Design and Validation of Portable SPME Devic es

for Rapid Field Air Sampling and Diffusion-Based

Calibration
Fabio Augusto,

J ac ek Koziel,

and J anusz Pawliszyn*

Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1
TheuseofSPME fiberscoatedwithporouspolymer solid
phases for quantitativepurposes is limitedduetoeffects
such as interanalyte displacement and competitive ad-
sorption. For air analysis, theseproblemscanbeaverted
byemployingshortexposuretimestoair samplesflowing
around the fiber. In these conditions, a simple math-
ematical model allows quantificationwithout theneedof
calibration curves. This work describes two portable
dynamic air sampling (PDAS) devices designed for ap-
plicationof this approachtononequilibriumSPME sam-
pling and determination of airborne volatile organic
compounds (VOCs). The use of a PDAS device resulted
in greater adsorbed VOC mass compared totheconven-
tional SPME extractioninstatic air for qualitativescreen-
ingof liveplant aromas and contaminants in indoor air.
For all studiedair samples, anincreaseinthenumber of
detected compounds and sensitivity was also observed.
Quantification of aromatic VOCs in indoor air was also
carried out using this approach and the PDAS/ SPME
device. MeasuredVOC concentrationswereinlowparts-
per-billion byvolumerangeusingonly30-s SPME fiber
exposureand werecomparableto thoseobtained with a
standardNIOSH method1501. TheuseofPDAS/ SPME
devices reducedthetotal air samplingandanalysis time
byseveral orders of magnitudecompared to theNIOSH
1501 method.
Sampling of air and related gas mixtures for chromatographic
analysis of contaminants has been performed using abroad range
of techniques. Sorbent adsorption, cryotrapping, and canister
sampling, followed by thermal desorption/ cryofocusing or solvent
desorption are the most employed procedures for air analysis.
1
However, most of these procedures have several serious draw-
backs, such as production of artifacts
2
and retention of large
amounts of water.
3
Techniques such as membrane extraction with
sorbent interface (MESI),
4
where the analytes present in asample
selectively permeate through a polymeric membrane and are
trapped in a sorbent interface for further desorption into a
chromatographic system, also had been suggested.
5
SPME is an attractive alternative to the aforementioned
techniques, considering features such as accuracy, cost, simplicity,
and speed,
6
and has been widely used in analysis of several
contaminants in air.
7-10
Many of these SPME methods reported
in the literature employ fibers coated with liquid polymeric phases,
such as poly(dimethylsiloxane) (PDMS) and polyacrylate. How-
ever, the use of fibers covered with mixed porous solid adsorptive
coatings, such as Carboxen/ PDMS and PDMS/ divinylbenzene
(PDMS/ DVB), seems to be especially interesting for analysis of
air contaminants. They are more efficient than the liquid-coated
fibers,
11
especially for extraction of analytes with low molecular
weight.
12
Both quantitative and qualitative applications of solid-
phase coated fibers have been described for analysis of food
contaminants,
13
fruit pulp volatiles,
14
and flavor compounds in
milk.
15
Adsorption is the physicochemical mechanism involved in
extractions using fibers coated with solid phases. Both the
theoretical foundations of the equilibrium
16
and the kinetics
17
of
adsorption by solid-phase coated fibers had already been ad-
dressed. These studies point to problems, e.g., competition
between the analytes for the adsorptive sites available in the fiber
and interanalyte displacement, as severe drawbacks to the ap-
plication of solid-phase coated fibers to quantitative analysis and
limiting the accuracy and precision of the results. However, in
recent work, Koziel et al.
18
presented an alternate methodological
approach to overcome these deleterious effects. According to the
* Corresponding author: (fax) (519) 746-0435; (e-mail) janusz@uwaterloo.ca.

Current address: Instituto de Qu mica, Unicamp, CP 6154-13083-970

Campinas, SP, Brazil.

Current address: Texas Agricultural Experiment Station, Amarillo, TX

79106.
