Atmospheric Environment 117 (2015) 99e109

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Modeling and analysis of sampling artifacts in measurements of

gas-particle partitioning of semivolatile organic contaminants
using filter-sorbent samplers
Xinke Wang a, b, Chenyang Bi b, Ying Xu b, *
a
School of Human Settlements and Civil Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China
b
Department of Civil, Architectural and Environmental Engineering, The University of Texas at Austin, TX, USA

h i g h l i g h t s

A mechanistic model to characterize air sampling process was developed and validated.

Positive sampling bias were observed for almost all the target SVOCs.

Correlations and plots provided can be used to estimate sampling bias for various SVOCs.

Particle penetration may result in underestimation of the gas/particle partition coefficient.

The option of backup filters must be considered carefully in field measurements.

a r t i c l e i n f o a b s t r a c t

Article history: Measurements of gas/particle partition coefficients for semivolatile organic compounds (SVOCs) using filter-
Received 6 April 2015 sorbent samplers can be biased if a fraction of gas-phase mass is measured erroneously as particle-phase due
Received in revised form to sorption of SVOC gases to the filter, or, if a fraction of particle-phase mass is measured erroneously as gas-
27 June 2015
phase due to penetration of particles into the sorbent. A fundamental mechanistic model to characterize the
Accepted 29 June 2015
Available online 6 July 2015
air sampling process with filter-sorbent samplers for SVOCs was developed and partially validated. The
potential sampling artifacts associated with measurements of gas-particle partitioning were examined for
19 SVOCs. Positive sampling bias (i.e., overestimation of gas/particle partition coefficients) was observed for
Keywords:
Air sampling
almost all the SVOCs. For certain compounds, the measured partition coefficient was several orders of
Sampling artifacts magnitude greater than the presumed value. It was found that the sampling artifacts can be ignored when
Gas/particle partitioning the value of log½Kf =ðKp ,Cp;a Þ is less than 7. By normalizing the model, general factors that influence the
Semivolatile organic compounds (SVOCs) sampling artifacts were investigated. Correlations were obtained between the dimensionless time required
Modeling for the gas-phase SVOCs within the filter to reach steady state ðTs;s * Þ and the chemical V values, which can be
p
used to estimate appropriate sampling time. The potential errors between measured and actual gas/particle
partition coefficients of SVOCs as a function of sampling velocity and time were calculated and plotted for a
range of SVOCs (vapor pressures: 108 ~ 103 Pa). These plots were useful in identifying bias from the
sampling in previously-completed field measurements. Penetration of particles into the sorbent may result
in significant underestimation of the partition coefficient for particles in the size range between 10 nm and
2 mm. For most of the selected compounds, backup filters can be used to correct artifacts effectively.
However, for some compounds with very low vapor pressure, the artifacts remained or became even larger
than they were without the backup filter. Thus, the option of backup filters must be considered carefully in
field measurements of the gas/particle partitioning of SVOCs. The results of this work will allow researchers
to predict potential artifacts associated with SVOC gas/particle partitioning as functions of compounds, the
concentration of particles, the distribution of particle sizes, sampling velocity, and sampling time.
© 2015 Elsevier Ltd. All rights reserved.

* Corresponding author. Department of Civil, Architectural and Environmental

Engineering, The University of Texas at Austin, 301 E Dean Keeton St. Stop C1752 ECJ
Hall 5.436, Austin, TX 78712-1094, USA.
E-mail address: xuying@mail.utexas.edu (Y. Xu).

