Research

Chlordane Enantiomers and Temporal Trends of Chlordane Isomers in Arctic Air

TERRY F. BIDLEMAN,* ,†
LIISA M. M. JANTUNEN, †
PAUL A. HELM, ‡
EVA BRORSTR O¨ M-LUND EÄ N, § AND SIRKKA JUNTTO #
Meteorological Service of Canada, 4905 Dufferin Street, Downsview, Ontario, M3H
5T4, Canada, Department
of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College
Street, Toronto, Ontario, M5S 1A4, Canada, Swedish
Environmental Research Institute, Box 47086, Gothenburg, SE-402 58, Sweden, and
Finnish Meteorological Institute, Sahaajankayu 20E, FIN-00810, Helsinki, Finland

A 14-year data set (1984-1998) for chlordane compounds in arctic air was examined
to discern temporal trends. trans- Chlordane (TC), cis-chlordane (CC), and trans-
nonachlor (TN) declined significantly (p < 0.001-0.02), with apparent
times for 50% reduction of 4.9-9.7 y. The isomer fraction of TC ) (TC/(TC + CC)
also declined significantly (p < 0.001-
0.014) over the same time period. The enantiomeric composition of TC and CC was
determined in air samples collected at arctic stations in Canada (1993-1996),
Russia (1994), and Finland (1998), and a temperate station on the Swedish west
coast (1998). Enantiomer fractions, EF ) (+)/[(+) + (-)], were significantly
different from measured EFs of racemic standards (0.498-0.501) at all
stations for TC (p < 0.001) and two stations for CC (p < 0.001 to <0.05). These
observations suggest changing source composition of chlordane in arctic air, with a
greater proportion of weathered residues in recent years, possibly derived from
soils. Identification of nonracemic (mean EFs ) 0.662-
0.703) heptachlor exo-epoxide (HEPX) at the four air stations further exemplifies
contributions of soil emissions to long-range transport of chlordane-related
compounds.

Introduction
Technical chlordane contains the major components trans- chlordane (TC, 13%), cis-
chlordane (CC, 11%), trans-non- achlor (TN, 5%), and heptachlor (5%) (1-3), and
over 30 less abundant chlordanes, chlordenes, and nonachlors (4). Chlor- dane
production began in 1948, and the pesticide was used worldwide over the next 50
years. In the United States, chlordane was used in agriculture for vegetable
crops, as a soil insecticide, for home lawns and gardens, and as a
termiticide until the mid-1980s. After 1983, most registrations were canceled
except for termite control, and in 1988 the termiticide registration was also
canceled (5). The major

* Corresponding author phone: (416)739-5730; fax: (416)739-5708;

e-mail: terry.bidleman@ec.gc.ca.
† Meteorological Service of Canada.
‡ University of Toronto.
§ Swedish Environmental Research Institute.
# Finnish Meteorological Institute.
manufacturer, Velsicol Chemical Co., voluntarily stopped global production in
1997 (6).
Chlordane compounds are widespread in the arctic environment. TC, CC, and
TN are found in arctic air (7, 8) and seawater (9). These and a number of minor
chlordanes, nonachlors, related compounds, metabolites (e.g.: hep- tachlor exo-
epoxide ) HEPX, and oxychlordane ) OXY), and photoproducts occur in ringed seal and
polar bear (10-13). Dietary intake of chlordanes (including nonachlors and OXY) by
some aboriginal peoples from consumption of traditional foods exceeds the
tolerable daily intake (TDI) value (14).
Chlordanes have been measured in arctic air since 1982, when they were first
detected at the Norwegian air monitoring station Ny Ålesund (15). Only CC was
reported in the 1982 samples, but from 1984 to the present TC, CC, and TN were
quantified in several arctic locations by various workers (Table
1). Hung et al. (8) analyzed the 1993-1998 chlordane mea-
surements from the Alert atmospheric monitoring station in the Canadian Arctic
using three techniques of data treat- ment: (a) simple linear regression (SLR) of
the natural loga- rithm of partial pressure vs time after normalizing for temper-
ature, (b) multiple linear regression (MLR) which considered both temperature and
time, and (c) digital filtration which smoothed the data to remove seasonal
fluctuations and outliers. The three data treatment methods showed that chlordanes
were declining with times for 50% reduction (t1/2) of 8.3-9.6 y for TC, 4.1-4.8 y
for CC, and 6.2-8.1 y for TN, the range indicating variation according to method
of data treatment. Chlordane data in air at Great Lakes monitoring stations were
analyzed by SLR and MLR techniques and in most cases showed downward trends
from 1992 to 1995. Values of t1/2 at Sturgeon Point, Lake Erie, and Sleeping
Bear Dunes, Lake Michigan were 3.2-5.2 y for TC, 5.9-9.7 y for CC, and 5.0-6.0 y
for TN. At Eagle Harbor, Lake Superior, TC showed a significant decline with t1/2 )
6.9 y for TC, but no significant decline was found for CC nor TN (16, 17).
The 14-year record of chlordane measurements in arctic air (Table 1) provided an
opportunity to examine longer- term trends in concentration and the relative
proportion of isomers. In addition, the enantiomer composition of certain chlordane
components in air samples from the mid to late
1990s were determined as an indicator of historical residue emissions, since
nonracemic chlordanes have been found in soils (18), overlying air (19), and
ambient air from the Great Lakes region (20, 21).

