Arch. Environ. Contam. Toxicol.

35, 218–228 (1998)

A R C H I V E S O F Environmental Contamination a n d Toxicology
r 1998 Springer-Verlag New York Inc.

Organochlorine Pesticides and Enantiomers of Chiral Pesticides in Arctic Ocean

Water

L. M. M. Jantunen,1 T. F. Bidleman2

1 Department of Chemical Engineering and Applied Chemistry, University of Toronto,

200 College Street, Toronto, Ontario, M3S 3E5, Canada
2 Atmospheric Environment Service, ARQP 4905 Dufferin Street, Downsview, Ontario,
M3H 5T4, Canada

Received: 4 October 1997/Accepted: 19 February 1998

Abstract. In the summers of 1993 and 1994, seawater samples from the surface layer
(40–60 m) were collected to determine the spatial distribution of organochlorine
pesticides on expedi- tions that crossed the Arctic Ocean from the Bering and
Chukchi seas to the North Pole, to a station north of Spitsber- gen, and then south
into the Greenland Sea. Spatial differences in concentration were found that varied
with the pesticide. Heptachlor exo-epoxide (a metabolite of heptachlor) and a-
hexachlorocyclohexane (a-HCH) increased from the Chukchi Sea to the pole, and then
decreased toward Spitsbergen and Greenland Sea. Chlorinated bornanes (toxaphene)
followed a similar trend, but levels were also high near Spitsbergen and in the
Greenland Sea. A reverse trend was found for endosulfan, with lower concentrations
in the ice-covered regions. Little variation was seen in chlordane concentrations,
although the ratio of trans-/cis-chlordane decreased at high latitudes. Several of
these pesticides are chiral: a-HCH, cis- and trans-chlordane, and heptachlor exo-
epoxide. Enantioselective degradation of (2)a-HCH was found in the Bering and
Chukchi seas, whereas the (1) enantiomer was depleted in the Arctic Ocean and
Greenland Sea. Enrichment of (1) heptachlor exo-epoxide was found in all regions.
Trans- and cis-chlordane were nearly racemic.
1993, 1995; Hu¨hnerfuss et al. 1992) and preferential transport through biological
membranes (Mo¨ller et al. 1994; Hu¨hnerfuss et al. 1993).
Selective degradation or accumulation of single enantiomers may have toxicological
implications. For example, the (2) enantiomer of o,p8-DDT has a higher estrogenic
activity than (1)o,p8-DDT (McBlain et al. 1976) and the (1) enantiomer is depleted
in human fat (Mu¨ller and Buser 1995). Enantiomers are also useful as marker
compounds to follow transport processes. Microbially processed pesticides often
have nonrace- mic ERs and can be thereby be distinguished from the freshly applied
racemic compounds. Enantioselective breakdown of a-hexachlorocyclohexane (a-HCH)
has been found in Lake Ontario and arctic seas, where volatilization from water was
signaled by the appearance of nonracemic a-HCH in the overlying air (Jantunen and
Bidleman 1996, 1997; Ridal et al.
1997).
In July–September 1994, samples were collected on a transect from the Chukchi Sea
to the Greenland Sea across the North Pole, on the Canadian icebreaker Louis S. St.
Laurent (AOS-94). The cruise track is shown in Figure 1, and coordi- nates of
stations and hydrographic information are given in Table 1. Measurements of OC
pesticides in surface waters were made to determine their spatial distribution in
the western
Arctic Ocean. A previous expedition (BERPAC-93) (Jantunen and Bidleman 1995)
covered the Bering and Chukchi seas for

Organochlorine (OC) pesticides are well-known contaminants of the arctic food

chain, moving from water into plankton and bioaccumulated by fish, birds, and
marine mammals (Hargrave et al. 1992, 1993; Muir et al. 1988, 1992; Norstrom and
Muir
1994). OC pesticides and their stable metabolites are ultimately passed on to
aboriginal people through consumption of tradi- tional foods (Jensen et al. 1997;
AMAP 1997). Many OC pesticides and components of technical pesticide products are
chiral and are applied as racemic mixtures, in which the ratio of the (1)/(2)
enantiomers (ER) is 1.00. Physical transport processes and abiotic chemical
degradation are not enantioselec- tive, but biological pathways have the ability to
alter ER values from racemic. Such pathways include enzymatic degradation (Mu¨ller
and Buser 1994; Faller et al. 1991a; Buser and Mu¨ller

Correspondence to: L. Jantunen

HCHs. Air–water gas exchange of HCHs and the use of a-HCH enantiomers as a tracer
of volatilization from arctic waters has been reported previously (Jantunen and
Bidleman 1995, 1996,
1997). This article describes the surface water concentrations of HCHs,
chlorobornanes (CHBs, e.g. toxaphene), the cyclodiene compounds trans- and cis-
chlordane (TC, CC), trans- and cis-nonachlor (TN, CN), heptachlor exo-epoxide
(HEPX, a metabolite of heptachlor), and endosulfan-I and -II (Endo-I and Endo-II).
The ERs of the chiral compounds a-HCH, TC, CC, and HEPX are also reported.