http://dx.doi.org/10.1016/j.atmosenv.2015.06.053
1352-2310/© 2015 Elsevier Ltd. All rights reserved.
100 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109
1. Introduction
Semivolatile organic compounds (SVOCs) are a class of chemical
compounds that typically have vapor pressure (Vp) values between
109 and 10 Pa (Weschler and Nazaroff, 2008). Many SVOCs, such as
polycyclic aromatic hydrocarbons (PAHs), polybrominated diphe-
nylethers (PBDEs), polychlorinated biphenyls (PCBs), and phtha-
lates, are persistent organic pollutants that are ubiquitous in
ambient and indoor environments. Exposure to some of the SVOCs
may result in adverse health effects, including allergic reactions
(Bornehag et al., 2004, Jaakkola and Knight, 2008), irreversible
changes in the development of the human reproductive tract
(Albert and Je
gou, 2014; Latini et al., 2006; Saillenfait et al., 2013; Su
et al., 2014 and Wolff et al., 2014), neurodevelopmental and
behavioral disorders (Le Cann et al., 2011 and Wang et al., 2015),
immunotoxicity (Birnbaum, 1994 and Van den Berg et al., 2006),
and even cancer (Bostro € m et al., 2002; Denissenko et al., 1996 and
Lewtas, 2007).
Inhalation, dermal absorption, and nondietary ingestion of
settled dust have been identified as the major exposure pathways
to SVOCs (Allen et al., 2007; Frederiksen et al., 2009; Harrad et al.,
2006; Meeker et al., 2009; Weschler and Nazaroff, 2010, 2014;
Wilson et al., 2009; Xu et al., 2009 and Xu et al., 2010). A number
of field campaigns have been conducted to measure air concen-
trations of SVOCs in indoor (Blanchard et al., 2014; Kolarik et al.,
2008; Trabue et al., 2008; Wang et al., 2014 and Xu et al., 2014)
and outdoor environments (Albinet et al., 2007; Chao et al., 2003;
He and Balasubramanian, 2010; MacLeod et al., 2007 and Xie
et al., 2014b). The fate and transport of SVOCs, as well as human
exposures to them, can be influenced significantly by gas/particle
partitioning. Particle-phase SVOCs are expected to account for a
great fraction of the air concentrations due to their low Vp, partic-
ularly for compounds with high molecular weight (Wang et al.,
2014; Weschler and Nazaroff, 2008 and Weschler et al., 2008).
Recent studies have shown that inhalation of particle-phase
phthalates is significant because such exposure is capable of
creating high local concentrations in airways at the particle depo-
sition site and potentially causing bronchial obstruction (Jaakkola
and Knight, 2008; Oie et al., 1997 and Pankow, 2001). Both the
location and the efficiency of the deposition of SVOCs in the res-
piratory tract are dependent strongly on gas/particle partitioning.
Furthermore, because the kinetics of gas-particle sorption/
desorption are sufficiently rapid (Benning et al., 2013; Odum et al.,
1994 and Weschler and Nazaroff, 2008 and Liu et al., 2013), in in-
door environments, airborne particles might be important carriers
that accelerate the transport of SVOCs from their original sources to
other indoor locations through deposition, resuspension and air
advection, although particle-phase SVOCs typically have lower
characteristic transport distances than the gas-phase in outdoor
environments. Therefore, to understand the fate and transport of
SVOCs, accurate estimations of the partition coefficients between
SVOC gases and particles are necessary (Hung et al., 2013, Melymuk
et al., 2014).
Several field measurements were conducted to determine the
gas/particle partitioning for SVOCs (Cincinelli et al., 2014; Saral
et al., 2015; Wang et al., 2014 and Xie et al., 2014a,b). In those
studies, filter-sorbent samplers were used extensively, in which air
was pulled through a filter to collect the particle-phase SVOCs and
then followed by a sorbent to collect the gas fraction. This tech-
nique has been one of the most popular methods of sampling
SVOCs over the past 40 years because of its simplicity and its ability
to sample large volumes of air (Galarneau and Bidleman, 2006,
Melymuk et al., 2014). Although measurements of the total
airborne concentrations of SVOCs usually were acceptable, sam-
pling artifacts were identified in the determination of gas/particle
partitioning (Ahrens et al., 2011, Melymuk et al., 2014). When gas-
phase molecules not being fully trapped by the sorbent, break-
through happens and results in overestimation of the particle/gas
partition coefficient. This positive bias may occur due to saturated
sorbents or desorption of compounds from sorbents and is affected
by the type and geometry of sampling medium, target compound
properties and concentrations, and sampling volume, flow rate,
temperature, and humidity (Melymuk et al., 2014). Breakthrough
has been investigated extensively in previous studies (Harper, 1993;
Peter et al., 2000; Martin et al., 2002 and Galarneau and Harner
et al., 2006). In contrast, gas-phase SVOCs may sorb strongly to
the filter, thereby increasing the mass of SVOCs on the filter. Mader
and Pankow (2000) conducted systematic experiments and found
that artifacts could be orders of magnitude for certain SVOC com-
pounds due to their adsorption on the filter (Mader and Pankow,
2000, 2001a). Arp et al. (2007) studied the equilibrium sorption
of SVOCs on fiber filters and derived linear free energy relationships
for predicting the sorption isotherms. Corrections for the gas/filter
adsorption artifacts were made by using a backup filter and sub-
tracting the mass of SVOCs found on the backup filter from the total
amount found on the front filter. However, the assumption that the
sorption of the SVOCs on the front and backup filters is equal is not
valid if the gas/filter sorption equilibrium has not been reached on
either of the filters (Mader and Pankow, 2001b). In addition, par-
ticles may pass through the filter and subsequently be captured by
the gas-phase sorbent material. However, there is limited infor-
mation on how particles are distributed within the sampler and
how the penetration contributes to uncertainty in the gas/particle
partitioning of SVOCs.
Theoretical analyses have been conducted to estimate the
sampling artifacts associated with various sampling parameters.
McDow (1999) presented a basic mass balance model to analyze
the adsorption artifacts with various sampling volumes and types
of filters. Galarneau and Bidleman (2006) used a simple mathe-
matic model to study the bias due to temperature variations over
the sampling period. Mader and Pankow (2001b) examined the
partitioning of SVOCs to two types of filters and predicted the
magnitude of the compound-dependent gas adsorption artifacts.
However, the process of air samples passing through filter-sorbent
samplers has not been fully characterized. Typically, some impor-
tant processes, such as the diffusion of gas-phase SVOCs within the
filter, the distribution of particles and particle-phase SVOCs in the
filter, and the extent of penetration of particles, have been ignored
even though they may have significant impacts on the estimation of
sampling artifacts.
The aim of this study was to analyze the sampling artifacts
associated with measurements of gas-particle partitioning of
SVOCs using filter-sorbent samplers. The specific objectives were
to: 1) develop and validate a fundamental mechanistic model to
characterize the air sampling process with filter-sorbent samplers
for SVOCs; 2) examine the potential sampling artifacts of gas/par-
ticle partitioning for a range of SVOC contaminants; and 3)
normalize the model and investigate the general factors that in-
fluence sampling artifacts and the effectiveness of backup filters.
The results of this work can be used by researchers to predict the
sampling artifacts in measurements of SVOC gas/particle parti-
tioning as a function of compounds, sampling velocity, sampling
duration, and the concentration and size distribution of particles.
2. Development of the model
Fig. 1 shows a schematic representation of the air sampling
process with filter-sorbent samplers. The air is passed through the
filter in which the particle-phase SVOCs are expected to be trapped;
in addition, gas-phase SVOCs can be captured via adsorption and
 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109 101

