ARTICLE IN PRESS

Atmospheric Environment 38 (2004) 6425–6429

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A field evaluation of a SO2 passive sampler in tropical

industrial and urban air
Lı́cia P.S. Cruz, Vânia P. Campos, Adriana M.C. Silva, Tania M. Tavares
Analytical Chemistry Department, Chemistry Institute, Federal University of Bahia, Salvador, Bahia 40210-340, Brazil

Received 28 November 2003; received in revised form 22 June 2004; accepted 12 July 2004

Abstract

Passive samplers have been widely used for over 30 years in the measurement of personal exposure to vapours and
gases in the workplace. These samplers have just recently been applied in the monitoring of ambient air, which presents
concentrations that are normally much smaller than those found in occupational environments. The locally constructed
passive sampler was based on gas molecular diffusion through static air layer. The design used minimizes particle
interference and turbulent diffusion. After exposure, the SO2 trapped in impregnated filters with Na2CO3 was extracted
by means of an ultrasonic bath, for 15 min, using 1.0
102 mol L1 H2O2. It was determined as SO2 4 by ion
chromatography. The performance of the passive sampler was evaluated at different exposure periods, being applied in
industrial and urban areas. Method precision as relative standard deviation for three simultaneously applied passive
samplers was within 10%. Passive sampling, when compared to active monitoring methods under real conditions, used
in urban and industrial areas, showed an overall accuracy of 15%. A statistical comparison with an active method was
performed to demonstrate the validity of the passive method. Sampler capacity varied between 98 and 421 mg SO2 m3
for exposure periods of one month and one week, respectively, which allows its use in highly polluted areas.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Passive sampling; Sulphur dioxide; Diffusive sampler; Environment monitoring; Brazil

1. Introduction Adverse health effects, associated with SO2 concentra-

Sulphur dioxide is emitted into the atmosphere by
natural sources (volcanoes, sulphur gases oxidation
produced by plant decomposition) and also by anthro-
pogenic sources, such as the combustion of sulphur-
containing fossil fuels (coal, oil and natural gas), the
smelting of ores (mostly copper, lead and zinc), and
other industrial processes (Cullis and Hirschler, 1980).
Corresponding author. Tel./fax: +55-71-237-4024.
E-mail addresses: lila@ufba.br (L.P.S. Cruz),
vaniaroc@ufba.br (V.P. Campos),
adriana@laquam.qui.ufba.br (A.M.C. Silva),
ttavares@ufba.br (T.M. Tavares).
tions in ambient air, include respiratory and cardiovas-
cular diseases. The maximum permissible limits for SO2
in Brazil is 365 mg m3 as a 24 h average and 80 mg m3
as mean annual (CONAMA, 1990), although
the guideline from World Health Organization
(WHO, 2000) recommends daily levels not exceeding
125 mg m3 and mean annual levels below 50 mg m3.
SO2 is oxidized in the atmosphere to sulphuric acid,
by reactions occurring in the gaseous phase, in the
liquid phase, or on the surfaces of solids. It contributes
to acidic deposition in the form of dry-deposited
gas or wet deposition form, when dissolved in clouds,
fog, rain, or snow. All of these deposition forms
impact humans, aquatic ecosystems, forests and

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doi:10.1016/j.atmosenv.2004.07.022
 ARTICLE IN PRESS
6426 L.P.S. Cruz et al. / Atmospheric Environment 38 (2004) 6425–6429