Experimental Section
Atmospheric concentrations of TC, CC, and TN, summarized in Table 1, were taken
from literature reports as indicated at sampling locations shown in Figure 1.
Before 1993, most measurements were from occasional samples collected over
relatively short campaigns of a few weeks to months. Some of these were land-
based, others were from shipboard expeditions and the Canadian Ice Island, a
floating natural platform in the Beaufort Sea. A number of different labo-
ratories were involved in these studies, and comparison of the quality control
measures taken is difficult. Year-around data became available starting in 1993 at
Ny Ålesund (78 55 N,
11 56 E, Norway), Alert (82 30 N, 62 20 W, Canada), Tagish
(60 20 N, 134 15 W, Canada, 1993-1994 only), Dunai (74 00 N,
125 00 E, Russia, 1993-1994 only), and in 1996 at Pallas (68 58 N, 24 07 E,
Finland). The latter data come from three monitoring programs which have long
experience with sampling and analysis and well-established quality control

10.1021/es011142b CCC: $22.00 2002 American Chemical Society

VOL. 36, NO. 4, 2002 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 539
Published on Web 01/05/2002
TABLE 1. Chlordanesa in Arctic Air, pg/m3

year month samples

TC
mean TC SD

Summer-Fall
CC
mean CC SD

TN
mean TN SD

FTC
mean FTC SD ref
Mould Bay, Canada 1984 June-July 6 0.96 0.45
1.50 0.26 1.30 0.18 0.39 0.20 (40) Ny Ålesund, Norway
1984 June-July 12 1.50 0.90 2.80 1.10
0.35 0.24 (22) Jergul, Norway 1984 June-July 12
0.88 0.30 2.20 0.60 0.29 0.12
(22) Ice Island, Canada 1986 June 7 1.10
0.40 2.80 0.70 1.50 0.50 0.28 0.12 (41) Ice Island,
Canada 1987 Aug-Sept 6 2.30 0.60 4.00
0.90 3.70 1.20 0.37 0.11 (41) Bering-Chukchi Seas 1988
Aug-Sept 4 2.30 0.80 2.80 0.70 1.50 0.50
0.45 0.18 (42) Bering-Chukchi Seas 1990 June-Aug 7
4.60 5.80 4.20 0.44
(43) Resolute Bay, Canada 1992 Aug-Sept 6 0.51 0.34
1.40 0.80 0.77 0.28 0.27 0.22 (44) Ny Ålesund, Norway
1993 May-Oct 22 0.37 0.20 1.11 0.37 0.84
0.27 0.25 0.15 (23) Alert, Canada 1993 May-Oct
23 0.58 0.50 1.44 0.80 1.29 0.87 0.29 0.28
(7) Tagish, Canada 1993 May-Oct 21 0.43
0.19 1.32 0.34 1.12 0.38 0.25 0.12 (7) Dunai, Russia
