Environ. Sci. Technol.

2003, 37, 1300-1305

Air-Soil Exchange of
Organochlorine Pesticides in
Agricultural Soils. 2. Laboratory
Measurements of the Soil-Air
Partition Coefficient
S . N . M E I J E R , , M . S H O E I B ,
K . C . J O N E S , A N D T . H A R N E R * ,
Meteorological Service of Canada, Environment Canada,
4905 Dufferin Street, Toronto, Ontario M3H 5T4, Canada,
and Environmental Science Department, Institute of
Environmental and Natural Sciences, Lancaster University,
Lancaster, LA1 4YQ, U.K.

This is the second of two papers that investigate soil-air

exchange of organochlorine (OC) pesticides. In the
present paper, a fugacity meter was used to measure soilair partition coefficients (KSA) under controlled laboratory
conditions for OC pesticides in three different soils as
a function of temperature and soil organic carbon content.
A strong temperature dependence of KSA was observed
for all three soils. A linear relationship between KSA and the
octanol-air partition coefficient (KOA) was observed for
all soils. The enthalpy of soil-air exchange (HSA) was
calculated and shown to be slightly greater than the enthalpy
of octanol-air exchange or the enthalpy of vaporization,
possibly because of interactions between the pesticides and
the organic matter in the soil. HSA values were very
similar for all soils, irrespective of organic matter content/
type. An expression for predicting KSA values on the
basis of KOA, fraction of organic carbon, and soil density
(Karickhoff relationship) was tested against the chamber
measurements and found to produce consistent values of
KSA. A small offset was observed between field-derived
values of QSA (soil-air quotient, an approximation of KSA)
and chamber-derived values of KSA. This was attributed
to several factors including possible incomplete equilibrium
during the field measurements and fluctuation of
meteorological parameters that govern soil-air exchange.
Ultimately, the findings of this work and the previous
field study of soil-air exchange indicate that the Karickhoff
relationship is useful and valid from a modeling standpoint
where it is necessary to compromise accuracy in
exchange for simple relationships that utilize readily
available input data.

Introduction
Because of their persistent and hydrophobic properties,
organochlorine (OC) pesticides can still be present in
* Corresponding author phone: (416)739-4837; fax: (416)739-5708;
e-mail: tom.harner@ec.gc.ca.
Environment Canada.
Present address: Environmental Science Dept., Institute of
Evironmental and Natural Sciences, Lancaster University, Lancaster,
LA1 4YQ, U.K.
Lancaster University.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 7, 2003

previously treated agricultural soils many decades after their

use has been discontinued. As a result of this large reservoir
of OC pesticides, soil-air exchange will be an important
process affecting the fate and transport of these chemicals.
Recently, an air-soil exchange model that was used to assess
the regional fate of pesticides in the U.S. Corn Belt (1)
identified the soil-air partition coefficient (KSA) as the most
important model parameter. KSA describes the equilibrium
partitioning of a chemical between air and soil and is defined
as

KSA ) CSFS/CA

(1)

where CS is the soil concentration (pg g-1 dw), CA is the air

concentration (pg L-1), and FS is the density of the soil solids
(g L-1). Note that alternate units may be used as long as they
are consistent and result in a dimensionless KSA.
KSA is dependent on temperature and humidity and the
properties of both the chemical and the soil. For example,
Hippelein and McLachlan found that the KSA for a sandy
loam soil increased with decreasing temperature and decreasing soil moisture (2, 3). However, as long as the relative
humidity (RH) of the soil was 100%, the soil moisture content
did not significantly influence KSA (2). Other authors have
also found that, in soil, sorption of pesticides is greatly affected
by soil water content (4, 5), with increased sorption observed
at lower soil water contents (5). It is generally believed that
hydrophobic chemicals such as OC pesticides and other
persistent organic pollutants (POPs) accumulate mainly in
the organic carbon fraction of the soil (6-9). Several studies
have investigated the influence of organic carbon on the
sorption of hydrophobic chemicals to different soils and
sediments in aqueous solutions (6-12). Some of these studies
have found that organic matter type as well as content
influence the sorption process (7, 11, 13). However, very few
studies have measured partitioning between air and soil and
investigated the controlling processes/variables. Hippelein
and McLachlan (3, 14) measured KSA values for PCBs, PAHs,
and chlorobenzenes in a fugacity meter for a sandy loam
soil. A similar system has been used to measure sedimentair partition coefficients for a range of PAHs (15, 16). Hippelein
and McLachlan formulated an empirical relationship based
on previous work by Karickoff (6) that relates KSA to KOA and
the organic carbon fraction of the soil. The expression takes
the form