(1) Dewulf, J.; Van Langenhove, H. J. Chromatogr., A 1999, 843, 163-177.
(2) Clausen, P. A.; Wolkoff, P. Atmos. Environ. 1997, 31, 715-725.
(3) Helmig, D.; Vierling, L. Anal. Chem. 1995, 67, 4380-4386.
(4) Yang, M. J.; Harms, S.; Luo, Y. Z.; Pawliszyn, J. Anal. Chem. 1994, 66,
1339-1346.
(5) Luo, Y. Z.; Pawliszyn, J. Anal. Chem. 2000, 72, 1064-1071.
(6) Pawliszyn, J. TrAC, Trends Anal. Chem. 1995, 14, 113-122.
(7) Chai, M.; Pawliszyn, J. Environ. Sci. Technol. 1995, 29, 693-701.
(8) Grote, C.; Pawliszyn, J. Anal. Chem. 1997, 69, 587-597.
(9) Martos, P. A.; Pawliszyn, J. Anal. Chem. 1997, 69, 206-215.
(10) Eisert, R.; Pawliszyn, J.; Barinshteyn, G.; Chambers, D. Anal. Commun.
1998, 35, 187-190.
(11) Mani, V. Properties of Commercial SPME Coatings. In Applicationsof Solid-
PhaseMicroextraction; Pawliszyn, J., Ed.; RSC.: Cornwall, UK, 1999; Chapter
5, pp 63-67.
(12) Gorecki, T. Solid versus Liquid Coatings. In Applications of Solid-Phase
Microextraction; Pawliszyn, J., Ed.; RSC.: Cornwall, UK, 1999; Chapter 7,
pp 92-108.
(13) Page, D. B.; Lacroix, G. J. Chromatogr., A 2000, 873, 79-94.
(14) Augusto, F.; Valente, A. L. P.; Tada, E. S.; Rivellino, S. R. J. Chromatogr., A
2000, 873, 117-127.
(15) Marsili, R. T. J. Chromatogr. Sci. 1999, 37, 17-26.
(16) Gorecki, T.; Yu, X.; Pawliszyn, J. Analyst 1999, 124, 643-649.
(17) Semenov, S.; Koziel, J.; Pawliszyn, J. J. Chromatogr., A 2000, 873, 39-51.
Anal. Chem. 2001, 73, 481-486
10.1021/ac000629k CCC: $20.00 2001 American Chemical Society Analytical Chemistry, Vol. 73, No. 3, February 1, 2001 481
Published on Web 12/30/2000
authors, when a fiber is exposed to a gaseous sample moving
perpendicularly to the fiber axis for aperiod of time much smaller
than the equilibration time, the coating behaves as a perfect sink
and all analyte molecules reaching the fiber surface are im-
mediately adsorbed. As alarge number of nonoccupied adsorptive
sites are available in these conditions, interanalyte competition
and displacement are minimized and can be disregarded. It can
be demonstrated that the extracted amount of an analyte n
depends only on its concentration in the gaseous matrix C
g
, its
diffusion coefficient in air D
g
, the fibers length and radius L and
b, respectively, the thickness of the effective static boundary layer
surrounding the fiber , and the sampling time t:
The extracted amount, n, can be calculated from the peak area
and from the detector response factor. Equation 1 holds true for
air speeds up to values between 4 and 10 cm s
-1
, depending on
the analyte. Further increase in the air velocity shows no effect
on the mass uptake rate, which becomes nearly constant and
limited by the diffusion of the analyte in the coating.
18
For practical
reasons, devices that allow extractions using air speeds superior
to this critical limit would be desirable because variations in air
velocity would not affect the mass uptake rate, ensuring better
analytical precision and accuracy.