1993 May-Oct 18 0.41 0.24 1.11 0.44 1.00
0.49 0.27 0.18 (7)
Bering-Chukchi Seas 1993 July-Sept 3 0.75 0.05
1.20 0.09 0.59 0.06 0.38 0.03 this work Alert, Canada
1994 May-Oct 27 0.52 0.34 1.38 0.72 1.42
0.79 0.27 0.21 (7) Tagish, Canada 1994 May-Oct
26 0.40 0.18 1.20 0.34 1.10 0.44 0.25 0.13
(7)
Alert, Canada 1995 May-Oct 27 0.27 0.15
0.70 0.50 0.92 0.38 0.28 0.22 (8) Alert, Canada
1996 May-Oct 25 0.30 0.19 0.72 0.32 0.67
0.28 0.29 0.21 (8)
Pallas, Finland 1996 May-Oct 6 0.32
0.09 0.95 0.16 0.76 0.15 0.25 0.08 this work
Alert, Canada 1997 May-Oct 23 0.28 0.12
0.55 0.25 0.63 0.22 0.34 0.18 (8)
Pallas, Finland 1997 May-Oct 6 0.24
0.03 0.89 0.17 0.69 0.12 0.21 0.04 this work
Pallas, Finland 1998 May-Oct 6 0.22
0.05 0.75 0.10 0.58 0.06 0.23 0.06 this work
Winter-Spring
Ny Ålesund, Norway 1984 Feb-March 12 2.00 1.10
2.20 1.20 0.48 0.32 (22) Jergul, Norway
1984 Feb-March 12 1.20 0.50 1.20 0.40
0.50 0.25 (22) Alert, Canada 1988 Feb-April
11 1.20 0.50 1.30 0.60 1.40 0.70 0.48 0.25
(45) Svanvik, Norway 1992 March-May 26 0.52 0.15
0.86 0.29 1.59 0.49 0.38 0.14 (46) Ny Ålesund, Norway
1992 Nov-April 20 0.73 0.61 0.98 0.38 1.83
0.83 0.43 0.40 (46) Ny Ålesund, Norway 1993 Nov-April
30 0.64 0.26 1.09 0.39 0.85 0.30 0.37 0.18
(23) Alert, Canada 1993 Nov-April 25 0.27
0.14 0.49 0.26 0.37 0.23 0.36 0.23 (7) Tagish, Canada
1993 Nov-April 23 0.60 0.36 1.11 0.58 0.88
0.43 0.35 0.25 (7) Dunai, Russia 1993 Nov-April
16 0.34 0.33 0.66 0.64 0.44 0.51 0.34 0.41
(7
Alert, Canada 1994 Nov-April 25 0.56 0.50
0.98 0.78 0.69 0.61 0.36 0.39 (7) Tagish, Canada
1994 Nov-April 24 0.59 0.23 0.93 0.36 0.77
0.39 0.39 0.19 (7) Alert, Canada 1995 Nov-April
25 0.44 0.33 0.69 0.53 0.66 0.62 0.39 0.36
(8) Alert, Canada 1996 Nov-April 27 0.33
0.20 0.62 0.51 0.64 0.93 0.35 0.29 (8
Pallas, Finland 1996 Nov-April 6 0.53 0.12
0.78 0.08 0.71 0.11 0.40 0.10 this work
Alert, Canada 1997 Nov-April 25 0.34 0.22
0.46 0.29 0.40 0.34 0.43 0.34 (8)
Pallas, Finland 1997 Nov-April 6 0.45 0.15
0.78 0.21 0.65 0.19 0.37 0.14 this work
Pallas, Finland 1998 Nov-April 6 0.40 0.10
0.68 0.14 0.58 0.16 0.37 0.11 this work
a TC ) trans-chlordane, CC ) cis-chlordane, TN ) trans-nonachlor.