agriculture, monuments and buildings (Finlayson-Pitts

and Pitts Jr., 1986).
Passive samplers are devices capable of taking samples
of gas or vapour pollutants from the atmosphere,
without involving air active movement through them.
The fixation rate is controlled by a physical process,
which can be diffusion through a static air layer or
permeation through a membrane (Brown et al., 1984).
The average atmospheric concentration is calculated by
Fick’s first law, using the exposure period (Palmes and
Lindenboom, 1979). Several passive samplers have been
developed since Palmes and Gunnison (1973) published
the principles of passive sampling. The use of these
samplers for gas or vapour monitoring has become an
attractive alternative, due to the advantages that they
present when compared to conventional active techni-
ques. In addition to being simple and cost-effective, this
device presents the following benefits: the possibility of
simultaneous sampling of numerous interesting areas;
easy transportation to difficult locations, such as forests
and mountains, due to its small dimensions and light
weight; silent operation; reusability; a 100% time Fig. 1. Passive sampler diagram.
coverage is obtainable; and does not need field calibra-
tion, sampled air volume measurements, electricity nor
technical personnel at the sampling site. These char-
acteristics indicate that passive samplers are suitable for sampler model has been used in cold climates, with
determining the spatial distribution of gases over large temperatures ranging between 15 and +161C, and in
areas, checking atmospheric transport and deposit dry climates, with very low relative humidity, to
models, screening studies, establishing atmospheric determine SO2. The sorbent used was an NaOH 1%
monitoring networks, personal monitoring, mapping solution in methanol (Ferm and Svanberg, 1998; Ayers
concentrations in cities, and measuring concentrations et al., 1998; Makkonen and Juntto, 1997). The sampler
in remote sites (Carmichael et al., 2003; Cox, 2003; Cruz consists of a cylindrical polyethylene tube (internal
and Campos, 2002). diameter 21 mm, length 12 mm) sealed at the bottom to
Several types of SO2 passive samplers have been avoid convective transport, which produces positive
described with variations regarding dimensions, diffu- errors in determined pollutant concentration. To mini-
sion barriers and pollutant trapping reagents. Ferm and mize internal turbulent diffusion and particle interfer-
Svanberg (1998) carried out comparisons between SO2 ence, a Teflon membrane (pore 0.5 mm, diameter 25 mm)
passive samplers and active techniques at both urban was used in the air inlet. The membrane was protected
and remote sites in Sweden. The results demonstrated from mechanical damage by a stainless steel screen
close agreement between the two methods (within (thread diameter 0.08 mm and mesh size 0.125 mm).
715%). Nevertheless, it lacks validation for tropical After migration through the diffusion layer, SO2 is
environments, where high temperatures and relative trapped on a cellulose filter impregnated with a Na2CO3
humidity are present at all times. solution. Several tests were carried out to compare
This paper evaluated passive sampler performance in absorption efficiency and select the most adequate
the determination of SO2 concentrations in a tropical solution to impregnate the filters, used in the passive
environment. Passive sampler precision was determined sampler that would be exposed under conditions of
and its accuracy was estimated by comparison with relative temperature and humidity present in typically
active methods. tropical air. These tests consisted in bubbling a standard
SO2 atmosphere produced by a commercial permeation
tube (Dynacal), gravimetrically calibrated (permeation
2. Materials and methods rate: 141713 ng min1 SO2) and kept in a thermostatic
bath (25.070.1 1C). Three serial bubblers containing
2.1. Description and preparation of the passive sampler 10 mL of test solution each were used. As carrier gas,
commercial nitrogen was used at a rate of 40 L h1 for
In this experiment, a wide and shorter passive sampler periods of 1 h. The tested solutions and their respective
first designed by Ferm (1991) was tested (Fig. 1). This SO2 absorption were: 1.0
102 mol L1 potassium
 ARTICLE IN PRESS
L.P.S. Cruz et al. / Atmospheric Environment 38 (2004) 6425–6429
tetrachloromercurate (TCM: K2HgCl4), 100%; 7 mmol L1
buffered formaldehyde, 99%; 1.0
102 mol L1
Na2CO3, 97%, and 1.0
101 mol L1 triethanolamine
(TEA: 2,20 ,200 – nitrilotriethanol), 88%. The Na2CO3
solution was chosen as the trapping reagent due to other
advantages it offers, when compared to other reagents
tested, aside from presenting high SO2 absorption: it is a
stable, non-toxic reagent and the analysis method