Several models are available to estimate diffusion coefficients
in air needed for the use of eq 1 with the Fuller-Schettler-
Giddings
19
model being the most adequate for a large number of
analytes in normal air sampling conditions:
where T is the absolute temperature, M
air
is the air apparent
molecular weight (i.e., the weighted average of the molecular
weights of the components of air), M
voc
is the molecular weight
of the analyte, p is the ambient pressure, and V
air
and V
voc
are
respectively the molar volumes of air and of the analyte.
The thickness of the effective static boundary layer sur-
rounding the fiber can be calculated from eq 3, where Rerefers
to the Reynolds number (Re) 2ub/ j; u is the linear velocity of
the air and is the air kinematic viscosity) and Scto the Schmidt
number (Sc ) / D
g
).
Using these equations, the concentration of an analyte can be
directly estimated from the chromatographic peak area, given that
the sampling conditions (sampling time, air velocity, temperature,
and pressure) and constants (diffusion coefficient and fiber
dimensions) are known. For that reason, apart from the suppres-
sion of interanalyte effects, this methodology also allows quanti-
tation of analytes in air without construction of calibration curves.
Another benefit would be the increase of the extracted amounts
(and, therefore, of the sensitivity), when this approach is compared
to the traditional static SPME sampling (simple exposure of the
fiber to the air). It can be proved, from eqs 1 and 3, that increasing
the air speed also increases the fibers mass uptake, due to the
decrease of the boundary layer thickness. Under static conditions,
the extraction would depend on transport of the mass through a
boundary layer which would turn progressively thicker during the
process, due to the depletion of the analyte.
20
This, in turn, would
limit the amount extracted in short periods of fiber exposure to
the sample.
This work describes several portable devices designed to apply
the dynamic nonequilibrium sampling concept to analysis of
airborne chemicals. The suitability of this approach both for
qualitative analysis of living plant aroma compounds and for
volatile organic contaminants in indoor air was examined. Also,
quantitation of air contaminants using dynamic SPME sampling
was compared to results obtained using a standard air analysis
method.
EXPERIMENTAL SECTION
Materials. Chemicals and Supplies. All chemicals were of
analytical grade and used as supplied: benzene, toluene, ethyl-
benzene, o-xylene, p-xylene, and mesitylene (Sigma-Aldrich, Mis-
sissauga, ON, Canada) and carbon disulfide (BDH, Toronto, ON,
Canada). The SPME holder and 65-m PDMS/ DVB fibers were
obtained from Supelco (Oakville, ON, Canada); the fibers were
conditioned at 210 C for 8 h prior to their use. Supelco ORBO-
32 charcoal tubes and a model I.H. portable air pump (A.P. Buck,
Orlando, FL) wereemployed for thevalidation quantitativeanalysis
according to NIOSH method 1501.
21
All preparations involving CS
2
(flammable and toxic) and benzene (suspect carcinogen) were
carried out in a ventilated hood.
GasChromatography. Qualitative chromatographic analyses of
aromas were carried out in aSaturn IV GC-ITMSsystem (Varian
Associates, Sunnyvale, CA) fitted with a 30 m 0.25 mm 0.25
m HP-5 column (Hewlett-Packard, Avondale, PA) and a septum-
purged injector (SPI). The carrier gas was 1.5 mL min
-1
helium
at 12 psi. The SPI was kept at 210 C, and the column oven
temperature was ramped from 60 to 280 C at 5 C/ min. Profiles
of indoor air contaminants and quantitative data were obtained
using a Varian Star 3400 GC-FID chromatograph equipped with
a 30 m 0.25 mm 0.25 m Supelco SPB-5 column and SPI; 2.0
mL min
-1
helium at 20 psi was used as carrier gas. The
temperatures were set at 250 C for the FID and 210 C for the
SPI, and the column oven program for all injections was as
follows: 1 min hold at 60 C, followed by a 15 C/ min ramp until
ramped to 180 C, and hold there for 3 min.
Plant Sample. Aroma from juniper bushes (Juniperuscommu-
nis) from the University of Waterloo campus gardens was used
as a sample for the qualitative application in this work.