Materials and Methods

Sample Collection and Preparation

Water samples of 4–20 L were collected and HCH compounds were adsorbed on solid-
phase extraction cartridges containing1g C8-bonded
Pesticides in Arctic Ocean Water
219
Fig. 1. Cruise track of AOS-94. Dots running from the Chukchi Sea to the Greenland
Sea correspond the station numbers in Table 1

Table 1. Hydrographic information and concentrations (pg/L) of dissolved pesticides

in surface water

SCHBs

Station

Latitude
North Longitude

Tempera- ture (°C)

Salinity
(psu) a-HCH g-HCH HEPX TC CC TN CN Endo-I Endo-II

Single
RF

Multiple
RF

T2 T12

1 67°478 168°478W 20.1 32.69 1700 320 6.6

2.0 1.4 0.88 0.26 5.6 2.8 14 18 0.29 0.36
2 72°088 168°508W 21.7 32.14 1290 250 6.0
1.6 0.92 0.63 0.40 8.8 7.8 24 33 0.24 0.37
7 75°008 169°598W 21.5 30.63 2490 410 na
na na na na na na na na na
na
11 76°388 173°198W 21.6 31.01 2360 370 9.6
1.1 0.94 0.66 0.23 1.2 1.4 26 25 0.40 0.29
13 77°488 176°188W 21.6 30.44 2550 360 10.7
1.8 1.3 1.0 0.40 3.1 2.4 37 40 0.64
0.46
16 78°598 175°498W 21.6 30.15 2400 400 18.8
1.0 1.0 0.73 0.30 3.1 0.6 34 35 0.81 0.56
18 80°098 173°158W 21.7 32.43 2160 330 na
na na na na na na na na na
na
19 80°098 176°468W 21.6 30.73 2180 400 na
na na na na na na na na na
na
20 80°208 178°388W 21.6 31.18 2180 400 13.6
0.92 0.91 0.55 0.29 2.3 1.0 50 44 0.77 0.59
24 82°288 175°408E 21.7 32.07 2490 470 19.6
0.83 0.88 0.52 0.26 1.9 1.3 81 65 1.0 0.90
25 83°108 173°568E 21.7 32.23 2620 580 17.5
1.6 1.5 1.0 0.51 3.6 4.1 74 74 1.1
1.0
26 84°048 175°048E 21.6 31.05 2070 580 na
na na na na na na na na na
na
28 85°548 166°428E 21.6 31.57 2740 380 12.6
0.70 0.78 0.46 0.26 1.8 1.0 55 46 0.73 0.62
29 87°098 160°428E 21.6 32.10 2090 700 17.4
1.4 1.3 0.74 0.33 0.4 0.9 75 52 1.0
0.83
30 88°048 174°508E 21.7 33.64 2630 520 na
na na na na na na na na na
na
31 88°478 142°448E 21.7 32.58 2430 560 14.2
1.5 1.5 0.91 0.39 1.5 0.6 92 65 1.1
0.97
35 90°008 21.7 31.89 2690 550
13.7 2.0 2.1 1.4 0.35 1.3 0.1 55 66
0.87 0.41
37 84°158 35°058E 21.6 33.41 950 220
8.4 2.3 1.2 1.6 0.49 3.1 0.5 96 96
1.0 0.90
38 83°518 35°418E 21.8 34.09 1040 170 na
na na na na na na na na na
na
39 75°008 06°038W 4.0 34.29 630 200
4.7 0.84 0.48 0.42 0.28 4.2 0.2 57 58 0.55
0.45

nd: not detected; na: not analyzed, low volume samples for a-HCH only

silica, using procedures described elsewhere (Jantunen and Bidleman

1995). Cartridges were extracted with ,10 ml of dichloromethane, cleaned up over a
1 g alumina (6% water) column, and shaken with 18
M sulfuric acid. The final volume for analysis was 1.0 ml. Sampling for other OCs
was done by collecting ,200 L of surface water via a
submersible pump; the line running from the pump was Teflon surrounded by a metal
mesh. Water was stored in pressurizable stainless steel cans, passed through a
glass fiber filter (142 mm Whatman GF/F, nominal cut-off 0.7 µm), to collect
particulate matter and then pulled at 150 ml/min with a peristaltic pump through a
1.5 cm
220
L. M. M. Jantunen and T. F. Bidleman

ID glass column containing ,50 ml of precleaned XAD-2 resin to collected the

dissolved OCs. After use, the XAD-2 was transferred to amber bottles with Teflon-
lined lids and stored at 4°C.
The filters were cleaned by baking for 12 h at 400°C in a muffle furnace, wrapped
in aluminum foil, and stored in plastic bags. The XAD-2 was prepared by sieving
under water and precleaned by soxhlet extraction for 24 h each with the following
sequence of solvents: acetone, petroleum ether, dichloromethane, petroleum ether,
and acetone. The XAD-2 was stored at 4°C in water prior to preparing the
extraction columns.
toxaphene was chromatographed, with hexachlorobenzene and mirex as retention time
markers, on a 30-m DB-5 column using the same temperature program for GC-FID as in
the GC-MS analytical method. To correct for injector discrimination, toxaphene
peak areas were normalized to GC-FID response factors (area/ng carbon) for series
of PCBs that spanned the retention time range of toxaphene. The mass contribution
of individual peaks was obtained by:

(AiMi)(100) Mass % 5
The XAD-2 resin from water sampling was soxhlet-extracted in precleaned thimbles
with methanol for 24 h followed by dichlorometh- ane for 24 h. Both extracts were
concentrated to ,150 ml with a rotary evaporator. The dichloromethane extract and
100 ml water were added
n
AiMi i51

where A is the corrected area of peak i, M is the molecular weight of

to a separatory funnel, mixed well, and the dichloromethane was
i
i
removed. The aqueous layer was extracted with another 50 ml dichloromethane. The
methanol extract was diluted with 50 ml saturated sodium chloride and 100 ml water,
and shaken with 50 ml dichloromethane. Extraction of the water-methanol layer was
repeated twice. All dichloromethane extracts were combined and dried over granular
anhydrous sodium sulphate. Water filters were extracted by refluxing for 12 h with
400 ml dichloromethane. The extracts of the XAD-2 and filters were concentrated
separately to 1–2 ml and the solvent was exchanged into hexane by rotary
evaporation and blowing down with a gentle stream of nitrogen. The extracts were
cleaned up on a 1-g column of neutral alumina (deactivated with 6% water) eluted
with 10 ml of 20% dichloromethane in petroleum ether. The eluate was exchanged into
isooctane, cleaned up with 18 M sulfuric acid (omitted for HEPX and endosulfan
analysis) and reduced by nitrogen blowdown to 100–200 µl for analysis. The water
and solvents that were used were chromatographic quality.

Analysis

Quantitative and enantiomer analyses were done on a Hewlett Packard

5890 GC-5989B MS engine operated in in the negative ion mode with methane at a
nominal pressure of 1.0 Torr. The ions monitored (target/qualifying) were: HCHs
(255/257), TC and CC (412/410), TN and CN (444/446), HEPX (388/386), OXY (422/420),
endosulfan, and mirex (404). The 7-Cl, 8-Cl, and 9-Cl homologs of CHBs were
determined by monitoring the 343/345. 379/381 and 413/415 ions (Bidleman et al.
1995). The column used for quantitative analysis was a DB-5MS (J&W Scientific, USA,
30 m 3 0.25 mm ID, 0.25 µm film thickness), operated at a helium carrier gas flow
of 40 cm/s. The temperature program was: initial temperature 90°C, 15°C/min
to
160°C, 3.5°C/min to 210°C, hold 1.0 min, 20°C/min to 260°C, hold 5.0 min. Sample
volumes of 2 µl were injected splitless (split opened after
1.5 min). Other temperature conditions were: injector and transfer line
250°C, ion source 150°C, and quadrupole 100°C. Quantification carried out against
five standards that spanned the concentration range of the samples, using HP MS
Chemstation software. Mirex was added to extracts before injection as an internal
standard. Random samples were checked for native mirex and found negative.
The sum of CHBs containing seven to nine chlorines was quantified by two methods
based on single and multiple response factors. The first used the total GC-MS peak
area (sum of peaks at all monitored CHB ions, relative to mirex) and the mass of
toxaphene injected. Because the response of CHBs in negative ion MS varies
substantially among congeners (Shoeib et al. 1997), a multiple-response factor
method was also employed. Response factors were assigned to 41 individual peaks or
groups of peaks of the technical toxaphene, similar to the Webb- McCall methods for
PCBs (Webb and McCall 1973). The mass contribution of peak groups was obtained by
GC with flame ionization detection (GC-FID), which was assumed to respond to the
carbon skeleton of the CHBs (Harder et al. 1983). A standard of technical
compound i (376, 410 or 444 for CHBs having seven, eight, or nine
chlorines), and n is the number of peaks integrated. Negative ion MS response
factors (relative to mirex) were calculated for individual peaks using their
percent mass contribution and the total mass of toxaphene standard injected; 84% of
the total GC-FID peak area and
60% of the total MS peak area were accounted for. In the case of water samples, .
90% of the total MS peak area was accounted for by the peaks employed in the
multiple RF method. Peaks with retention times matching the two single CHB
congeners which bioaccumulate strongly were also determined. These were 2-exo, 3-
endo, 5-exo, 6-endo,8,8,10,
10-octachlorobornane, designated as T2 by Stern et al. (1992), P26 by
Frenzen et al. (1994), and B8-1413 by Andrew and Vetter (1995);
2-exo, 3-endo, 5-exo, 6-endo,8,8,9,10,10-nonachlorobornane, also called T12, P50,
and B9-1679 by the above authors. Pure standards of T2 and T12 (obtained from
Axact, Inc., Commack, NY) were used to identify and quantify these two congeners.
Two different chiral columns were used for the enantiomer analysis: Beta-DEX (20%
permethylated b-cyclodextrin in polydimethylsilox- ane, 30 m 3 0.25 mm ID, 0.25 µm
film thickness, Supelco Corp., USA) and BGB-172 (20% tert-butyldimethylsilylated b-
cyclodextrin in OV-
1701, 30 m 3 0.25 mm ID, 0.25 µm film thickness, BGB Analytik AG, Switzerland). The
Beta-DEX temperature program was: initial tempera- ture 90°C, hold for 1.0 min,
15°C/min to 130°C, 1.0°C/min to 210°C,
20°C/min to 230°C hold for 5.0 min. The BGB-172 temperature program was:
90°C, hold for 1.0 min, 15°C/min to 140°C, 1.0°C/min to
190°C, hold for 2.0 min, 20°C/min to 240°C, hold for 5.0 min. Both columns were
operated at a He carrier gas flow of 40 cm/s. Other conditions were: splitless
injection (split opened after 1.5 min), injector temperature 220°C, ion source
temperature 150°C, transfer line temperature 220°C, and quadrupole temperature
100°C. Enantiomers of a-HCH and HEPX were separated on the BGB-172 column. The
Beta-DEX column was used as a confirmation column for a-HCH because the elution
order of the enantiomers was reversed from that on BGB-172 (Jantunen and Bidleman
1996, 1997). The Beta-DEX column also resolved the enantiomers of TC and CC, but
Endo-I interfered with the second-eluting (2) enantiomer of CC. A tandem column
consisting of Beta-DEX (30 m) followed by DB-210 (J&W Scientific, 30 m 3 0.25 mm
ID, 0.25 µm film thickness) was used to separate Endo-I from (2) CC. The
temperature program for these separations was: initial temperature 90°C, hold for
1.0 min, 15°C/min to 140°C, 0.5°C/min to 210°C, 20°C/min to 230°C, hold for 5.0
min. The tandem column was operated at a carrier gas flow of 40 cm/s, with other
conditions the same. Elution orders of the (1) and (2) enantiomers were determined
by injecting enriched standards of (1) enantiomers, obtained from Axact.