KSA ) 0.411FSOCKOA

(2)

where OC is the fraction of organic carbon on a dry soil basis

and FS is the density of the soil solids (kg L-1). This is useful
for modeling purposes as KSA is soil-specific, whereas KOA is
universal and may be directly measured for compounds of
interest.
This is the second of two papers that investigate soil-air
exchange of OC pesticides. In the first paper, results were
presented from a field study that investigated agricultural
soils as sources of OC pesticides to the atmosphere (17). A
novel device was used to derive in situ soil-air quotients
(QSA) that were considered an approximation of the true
partition coefficient (KSA). In the present paper, we investigate
KSA in more detail for OC pesticides and show how this
property varies with temperature and soil type. Measurements were conducted using a fugacity meter similar to one
described by others (3, 14, 18). Three test soils of different
type were taken from agricultural fields with past usage of
OC pesticides. For two of these soils, in situ QSA values are
10.1021/es020541j CCC: $25.00

2003 American Chemical Society

Published on Web 02/21/2003

FIGURE 1. Schematic of chamber setup.

presented in ref 17. The present study aims to address the
following issues: (i) determining if there is consistency
between in situ measurements of QSA and lab-based measurements of KSA; (ii) validating the KOA parametrization of
the Karickhoff model for different soil types; (iii) investigating
the temperature dependence of KSA and whether this is
consistent between different types of soil. These issues are
unique to this study and have not been tested in previous
investigations of the soil-air partition coefficient for semivolatile organic chemicals (3, 14, 18). An important difference
between these measurements and most chamber experiments is that here naturally aged soils are used (i.e.,
compounds are not spiked into the soil). Even though some
chamber studies with spiked soils have found no aging effect
(2, 18), it is generally known that a portion of the chemical
becomes more strongly bound to the soil with time, resulting
in slower desorption of that fraction of the chemical (1921).

Materials and Methods

Chamber Setup and Experimental Design. The chamber
consists of two compartments, a lower compartment filled
with ultrapure water and the upper compartment containing
the soil. Ultrapure nitrogen is bubbled through the water of
the lower compartment to obtain 100% RH before passing
through the soil, which rests on a frit in the upper compartment. Pesticides will partition from soil to air depending on
temperature and KSA for the particular soil. These gas-phase
compounds are collected on a C-18 bonded silica (IST Ltd.,
Mid Glamorgan, U.K.) trap, which is extracted and analyzed.
The temperature of the chamber is controlled with a water
mantle, which is built around the two compartments of the
chamber (see Figure 1). Measurements were made at several
temperatures ranging from 5 to 54 C. At the beginning and
end of each measurement, the temperature was measured
in the soil and above the soil using a digital hygrometer
(accuracy: RH (1.5%, temperature (0.2 C; VWR Canlab,
Mississauga, ON, Canada). The RH of the air was measured
above the soil. The chamber typically contained 200-400 g
of soil (wet weight), which corresponds to a height of the soil
column of 7-9 cm (the diameter of the column is 7.5 cm, see
Figure 1). The N2 flow was measured regularly with a bubble
flow meter. The flow rate was generally set between 0.1 and
1 L/min, resulting in a residence time of approximately 6-70
s. A subsample of the soil was collected and analyzed at the
beginning of the experiment. On the basis of this soil