PortableDynamicAir SamplingDevices(PDAS) for SPME. Two
devices to perform air sampling under dynamic conditions were
(18) Koziel, J.; Jia, M.; Pawliszyn, J. Anal. Chem. 2000, 72, 5178-5186.
(19) Fuller, E. N.; Schettler, P. D.; Giddings, J. C. Ind. Eng. Chem. 1966, 58,
19-27.
(20) Pawliszyn, J. Solid-PhaseMicroextraction: Theoryand Practice; Wiley-VCH:
New York, 1997; pp 67-69.
(21) National Institute of Occupational Safety and Health. Manual of Analytical
Methods, 4th ed.; U.S. Department of Health and Human Services: Cincin-
nati, OH. 1994; Vol. I (Method 1501 (Hydrocarbons, Aromatic).
C
g
) n ln
(
b+
b
)
/ 2D
g
Lt (1)
D
g
)
0.001T
1.75

1
M
air
+
1
M
voc
p[ (

V
air
)
1/ 3
+ (

V
voc
)
1/ 3
]
2
(2)
) 9.52b/ Re
0.62
Sc
0.38
(3)
482 Analytical Chemistry, Vol. 73, No. 3, February 1, 2001
projected and built; the design concepts for these apparatus are
discussed in Results and Discussion. Figure 1 shows the schemat-
ics of the first device, built using a VS-513F household hair-dryer
(Helen of Troy, El Paso, TX) modified to revert the air flow
direction and to disable the internal heating coil. An aluminum
tube was machined and adapted to the front part of the modified
hair-dryer. Two plain cardboard sheets fixed to the opposite side
of the aluminum tubing creating a 3-mm slit; the modified hair-
dryer suction forces the passage of the ambient air through this
slit. PDAS-SPME sampling is performed by exposing the fiber
to the flowing air in front of the slit. The average air speed in
front of the slit was measured to be 1.5 m s
-1
with an HHF51
digital wire anemometer (Omega Engineering, Stamford, CT).
This value is greater than the critical air speeds mentioned in the
introduction. All datapresented in this work were collected using
this apparatus.
A different PDAS-SPME (sandwich design), shown in
Figure 2, was also projected and assembled. A portable air
sampling pump was used to force ambient air through the
rectangular orifice of the device; a small hole (diameter 0.6 mm)
in the Teflon spacer allowed exposure of the SPME fiber to the
ambient air flowing through the orifice. Using a Buck I.H. air
pump, it is possible to sample air flowing with controllable speeds
up to 1.38 m s
-1
. This device is presented here as an alternative
to that described above, and its use is currently being evaluated.
Methods. Screeningof LivingPlant Aromas. PDAS-SPME was
compared with conventional (static) SPME sampling for identifica-
tion of compounds found in the fragrance released by an aromatic
plant (juniper). Both for static SPME and for PDAS-SPME, the
SPME fiber was exposed to the air surrounding the living
specimen for 30 s, and the approximate distance between the
SPME fiber and the specimen was 5 cm. The extracted materials
were separated and identified by GC-ITMS. The desorption time
was 5 min. The time between sampling and chromatographic
analysis was kept lower than 20 min for all extractions performed
here and in the subsequent essays; under these conditions, loss
of sorbed materials can be assumed as negligible.
22,23
QualitativeProfilesof Contaminantsin Indoor Air. Qualitative
profiles of the contaminants present in the air of the Motor Vehicle
Maintenance Shop of the University of Waterloo were obtained
using PDAS-SPME and conventional SPME. Extractions with a
fiber exposure time of 30 s were carried out simultaneously by
both methods. The SPME fibers were kept refrigerated under dry
ice and capped during their transportation to the laboratory and
storage. Several samples were collected during one workday to
show the variation of the air contamination profile during this time
span.
QuantitativeAnalysisof AromaticHydrocarbonsin Indoor Air.