programs. Data were grouped into “summer-fall” (May- October) and “winter-
spring” (November-April) periods, since previous reports indicated changing ratios
of TC/CC between these seasons (7, 8, 22-24).
Enantiomers of TC, CC, chlordane MC5 (25), and HEPX were determined in selected
air samples collected from the arctic stations Alert (1993-1996) and Dunai
(1994-1995), and Pallas (1998), and at Ro¨rvik (1998), a European Monitor- ing
Evaluation Program (EMEP) station on the Swedish west coast (57 25 N, 11 56 E)
(Figure 1). Sample extracts were used for enantiomeric analysis after quantitative
analysis had been performed under the routine monitoring programs in Canada and
Sweden (7, 8, 26, 27). Air sampling at Alert and Dunai was done for a 7-d (168-h)
period, with four samples taken per month (7, 26). A few weekly air samples from
Alert were analyzed, but most of the Alert and all of the Dunai samples
represented monthly composites of the four weekly sample extracts. Sampling at
Pallas and Ro¨rvik was done once a month, each sample representing 7 d.
Collections at all stations were made using a high volume sampler with a glass
fiber filter followed by a polyurethane foam (PUF) trap.
Extraction, cleanup, and quantitative analytical methods have been reported
elsewhere (7, 26-28) and are briefly explained here. Samples from Alert and
Dunai were Soxhlet extracted with hexane (PUF plugs) or dichloromethane
(filters). The extracts were split, one-half for archiving and
the other half for quantitative analysis. After spiking with the surrogates PCB-30
and octachloronaphthalene, the extracts were cleaned up, fractionated on Florisil,
and then analyzed by capillary GC with electron capture detection on a 60-m
× 0.25 mm i.d. DB-5 column (J& Scientific, U.S.A.) vs external standards.
Procedural recoveries of the surrogates were >90%.
Samples from Pallas and Ro¨rvik were Soxhlet extracted with acetone. The
acetone was diluted with water, and the analytes were partitioned into pentane-
ethyl ether. Sur- rogates of o,p -DDD and -hexachlorocyclohexane ( -HCH) were
added, and cleanup was achieved by shaking with concentrated sulfuric acid. The
extract was then fractionated on aluminum oxide. Determination was made by
capillary GC with electron capture detection using a 50-m × 0.25 mm i.d. CP-Sil
8CB column (Chrompack, Holland). Samples were corrected for the surrogate
recoveries, which ranged from 50 to 70%.
Enantiomers were separated by chiral-phase capillary gas chromatography with
detection by negative ion mass spec- trometry using a Hewlett-Packard 5890GC -
5989B MS- Engine or 6890 GC - 5973 Mass Selective Detector and two columns: (a)
20% permethylated â-cyclodextrin in SPB-25 (Betadex-120, Supelco, U.S.A., 30 m ×
0.25 mm i.d., 0.25 µm film) and (b) 20% tert-butyldimethylsilyl-â-cyclodextrin
in OV-1701 (BGB-172, BGB Analytik, Switzerland, 30 m × 0.25 mm i.d., 0.25 µm
film). These two columns are referred to

540 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 36, NO. 4, 2002

TABLE 2. Temporal Trends of Chlordane Concentrations (pg/m3) and FTC in Arctic
Air
Summer-Fall

Winter-Spring
slope (m) p
Intercept (b) r2 t1/2, y slope (m) p
Intercept (b) r2 t1/2, y

Ln TC ) m*year + b -0.1409 <0.001 280.14 0.583 4.9 ( 0.9 -

0.1076 <0.001 213.94 0.708 6.4 ( 1.1
(0.0273
(0.0178
Ln CC ) m*year + b -0.1034 <0.001 206.28 0.590 6.7 ( 1.3 -
0.0712 <0.001 141.88 0.587 9.7 ( 2.1
(0.0198
(0.0154
Ln TN ) m*year + b -0.0943 0.0017 188.00 0.449 7.4 ( 2.0 -
0.1096 0.020 218.28 0.352 6.3 ( 2.4
(0.0254
(0.0413
FTC ) m*year + b -0.00794 0.014 16.11 0.279
-0.00888 <0.001 18.1 0.544
(0.00293
(0.00210

FIGURE 1. Locations of arctic stations where air samples (literature and this
work) have been collected for chlordanes (Table 1). ALT
) Alert, DUN ) Dunai, ICI ) Canadian Ice Island, JER ) Jergul, MB ) Mould Bay,
NYA ) Ny Ålesund, PAL ) Pallas, RB ) Resolute Bay, SVK ) Svanvik, TAG ) Tagish.