concentration and the air concentration (which is calculated

from the temperature-corrected air volume and the amount
of pesticide in the C-18 trap), the KSA can be calculated using
eq 1. A subsample of the soil was also analyzed at the end
of the experiment in order to perform a mass balance for
each pesticide.
The three different soils deployed in the chamber were
selected to give a range of densities and organic carbon
contents. (The soil properties were measured as described
in ref 17.)
(i) Hawaiian soil. This is a volcanic soil with low organic
carbon content (mass fraction of the dry soil, 0.017), dry soil
solids density of 2.14 kg L-1, and a water content of 16% by
mass.
(ii) Muck soil. This is a black peaty soil from the Holland
Marsh area, north of Toronto, ON, Canada, with high organic
carbon content (mass fraction of the dry soil, 0.44), high
water content (72% by mass), and a low dry soil solids density
(1.53 kg L-1).
(iii) Soybean soil. This is a typical agricultural soil with
low organic carbon content (mass fraction of the dry soil,
0.018) taken from a soybean field in the Tobacco Belt region
(southwest Ontario, Canada). This soil had a high soil solids
density (2.54 kg L-1) and a water content of 20% by mass.
The soils were mixed, and stones and roots were removed
before the soil was put in the chamber. No changes were
made to the water content, particle size, or pesticide levels
of the soil.
Sample Extraction and Analysis. Gas-phase compounds
collected on the C-18 trap were extracted/collected by first
spiking with a deuterated recovery surrogate containing
R-HCH-d6 and p,p-DDT-d8 and extracting immediately with
10-15 mL of a 50:50 mixture of hexane/dichloromethane
(DCM). The extracts were cleaned on a 1-g alumina column
as described in ref 17 and analyzed on a Hewlett-Packard
GC-ECD (60 m DB5 column from J&W Scientific, 0.25 mm
i.d., 0.25 m film thickness) operated with hydrogen carrier
gas at 50 cm s-1. The temperature program was 90 C for 0.5
min, 15 C min-1 to 160 C, 2 C min-1 to 260 C, held for
6 min. Injector and detector temperatures were at 250 and
300 C, respectively.
The soils were dried with Na2SO4, spiked with the
deuterated recovery spike, and extracted in a Soxhlet
apparatus for 20 h using DCM. The soil extracts were reduced
in a rotary evaporator under vacuum to 5 mL and
subsequently cleaned and analyzed as described in ref 17.
The following OC pesticides were screened for in the
samples (in elution order): R-HCH, HCB, -HCH, -HCH,
heptachlor (HEPT), aldrin, heptachlor epoxide (HEPX), transchlordane (TC), o,p-DDE, cis-chlordane (CC), trans-nonachlor (TN), dieldrin, p,p-DDE, o,p-DDD, endrin, p,p-DDD,
o,p-DDT, and p,p-DDT. The water content and organic
carbon content of the soils and the density of the soil solids
were determined as described in ref 17.
QA/QC. Blanks were routinely included with the trap
extracts and the soil samples. The only compounds detected
in the blanks were dieldrin, p,p-DDE, and p,p-DDT. Results
were blank corrected, and the limit of detection (LOD) was
calculated as 3 times the standard deviation (SD) of the mean
blank. Results that were below LOD were not included in the
KSA calculations. The reproducibility of the soil extraction
was tested previously for individual compounds (17), and
triplicate analysis showed a relative standard deviation (RSD)
ranging from 1.4% to 16.5% for the soybean soil and from
0.9% to 12.4% for the muck soil for the different compounds.
Method recoveries were tested by spiking a solution
containing all OC pesticides into a blank trap (n ) 3). Average
recovery after blank subtraction was 86% ranging from 67%
to 106%. This excludes the results for p,p-DDT for which the
recoveries were very inconsistent because of the large mean
VOL. 37, NO. 7, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