PDAS-SPME was employed to quantify aromatic hydrocarbons
present in the air of several sites in the University of Waterloo.
These sites included two different locations in a chemical labora-
tory (close to a solvent storage cabinet and in an analytical
instrument room), the Motor Vehicle Maintenance Shop, and in
the Engineering Mechanical Shop. Replicate measurements
exposing the SPME fiber to the flowing air for 30 s were made.
Uncertainties were expressed as estimates of standard deviation
of replicates, i.e., vehicle and mechanical shop air analysis, three
replicates, and laboratory air analysis, eight replicates. Concentra-
tions of the aromatic hydrocarbons were calculated using eq 1
for nonequilibrium dynamic SPME extraction. It was assumed that
the thickness of the boundary layer did not significantly change
when air velocity was greater than 10 cm s
-1
. Thus, the threshold
air velocity of 10 cm s
-1
was used to estimate the thickness of
the boundary layer in eq 3.
For comparison purposes, vehicle and mechanical shop samples
were simultaneously analyzed using the NIOSH method 1501 for
aromatic hydrocarbons.
21
Air was pumped through ORBO-32
charcoal adsorption tubes with sampling times and flow rates
adjusted according to the level of contamination of each sample
(see Results below). Immediately after the sampling, both the
charcoal portion of the tube containing the extracted analytes and
the breakthrough control portion were transferred to separate
4-mL glass vials sealed with Teflon-coated silicone septa. Two
milliliters of CS
2
was added to each vial. After 1 h, 1 L of the
(22) Mu ller, L. Field Analysis by SPME. In Applications of Solid-Phase Micro-
extraction; Pawliszyn, J., Ed.; RSC.: Cornwall, UK, 1999; Chapter 20, pp 269-
283.
(23) Koziel, J.; Pawliszyn, J. J. Air WasteManag. Assoc., in press.
Figure 1. Side view (A) and front view (B) of the portable dynamic
air sampling device for SPME. (1) modified hair-dryer; (2) aluminum
tube; (3) 18 VDC power supply cable; (4) fixing brace; (5) cardboard
pieces; (6) 3-mm slit; (7) SPME holder and fiber.
Figure 2. Sandwich PDAS-SPME; (A) unassembled and (B)
assembled device. (1) 1-mm-thick stainless steel sheets; (2) 3-mm-
thick Teflon spacer; (3) 0.6-mm hole; (4) ) SPME holder and fiber;
(5) silicone tube.
Analytical Chemistry, Vol. 73, No. 3, February 1, 2001 483
CS
2
phase in the vials was injected into the GC-FID system using
the same operational conditions employed for the PDAS-SPME
analysis.
RESULTS AND DISCUSSION
Design Aspects of the PDAS-SPME. The PDAS-SPME
complements previously described devices for field SPME sam-
pling.
22
These already reported devices and the techniques used
extractions under analyte/ fiber equilibrium conditions, which
demands the use of calibration curves or quantitation based on
chromatographic retention data.
24
However, quantitation in pre-
equilibrium conditions, where the analyte uptake depends only
on its diffusion through the static boundary layer,
18
has several
advantages for field use. Since no calibration procedures are
needed for well-defined flow rates, the analytical process is
simplified. Also, the sampling time is noticeably shorter when
compared to the typical equilibrium times for airborne analytes,
resulting in faster analysis. The main design feature of the PDAS-
SPME project is to ensure aconstant and uniform air flow around
the fiber, consistent with the demands of diffusion-based extrac-
tion. These devices should also provide flow rates high enough
to have air speeds higher than the critical values mentioned in
the introduction, where the extraction rate is dependent mainly
on diffusion of the analyte through the adsorbent pores or through
the liquid coating film.