Quality Control

Detailed information on recovery efficiencies and blanks for HCHs has been reported
elsewhere (Jantunen and Bidleman 1995, 1996, 1997)
Pesticides in Arctic Ocean Water
221

Table 2. Average regional concentrations of pesticides in surface water (pg/L)

a-HCH g-HCH HEPX TC CC TN CN Endo-I

Endo-II SCHBs Reference

Bering Sea
1993 2002 454
Jantunen and Bidleman
1995
1990 1500 190 1.5
1.9 0.50
Iwata et al. 1993
1988 2400 570
Hinckley et al. 1991
1988 2440 720
Rice and Shigaev 1997
Chukchi Sea
1993–94 2060 430 6.3 1.8 1.2
0.76 0.33 7.2 5.3 19 This work and Jantunen and
Bidleman 1995
1990 1400 180 0.90
2.6 0.60
Iwata et al. 1993
1988 2400 620
Hinckley et al. 1991
1988 2460 690
Rice and Shigaev 1997
Western Arctic Ocean
1994 2420 470 14.8 1.3
1.2 0.80 0.33 2.0 1.3 58 This work
1992–1993 2000–3000 500–1100
Macdonald et al. 1996 and Jensen et al. 1997
Beaufort Sea and Canadian Archipelago
1993 3640 520 0.5
1.3 2.6 85
Hargrave et al. 1997
1992–1993 3500–5500 500–700
Macdonald et al. 1996 and Jensen et al. 1997
1992 4700 450 7.3
4.5 1.5 48
Bidleman et al. 1995
1987 7100 810
Patton et al. 1989
1986–87 4465 610 ,3–11 3.7 (TC 1
CC) 0.50 145–175a Bidleman et al.
1989 and Hargrave et al.
1988
Near Spitsbergen and
Greenland Sea
1994 870 200 6.6 1.6
0.84 1.0 0.36 3.7 0.35 77 This work

a Reported erroneously as 360 pg/L in original paper

and is summarized here. Water samples on the AOS-94 and BER- PAC-93 cruises were
spiked with HCHs and yielded mean recoveries (n 5 28) from solid-phase extraction
cartridges of 71 6 12% for a-HCH and 73 6 14% for g-HCH. The mean blank values (n
5 10) for a- and g-HCH were 0.21 6 0.03 and 0.12 6 0.05 ng. From AOS-94, average
blanks (n 5 3) were: , 20 pg HEPX, 26 6 20 pg CC, 45 6 24 pg TC, 47 6 31 pg TN, 70
6 28 pg Endo-I, and 478 6 102 pg toxaphene. Two recovery experiments for OCs other
than HCHs were done by spiking ,180 L seawater with 1.8–2.5 ng cyclodienes and 100
ng toxaphene, dividing the spike among the stainless steel cans containing the
water, and passing the water through XAD-2. Average recoveries, after adjusting for
the native amounts in seawater, were: chlordanes and HEPX 44%, Endo-I 75%, and
toxaphene 57%. In previous studies using the same XAD-2 sampling and extraction
procedures, recoveries of TC, CC, and TN averaged 56% and toxaphene was 102%
(Bidleman et al. 1995); PCB congeners and p,p8-DDT were 71–94% (Kucklick et al.
1994). Losses were probably incurred mainly during final evaporation of the samples
to 100–200 µl for the GC-MS analysis. This was confirmed by carrying out laboratory
blow-down tests with standards, for which recoveries of cyclodienes and toxaphene
averaged 50% and 77%. Losses of HCHs were only moderate (recoveries 71–73%, see
above) because the final blow-down volume was 1.0 ml instead of 100–200 µl.
Concentrations of OCs in Table 1 have been corrected for recovery factors of
71–73% for HCHs, 50% for chlordanes and HEPX, and 75% for endosulfans and CHBs.
Quality control issues in enantiomer analysis are precise integration of two peak
areas and elimination of interferences. Racemic standards were repeatedly
injected on the two columns to determine the
reproducibility of measuring the area ratio of (1)/(2) enantiomers (ER). Average ER
values were: a-HCH 5 1.00 and HEPX 5 1.01 (BGB-172), a-HCH 5 0.99 (Beta-DEX), TC 5
0.99 and CC 5 0.99 (tandem column), with a relative standard deviations of
6 0.01 (n 5 6–11 for each compound). The criterion used for enantiomer peak purity
was agreement of the target/qualifying ion ratio within 65% of the standard values
(Falconer et al. 1997). Confirmation of the ERs for a-HCH in water samples was done
by analysis on both the Beta-DEX and BGB-172 columns. The order of enantiomer
elution is reversed on these two column with (1)a-HCH eluting first on Beta-DEX
and (2)a-HCH first on BGB-172 (Jantunen and Bidleman 1996, 1997). The average
percent difference in ER values between the two columns was 3.6 6 2.9% (n 5 44).