1301

FIGURE 2. Air concentration (pg L-1) as a function of flow rate (L

min-1) for muck (a) and soybean (b).
blank value and the large difference between the various
blanks. However, the p,p-DDT-d8 recoveries were always
within the acceptable range.
In addition to these recovery tests, recoveries were
routinely monitored in every sample using deuterated
surrogates (R-HCH-d6 and p,p-DDT-d8) that were chromatographically resolved from their unlabeled analogues.
The average recovery was 89% (SD 18%) for R-HCH-d6 and
102% (SD 13%) for p,p-DDT-d8.
Throughout the experiments, the measured temperature
both in the soil and above the soil was always within 0.5 C
of the set temperature. The RH was always 100%. The flow
rate showed a maximum variation of 15% (RSD) within one
measurement.
A mass balance was performed on the chamber soil by
sampling before and after a set of measurements. For most
compounds the percent difference fell within 25%. Such a
difference can be attributed to analytical error, indicating
that loss of compound over the time period of the experiment
was not significant. This is consistent with the relatively small
amount of chemical sampled in the air (between 1 and 300
ng) as compared to the total burden in the soil column
(between 100 ng and 1 mg).

Results
Test of Equilibrium. Equation 1 which is used to calculate
KSA requires that the soil-air system be at equilibrium. To
verify this, measurements at 25 C were performed at different
flow rates for the muck soil and the soybean soil. Disequilibrium in the soil-air system is indicated when an increase
in airflow rate (reduction of the residence time for air in the
soil column) results in a decrease in air concentration. Figure
2 shows constant air concentrations for a wide range of flow
rates (0.1 to 0.7 L min-1) for (a) muck soil and (b) soybean
soil at 25 C for a selection of compounds. These results
confirm that equilibrium is established for the flow rates
used in the chamber determinations of KSA.
When dealing with equilibrium partitioning in soils, the
following issues are of concern. Many studies have found
that the desorption of organic contaminants from soils
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 7, 2003

involves a rapidly desorbing fraction and a slowly desorbing

fraction that is more strongly bound to the soil matrix (2123). It is important to consider how these fast and slow
fractions relate to air-soil exchange and equilibrium partitioning (21, 24). Cornelissen et al. (20) formulated the
following relationship to describe desorption of the fast
fraction: K(rap) ) K(overall) F(rap), where K(rap) is the
partition coefficient of the rapidly desorbing fraction, K(overall) is the true equilibrium partition coefficient in a static
system that is allowed to achieve equilibrium over very long
time scales (e.g., years), and F(rap) is the fraction of the
chemical in the soil that is rapidly desorbing. The time scales
for the rapidly desorbing fraction are thought to be on the
order of hours, whereas for the slow desorbing fraction they
are on the order of days to months or years (21, 22). Therefore
in the present study, strictly speaking, we are measuring KSA(rap), and if we allowed the air to come to complete static
equilibrium with the soil over a much longer time scale than
achievable in the present experiment, a higher equilibrium
air concentration would be established. This would represent
a combination of fast desorbing and slow desorbing chemical.
However, the fast desorbing fraction is likely to be more
representative of the chemical that is actively involved in
soil-air exchange in the environment. One potential complication is knowing the size of F(rap) because of the
uncertainty about the relative sizes of the fast and slow
desorbing fractions. This issue is further complicated by the
methods used to determine soil residues (i.e., the solvents
used might extract some of the more tightly bound chemical).
However, the high soil concentrations and soil-air partition
coefficients of the OC pesticides we are dealing with in this
study ensure that a small amount of soil will be able to supply
a large volume of air. For instance, the amount of chemical
collected in a typical air sample is equivalent to the residue
of only a few grams of soil, thus ensuring that depletion of
the fast fraction will be negligible over the time scale of the
KSA measurements and the slow fraction will not be involved.
Breakthrough Test. To check that all compounds were
trapped on the C-18 trap and no breakthrough occurred, a
backup trap was used on several occasions (various temperatures/soil types). No breakthrough was observed except
on one occasion where a breakthrough of about 20% occurred
for HCB (the most volatile of the compounds studied here)
from the muck soil at 30 C. However, a duplicate measurement at this temperature showed no breakthrough.
Temperature Dependence of KSA. Log KSA was regressed
against reciprocal absolute temperature for all detected
compounds in the three soils. Slopes (A) and intercepts (B)
for the relationship log KSA ) A/T + B are given in Table 1.
Figure 3 provides an example of the output, showing a plot
of log KSA versus 1/T for a selection of OC pesticides in the
Hawaiian soil. Most correlations are very good, with r 2 >
0.99. Poor regressions (r 2 < 0.8) were encountered for three
compounds and are attributed to interferences during the
ECD analysis. These results will not be used. Similarly, results
for p,p-DDT were omitted because of high and variable
blanks influencing the reliability of the results. The data
omitted from the analysis are highlighted in bold in Table
1. Using the slope and intercept, log KSA was calculated at 25
C for all detected compounds in the three soils. Log vapor
pressures (PL) and log octanol-air partition coefficients (KOA)
are also shown at 25 C.
Temperature slopes (A) in Figure 3 are related to the
enthalpy of phase change for soil-air transfer, HSA (J mol-1),
where HSA ) 2.303AR, with R being the ideal gas constant.
This enthalpy term represents the amount of energy that is
associated with the phase transfer of a chemical from the
soil to the air. Strictly, the term +RT should be added to
correct for the fact that KSA is calculated on a volume basis
instead of a molar basis. However, this is a minor correction