as BDX and BGB. Carrier gas was He at 40 cm/s, and the reagent gas was methane
at a nominal pressure of 1.2 Torr. Samples of 2 µL in isooctane were injected
splitless (split opened after 1 min). Temperature programs were varied to
achieve optimal separation conditions on the different columns; typical
ones are given in refs 18-20. Other conditions were as follows:
injector and transfer line 220 , ion source 150 , quadrupole 100 . Selected ion
monitoring was used for chlordanes (410/412), nonachlors (444/446), and HEPX
(316/318). Racemic standards included pure isomers of TC, CC, and HEPX
(Supelco Corporation) and technical chlordane (U.S. EPA Repository for Pesticides
and Industrial Chemicals, Research Triangle Park, NC). Enan- tioenriched
standards of (+)TC, (+)CC, and (+)HEPX (Eh- renstorfer Laboratories) were used to
check elution orders on the chiral columns.
Results are expressed as the enantiomer fraction, EF ) area ratio of
(+)/[(+) + (-)], which is preferred to the enantiomer ratio ER ) (+)/(-)
(29, 30). An EF ) 0.500 indicates a racemic compound. The orders of
enantiomer elution were as follows: BDX (+)TC, (-)TC, (+)CC, (-)CC; BGB (+)TC,
(+)CC, (-)CC, (-)TC. Enantiomers of MC5 were also resolved on BDX, but
their signs have not been determined. The EF of MC5 was calculated as the
first/(first
+ second) eluting peak.
Ratios of the two monitored ions were closely followed over the course of
the analyses. The ion ratios (( SD) for standards were 1.56 ( 0.052 for
chlordanes (n ) 28) and 0.71 ( 0.045 for HEPX (n ) 8). Ion ratios of both
enantiomer peaks for samples were required to fall within 2 SD of these means to
qualify, otherwise no EF value was reported.
FIGURE 2. Time trends of the natural logarithm of trans-chlordane (TC, open
circles) and cis-chlordane (CC, solid circles) concentra- tions (pg/m3) and
fraction of TC, FTC ) TC/(TC+CC), in arctic air during winter-spring (W-S) and
summer-fall (S-F). See Table
1 for data and Table 2 for regression parameters.

Results and Discussion

Trends in Concentrations and Proportions of Chlordanes. Ln-linear (first order)
plots of chlordane concentration versus year were constructed to determine time
trends, with data treatment by SLR and analysis of variance (ANOVA). TC and CC
measurements were available since 1984, but TN was missing from some of the
earlier data sets (Table 1). No adjustments for temperature were made, since the
data were obtained from widely separated stations in many cases. Temperature,
which governs air-surface exchange, is a minor factor affecting pesticide
concentrations in arctic air com- pared to long-range transport (7, 8). Results are
given in Table
2, and first-order plots are shown in Figure 2. Regression slopes were
negative and significant at p < 0.001 for TC and CC, and p ) 0.0017-0.02 for TN.
Times for 50% reduction (t1/2) of TC, CC, and TN were 4.9, 6.7, and 7.4 y in
summer- fall and 6.4, 9.7, and 6.3 y in winter-spring (Table 2). The t1/2 values in
this work are within the range of estimates by Hung et al. (8) from 1993 to 1998
measurements at Alert, suggesting that the atmospheric dynamics of chlordanes
are similar across the Arctic and have been relatively constant over the last
14 years.
Previous studies have shown that the ratio of TC/CC in arctic air is higher in
winter-spring than summer-fall (7, 8,
22-24). Reasons for this are not known, but it has been speculated that TC
is more labile to photochemical reaction and therefore more readily lost in the
season with more sunlight (7, 22). The long-term trend analysis shows that the
fraction of trans-chlordane, FTC ) TC/(TC+CC), not only followed this annual
cycle but also decreased significantly
between 1984 and 1997 for both summer-fall (p ) 0.014) and winter-spring (p )
<0.001) seasons (Table 2, Figure 2). This suggests that sources of chlordane in
arctic air have changed over the last 14 years and are now more depleted
in TC. FTC in technical chlordane is 0.49-0.54 (1, 3). When

VOL. 36, NO. 4, 2002 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 541

TABLE 3. Enantiomer Fractions (EFs) of Chiral Chlordanes and HEPX in Arctic Air

a Average EF determined on BDX and BGB columns. b BGB column. c BDX column. d At
Alert, a 7-day sample is indicated; others are monthly composites.