Results and Discussion

Spatial Distribution of Pesticides in Surface Water

Concentrations of dissolved OC pesticides in surface water on the transect from the

Chukchi Sea across the polar cap to the Greenland Sea are given for each station in
Table 1 and summarized as regional averages in Table 2. Trends with latitude are
shown in Figure 2. The data for HCHs in Figure 2 include AOS-94 and the Chukchi
portion of BERPAC-93 (Jantunen and Bidleman 1995, 1996, 1997).
In the upper 40 m of the northern Chukchi Sea, a-HCH and
g-HCH averaged 2.06 6 0.48 ng/L and 0.43 6 0.09 ng/L (AOS
222
L. M. M. Jantunen and T. F. Bidleman
Fig. 2. Concentration of OCs in the upper
40–60 m of the water column, summa- rized by latitude (N. HCHs: 65–69 5 station 1 1
BERPAC-93 data; 70–74 5 station 2 1 BERPAC-93 data; 75–79 5 stations 7, 11, 13, 16;
80–84 5 stations
18, 19, 20, 24, 25, 26; 85–89 5 stations
28, 29, 30, 31; 90 5 station 35; 84–80 5 stations 37, 38; 75 5 station 39. Other
OCs: 65–69 5 station 1; 70–74 5 station
2; 75–79 5 stations 11, 13, 16; 80–84 5
stations 20, 24, 25; 85–89 5 stations 28,
29, 31; 90 5 station 35; 84–80 5 station
37; 75 5 station 39. Bar shades are: a-HCH (black) and g-HCH (white), CHBs: single
response factor (black) and multiple-response factor (white); HEPX (black), TC
(black), and CC (white); Endo-I (black) and Endo-II (white); TN (black)

stations 1–2 and BERPAC results, n 5 21). These compared well with results from a
1988 survey of the same region (Hinckley et al. 1991; Rice and Shigaev 1997) and
were ,40% higher than concentrations measured at two Chukchi stations in
1990 (Iwata et al. 1993). In the polar mixed layer (60 m) of the western Arctic
Ocean along AOS-94 track (stations 7–35), a-HCH and g-HCH averaged 2.42 6 0.23
ng/L and 0.47 6 0.11 ng/L. Concentrations were ,2–3 times lower than these means at
stations 37–38 near Spitsbergen and station 39 in Greenland Sea, averaging 0.87 6
0.22 ng/L a-HCH and 0.20 6 0.03 ng/L g-HCH. Summarizing, HCHs in the upper 40–60 m
increased slightly along the AOS-94 track from the Chukchi Sea to the pole, then
dropped off in the Eurasia Basin and the Greenland Sea (Figure 2). Peak
concentrations of 2.5–2.7 ng/L a-HCH in waters north of 85 are nevertheless lower
than those found in
the Beaufort Sea and Canadian Archipelago at latitudes of
,75–81N (3.5–7.1 ng/L, Table 2). In recent years water of Atlantic origin has
intruded from the Eurasian side into the northern portion of the Canada Basin
(Macdonald 1996). The AOS-94 track traversed the region of the Arctic Ocean where
the two water types, containing lower and higher a-HCH concentrations, are mixed.
Spatial trends for other OCs are less well defined due to the limited number of
large-volume water samples, and several of the latitudinal trend bars in Figure 2
are based on single measurements. HEPX was lower in the Chukchi Sea, near
Spitsbergen and in Greenland Sea (6.6 6 1.9 pg/L, stations 1, 2,
37, 39) but higher in the western Arctic Ocean (14.8 6 3.4, stations 11, 13, 16,
20, 24, 25, 28, 29, 31, 35) (Figure 2). Measurements of HEPX at the Ice
Island (81N, 100W),
Pesticides in Arctic Ocean Water
223