For the device shown in Figure 1, this was achieved by using
a modified dc-powered hair-dryer. The reversion of the direction
of the air flow was made to avoid contact of the fiber with potential
artifacts originated from the dryer body and motor. The device
shown in Figure 2 was intended to use with industrial hygiene
air sampling pumps, a resource already existent in several
laboratories, as a source of air motion. In addition to these
features, characteristics such as weight, cost, and handiness of
use were taken in account. An alternate version of this device
without the two cardboard sheets allows sampling of large volume
air samples, i.e., indoor air, under higher flow rates. In this case,
a special 1-in.-O.D. short tube is mounted perpendicularly to the
main aluminum tube to position the SPME holder and to allow
one-hand operation. A 1-mm hole was made in the aluminum tube
for insertion of the SPME needle and fiber in the sampled air
stream.
Screening of Living Plant Aroma. Figure 3 allows the
comparison of a selected section of GC-ITMS chromatograms
obtained with PDAS-SPME and conventional SPME for juniper
aroma. Three compoundsslimonene, 3-nonen-1-ol, and 2-decen-
1-olswere identified in this section of the PDAS-SPME chro-
matogram (Figure 3A). Peaks corresponding to the same com-
pounds in the static SPME chromatogram section were considerably
lower (Figure 3B). In addition, the 3-nonen-1-ol peak is not distinct
from the baseline noise and not detected with static SPME
sampling.
As shown by these results, the application of PDAS-SPME
produced a significant increase in the number of detectable
compounds in the analyzed samples, when compared to conven-
tional SPME. This observation agrees with the theory; i.e., the
air flow around the fiber increases the extracted amount of
analytes per unit of time due to the reduction of the effective
boundary layer thickness. The increase in the analyte uptake is
also reflected in the increase of the number of detected com-
pounds.
QualitativeProfilesofContaminantsinIndoor Air. Figure
4 shows the chromatographic data profiles obtained after extrac-
tion of the indoor air at the UW Vehicle Maintenance Shop, using
both PDAS-SPME and static conventional SPME sampling,
respectively. The signal scale for the chromatograms in both sets
was adjusted to the same value. Both the number of detectable
peaks and the peak intensities are considerably greater in the
chromatograms in the PDAS-SPME profile (Figure 4B), allowing
easier visual assessment of the correlation between the pattern
of air contamination in this environment and the activities taking
place there. For example, it can be seen that the intensity of the
peak attributed to toluene (large peak with t
R
) 2.6 min) decays
during the period between 9:15 a.m. (just after the beginning of
the work shift) and 12:15 p.m., becoming roughly constant after (24) Martos, P.; Pawliszyn, J. Anal. Chem. 1997, 69, 206-215.
Figure 3. Section of GC-ITMS chromatogram of living juniper
aroma. (A) PDAS-SPME; (B) static SPME; (C) fiber blank). Peak
identification: (1) limonene; (2) 3-nonen-1-ol; (3) 2-decen-1-ol.
Figure 4. Variation of the GC-FID chromatographic profiles of
contaminants in the UW Vehicle Maintenance Shop monitored in a
workday using conventional SPME (A) and PDAS-SPME (B) col-
lected during a work shift. Chromatograms: (1) 9:15 a.m.; (2) 9:55
a.m.; (3) 10:20 a.m.; (4) 11:10 a.m.; (5) 12:15 p.m.; (6) 12:55 p.m.;
(7) 1:55 p.m.; (8) 3:05 p.m. For peak identification see Results and
Discussion.
484 Analytical Chemistry, Vol. 73, No. 3, February 1, 2001
this time. This was credited to the residues of degreasing solvents
containing toluene that were left for overnight cleanup of motor
parts. The group of peaks with retention times between 4 and 8
min were found to be volatile hydrocarbons present in gasoline
and diesel fuels. The intensity of these peaks was found to be at
maximum around 12:55 p.m., which correlated to the admission
of several vehicles to the shop.