utilized, i.e. ion chromatography, is simple and fast.
Samplers were prepared in the following manner:
cellulose filters with 25 mm in diameter were cut to fit
into the sampler bottom. Then, they were submitted to
three washings with deionized water in an ultrasonic
bath, and one with ethanol, for 15 min each. After
drying in a stove at 50 1C, the filters were impregnated
with 1.0
102 mol L1 Na2CO3 solution, for 2 h, and
dried again before being put into the samplers. All other
components of the passive sampler, as well as poly-
ethylene vials used for storing and transport, underwent
a similar cleaning treatment. Rubber gloves and tongs
were used to handle passive samplers and avoid
contamination.
Passive sampler performance in the laboratory was
checked by exposing sets of six passive samplers in a
Teflon chamber (Cruz et al., 2004). Several experiments
were carried out with the purpose of studying face
velocity, exposure time, pollutant concentration, relative
humidity, exposure to zero concentration and inter-
ference effects. Storage effect of exposed samplers was
also studied. All the tests were based on the protocol
recommended by the Comité Européen de Normalisation
(CEN, 1998) for passive sampler validation. The
sampler presented good performance, except for air in
total stillness condition (0 m s1), for very short ex-
posure periods (0.5 h), for atmosphere with
O3X150 mg m3 and high concentrations of reduced
sulphur compounds (H2SX7 mg m3 and others VSCs
20–30 mg m3).
2.2. Sampling
Two different tropical sites with varied sources and
levels of SO2 were selected for passive sampler exposure:
Vitória, a wind-tunnel type street, in the city of
Salvador, Bahia, located on the eastern coast of Brazil;
and Lamarão do Passé, a district 60 km NW from the
city of Salvador, downwind of a copper smelter and of
the largest petrochemical complex (Camac- ari, Bahia) in
the Southern Hemisphere. Sets of 3 samplers were
established under a PVC shelter, with concave borders
for protection against rain and sun, at a minimum height
of 2 m. After an exposure period of 7, 14, 21 or 28 days,
the samplers were closed, placed into polyethylene vials,
taken to the laboratory, and stored in a refrigerator at
4 1C until analysis. The SO2 diffusion coefficient was
corrected to average ambient temperature for each
6427
sampling period. To determine if contamination oc-
curred during sampler preparation, transport or analy-
sis, the passive samplers’ field blanks followed the same
trajectory as exposed samples, that is, they were taken to
the field and returned to the laboratory at the same
periods. Comparisons between passive sampling and
active techniques were performed in both urban and
industrial areas.
2.3. Analysis
After exposure of the passive samplers, the filters were
transferred to micro tubes, and the trapped SO2 was
extracted in an ultrasonic bath, using a 1.5 mL of
1.0
102 mol L1 H2O2 solution, for 15 min, to ensure
complete oxidation to sulphate. The extract was
centrifuged for 5 min, and analysed by suppressed ion
chromatography. The analysis conditions were as
follows: 120
6 mm BT I AN 5311111 anion analytical
column, 1.8 mL min1 flow rate, eluent 2 mmol L1
Na2CO3/0.75 mmol L1 NaHCO3 and ion suppresser
Dionex regenerated with 40 mmol L1 solution of
sulphuric acid. To determine the precision of the
analysis (defined as the relative standard deviation) each
sulphate standard solution of the analytical calibration
curve was analysed four times. An average value of 2%
was obtained for the precision of the analysis. Its
accuracy was estimated at 4% through two artificial rain
samples containing 2.5 and 8.5 mg SO2 1
4 mL . The
detection limit of the method was estimated at the
threefold standard deviation of the average field blanks
for each exposure time. For a 4-week period, the
detection limit was 0.10 mg SO2 m3.
2.4. Sampler capacity
Based on the quantity of CO23 used to impregnate the
SO2 sorbent in the passive sampler, and considering the
stequiometry of the reaction, it is noted that the device is
capable of absorbing up to 95 mg SO2. Taking different
exposure periods into account, it is estimated that the
sampler can be exposed in an atmosphere containing up
to 98 mg SO2 m3 and 421 mg SO2 m3 during periods
that last 1 month and 1 week, respectively.
3. Results and discussion
3.1. Field validation
When SO2 levels were high enough, stable electric
power was available and equipment security could be
assured, continuous monitoring was applied. These
conditions were only achieved at Lamarão do Passé,
where a SO2 continuous analyser, belonging to the air
monitoring network of the petrochemical complex, was
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6428 L.P.S. Cruz et al. / Atmospheric Environment 38 (2004) 6425–6429