TABLE 1. Temperature Dependence of KSA for Three Soils (log KSA ) A/T + B)a
Hawaii
log Ksa
R-HCH
HCB
-HCH
-HCH
HEPT
aldrin
HEPX
TC
o,p-DDE
CC
TN
dieldrin
p,p-DDE
o,p-DDD
endrin
p,p-DDD
o,p-DDT
p,p-DDT

soybean

r2

log KSA
at 25 C

4474

-9.33

0.997

5.68

4276

-7.70

0.995

6.65

4832
4960
5102
5082
5083

-9.79
-9.77
-10.23
-10.22
-10.29

0.999
0.999
0.998
0.999
0.999

6.42
6.87
6.89
6.83
6.76

5313

-10.94

0.998

6.89

3980

3821

-5.91

-7.07

at 25 C

muck
log KSA
at 25 C

r2

0.979

r2

log KSA
at 25 C

4032

-7.18

0.996

6.35

6.28

5299
5042
4861
5069
5018
5639
5713

-11.02
-10.36
-9.74
-10.45
-10.12
-12.25
-11.74

0.993
0.999
1.000
0.993
0.992
0.995
0.993

6.76
6.56
6.58
6.56
6.71
6.68
7.43

4317
5661

-6.99
-11.64

0.993
0.998

7.49
7.36

0.908

3334

-4.62

0.801

1858
5610
1191
5865
5078
5507
6109
5038
5565
5484
2913

0.58
-11.30
2.98
-12.36
-9.30
-10.51
-12.03
-8.99
-9.86
-10.13
-1.32

0.654
0.996
0.366
0.993
0.993
0.997
0.994
0.992
0.991
0.995
0.925

log
KOAb

-log
PL c

7.61
7.38
8.88
7.85
7.64
8.08

0.66
0.91

8.87

2.19

8.92
9.29
8.90
9.68

2.34
2.43
2.00
2.49

8.14
10.10
9.45
9.82

3.02
2.75
3.31

1.20
1.53
1.13

7.53
7.32
7.74
7.97
8.47
7.92
8.82
8.27

Log KSA for each soil at 25 C and log KOA and -log PL at 25 C are also given. Boldface numbers have a correlation <0.99 and are not used
in further calculations/correlations. Initial oil concentrations for the soybean and muck soils are given in ref 17. The concentrations (ng g-1) in the
Hawaii soil were as follows: R-HCH, 0.49; HCB, 0.59; -HCH, 3.9; HEPT, 13; HEPX, 120; TC, 120; o,p-DDE, 5.6; CC, 20; TN, 12; p,p-DDE, 370; o,p-DDD,
6.8; p,p-DDD, 30; o,p-DDT, 240; and p,p-DDT, 520. b From Shoeib and Harner (25). c From Hinckley et al. (26).
a