Fig. 1. (a) Schematic representation of a filter-sorbent sampler collecting air samples; (b) gas- and particle-phase SVOCs within the filter.

particle penetration may occur. To simplify the model, we assumed

that the air flow through the filter and the mass transfer of SVOC vCp;f
¼ kdep Cp;p (5)
molecules within the filter were one-dimensional. Because break- vt
through (i.e., loss of compounds downstream of the sampling
medium) is typically examined in sampling set-ups or checked where kdep (s1) is the deposition constant of particles in the filter.
using a framework based on early breakthrough studies (Melymuk The governing equation that describes the transient mass
et al., 2014), it is not included within the scope of the current study. transfer of SVOCs in the filter is:
Therefore, we assumed that gas-phase SVOCs and the particles that
penetrated the filter and entered the downstream air were fully vCs;g vCs;p vCs;f v2 Cs;g v2 Cs;p;p vCs;g
ε þ þ ð1  εÞ ¼ Ds þ Dp v
captured by the sorbent. In addition, re-suspension of particles vt vt vt vx 2 vx2 vx
from the filter and the drift effect of the particles in the air flow vCs;p;p
v
were ignored. Finally, we assumed an equilibrium relationship vx
between gas- and particle-phase SVOCs and ignored the internal (6)
mass transfer resistance inside particles (Liu et al., 2013).
With reference to Fig. 1, the concentration of particles in the where Cs;g (mg/m3) is the concentration of gas-phase SVOCs in the
filter is governed by the following mass balance equation in pores of the filter, Cs;p (mg/m3) is the total concentration of SVOCs in
Eulerian form: the particle phase in the filter, Cs;f (mg/m3) is the concentration of
SVOCs adsorbed on the fibers of the filter, Ds (m2/s) is the effective
diffusion coefficient of the gas-phase SVOCs in the filter, and Cs;p;p
vCp;p v2 Cp;p vCp;p vCp;f (mg/m3) is the concentration of particle-phase SVOCs in the pores of
ε ¼ Dp v  ð1  εÞ (1)
vt vx2 vx vt the filter. The related initial and boundary conditions are expressed
in Equations (7)e(9):
where Cp,p (mg/m3) is the concentration of particles in the pores of
the filter, ε is the porosity of the filter, t (s) is the time, Dp (m2/s) is Cs;g ¼ Cs;p ¼ Cs;f ¼ 0; for 0  x  L; t ¼ 0 (7)
the effective diffusion coefficient of the particles in the filter, x (m)
is the distance from the front of the filter, v (m/s) is the face velocity
across the filter, Cp,f (mg/m3) is the concentration of particles trap- Cs;g ¼ Cs;g;a ; for x ¼ 0; t > 0 (8)
ped by the fibers of the filter. The initial and inlet boundary con-
ditions are expressed in Equations (2) and (3): vCs;g
¼ 0; for x ¼ L; t > 0 (9)
vx
Cp;p ¼ 0; for 0  x  L; t ¼ 0 (2) where Cs;g;a (mg/m3) is the gas-phase concentrations of SVOCs in the
sampling air. A linear, instantaneously reversible, equilibrium
relationship was assumed to exist between the particles and the
Cp;p ¼ Cp;a ; for x ¼ 0; t > 0 (3) gas-phase SVOCs in the sampling air as well as between the filter's
fibers and the gas-phase SVOCs, or
where L (m) is the thickness of the filter, and Cp, a (mg/m3) is the
concentration of particles in the sampling air. Assuming that the h i
Cs;p ¼ Kp εCp;p þ ð1  εÞCp;f Cs;g ; Cs;p;p ¼ Kp Cp;p Cs;g ; Cs;f ¼ Kf Cs;g
outlet boundary condition of the filter obeys the zero gradient
condition (Brenner, 1962): (10)

where Kp (m3/mg) is the gas/particle partition coefficient of SVOCs,

vCp;p
¼ 0; for x ¼ L; t > 0 (4) Kf (dimensionless) is the gas/filter partition coefficient of SVOCs.
vx The fundamental mechanistic model that characterizes the air
In addition, the capture rate of particles was assumed to be sampling process for SVOCs using filter-sorbent samplers is ob-
proportional to the concentration of particles in the pore (Song and tained by combining Equations 1e10. The model can be used to
Elimelech, 1993): analyze the sampling artifacts in measurements of gas-particle
102 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109