QuantitativeAnalysisofAromaticHydrocarbonsinIndoor
Air. Table 1 compares concentrations of several aromatic hydro-
carbons found after PDAS-SPME sampling, combined with
nonequilibrium diffusion-based quantification, with concentrations
obtained after simultaneous application of NIOSH 1501 standard
method to the same samples. For PDAS-SPME calculations, the
values for the needed constants were as follows: b) 0.0120 cm;
L ) 1 cm (both previously measured in the laboratory); M
air
)
28.97 g mol
-1
; V
air
) 20.1 mL, and ) 0.15 cm
2
s
-1
.
25
Values for
V
voc
needed for estimation of D
g
(eq 2) were calculated according
to the literature.
25
The sampling time and air flow rate for NIOSH
analysis was adjusted according to the expected concentrations
of contaminants in each sample, based on preliminary exploratory
extractions: 91 min for the vehicle shop air and 215 min for the
mechanical shop air, with a flow rate of 138 mL min
-1
(sampled
air volumes: 12.6 L for vehicle shop and 29.7 L for mechanical
shop). Under these conditions, no analyte breakthrough was
observed when the NIOSH method was applied. It should be
emphasized that the sampling time for the NIOSH-based sampling
was a few orders of magnitude greater than the sampling time
associated with PDAS-SPME. However, none of the existing
standard methods could be compared with the 30-s PDAS-SPME
sampling time.
The PDAS-SPME results obtained for the vehicle and me-
chanical shops were similar to those from NIOSH analysis, except
for the hydrocarbons with higher molecular weight in the set (o-
xylene and mesitylene), which are underestimated by the NIOSH
method. A possible cause for this could be associated with the
incomplete desorption of these analytes from the charcoal tubes
employed in the NIOSH method, when the recommended de-
sorption procedure was used. Another reason for the observed
discrepancies in measured concentrations could be due to the
widely different sampling times used in both methods. The
NIOSH-based concentration can be considered as atime-weighted
average sample over a long sampling period. In contrast, the
PDAS-SPME concentrations can be associated with spot or grab
30-s sampling. In addition, it was not possible to measure benzene
concentration in the evaluated samples using this method.
Benzene is a common and significant contaminant in the CS
2
solvent recommended for the desorption step in the NIOSH
method.
The method precision can be estimated from the uncertainties
presented in Table 1. VOCconcentration levels can be considered
typical of indoor air in occupational environments. Expressed as
estimates of relative standard deviations (s
R
), the precision of
PDAS-SPME results ranged from 13 to 28%, with an average
value of 20%. These results can be compared to those presented
in an extensive study of NIOSH charcoal tube collection methods
for airborne organics.
26
The s
R
values calculated from the data
presented in this study ranged from 0.4%to as much as 69%, with
an average of 15%(for xylene s
R
ranged from 5.2 to 22%, with an
average of 10%, and for benzene, from 4.3%to as much as 43%,
with an 15%average). Therefore, precision for the PDAS-SPME
method can be considered in the same order of magnitude (if
not better for some analytes) to the range of precision reported
for the NIOSH standard method.
An estimate of the detection limits of PDAS-SPME was
provided by thelaboratory air samples analysis. For sampling close
to the solvent cabinet 18 ( 6 ppbv benzene, 6 ( 3 ppbv toluene,
and 2 ( 1 ppbv p-xylene were detected, and for the air in the
instrument room, 3 ( 1 ppbv toluene and 2 ( 1 ppbv p-xylene;
other analytes were not detected. Those results show that the
detection limits for PDAS-SPME are in the low-ppbv range.
Comparison with the NIOSH method was not considered valid
here, since for the same samples no aromatic hydrocarbons were
detected with this method even extending the sampling volumes
to values up to 50 L, except for toluene in one of the samples.
For the sampling volumes employed in the vehicle and mechanical
shops analysis, the detection limits calculated according to data
provided in method 1501 would be in the range between 6 and
100 ppbv for mechanical shop air sampling and 15-230 ppbv for
vehicle shop air sampling, depending on the analyte in consider-
ation. Therefore, PDAS-SPME can be considered as more
sensitive than the standard NIOSH 1501 method.