TABLE 2. Enthalpies of Phase Change

HSA
Hawaii

FIGURE 3. Log KSA vs 1/T for a selection of OC pesticides in the

Hawaiian soil.
and can therefore be omitted (25). Table 2 shows HSA for
each soil as well as HOA and HVAP where available. HOA
and HVAP represent the energy involved with the phase
transfer of a chemical from octanol to air (calculated from
temperature-dependent KOA values reported in ref 25) and
from the supercooled liquid phase of the chemical to air
(calculated from temperature dependent vapor pressures (PL)
reported in ref 26), respectively.
HSA values are very similar for all soils, irrespective of
organic matter content or type. Values for muck are generally
slightly higher but not for all compounds. In general HSA
is larger than HOA and HVAP. This indicates that additional
energy is required to remove a compound from soil as
compared to octanol or the pure compound itself. Previous
research has indicated that various interactions exist between
organic chemicals and soil organic carbon, such as van der
Waals forces, dipole-dipole interactions, and hydrogen
bonding (21, 27).
Influence of Physical-Chemical Properties. Figure 4
shows the regression of (a) log KSA versus log KOA and (b) log
KSA versus -log PL for all three soils at 25 C. All regression
lines were significant (p < 0.05) except for the log KSA versus
log KOA regression for the Hawaii soil. ANOVA carried out on
the regressions showed that the slopes of the regression lines

R-HCH
HCB
-HCH
-HCH
HEPT
aldrin
HEPX
TC
o,p-DDE
CC
TN
dieldrin
p,p-DDE
o,p-DDD
endrin
p,p-DDD
o,p-DDT
p,p-DDT
a

soybean

85.6

muck
77.1

76.1
81.8
92.4
94.8
97.6
97.2
97.2
101.6

101.3
96.4
93.0
96.9
95.9
107.8
109.2

HVAPb

61.8
55.7
94.4
65.3
66.1
70.9

68.5
68.6
70.5
76.5
75.1

96.3

80.7

98.0
105.2
72.5
97.8
0.0
84.8
80.0
87.8
88.0

82.0
85.5
82.5
87.2

107.3
112.2
97.1
105.3
116.8
96.3
106.4
104.9

82.6
108.2

From Shoeib and Harner (25).

HOAa

88.5
88.6
93.2

From Hinckley et al. (26).

for the different soils were not significantly different from

each other at the p < 0.05 level. Goss and Schwarzenbach
(28) suggested that a deviation of the slope away from 1
indicates a different affinity of the molecules for the absorbing
phase as compared to their pure liquid phase (in the case of
regression versus vapor pressure) or that the sorption medium
behaves differently from octanol (in the case of regression
versus log KOA). The 95% confidence levels of the regression
lines are as follows. Regressions with log KOA: Hawaii, -0.062
to 0.839; soybean, 0.158-0.776; muck, 0.311-1.155. Regressions with -log PL: Hawaii, 0.221-1.111; soybean, 0.1841.052; muck, 0.458-1.649. It seems that the sorption medium
in the muck soil behaves most similar to octanol, although
the large confidence intervals prohibit any firm conclusions.
Assuming one same slope for the regression lines of all
three soils, we can investigate the difference in intercept
between the regression lines. ANOVA showed that the
intercept (a measure of the sorbing capacity) of the muck
VOL. 37, NO. 7, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

1303

FIGURE 6. Log QSA field vs log KSA chamber for two soils.

FIGURE 4. (a) Log KSA vs log KOA and (b) log KSA vs log -PL for all
soils.