partitioning of SVOCs and to predict temporal and spatial variations mea ), gas-phase concentration (C mea ) and particle mass concen-
(Cs;p;a s;g;a
of SVOCs in the filter. mea ):
tration (Cp;a
mea
Cs;p;a
3. Estimation of parameters and validation of model
Kpmea ¼ mea mea (11)
Cs;g;a Cp;a
The effective diffusion coefficient of particles in the filter's pores
(Dp) was estimated based on the filter's porosity (ε) (Ho and Webb, mea can be determined based on mass balance:
Cp;a
2006) and the diffusion coefficient of particles in air (Dp,a). Simi-
Z Lh i
larly, the effective diffusion coefficient of gas-phase SVOCs in the
εCp;p þ ð1  εÞCp;f dx
filter's pores (Ds) was calculated based on ε and the diffusion co- mea 0
Cp;a ¼ (12)
efficient of SVOCs in air (Da). Dp,a is related to particle size and can vts
be determined by using the StockseEinstein Equation (Kulkarni
et al., 2011). Da was estimated by OnSite (EPA, 2014) and other where ts is the sampling time. Because a certain amount of gas-
SVOC chemical properties were obtained by using EPI Suite TM. The phase mass could be measured improperly as being in the
deposition constant (kdep) was determined based on the collection particle-phase due to adsorption onto the filters, the actual
mea ) can be calcu-
efficiency of a single fiber (Sun et al., 2001). Detailed information on measured particle-phase SVOC concentration (Cs;p;a
the estimation of these parameters is presented in the Supporting lated using the following equation:
Information (SI). Z L 
Quartz fiber filters (QFFs) and Teflon membrane filters (TMFs)
εCs;g þ Cs;p þ ð1  εÞCs;f dx
are the two most commonly used filters in filter/sorbent air mea 0
Cs;p;a ¼ (13)
samplers. Mader and Pankow (2000, 2001a and 2001b) vts
measured gas adsorption onto QFFs and TMFs for various
Similarly, particle penetration may result in erroneous mea-
SVOCs, including polycyclic aromatic hydrocarbons (PAHs), pol-
surements of gas-phase concentration, or
ychlorinated dibenzofurans (PCDFs), and polychlorinated diben-
zodioxins (PCDDs). In this study, we corrected their data using Z ts  
the filter's porosity and density and then used the data to obtain Cs;g x¼L þ Cs;p x¼L dt
mea 0
the gas/filter partition coefficient (Kf) for SVOCs. Simple log- Cs;g;a ¼ (14)
ts
linear relationships were established between Kf and chemical
Vp, as shown in Figure S1 (Table and Figure numbers preceded by Therefore, the measured gas/particle partition coefficient (Kpmea )
an “S” are in the SI), and then the correlations were used to can be calculated and compared with the actual partition coeffi-
obtain Kf for other SVOCs that were not included in their mea- cient (Kp) in the model.
surements. The partition coefficients between gas- and particle- Nineteen SVOC compounds, including PAHs, PCDFs, PCDDs, and
phase SVOCs (Kp) were calculated using four different methods, phthalates, were investigated in this study. Their physical and
as described in detail in the SI, and the median values were used chemical properties are listed in Tables S1 through S3. The calcu-
in this study. lated median values of Kpmea were compared with those of the
Mader (2000) conducted experiments to examine the adsorp- presumed Kp in the model at a sampling velocity of 0.1 m/s and
tion of SVOCs by TMFs at a temperature of 25  C. Air flow with sampling time of 24 h. As shown in Fig. 3, positive bias was
constant SVOC concentrations was produced and drawn through observed for almost all target SVOCs. For certain compounds, such
two clean TMF filters, and the outlet concentrations were measured as chrysene and 1,2,4,7,8-PeCDD, the measured partition coefficient
periodically. Unfortunately, airborne particles were not included in could be several orders of magnitude greater than the presumed
the study, and the measured gas/filter partition coefficient (Kf) was value. The uncertainties associated with the data in the figure were
not reported. Therefore, we fitted their experimental data to obtain due to the different methods used to determine Kp for each SVOC
Kf and compared the fitted Kf with those in the literature, partially compound (Table S3). It was also found that the sampling artifact
validating the model. Three SVOC compounds were selected, i.e., was smaller with TMFs than QFFs, and this was because of their
chrysene, 1,3,7,8-tetrachlorodibenzofuran (1,3,7,8-TetraCDF), and smaller gas/filter partition coefficient (Table S2). Theoretically, gas/
1,2,4,7,8-pentachlorodibenzo-p-dioxin (1,2,4,7,8-PeCDD), and filter sorption artifacts will be small when the amount of SVOCs
Table 1 summarizes the parameters used in the model. Since the adsorbed on the filters is small compared to that adsorbed on the
face velocity was not provided by Mader (2000), it was estimated collected particles. To further investigate the relationship, we
based on the given general range of sampling volume flow rates. plotted the potential sampling artifact (Kpmea =Kp ) with the mass
(No information of sampling flow rate for each specific measure- ratio of SVOCs adsorbed on the filter to that on the particles
ment could be found.) As shown in Fig. 2, Kf was obtained by fitting [Kf =ðKp ,Cp;a Þ], as shown in Fig. 4. We found that the sampling ar-
the model to the experimental data of concentration ratio between tifacts can be ignored when the value of log½Kf =ðKp ,Cp;a Þ is less
the outlet and inlet SVOCs (Cout/Cin) vs. sampling volume. The two than 7, and small sampling artifacts will be achieved when the gas/
solid lines represent model fitting at the minimum and maximum filter partition coefficients (Kf) are low, the particle loading on the
sampling face velocities, respectively, and the shadow area in- filter (Cp,a) is high, and/or the sampling time is long.
dicates the possible zone into which the model's prediction may
fall. Then, the fitted Kf values were compared with those reported in 5. Normalization of the model and discussion
the literature, as shown in Table 1. The small relative deviations
partially validated the accuracy of the model. 5.1. Normalization of the model