available. Measurements were made during the rainy
season, with temperature varying between 21 and 27 1C
and relative humidity between 85% and 100%. Passive
sampler precision, defined as the relative standard
deviation for three simultaneously exposed samplers,
varied between 2.4% and 10%, with an average of 5.1%
for air concentration levels ranging from 6 to 13 mg
SO2 m3. In the urban area of Salvador (Vitória street)
the measurements were taken during a period of intense
rain, with temperatures ranging between 22 and 31 1C,
and relative humidity of 70% and 100%. Passive
sampler precision was within 4–10%, with an average
value of 6.2% for SO2 levels ranging between 1.9 and
3.0 mg SO2 m3.
The accuracy of the passive sampler measurements
was determined, in the industrial area, by comparison to
readings performed by a continuous SO2 analyser
(Environnement, Mod. AF 21M), and in the urban
area, by comparison to a standard denuder technique
for SO2. The continuous analyser was calibrated with a
dynamic gas calibrator (Environment, Mod. VE–3M)
and provided readings every 15 min. These were used to
calculate the averages corresponding to the passive
samplings periods that were performed in parallel. The
results obtained showed accuracy for the SO2 passive
samplers ranging between 10%–32% when applied to
heavily industrial areas and compared to readings
produced by the continuous analyser. In the urban
area, the accuracy was between 8% and 14%, when
parallel measurements were made using active sampling
with a 1.0
101 mol L1 potassium tetracloromercurate
(TCM) coated diffusion tube (length 35 cm, diameter
0.6 cm), air flow of 40 L h1 for 24 h (Table 1). This
method was chosen because the available SO2 continuous
analyser has a detection limit of 2.6 mg SO2 m3, and
lower values were expected. Overall, the passive technique
agreed with active techniques within ca. 715%, which is
considered a reasonable percentile for routine passive
monitoring (Ferm and Svanberg, 1998).
Based on data regarding passive sampler accuracy
(Table 1), it is evident that sampler performance was
best in the urban area, as opposed to the industrial one,
in which SO2 concentrations were, on average, 4 times
higher. A least-square regression analysis of the results
for the passive sampler versus concentrations measured
by the SO2 continuous analyser showed a good, positive,
and linear correlation between the two methods
(R=0.9784, po0.0001).