FIGURE 5. (a) Log KSA corrected for OOC vs log KOA and (b) log KSA
corrected for OOC vs -log PL for all soils.
soil is significantly higher than that of the other two soils (p
< 0.05).
Figure 5 shows regressions of log KSA corrected for organic
carbon content versus log KOA and -log PL. If organic carbon
content alone controlled partitioning, one would expect that
correcting for it would bring the KSA values of the muck soil
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 7, 2003

in line with the two other soils. Assuming a same slope for
all regression lines, the difference between the intercept of
muck and the two other soils has now indeed decreased (by
approximately 50%), and statistical analysis (ANOVA, p <
0.05) shows that, in the case of regression against log KOA,
there is no significant difference between the intercept of
muck soil and the intercepts of the other soils. However, the
KSA values for the low organic carbon Hawaiian and soybean
soils are now slightly higher as compared to the muck soil.
This might indicate that the organic matter in the Hawaiian
and soybean soils has a stronger affinity for the OC pesticides.
It has been shown in previous studies that a difference in
organic matter properties (e.g., aromatic content) can explain
differences in sorption to soils and sediments (7, 13, 29).
Alternatively, it is possible that in these mineral-rich soils
adsorption onto mineral matter plays a significant role
besides absorption into organic matter. This has previously
been shown for soils with low water content (<50% RH) (30).
Comparison with Field Experiments. QSA values were
previously measured in the field for the muck and soybean
soils using a novel apparatus (17). These values are thought
to approach the true equilibrium KSA value within a factor
3. These measurements were done at only one temperature.
To be able to compare our laboratory results with the field
study, log KSA chamber values were calculated at the
temperature of the field experiments (23.9 C for muck and
16.5 C for soybean) using the temperature regressions from
Table 2. Log KOA values were also calculated at these
temperatures using temperature regressions from Shoeib and
Harner (25). Log QSA from the field experiments are plotted
against the chamber KSA values in Figure 6. The agreement
between the chamber and the field measurements is better
for the muck soil. In general, the field QSA values are
overestimated by a factor of 2-5 as compared to the
chamber KSA values. It was suggested in ref 17 that, because
of suspected incomplete equilibrium during the in situ
measurements, the air concentration was most likely underestimated, possibly by a factor 3. This would result in a
field QSA value that is higher than the true KSA value. This
agrees with the difference between the field and the lab values
that we observe here. However, possible other explanations
could be that either the temperature or the soil concentration
in the field experiments was overestimated. In the chamber,
air was flowing through the soil, and the temperature was
measured inside the soil. In the field situation, however, air
was flowing over the soil so that the temperature should
theoretically be measured at the soil-air interface, which is
in reality very difficult to achieve. Similarly, the soil concentration for the field experiment should theoretically be
measured in the top few millimeters only, as that is where

air-soil exchange will occur. Again, this was difficult to

achieve, and in reality the top few centimeters were sampled,
resulting in an overestimation of the soil concentration (i.e.,
a concentration gradient should exist in the top 2 cm with
lowest values near the surface). This error would result in a
higher than expected QSA value for the field study. Finally,
the relative humidity during the field measurements at the
soybean site was lower than during the lab measurements,
which could have led to increased sorption (30). Considering
the factors that influence soil-air partitioning, we are satisfied
with a factor of 2-5 offset between field and laboratory data.
Ultimately, the findings of this work and the previous field
study of soil-air exchange indicate that the Karickhoff
relationship is useful and valid from a modeling standpoint
where it is necessary to compromise accuracy in exchange
for simple relationships that utilize readily available input
data.

Acknowledgments
We thank Professor Terry Bidleman for use of his resources
and helpful discussions. This work was supported by the
Toxic Substances Research Initiative (Project 11), a research
program managed jointly by Health Canada and Environment
Canada. We thank the anonymous reviewers for their helpful
suggestions.

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Received for review January 19, 2002. Revised manuscript

received December 19, 2002. Accepted January 13, 2003.
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