4. Results In order to investigate the general factors that influence the

According the definition of gas/particle partition coefficient for
SVOCs (Pankow, 1994), the measured partition coefficient (Kpmea )
can be expressed by the measured particle-phase concentration
sampling artifacts, it is helpful to nondimensionalize the model.
First, dimensionless variables and parameters were defined,
including dimensionless linear distance (X * ; X * ¼ x=L), time (T * ;
T * ¼ t=L=v), concentration of particles in the filter's pores (Cp;p
* ;
 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109 103

Table 1
Model parameters for SVOC adsorption to TMFs.

Compounds Chrysene 1,3,7,8-TetraCDF 1,2,4,7,8-PeCDD

Ds (106 m2/s)a 1.85 1.98 1.84

L (mm)b 0.152  2
Sampling flow rate (L/min)c 11e77
Filter cross-sectional area (cm2)c 77
Porosity (ε)d 0.50
Log (Kp,face) (at 20  C) (m3/cm2) 0.61e 0.53f 0.04e
Log(Kf) (at 25 ºC)g 7.70 7.69 8.25
Fitted log(Kf) (at 25 ºC)h 7.85 ~ 7.90 7.90 ~ 7.95 8.00 ~ 8.11
a
See Table S2.
b
There were two TMFs in the experiments (Mader, 2000).
c
Mader, 2000.
d
See Table S4.
e
See Tables 2 and 3 in Mader and Pankow, 2001a.
f
Obtained by the equation listed in Table 1 in Mader and Pankow, 2000.
g
Kp,face in Mader and Pankow 92001a) was converted to Kf, using Kf ¼ Kp,face/L/(1-ε). The values of Kf at 20  C were then corrected to a temperature of 25  C using the
equation listed in Table 1 in Mader and Pankow, 2000.
h
The minimum and maximum values correspond to the sampling flow rates of 11 and 77 L/min, respectively.

* ¼C
Cp;p p;p =Cp;a ), concentration of particles captured by the filter's
* ; C * ¼ C =C ), gas-phase SVOC concentration (C * ; *
vCp;f
fibers (Cp;f p;f p;a
¼ k* Cp;p
*
p;f s;g
* ¼ C =C
Cs;g (19)
s;g s;g;a ), particle-phase SVOC concentration vT *
* ;C * ¼ C =C * *
(Cs;p s;p s;p s;g;a Cs;p;p ; Cs;p;p ¼ Cs;p;p =Cs;g;a ), effective diffusion
coefficient for particles in filter pores (D*p ; D*p ¼ Dp =Lv ), deposition
constant (k* ; k* ¼ kdep L=v), effective diffusion coefficient of SVOCs
in the filter's pores (D*s ; D*s ¼ Ds =Lv), and gas/particle partition co-
efficient (Kp* ¼ Kp Cp;a ). Then, these variables and parameters were
substituted into Equations 1e10 to obtain the following dimen-
sionless equations:

* * * *
vCp;f
vCp;p v2 Cp;p vCp;p
ε ¼ D*p   ð1  εÞ (15)
vT * vX *2 vX * vT *

*
Cp;p ¼ 0; for 0  X *  1; T * ¼ 0 (16)

*
Cp;p ¼ 1; for X * ¼ 0; T * > 0 (17)

*
vCp;p
¼ 0 for X * ¼ 1; T * > 0 (18)
vX *

Fig. 2. Comparison of fitted SVOC concentration ratio between outlet and inlet (Cout/ Fig. 3. Comparison of the measured gas/particle partition coefficient Kpmea and the
Cin) with data measured by Mader (2000). presumed value (Kp): (a) QFFs; (b) TMFs.
104 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109

Z 1 h i Z 1 h i
* * *
Cs;g εCp;p þð1εÞCp;f dX * *
Cs;g *
εCp;p *
þð1εÞCp;f dX *
f2 ¼ 0Z 1 h i z 0
* * *
hf Ts*
εCp;p þð1εÞCp;f dX
0
(27)
Z Ts*
* 

Cs;g X * ¼1
dT *
0
f3 ¼ (28)
Ts*
These scales are in the range between 0 and 1, and the smaller
the value, the more non-uniform the distribution is in the filter; and
when the value is equal to 1, a uniform distribution of the gas-phase
SVOCs in the filter's pores will be achieved. The normalized model
suggests that several factors may have strong impacts on Kp*mea and
the air sampling artifacts, and these factors are discussed in the
following sections.