Table 1
Accuracy and precision of field measurements with SO2 diffusive passive sampler

Duration of Exposure period Site type/location Average concentration (mg SO2 m3) Accuracy Precision
exposure of (%) (%)
passive sampler
Passive sampler Active method

1 week 07/12–19/1999 Industrial 6.070.6 7.8 23 10

07/19–26/1999 1370.5 18 28 3.9
07/26–08/02/1999 7.070.3 7.8 10 4.3
08/02–09/1999 8.270.6 12 32 7.3
2 weeks 07/12–26/1999 Lamarão do 9.070.4 11 18 4.4
Passé—BA
07/26–08/09/1999 T: 21–27 1C 8.270.4 9.1 9.9 4.9
RH: 85–100%
3 weeks 07/12–08/02/1999 8.870.3 10 15 3.4
4 weeks 07/12–08/09/1999 8.470.2 10 20 2.4
03/06–04/03/2003 1070.5 12 17 5.0
04/03–30/2003 5.570.2 6.7 18 3.6
04/30–05/29/2003 7.370.5 8.5 14 6.9
1 week 07/30–08/06/1999 Urban 1.970.2 2.2 14 10
08/06–13/1999 2.170.1 1.9 10 4.8
08/20–27/1999 Vitória St— 3.070.3 2.8 7.1 10
Salvador—BA
T: 22–31 1C
RH: 80–100%
2 weeks 07/30–08/13/1999 2.570.1 2.2 14 4.0
3 weeks 07/30–08/20/1999 2.470.1 2.5 4.0 4.2
4 weeks 07/30–08/27/1999 2.370.1 2.5 8.0 4.4
Average accuracy in comparison to the continuous analyser (industrial area) 1976.9 —
Average accuracy in comparison to the TCM-denuder (urban area) 9.574.0 —
Average global accuracy 1577.4 —
 ARTICLE IN PRESS
L.P.S. Cruz et al. / Atmospheric Environment 38 (2004) 6425–6429
4. Conclusions
The SO2 diffusive passive sampler using Na2CO3 filter
impregnation was tested under ambient conditions in
Brazil, during periods of exposure ranging from 1–4
weeks. Its precision varied between 2.4% and 10% for a
SO2 concentration range of 1.9–13 mgSO2 m3, when
applied to two different types of tropical environments.
The field measurement results showed good agreement
between passive and active methods, during the same
exposure period. The overall accuracy of the measure-
ments was 15%. Considering the growing demands for
environmental monitoring, passive samplers represent a
cost-effective tool for SO2 monitoring.
Acknowledgements
Authors acknowledge CAPES for fellowship, FINEP
for grants and CETREL for supplying the SO2
continuous analyser’s data from the station located at
Lamarão do Passé.
References
Ayers, G.P., Keywood, M.D., Gillett, R., Manins, P.C.,
Malfroy, H., Bardsley, T., 1998. Validation of passive
diffusion samplers for SO2 and NO2. Atmospheric Envir-
onment 32, 3587–3592.
Brown, R.H., Harvey, R.P., Purnell, C.J., Saunders, K.J., 1984.
A diffusive sampler evaluation protocol. American Indus-
trial Hygiene Association Journal 45, 67–75.
Carmichael, G.R., Ferm, M., Thongboonchoo, N., Woo, J.-H.,
Chan, L.Y., Murano, K., Viet, P.H., Mossberg, C., Bala,
R., Boonjawat, J., Upatum, P., Mohan, M., Adhikary, S.P.,
Shrestha, A.B., Pienaar, J.J., Brunke, E.B., Chen, T., Jie, T.,
Guoan, D., Peng, L.C., Dhiharto, S., Harjanto, H., Jose,
A.M., Kimani, W., Kirouane, A., Lacaux, J.-P., Richard,
S., Barturen, O., Cerda, J.C., Athayde, A., Tavares, T.,
Cotrina, J.S., Bilici, E., 2003. Measurements of sulfur
dioxide, ozone and ammonia concentrations in Asia, Africa
6429
and South America using passive samplers. Atmospheric
Environment 37, 1293–1308.
CEN/TC264/WG11, 1998. Ambient air quality. Diffusive
samplers for the determination of gases or vapour—
requirements and test methods. Comité Européen de
Normalisation, Brussels.
CONAMA—Conselho Nacional do Meio Ambiente, 1990.
Resoluc- ão No. 003, Diário Oficial da República Federativa
do Brasil, Brası́lia, Brazil. Available: http://www.mma.
gov.br.
Cox, R.M., 2003. The use of passive sampling to monitor forest
exposure to O3, NO2 and SO2: a review and some case
studies. Environmental Pollution 126, 301–311.
Cruz, L.P.S., Campos, V.P., 2002. Amostragem passiva de
poluentes atmosféricos. Aplicac- ão ao SO2. Quı́mica Nova
25, 406–411.
Cruz, L.P.S., Campos, V.P., Novaes, J.A.P., Tavares, T.M.,
2004. Laboratory validation of a passive sampler for SO2
atmospheric monitoring. Journal of the Brazilian Chemical
Society, in press.
Cullis, C.F., Hirschler, M.M., 1980. Atmospheric sulphur:
natural and man-made sources. Atmospheric Environment
14, 1263–1278.
Ferm, M., 1991. A sensitive diffusional sampler. IVL Report
L91-172. Swedish Environmental Research Institute,
Göteborg, Sweden.
Ferm, M., Svanberg, P.A., 1998. Cost-efficient techniques for
urban and background measurements of SO2 and NO2.
Atmospheric Environment 32, 1377–1381.
Finlayson-Pitts, B.J.F., Pitts Jr, J.N., 1986. Atmospheric
Chemistry—Fundaments and Experimental Techniques.
Wiley, New York.
Makkonen, U., Juntto, S., 1997. Field comparison of measure-
ment methods for sulphur dioxide and aerosol sulphate.
Atmospheric Environment 31, 983–990.
Palmes, E.D., Gunnison, A.F., 1973. Personal monitoring
device for gaseous contaminants. American Industrial
Hygiene Association Journal 34, 78–81.
Palmes, E.D., Lindenboom, R.H., 1979. Ohm’s law, Fick’s law,
and diffusion samplers for gases. Analytical Chemistry 51,
2400–2401.
WHO—World Health Organization, 2000. Air Quality Guide-
lines for Europe, Second ed. WHO Regional Publications,
European Series, No. 91, Copenhagen.