weighed for the slightly higher vapor pressure of TC, the expected atmospheric
FTC in equilibrium with technical chlordane is 0.61 (1). The FTC in soils is
about the same or lower than in technical chlordane (1, 3, 18, 31). Lower ob-
served FTC in air during summer-fall may be due to in- creased outgassing of
chlordanes from soil in warmer weather relative to other sources. Confounding the
interpretation of FTC values is the fact that technical heptachlor was also
used in agriculture and as a termiticide. Technical hepta- chlor is contaminated
with chlordane isomers, especially TC (32), so higher FTC in soils or air could
be associated with this source. Indeed, Hung et al. (8) identified occasional
spikes of high FTC in arctic air samples during 1995. A num- ber of these
events also showed elevated heptachlor levels.
Enantiomers in Arctic Air. Both chiral columns were used for analysis of TC in 28
samples, with the result that the BDX
column gave slightly higher EF values. EFs of TC on the BDX column averaged 101.7 (
2.5% of the mean BGB result, which was significantly different from 100% (t-test
of means, p <
0.01). CC enantiomers were, in general, determined only on the BGB column due to
endosulfan I interference with (-)- CC on the BDX column (9). However, both
columns were employed for five Pallas and six Ro¨rvik air samples which showed
no endosulfan I interference. The average EF for CC on the BDX column was 99.5
( 1.0% of the mean BGB value and was not significantly different from 100% (p >
0.1).
Results of the chiral analysis are given in Table 3 and Figure 3. Depletion
of (+)TC and (-)CC was found for many of the samples; example chromatograms on the
two chiral columns are shown in Figure 4. Average EFs of air samples were
compared to those determined for racemic standards (Table 3) using a two-tailed t-
test of means. The average EFs of TC were nonracemic at all stations at a
high level of

542 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 36, NO. 4, 2002

TABLE 4. Average Enantiomer Fractions of Chlordanes in Soil and Air

TC CC MC5 HEPX ref

Agricultural Soil
Alabama, 1996 0.479 0.531 0.416 0.710 (33, 34)
Midwest U.S.,
1995-1997
0.406 0.540 0.713 (18)
Hawaii, 1998 0.459 0.519 0.550 (33)

FIGURE 3. Enantiomer fractions of TC, CC, and chlordane MC5 in air samples,
means ( s.d. Racemic EFs in Arctic Ocean surface water from ref 9.
British Columbia,
1989
Luddington, U.K.,
1972-1990
air above soils,b
1996-1998

Arctic,
1993-1998a
Ro¨ rvik, Sweden,
1998
0.496 0.500 0.565 (47)
0.437 0.541 (36)

0.423 0.526 0.699 (19)

Ambient Air
0.473 0.505 0.488 0.677 this work

0.463 0.511 0.471 0.696 this work

Alabama, 1996 0.492 0.500 0.492 0.639 (1)
Midwest U.S.,
1997-1998
Lake Ontario,
1992
Lake Superior,
1994-1995
Lake Michigan,
1994-1995
Lake Erie,
1994-1995
Columbia, SC,
1994
0.481 0.509 0.483 (19)

0.477 0.507 0.472 0.651 (20)

0.468 0.502 0.677 (21)

0.454 0.505 0.667 (21)

0.488 0.528 0.667 (21)

0.500 0.503 0.602 (33)

a Average of Alert, Dunai, and Pallas for TC, CC, and HEPX; Pallas only for MC5. b
Air over midwest U.S. soils sampled in 1996-1998.

FIGURE 4. Chromatographic separations of chlordane enantiomers in April air

samples from: A. Ro1rvik, BGB column, B. Pallas, BDX column. TC ) trans-chlordane,
CC ) cis-chlordane, TN ) achiral trans-nonachlor, MC5 ) octachlordane compound. TN
elutes at 53 min on the BGB column and is not shown.

significance (p < 0.001): Alert ) 0.471 ( 0.011, Dunai )