5.2. Sampling time and velocity

Fig. 4. Logarithmic relationship between potential sampling artifact (Kpmea =Kp ) and the
mass ratio of SVOCs adsorbed on the filter to that on the particles [Kf =ðKp ,Cp;a Þ].
When sampling SVOCs with filter/sorbent samplers, the mass
* ) reaches steady
concentration of particles in the filter's pores (Cp;p
state quickly and distributes non-uniformly within the filter
(Figures S2 and S3). However, the concentration of particles on the
* * *
vCs;f * * * * * ) increases continuously as more particles are
vCs;g vCs;p v2 Cs;g v2 Cs;p;p vCs;g vCs;p;p filter's fibers (Cp;f
ε þ þ ð1  εÞ ¼ D*s þ D*p   captured during air sampling. Meanwhile, gas-phase SVOCs diffuse
vT * vT * vT * vX *2 vX *2 vX * vX *
(20) within the filter and sorb strongly to the filter's fibers. As a result,
the adsorptive partition relationship of SVOCs between the gas,
particle, and filter phases was re-established. Similar to particles,
gas-phase SVOC concentrations (Cs;g * ) have a non-uniform distri-
* * *
Cs;g ¼ Cs;p ¼ Cs;f ¼ 0; for 0  X *  1; T * ¼ 0 (21)
bution within the filter, which decreases along the filter depth and
changes with time. Fig. 5 shows an example of the distribution of
*
the gas-phase concentration of 1,2,4,7,8-PeCDD along the filter as a
Cs;g ¼ 1; for X * ¼ 0; T * > 0 (22) function of time. Thus, the gas-phase SVOC concentrations
measured by the downstream sorbent are typically lower than the
actual concentrations in the upstream air until the filter is saturated
*
vCs;g * distributes uniformly
with SVOCs. After the filter is saturated, Cs;g
¼ 0; for X * ¼ 1; T * > 0 (23) within the filter and does not change with time, i.e., it reaches
vX *
steady state. Therefore, the longer the non-steady state lasts in
h i comparison to sampling time, the greater the difference will be
*
Cs;p ¼ Kp* εCp;p
* *
þ ð1  εÞCp;f *
Cs;g *
; Cs;p;p ¼ Kp* Cp;p
* *
Cs;g *
; Cs;f between the measured and actual gas-phase SVOC concentrations.
Assume the criterion to identify steady state for the gas phase is
*
¼ Kf Cs;g
(24)
The dimensionless forms of measured gas- and particle-phase
SVOC concentrations, as well as the mass concentrations of parti-
cles, can be expressed as shown in Equations (S7) e (S9) in the SI.
Therefore, the measured dimensionless gas/particle partition co-
efficient can be obtained:

εf1 þ Kp* f2 hf Ts* þ ð1  εÞKf f1

Kp*mea ¼ h   i (25)
f3 1 þ 1  hf Kp* Ts* hf

where hf is the filter's collection efficiency, and f1 , f2 , and f3 are

the defined non-uniform scales that were expressed in Equation
26e28, respectively:

Z1
*
f1 ¼ Cs;g dX * (26)
0
* )
Fig. 5. Distribution of dimensionless gas-phase concentration of 1,2,4,7,8-PeCDD (Cs;g
within QFF at different dimensionless sampling time (Ts* ).
 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109 105

that the concentration of the gas-phase SVOC downstream of the

filter is no less than 99.9% of the incoming air flow. We calculated
the time for the gas-phase concentration of selected compounds to
reach steady state. Fig. 6 shows that correlations were obtained
between the dimensionless time for Cs;g * to reach steady state (T * )
s;s
and chemical Vp for both QFFs and TMFs. In addition, Ts;s * may also

be influenced by the sampling velocity (v), but we found that this

impact was small when v is was greater than 0.1 m/s (Figure S4),
which is typical for high-volume air sampling (EPA, 1999). The main
reason is that the diffusion terms in Equation (6) become negligible
in comparison to the advection terms when v is large, resulting in a
shorter time to reach steady state (t); the increase of v counters the
decrease of t and makes Ts;s * relatively constant. Therefore, the