Canadian Archipelago, in 1986–87 ranged from , 3–11 pg/L (Bidleman et al. 1989;
Hargrave et al. 1988) (Table 2).
Chlordanes and nonachlors showed little trend with latitude, other than slightly
higher concentrations at stations 35–37 and lower values at station 39.
Oxychlordane was detected in some samples at estimated concentrations # 0.5 pg/L.
The ranges of chlordanes and nonachlors at all stations were (pg/L): TC 5
0.70–2.3, CC 5 0.48–2.1, TN 5 0.42–1.6, and CN 5 0.23–
0.51. The sum of TC 1 CC concentrations compared well with the measurements at the
Ice Island during 1986–87 (Hargrave et al. 1988), Resolute Bay in the Canadian
Archipelago (74N,
95W) in 1993 (Hargrave et al. 1997) and the Bering Sea in 1990 (Iwata et al. 1993),
all of which ranged from 1.8–3.7 pg/L, but were lower than those found at Resolute
Bay in 1992 (11.8 pg/L) (Bidleman et al. 1995) (Table 2). Ratios of TC/CC ranged
from 0.9–1.9, with a mean of 1.2 (Table 1). The proportion of TC/CC appeared to be
lower in the ice-covered regions, decreasing from 1.4–1.7 at stations 1–2, to 1.1 6
0.1 at stations
11–35, and then increasing to 1.8–1.9 at stations 37 and 39 (Figure 2).
Concentrations of Endo-I 1 Endo-II at stations 1–2 in the Chukchi Sea averaged 12.5
pg/L and were higher than in the western Arctic Ocean (3.4 6 1.9) or at stations 37
and 39 (3.6 and 4.4 pg/L). By comparison, 2.6 pg/L Endo-I was reported in surface
water from Resolute Bay in 1993 (Hargrave et al.
1997). Endosulfant is used throughout the world and is one of the few OC
insecticides that is still permitted in Canada, the United States, and Europe.
Endosulfan in air from the Great Lakes region showed a strong seasonal pattern of
high concen- trations in summer and lower in winter (Hoff et al. 1992; Burgoyne
and Hites 1993), a trend also found at arctic air-monitoring stations
(Halsall et al. 1998). The proportion of Endo-I to Endo-II in surface water was
quite variable, ranging from nearly all Endo-I (stations 35 and 39), approximately
equal concentrations of the two isomers (stations 2, 11, and 25), and more Endo-II
(station 29). Technical endosulfan contains a
2/1 ratio of Endo-I/Endo-II. Endo-I is more volatile and is usually enriched in air
samples (Burgoyne and Hites 1993). However Endo-II has a lower air/water partition
coefficient (Henry’s law constant) (Rice et al. 1997) and therefore should be
preferentially deposited by precipitation and air-water gas exchange. Chan et al.
(1994) reported that Endo-II exceeded Endo-I in precipitation samples from the
Great Lakes. More- over, it has recently been shown that Endo-II can be converted
to Endo-I under environmental conditions (Schmidt et al.
1997). Thus the factors that control the proportion of Endo-I/
Endo-II in open-ocean water are complex and not well under- stood.
CHBs (Table 1, single response factor values) were lowest in the northern Chukchi
Sea (stations 1–2, 14–24 pg/L) and increased to an average of 58 6 22 pg/L in the
western Arctic Ocean (stations 11, 13, 16, 20, 24, 25, 28, 29, 31, 35). Stations
38 and 39 were also fairly high (96 and 57 pg/L) CHBs in Resolute Bay were 48 pg/L
in August–September 1992 (Bidle- man et al. 1995) and followed a seasonal cycle in
1993 from
40–140 pg/L with a yearly average of 85 pg/L (Hargrave et al.
1997).
The CHB chromatograms were dominated by the more volatile early eluting congeners,
suggesting an atmospheric source (Figure 3). The single and multiple-
response factor
approaches were compared for quantification of SCHBs. The ratio of concentrations
obtained by the multiple/single methods (Cm/Cs) ranged from 0.69–1.38, with an
average of 0.99. Regression analysis gave: Cm 5 0.73Cs 1 10.8, r2 5 0.82. The two
methods agreed surprisingly well, considering that the GC-NIMS response factors for
toxaphene congeners vary widely (Shoeib et al. 1997).
Peaks matching retention times of the two highly bioaccumu- lating individual
congeners of toxaphene, T2 and T12, were also identified in the surface water and
were quantified using single-component standards (Table 1). The T12 peak was the
only nine-chlorinated CHB that was detected in substantial amounts. Stern et al.
(1992) found that the T2 and T12 peaks in biological samples were nearly pure
compounds, but this is unlikely to be the case in abiotic media. Shoeib et al.
(1997) and DeBoer and DeGeys (1997) examined technical toxaphene and found that
peaks having the retention times of T2 and T12 on a DB-5 capillary column could be
further separated into several components by multidimensional GC. So the T2 values
re- ported in Table 1 are probably inflated because the peak contains a mixture of
co-eluting octachloro-compounds. Like- wise, the T12 peak may contain co-eluting
nonachloro- compounds. As a percent of SCHBs in seawater, the T2 and T12 peaks
averaged 1.5 and 1.3%. These peaks accounted for
0.52 and 1.2% of technical toxaphene (this work, and Shoeib et al. 1997).
The OC pesticides were predominantly found in the dis- solved phase, with , 0.3–
1% on the glass fiber filter for a-HCHs, , 0.5% for g-HCH, , 0.3–27% for
cyclodienes, and
2–27% for CHBs. Exceptions to this were at stations 16, 20, and
24, where 16–28% of the a-HCH was retained by the filter (but
g-HCH was ,0.5%) and station 2 in the Chukchi Sea, where
32–66% of the chlordanes was found on the filter. The latter station was in a
region of high productivity and the water was green with plankton. The stations
that showed higher percent- ages of particulate a-HCH were in a region of low
suspended matter (clear blue water), although under-ice algae were present. The
unusually high values for particulate a-HCH, along with a different degree of
enantioselective degradation at two of the three stations (see next section)
suggests that the filters may have collected some plankton, although it is puzzling
why the more hydrophobic pesticides did not also show greater retention on the
filter at these locations.

