of inorganic ions, BC,
WSOS and WINSOS at the three sampling sites. For the Mace
Head aerosol BC is not shown because its contribution is o
1%. ‘‘Total’’ means the sum of the mass concentrations of the
determined components (SD values referring to the natural
variation of the components are shown in parenthesis). At the
JFJ ‘‘other inorganics’’ mean 30 ng m3 calcium and 6 ng m3
magnesium. At K-puszta ‘‘other inorganics’’ mean 0.24 mg m3
nitrate and 0.51 mg m3 potassium (indicative of biogenic origin
of the aerosol). At Mace Head ‘‘nss-ions’’ mean 0.34 mg m3
nss-sulphate and 0.19 mg m3 nitrate.
!
Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
6239
Table 4
Mass ratio of carbonaceous matter and water-soluble organic substances against inorganic ions
Sampling site
Mass ratio of carbonaceous
matter vs. inorganic ions
Mass ratio of WSOS vs. inorganic ions
Jungfraujoch
K-puszta
Mace Head (total particulate matter)
Mace Head (fine mode aerosol)a
1.32
1.94
0.10
1.47
0.77
1.32
0.05
0.79
2
1.8
1.4
1.4
1.2
1
y = 0.155x + 0.034
r = 0.6875
0.8
0.6
0.4
0.2
0
0
2
4
6
8
10
sulphate [µg m-3 ]
(a)
0.8
y = 0.251x + 0.047
r = 0.9280
0.7
BC [µ g m-3 ]
1991; O’Dowd et al., 1997; M!esz!aros, 1999). Unfortunately, data concerning the size distribution of carbon in
marine environments are extremely scarce. Neusub
. et al.
(2000a) studied the marine aerosol arriving at Sagres,
Portugal from the North Atlantic. The sampling
conditions (e.g. elevation, season, wind direction) were
very similar to those at Mace Head. About 70% of TC
was present in the fine particles (da o1:2 mm), while
about 20% of TC was in the size range of
da ¼ 3:5210 mm. These large particles may largely be
primary biological particles. In other study over
the Pacific Ocean about 50–60% of WSOC was found
in the PM2.5 fraction (Matsumoto et al., 1998). Despite
the limited number of study, it seems to be likely that
ratio of the coarse-mode carbon is higher in marine than
continental aerosol. Based upon the information available we used the low-limit value of 50% to estimate the
fine mode carbon mass from the mass of TC. The ratios
of the carbonaceous matter and WSOS vs. inorganic
ions for the ‘‘fine-mode extrapolated’’ Mace Head
aerosol are in Table 4. Now the values are certainly
much higher and more comparable with those obtained
for the continental sites.
The mean concentrations of TC and sulphate, the two
predominant and directly measurable aerosol components, and their mass ratios are summarised in Table 5.
The table also shows similar values presented by
Heintzenberg (1989) who reviewed the average chemical
composition of rural and remote fine-mode aerosol. It
is interesting to note that at the JFJ and K-puszta
the sulphate concentrations are similar to those in the
review, but TC concentrations are much higher. For
the ‘‘fine’’ Mace Head aerosol the TC concentration is
comparable but the sulphate concentration is significantly lower than the referred values. The TC/sulphate
ratios for all locations are more than twice than those
obtained by Heintzenberg (1989) which draws attention
to the importance of organic aerosol in the control of
atmospheric processes, at least in the region of our
sampling sites.
It is still worth noting that the variability of sulphate,
OC and BC was different at all three sites. This can be
observed by looking at the lowest and highest concen-
BC [µ g m-3 ]
a
Chemical composition of the fine mode Mace Head aerosol was derived by assuming that all sea-salt sulphate is found in the coarse
mode and that 50% of TC is found in the fine mode (Matsumoto et al., 1998; Neusub
. et al., 2000a).
0.6
0.5
0.4
0.3
0.2
0.1
0
0
(b)
0 .5
1
sulphate [µg
1.5
2
2 .5
m-3 ]
Fig. 5. Correlation between sulphate and BC for the (A) Kpuszta and (B) Jungfraujoch samples.
tration values in Tables 3 and 5. The fluctuation of the
concentration of all components was relatively low at
Mace Head which is not surprising as the samples were
carefully selected to represent background marine
aerosol. OC concentrations were also fairly constant at
JFJ and K-puszta. At K-puszta this fact may be
indicative of the high strength of local biogenic sources.
At the JFJ the situation might be more complex but the
influence of regional biogenic aerosol arriving by PLB
airmasses cannot be excluded. On the other side,
however, the variations in sulphate and BC concentrations were rather high at both continental sites, and this
fact led to an interesting aspect. The correlation between
sulphate and BC concentrations was studied and found
to be significant at the 0.001 probability level for both
sites (Fig. 5). Some earlier studies in remote marine
!
Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
6240
Table 5
Mass concentrations of total carbon (TC) and sulphate (minimum and maximum values in parentheses), and TC/sulphate ratios for
our sampling sites and world-wide averages by Heintzenberg (1989)
Sampling site
TC (mg m3)
Sulphate (mg m3)
TC/sulphate
Jungfraujoch
K-puszta
Mace Head (fine mode aerosol)a
Fine mode particulates at rural sites (Heintzenberg, 1989)
Fine mode particulates at remote sites (Heintzenberg, 1989)
1.34 (0.87–2.04)
8.35 (5.00–13.51)
0.34 (0.27–0.44)
4.35
0.54
1.08 (0.19–2.15)
4.71 (0.73–9.58)
0.34 (0.18–0.44)
5.55
1.06
1.24
1.77
1.00
0.78
0.51
a
Chemical composition of the fine mode Mace Head aerosol was derived by assuming that all sea-salt sulphate is found in the coarse
mode and that 50% of TC is found in the fine mode (Matsumoto et al., 1998; Neusub
. et al., 2000a).
regions have also shown a positive correlation between
sulphate and BC (O’Dowd et al., 1993; Van Dingenen
et al., 1995; Clarke et al., 1996). As anthropogenic
aerosol is mostly delivered to these sites by long-range
transport the significant correlation between sulphate
and BC might suggest that both components are at least
partly on the same particles. Previously formation of
sulphate on the surface of soot particles has been
observed (Me! sta! ros and Me! sza! ros, 1988), and evidence
for sulphate–soot mixed particles has been shown by
!
SEM techniques at other remote locations (Posfai
et al.,
!
1998, 1999; Buseck and Posfai,
1999) too.
3.4. Chemical composition of WSOS fraction
Two main classes of water-soluble organic compounds have been studied in this work. They are low
molecular weight (LMW) carboxylic acids and humiclike substances (HULIS). The LMW carboxylic acids
are ubiquitous in the atmosphere and the most abundant
species can be relatively easily identified and quantified
(Chebbi and Carlier, 1996). Mean concentrations of
these substances and their contribution to WSOC and
WSOS fractions are listed in Table 6. The predominant
component at all sites is oxalic acidFthe only acid
which was found in every sample. On average, it was
responsible for 51%, 58% and 70% of the total mass of
the quantifiable LMW carboxylic acids at Mace Head,
the JFJ and K-puszta, respectively. At K-puszta the
concentration of formic acid was also relatively high,
whereas the concentrations of malonic and succinic
acids were found to be almost negligible. At Mace Head,
similarly to oxalic acid, malonic acid was found in all
samples and its mean concentration was comparable to
that of oxalic acid. However, it is interesting to note that
succinic acid was not detected in any marine sample.
The contribution of LMW carboxylic acids to WSOC
and WSOS fractions was only a few percent in the
continental aerosol. This ratio will probably be about
the same for the total aerosol since, similarly to the
inorganic ions and carbonaceous compounds, the
majority (80–90%) of LMW carboxylic acids are present
in the fine fraction of the continental aerosol (M!esz!aros
et al., 1997; Kriv!acsy and Moln!ar, 1998). In this manner,
values obtained for the continental and marine samples
can be compared. It can be concluded that unlike at the
continental sites the contribution of LMW carboxylic
acids to the carbonaceous fraction of the marine aerosol
is quite significant. Oxalic, malonic and formic acids
were responsible for about 10% of WSOC (in terms of
carbon) and about 20% of WSOS (in terms of mass) at
Mace Head. It should be noted that collecting total
particulate matter in Mace Head was advantageous for
the study of LMW carboxylic acids because other
investigations showed that a significant portion (up to
50%) of these compounds can be found in sea-salt
derived coarse particles (d a>1.2 mm) (Kerminen et al.,
2000; Neusub
. et al., 2000a,b).
The second type of water-soluble compounds,
HULIS, has been found in various atmospheric samples,
Table 6
Mean concentrations [minimum and maximum values in brackets] of LMW carboxylic acids, and their contribution to WSOC and
WSOS fractions (SD in parentheses)
Sampling site
Oxalic acid
(ng m3)
Malonic acid
(ng m3)
Succinic acid
(ng m3)
Formic acid
(ng m3)
Carbon mass
in WSOC (%)
Mass in
WSOS (%)
Jungfraujoch
K-puszta
Mace Head
49 [8–119]
269 [125–490]
48 [28–85]
15 [o6–39]
22 [o40–129]
33 [28–39]
11 [o2–21]
5 [o12–64]a
o2
9 [7–15]
91 [o27–309]
13 [o4–29]
3.7 (1.9)
2.4 (1.5)
10.6 (3.1)
6.5 (3.3)
4.6 (2.7)
18.7 (6.0)
a
Compound was detected in less than 20% of the samples. For the calculation of the mean concentration zero was used in all other
cases when the concentration of the compound was below the limit of detection.