CONCLUSIONS
This work demonstrated that the combination of SPME and
the simple and inexpensive (U.S. $10) PDAS-SPME device was
a powerful tool for both qualitative screening and quantitative
analysis of varied samples as aromas from living plants to
occupational air. When compared to SPME extraction with simple
static exposure of the fiber to the air, the application of PDAS-
SPME increased significantly the number of detectable analytes,
the adsorbed amounts, and the method sensitivities. Findings in
this work suggest that PDAS-SPME can provide more accurate
qualitative profiles of extremely diluted samples such as natural
aromas.
A few remarks should be made on the herein proposed
methodology. As it involves short sampling times, the assessment
(25) Tucker, W. A.; Nelken, L. H. Diffusion Coefficients in Air and Water. In
Handbookof Chemical PropertyEstimationMethods: Environmental Behaviour
of OrganicCompounds; Lyman, W. J., Reehl, W. F., Rosenblatt, D. H. Eds.;
McGraw-Hill: New York, 1982; Chapter 17, pp 17-1-17-25.
(26) Larkin, R. L.; Crable, J. V.; Catlett, L. R.; Seymour, M. J. Am. Ind. Hyg. Assoc.
J. 1977, 38, 543-554.
Table 1. Conc entrations in ppb v/v of Some Aromatic
Hydroc arbons in Indoor Air Measured by PDAS-SPME
and NIOSH Standard Method 1501
vehicle shop mechanical shop
SPME NIOSH SPME NIOSH
benzene 48 ( 10
a
b 17 ( 4 b
toluene 212 ( 43 215 62 ( 9 73
ethylbenzene 60 ( 8 48 nd
c
nd
p-xylene 189 ( 43 222 25 ( 5 nd
o-xylene 249 ( 35 137 18 ( 5 nd
mesitylene 202 ( 28 75 nd nd
a
Uncertainties expressed as estimates of standard deviation of
triplicates.
b
Not quantifiable (see text).
c
nd, not detected.
Analytical Chemistry, Vol. 73, No. 3, February 1, 2001 485
of long-term exposure of contaminants in indoor air, which is
frequently necessary, would require averaging several measure-
ments made during a period of time. For these cases, procedures
such as standard NIOSH methods, time-weighted average SPME
mode, or similar alternatives would be more adequate. Since the
sampling time is one of the variables needed to calculate the
concentration, errors in its measurement would reflect in the
accuracy and precision of results. Such errors could be significant
considering that these short exposure times should be manually
measured. Another possible handicap of the method is the
dependence of the results on dimensional parameters of the fibers
(their radius and length, which are constants in the models
equations). Fibers should be checked in respect to their real
dimensions to ensure accurate measurements, as well as the
integrity of the coating.
The use of PDAS-SPME also allowed the application of
nonequilibrium diffusion-based quantification to air samples using
fibers coated with solid (porous) polymers. The use of short
sampling time minimized the effects of interanalyte displacement
that in the past prevented the use of these fibers for accurate
quantitativeair analysis. Also, this nonequilibrium model can result
in quantitativeanalysis without need of calibration curves, provided
that some constants, e.g., analyte diffusion coefficient in air and
the detector response factor, are known. When compared to
standard methodologies, a 30-s sampling using PDAS-SPME
allowed measurement of VOC concentrations that where not
detected by the NIOSH standard method, even after several hours
of extraction using expensive (air sampling pumps) and nonreus-
able (charcoal tubes) materials.
ACKNOWLEDGMENT
The authors acknowledge the Fundac a o de Amparo a` Pesquisa
do Estado de Sa o Paulo (FAPESP) for the scholarship provided
to F.A. and also thank NSERC(Natural Sciences and Engineering
Research Council of Canada) for funding this study.
Received for review June 1, 2000. Accepted November 8,
2000.
AC000629K
486 Analytical Chemistry, Vol. 73, No. 3, February 1, 2001