Vertical Profiles of HCHs

In the Chukchi Sea, a-HCH decreased slowly from 2.1 ng/L at the surface to 1.5–1.7
ng/L at 300–350 m, whereas g-HCH did not change significantly over this depth
range. Concentrations in the 60–115 m layer of the western Arctic Ocean (2.25 6
0.24 ng/L a-HCH and 0.52 6 0.18 ng/L g-HCH) were not signifi- cantly different from
average values in the 60-m polar mixed layer (2.42 6 0.23 ng/L a-HCH and 0.47 6
0.11 ng/L g-HCH) but dropped off rapidly to 0.62 6 0.24 ng/L a-HCH and 0.26 6
0.13 ng/L g-HCH at 200–350 m. The sharp decline of HCHs through the pycnocline is
typical of the Arctic Ocean (Hargrave et al. 1988; Jantunen and Bidleman 1996,
1997; Jensen et al.
1997). At stations 37–38 north of Spitzbergen, a-HCH was
0.95–1.44 ng/L at 10–109 m and decreased to 0.53 ng/L at 235
224
L. M. M. Jantunen and T. F. Bidleman
Fig. 3. Chromatograms of the 7-, 8-, and
9-chlorinated CHBs in surface water at station 37

m and 0.26 ng/L at 762 m; g-HCH exhibited no significant trend in the upper 100 m,
although a decline was suggested for deeper samples. HCHs at station 39 in the
Greenland Sea were vertically well mixed. Concentrations of a-HCH ranged from
0.59–0.63 ng/L and g-HCH from 0.17–0.20 ng/L over a depth range of 10–540 m
(Jantunen and Bidleman 1996,
1997).

Enantiomers of Chiral Pesticides

The enantiomer ratios of dissolved a-HCH in arctic waters have been reported by
Jantunen and Bidleman (1996, 1997). ERs in surface water were generally . 1.00 in
the Bering-Chukchi seas, indicating preferential breakdown of (2)a-HCH. Deple- tion
of the (1)a-HCH was found in the Arctic Ocean and Greenland Sea, with ERs , 1.00.
Reasons for the opposite enantiomer depletion patterns is not known. One hypothesis
is that different microbial populations in these regions are respon- sible. Faller
et al. (1991b) found the (1)a-HCH was preferen- tially degraded in some regions
of the North Sea whereas
(2)a-HCH was depleted in others. ERs were , 1.00 in Lake Ontario (Ridal et al.
1997) and a freshwater arctic lake (Falconer et al. 1995a, 1995b), but . 1.00 in
soils from British Columbia, Canada (Falconer et al. 1997).
Even though HCHs were . 99% in the dissolved phase at most stations (except those
discussed earlier), levels of HCHs in water were high enough to allow ER values to
be measured on the filters of the large volume samples. The particulate a-HCH
showed the same, or more, enantioselective degradation than the dissolved fraction
(Table 3, Figure 4). Both fractions were depleted in the same enantiomer at most
stations, but there appeared to be no relationship between the two and reversal in
the depleted enantiomer was found at stations 16 and 29 (Figure 4). Some
particulate samples showed enhanced degrada- tion of a-HCH compared to the
dissolved phase. For ex- ample, the ER of dissolved a-HCH at station 20 was
0.82, whereas the ER on the filter was 0.18 (Table 3). This sample also contained
an unusually high proportion of a-HCH in on the filter, as noted earlier. Station
31 also showed enhanced degradation of particulate a-HCH (ER 5 0.42), but the
percent on particles was low (, 0.2%). Other paired dissolved and
Pesticides in Arctic Ocean Water
225

Table 3. Enantiomeric ratiosa of chiral pesticides in surface water

a-HCH BGB-172

a-HCH
Beta-DEX HEPX BGB-172

TC Tandemb

CC Tandem
Station
Dissolved Particle Dissolved Particle
Dissolved
Dissolved
Dissolved