correlations identified in Fig. 6 can be used to estimate the

appropriate sampling time in measurements of gas-particle parti-
tioning of SVOCs. For example, at a sampling velocity of 0.1 m/s, for
an SVOC compound with a Vp of approximately less than 104 Pa
using a QFF or with a Vp less than 106 with a TMF, steady state may
not be reached (i.e., sampling bias may be developed) if the sam-
pling time is less than 24 h.
Sampling volume (or sampling volume flow rate) has been the
focus when investigating the sampling bias in the gas/particle
partitioning of SVOCs (Mader and Pankow, 2001b). However, we
found that sampling velocity may be more important, because it is
the parameter that determines the dimensionless diffusivities of
particles and SVOCs, particle deposition velocity, and dimension-
less sampling time. Therefore, we calculated the potential error
between the measured and actual gas/particle partition coefficients
of SVOCs (relative bias ¼ ðKp*mea  Kp* Þ=Kp* , %) as a function of sam-
pling velocity and time, as shown in Fig. 7. For example, for one
SVOC compound with a particular Vp, sampling time, and sampling
velocity, the relative bias in measuring gas/particle partitioning can
be determined from Fig. 7. The results can be used to identify
sampling artifacts for a range of combinations of sampling times,
velocities, and filter thicknesses used in field measurements and to
develop appropriate protocols in measurements of gas-particle
partitioning of SVOCs using filter-sorbent samplers.

5.3. Particle penetration

Particles may pass through the filter and subsequently be Fig. 7. Relative bias between measured and actual gas/particle partition coefficients for
trapped by the gas-phase sorbent material, which would result in compounds with different chemical vapor pressures and with a range of combinations
of sampling times, velocities, and filter thicknesses: (a) QFFs and (b) TMFs.

sampling bias. Typical QFFs and TMFs have a collection efficiency of

* to reach steady state (T * )
Fig. 6. Correlations between the dimensionless time for Cs;g
and chemical vapor pressure (Vp).
99%, but they do not often have a specified cutoff for fine particles
(Melymuk et al., 2014). Researchers have found that ultrafine par-
ticles (typically < 100 nm) can penetrate the filter (Kim et al., 2007;
Lee and Nicholson, 1994 and Melymuk et al., 2014). There is very
limited information on how particles are distributed within the
sampler, and this may contribute to uncertainty in the measure-
ments of gas/particle partitioning.
With particle penetration, the concentration of particles in the
filter's pores (C*p,p) normally can reach steady state within a short
period of time (Figures S2 and S3). Therefore, the distribution of
C*p,p within the filter and the filter's collection efficiency (hf) are
relatively stable during the sampling process. Since the dimen-
sionless diffusion coefficient for particles (D*p) is much smaller than
1, the distribution of the steady state concentration of C*p,p in the
filter can be obtained by solving Equations 15e19 with ignorance of
the diffusion and unsteady terms, or:
   
s;s
Cp* X * ¼ exp  ð1  εÞk* X * (29)
106 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109

We assumed that the criterion used to identify particle pene-
tration was that more than 1% of the incoming particles pass
through the filter and reach the sorbent. Thus, penetration occurs
when k* is smaller than 4.6/(1-ε). Both k* and filter collection effi-
ciency (hf) depend strongly on particle sizes and can be calculated
(Kulkarni et al., 2011), as listed in Table S1 in the SI.
To investigate the influence of particle penetration on the
sampling artifacts, we ignored the adsorption of SVOCs onto the
filter's fibers as well as the non-uniform distribution of gas-phase
SVOCs in the filter. Therefore, the measured gas/particle partition
coefficient can be expressed as:
1 þ Kp*
hf Ts K*
Kp*mea ¼   z  p 
1 þ 1  hf Kp* 1 þ 1  hf Kp*
The ratio between Kp*mea and Kp* were plotted as a function of
particle size in Fig. 8. As expected, penetration may result in
negative sampling bias on the gas/particle partition coefficient,
because the particle-phase SVOCs are captured by the downstream
gas-phase sorbent. Particles with different sizes can cause different
degrees of sampling artifacts. For instance, there is no obvious
sampling bias for particles with sizes larger than 2 mm or smaller
than 10 nm because particles in this size range are collected very
efficiently by the filter. In contrast, significant underestimation of
the partition coefficient could occur for particles in the size range
between 10 nm and 2 mm. For some SVOC compounds with low
vapor pressure (i.e., high Kp) and/or high particle concentration (i.e.,
Cp,a), the underestimation can reach as much as two orders of
magnitude. Particles <2.5 mm in size (PM2.5) represent more than
75% of the total suspended particles by mass, and they are most
relevant for human health and risk assessment estimates (Englert,
2004, Melymuk et al., 2014). Considering that the majority of SVOCs
(80%) are typically found in particles at this size fraction
(Degrendele et al., 2014, Okonski et al., 2014), sampling artifacts
due to particle penetration in measurements of gas-particle parti-
tioning for certain SVOCs cannot be ignored.
5.4. The effect of backup filters
Air sampling with filter/sorbent samplers is sometimes
conducted using a backup filter to correct the adsorption of SVOCs
to the front filter (Mader and Pankow, 2001). Assume that the
amount of SVOCs sorbed on the front and backup filters have
reached equilibrium with the SVOCs in the incoming sampling air.
Corrections for the gas/filter adsorption artifact can be made by
subtracting the mass of SVOCs on the backup filter from the total
mass of SVOCs found on the front filter (particle phase þ sorbed on
filter). However, this method will be appropriate only if both filters
have reached equilibrium with the gas-phase SVOCs in the
incoming sampling air.
A backup filter was added in the dimensionless model, with the
concentrations of SVOCs and particles at the inlet of the backup
filter being equal to those of the outlet of the front filter. The gov-
(30) erning equation and the initial and other boundary conditions were
set the same for both filters. Then, in Fig. 9, we plotted the potential
sampling artifact Kp*mea =Kp* with and without backup filter correc-
tions for the selected SVOC compounds for sampling times of 10
and 72 h, respectively. As expected, the sampling artifacts with
QFFs were mostly larger than those with TMFs due to their larger
gas/filter partition coefficient; and an increase in the sampling time
reduced the artifacts because the gas-phase concentration gradient
decreased within the filter. For most of the selected compounds,
backup filters can be used to correct artifacts efficiently (sampling
time < 10 h) and effectively (log (Kp*mea =Kp* ) ¼ 0). However, for some
compounds with very low vapor pressures, such as chrysene
(compound number ¼ 4) and 1,2,4,7,8-PeCDD (compound
number ¼ 13), the artifacts remained or became even larger than
they were without the backup filter. The main reason for this
occurrence was that the gas/particle partition coefficient (Kp) is
related to both particle-phase concentration of SVOCs (Cs,p) and the
concentration of the gas phase (Cs,g). When the filters were not
saturated (i.e., non-steady state), subtracting the mass amount of
SVOCs on the backup filter from the mass on the front filter helped
to reduce the bias in the measured particle-phase concentration
(Cs,p) to some extent. However, the great concentration gradients
within the two filters made the gas-phase concentration (Cs,g)
measured by the downstream sorbent significantly lower than re-
ality. When the effect on Cs,g was stronger than the correction of
Cs,p, the artifact was increased by using backup filters, as shown in
the case of 1,2,4,7,8-PeCDD in Fig. 9. Therefore, the option of backup