!
Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
6241
Fig. 6. Electropherograms of the aqueous aerosol extracts when studying HULIS in the samples: (A) K-puszta; (B) Jungfraujoch; (C)
Mace Head. The curves were recorded by using a fused silica capillary (75 mm inner diameter), 5 mM Na2HPO4 (pH=9.0) electrolyte
and UV detection at 254 nm. (The curves are offset to each other).
e.g. in precipitation (Likens et al., 1983), fog (Fuzzi and
Zappoli, 1996; Facchini et al., 1999; Kriv!acsy et al.,
2000), dust (Havers et al., 1998a, b) and fine-mode
aerosol (Zappoli et al, 1999; Facchini et al., 1999;
Kriv!acsy et al., 2000). In alkaline solution, these
compounds are ionic and capillary electrophoresis
(CE) can be a simple but effective technique to indicate
their presence in samples. Aqueous aerosol extracts were
run at pH=9 and typical electropherograms are plotted
in Fig. 6. The first peak visible on each curve at about
1 min is for neutral organic compounds. These compounds do not possess their own electrophoretic
mobility and are transported by the movement of the
electrolyte (electroosmotic flow) to the detector. After
this first peak, a broad band (‘‘hump’’) is observed
between 1 and 3 min and is characteristic of HULIS
(Kriva! csy et al., 2000). In contrast to the class of LMW
carboxylic acids, HULIS are composed of hundreds of
different molecules which cannot be separated, and
hence cannot be individually identified and quantified.
Fig. 6 indicates that HULIS were found in the JFJ and
K-puszta aerosol samples but were not detected at Mace
Head. This does not necessarily mean that the Mace
Head aerosol never contains HULIS, but it unambiguously proves that HULIS are far more typical of
continental than marine samples. For the quantitative
determination of water-soluble HULIS, a solid phase
separation procedure has recently been established. The
details of this procedure, as well as the characterisation
of HULIS by different spectroscopic techniques (e.g.
UV–VIS, fluorescence, FTIR spectroscopy) in Hungarian and Swiss samples are presented elsewhere (Varga
et al., 2001; Kiss et al., 2000, 2001; Kriv!acsy et al., 2001).
Here we would like to mention that HULIS were
responsible for about 55–60% of WSOC both at the JFJ
and K-puszta. Since these compounds are known to be
refractory it can be calculated that they contribute about
40–50% to the nonvolC fraction.
4. Conclusions
At the continental sites (JFJ and K-puszta) carbonaceous compounds represent the major fraction of the fine
aerosol mass. In the marine (Mace Head) samples the
contribution of the organic compounds is probably
similarly significant in the fine mode which was
estimated by extrapolating the chemical composition
of the fine aerosol from that of total particulate matter.
Sampling of PM2.5 aerosol has already begun at
Mace Head which will allow direct comparison in the
future. The thermal behaviour, water solubility and
chemical composition of carbonaceous matter is found
to be similar at both continental sites but they differ
from those at the marine location. Organic compounds
are more water soluble in continental than marine
aerosol and a high fraction of WSOC is composed of
humic-like substances. On the other hand LMW
carboxylic acids are more characteristic of marine
environments. Based on the considerable water solubility of organic substances it can be assumed that these
compounds may exhibit a pronounced influence on
the hygroscopic behaviour of particles, and they may
consequently play a role in determining the radiative
forcing of tropospheric aerosol. To better assess
the effects of organics on aerosol properties our knowledge of the chemical composition and structure of
organic substances, as well as their size distribution and
6242
!
Z. Krivacsy
et al. / Atmospheric Environment 35 (2001) 6231–6244
state-of-mixing (i.e. internal or external) should be
improved in the future.
Acknowledgements
This work was supported by the Hungarian National
Scientific Fund (OTKA Project No. T030226, T030186,
F029610, F029607), Soros Foundation, Peregrinatio I.
Foundation, Bolyai scholarship, the British Council and
the Hungarian Ministry of Education (Project No. 022),
the Global Atmosphere Watch Programme through the
Swiss Meteorological Institute and the European
Commission (Marie Curie Research Training GrantContract No. ENV4-C798-5128). We also acknowledge
the support of the International Foundation for the
High Altitude Research Stations Jungfraujoch and
Gornergrat (HFSJG) who allowed access to the
Jungfraujoch station. The authors thank H. Kutasi for
! Moln!ar,
her valuable help in the experimental work, A.
A. Gelencs!er and Gy. Kiss for their helpful discussion in
preparing the manuscript.
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