0.471 ( 0.009, Pallas ) 0.477 ( 0.006, and Ro¨rvik ) 0.463 (
0.013. The average EFs of CC were nonracemic at Pallas (0.507 ( 0.005, p < 0.01)
and Ro¨rvik (0.511 ( 0.005, p < 0.001) but not significantly at Alert (0.504
( 0.005, p > 0.1) nor Dunai (0.503 ( 0.004, p > 0.2). At Alert, the EF of TC was
positively correlated with FTC (r2 ) 0.41, p ) 0.0032). The correlation was not
significant at Pallas (r2 ) 0.029, p > 0.6) nor at Dunai (r2 ) 0.0024, p > 0.9).
EFs of MC5 were determined in five Pallas and seven Ro¨rvik samples. Depletion
of the first-eluting enantiomer was found in all Ro¨rvik samples (EF ) 0.471
( 0.010, p <
0.01). The same depletion occurred in two of the five Pallas samples, but the
average EF (0.488 ( 0.013) was not sig- nificantly different from the standard
(p > 0.1). EFs of HEPX were determined in 3-7 samples from each station and were
highly nonracemic (p < 0.001) in all cases with enrichment of the (+) enantiomer
(Table 3).
Chlordanes and HEPX are often nonracemic in agricultural soils (18, 19, 33, 34) and
overlying air (35) and in ambient air of the Great Lakes region (19, 20, 21, 35)
and show the same order of enantiomer depletion/enrichment as the air samples in
this study (Table 4). Soils from the U.K. also contained nonracemic TC and CC
(Table 4) (36). Chlordanes in ambient air in or near southern U.S.A. municipalities
are racemic (1). The source of chlordane in this situation may be its former usage
as a termiticide. Indoor air sampled in eight southern U.S. (1, 20) and 30
midwestern U.S. (37) homes contained
racemic chlordanes and at concentrations orders of mag- nitude higher than
ambient air levels. The nonracemic chlordanes and HEPX in arctic air provide
strong evidence that soil-derived pesticides are revolatilizing in warmer
regions of the Northern Hemisphere and undergoing long- range atmospheric
transport.
Have chlordanes in arctic air always been nonracemic? This is difficult to
answer because no air samples from the
1980s and earlier are available for examination. However, chlordanes in Arctic
Ocean surface water were racemic (EFs
) 0.499 for TC and 0.501 for CC) for samples collected in
1994. Most of these samples were collected between 72 and
90 latitude and under ice cover (9), and the surface water would thus have
been removed from the influence of atmos- pheric exchange. The racemic EFs in
water may represent chlordane loadings to the Arctic Ocean sometime in the past.
HEPX in ocean water was nonracemic with an average EF )
0.639 (9). Racemic chlordane and nonracemic HEPX EFs in arctic cod (Boreogadus
saida), which feed on zooplankton, reflect those in water (38). Sources of
HEPX include me- tabolism of heptachlor in soils and photochemical oxidation of
heptachlor. The former process is thought to yield HEPX enriched in the (+)
enantiomer, as occurs when heptachlor is metabolized by rat liver microsomes,
while the second yields racemic HEPX (39). The nonracemic HEPX in air
samples from temperate regions suggests that emission from soils is the primary
source (35). Current EFs of HEPX in arctic air (0.662-0.703) are somewhat higher
than those in Arctic Ocean surface water (0.639) suggesting that in the past atmos-
pheric transport of heptachlor and photochemical produc- tion of HEPX was greater
than today. Photolysis of hepta- chlor, either in arctic air or at lower
latitudes and advected into the Arctic, is indicated by the occurrence of
photohep- tachlor in ringed seal blubber from the Canadian Arctic (13).
It appears that sources of chlordane have shifted over time, from atmospheric
transport of the freshly applied

VOL. 36, NO. 4, 2002 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 543

pesticide to a greater proportion of chlordane “recycled” from soils. The
nonracemic HEPX in arctic air and seawater exemplifies the volatilization of
soil residues on a large scale and the influence on atmospheric levels in remote
regions. Fresh releases of organochlorine pesticides are expected to cease under
the recently signed global POPs protocol, and chemical markers will become
increasingly useful for dis- tinguishing “old” and “new” sources.

Acknowledgments
Support for this work was provided by Indian and Northern Affairs Canada, Northern
Contaminants Program. We thank Phil Fellin and Henrik Li, AirZOne, for supplying
archived air sample extracts from Alert and Dunai. Thanks also to Pierrette
Blanchard and Hayley Hung (MSC) for sharing their data on chlordane levels in air
prior to publication.

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Received for review July 17, 2001. Revised manuscript re- ceived October 1,
2001. Accepted October 17, 2001.

ES011142B

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