Fig. 8. Potential sampling artifacts (Kp*mea =Kp* ) caused by particle penetration as a function of particle size: (a) QFFs; (b) TMFs.
 X. Wang et al. / Atmospheric Environment 117 (2015) 99e109
Fig. 9. Comparison of potential sampling artifact with and without backup filter corrections: (a) QFFs; (b) TMFs.
filters must be considered carefully when conducting field mea-
surements of the gas/particle partitioning of SVOCs.
6. Conclusions
A fundamental mechanistic model to characterize the air sam-
pling process with filter-sorbent samplers for SVOCs was developed
and partially validated. The potential sampling artifacts associated
with measurements of gas-particle partitioning were examined for
19 SVOC compounds. Positive sampling bias (i.e., overestimation of
gas/particle partition coefficients) was observed for almost all the
SVOCs. For certain compounds, the measured partition coefficient
was several orders of magnitude greater than the presumed value.
It was found that the sampling artifacts can be ignored when the
value of log½Kf =ðKp ,Cp;a Þ is less than 7, and small sampling artifacts
will be achieved when the gas/filter partition coefficients (Kf) are
low, the particle loading on the filter (Cp,a) is high, and/or the
sampling time is long.
We normalized the model and investigated the general factors
that influence the sampling artifacts. Correlations were obtained
between the dimensionless time required for the gas-phase SVOCs
within the filter to reach steady state (Ts;s * ) and the chemical V
p
values, which can be used to estimate appropriate sampling time.
The potential errors between measured and actual gas/particle
partition coefficients of SVOCs as a function of sampling velocity
and time were calculated and plotted for a range of SVOCs (vapor
pressures: 108 ~ 103 Pa). These plots were useful in identifying
sampling bias in previously-completed field measurements. Parti-
cle penetration may result in underestimation of the partition co-
efficient for particles in the size range between 10 nm and 2 mm;
this underestimation can be about two orders of magnitude,
especially for some SVOCs compounds with low vapor pressure
(i.e., high Kp) and/or high particle concentration (i.e., Cp,a). For most
of the selected compounds, backup filters can be used to correct
107
artifacts efficiently and effectively; however, for some compounds
with very low vapor pressures, such as chrysene and 1,2,4,7,8-
PeCDD, the artifacts remained or became even larger than they
were without the backup filter. Therefore, the option of backup
filters must be considered carefully in field measurements of the
gas/particle partitioning of SVOCs.
The results of this work will allow researchers to predict the
potential artifacts associated with SVOC gas/particle as functions of
the compounds involved, the concentrations of particles, the dis-
tribution of particle sizes, sampling velocity, and sampling time. It
will also help researchers develop appropriate protocols for the
measurement of gas-particle partitioning of SVOCs using filter-
sorbent samplers.
Acknowledgments
Financial support was provided by the National Science Foun-
dation (NSF) of United States (CBET-1150713 and CBET- 1066642),
American Society of Heating, Refrigerating and Air Conditioning
Engineers (ASHRAE) (Grant-In-Aid and NIA Awards), the National
Natural Science Foundation of China (No. 51206134), and the
Fundamental Research Funds for the Central Universities of China
(2015GIHZ14).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.atmosenv.2015.06.053.
Nomenclature
Cp,a concentration of particles in the sampling air (mg/m3)
Cp,f concentration of particles trapped by the fiber of the filter
(mg/m3)
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