Standard 1.00
0.99 1.01
0.99 0.99
1 1.11 1.27
1.08 1.26 1.52
1.00 1.00
2 1.09 1.05
1.09 1.03 1.47
1.00 1.04
11 1.06 nac
1.05 0.98 1.64
1.00 1.06
13 0.95 0.98
0.89 0.93 1.58
1.06 1.02
16 na 1.10
0.83 1.07 na
0.98 na
20 na 0.21
0.82 0.18 na
0.99 na
24 0.92 0.88
0.87 0.95 1.76
0.97 0.99
25 0.96 0.93
0.89 0.95 1.59
0.98 1.01
28 0.92 0.91
0.87 0.89 1.59
1.01 0.94
29 0.90 1.16
0.88 1.23 1.65
0.97 na
31 0.96 0.42
0.90 0.42 1.67
1.01 na
35 0.91 0.84
0.88 0.86 1.63
0.99 1.01
37 0.85 na
0.78 na 1.56
0.97 0.98
39 0.71 0.80
0.68 0.79 1.67
1.03 1.01

a ER 5 (1)/(2) enantiomer
b Beta-Dex 1 DB-210, see text
c na: not analyzed

Fig. 4. Enantiomeric ratios (ERs) of a-HCH in the dissolved (-) and particulate
(---) phases

particulate samples showed little difference in the ERs. These observations suggest
that enantioselective degradation in the dissolved and particulate phases are
decoupled and may in- volve different microbial populations. The ERs for dissolved
a-HCH generally decreased with depth (Jantunen and Bidle- man 1996, 1997). At
stations 37 and 38 north of Spitsbergen, surface ERs were 0.82, decreased to 0.64
at 109 m, 0.45 at 235 m, and 0.14 at 762 m. Two explanations are suggested to
account for the greater enantioselectivity with depth. As particles settle from the
surface, the sorbed a-HCH is metabo- lized and released back into the dissolved
phase. Alternatively, the ERs may be typical of older, Atlantic-layer water, which
lies below the pycnocline. Distinctive ratios of a-HCH/g-HCH have been found at
different depths in the North Atlantic near Bermuda, corresponding to water
masses of different

Fig. 5. Chromatograms of HEPX, CC, and TC enantiomers in the dissolved phase at

station 35

origin (Fischer and Ballschmiter 1991), however, no measure- ments of ER values

have been made in the temperate North Atlantic.
Figure 5 shows the chromatographic profiles of HEPX, CC and TC enantiomers, and the
ERs for the dissolved phase are given in Table 3. Amounts on the filters were too
low to obtain
226
L. M. M. Jantunen and T. F. Bidleman

good enantiomer signals. HEPX is a metabolite of heptachlor, so the ER . 1.00

probably results from preferential formation of the (1) enantiomer rather than
breakdown of the (2) enantiomer. The range of ERs for HEPX, 1.56–1.76, was
tight considering the wide expanse covered by the stations. Preferential formation
of (1)HEPX has been shown to take place on incubation of heptachlor with rat liver
microsomes (Buser et al. 1993) and (1)HEPX enrichment has been re- ported in
salmon, Adelaide penguin, gray seal and human adipose tissue (Buser and
Mu¨ller 1993; Mu¨ller and Buser
1994) and in agricultural soils (Aigner et al. 1998) but the (2) enantiomer of HEPX
predominates in herring and grey seal from the Baltic (Wiberg et al. 1997). The
origin of HEPX in polar water is uncertain. Photolysis of heptachlor yields
racemic photoheptachlor and HEPX (Buser and Mu¨ller 1993). Photo- heptachlor has
been identified in seal blubber, polar bear fat, and human plasma from the Canadian
Arctic (Zhu et al. 1994). However, photolysis cannot be responsible for the excess
of (1)HEPX found in surface water unless selective degra- dation of the (2)
enantiomer takes place after formation of racemic HEPX. A more likely
possibility is that atmo- spheric transport delivers non-racemic HEPX to the
Arctic. HEPX with ERs of 1.4–2.0 has been found in air samples from the southern
United States and the Great Lakes regions, apparently the result of volatilization
from soils (Bidleman et al. 1998).
The chlordane compounds TC and CC were close to racemic in the dissolved
phase (ER 5 0.94–1.06) (Table 3). Enantiomers of both TC and CC are resolved on the
Beta-DEX column but Endo-I overlaps (2)CC and the 410/412 ions monitored for
chlordanes also give a response for Endo-I. Endo-I was present in sufficient
concentrations to make chiral analysis impossible for (2)CC, so tandem Beta-
DEX and DB-210 columns were used to separate Endo-I from (2)CC as shown in Fig. 5.
Tandem columns have been previously employed to separate chlordane enantiomers from
each other and o,p8-DDT enantiomers from p,p8-DDD (Oehme et al.
1994).
Nonracemic residues of a-HCH, HEPX, and chlordanes have been found in birds, fish,
and marine mammals (Pfaffenberger et al. 1992; Mu¨ller et al. 1997; Tanabe et al.
1996; Vetter and Schurig 1997). These residues may be the result of enantioselec-
tive uptake and metabolism or differential permeation of enantiomers through
biomembranes (Mu¨ller and Buser 1994; Faller et al. 1991a; Buser and Mu¨ller 1995,
1993; Hu¨hnerfuss et al. 1992, 1994; Mo¨ller and Hu¨hnerfuss 1993). Reversals in
enantioselectivity are sometimes seen between predator and prey and health status
of the animal may be a factor in metabolism of chiral pesticides (Wiberg et al.
1997). The enantiomeric of composition of OC residues in arctic waters serves as a
basis for understanding their uptake and transfer in the lower food chain.

Acknowledgments. We wish to thank crew and scientists of the Russian ship

Ocean and the Canadian ship Louis S. St. Laurent for their assistance in sample
collection and the Canadian Department of Indian Affairs and Northern Development,
Northern Contaminants Program, for financial support.
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