Sources and Fate of Organochlorine Pesticides in North America and the Arctic by Liisa M ...

207 Pages·2010·3.42 MB·English

Sources and Fate of Organochlorine Pesticides in North America and the Arctic

by

Liisa M. Jantunen

A thesis submitted in conformity with the requirements
for the degrees of Doctor of Philosophy
Graduate Department of Department of Chemical Engineering and Applied Chemistry
University of Toronto

©Copyright by Liisa M. Jantunen 2010
Sources and Fate of Organochlorine Pesticides in
North America and the Arctic

Liisa M. Jantunen
Doctor of Philosophy
Department of Chemical Engineering and Applied Chemistry
University of Toronto

2010
ABSTRACT
Atmospheric transport and air-water exchange of organochlorine pesticides (OCPs) were investigated in
temperate North America and the Arctic. OCPs studied were hexachlorocyclohexanes (HCHs, a -, b - and g -isomers),
components of technical chlordane (trans- and cis-chlordane, trans-nonachlor), dieldrin, heptachlor exo-epoxide and
toxaphene. Air and water samples were taken on cruises in the Great Lakes and Arctic to determine concentrations
and gas exchange flux direction and magnitude. The Henry’s law constant, which describes the equilibrium
distribution of a chemical between air and water, was determined for several OCPs as a function of temperature and
used to assess the net direction of air-water exchange. Air samples were collected in Alabama to investigate southern
U.S. sources of OCPs. Chemical markers (isomers, and enantiomers of chiral OCPs) were employed to infer sources
and trace gas exchange. Elevated air concentrations of toxaphene and chlordanes were found in Alabama relative to
the Great Lakes, indicating a southern U.S. source. Profiles of toxaphene compounds in air were similar to those in
soil by being depleted in easily degraded species, suggesting that soil emissions control air concentrations. Gas
exchange fluxes in the Great Lakes indicated near-equilibrium between air and water with excursions to net
volatilization or deposition. Net volatilization of a -HCH from the Arctic Ocean was traced by evasion of non-racemic
a -HCH into the atmosphere.

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ACKNOWLEDGMENTS
This thesis would not have been possible without the support, guidance and assistance of family and colleagues.

I would like to thank Terry Bidleman, for being my supervisor and supporting me over the years and years that it
took this thesis to be completed.

Tim MacNaughtan, my husband, for telling me I had to finish.

I would like to thank Paul Helm and Andi Leone for their support in the laboratory.

I would also like to thank all the people who made the field studies possible. BERPAC-93: Alla Tsyban, Jackie
Grebmeier, Cliff Rice and crew and fellow scientists from the R/V OKEAH. AOS-94: Rob Macdonald and the
crew and fellow scientists from the CCGS Louis S.St. Laurent. TNW-99: Henrik Kylin and Swedish Polar
Secretariat for ship time and the crew and fellow scientists of the Louis S. St. Laurent. Great Lakes cruises: Janine
Wideman, Paul Helm and Jeff Ridal for help during sampling and the crew and fellow scientists of the CCGS
Limnos.

I would also like to thank Environment Canada and the Northern Contaminants Program for financial support.

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ABSTRACT ……………………………………………………………………………………… ii

ACKNOWLEDGEMENTS ……………………………………………………………………… iii

TABLE OF CONTENTS ………………………………………………………………………… iv

LIST OF TABLES .………………………………………………………………………………. vi

LIST OF FIGURES ……………………………………………………………………………… viii

Chapter 1.
1.1 CONCLUSIONS ……………………………………………………………………. 1
1.2 RECOMMENDATIONS …………………………………………………………… 3

Chapter 2: INTRODUCTION ………………………………………………………………… 4

Chapter 3: COMPOUNDS INVESTIGATED
3.1. Toxaphene ………………………………………………………………………….. 5
3.1.1 Toxaphene Congeners ……………………………………………………. 6
3.2. Cyclodienes …………………………………………………………………………. 8
3.2.1 Chlordane …………………………………………………………………. 8
3.2.2 Dieldrin …………………………………………………………………… 9
3.3. Hexachlorocyclohexanes …………………………………………………………… 10

Chapter 4: RELEVANT PROPERTIES AND PROCESSES
4.1. Physicochemical Properties ………………………………………………………… 11
4.1.1 Henry’s Law Constants …………………………………………………… 11
4.1.2 Determination of HLCs by the Gas Stripping Method …………………… 13
4.2. Air-Water Gas Exchange
4.2.1 Fugacity and the Net Exchange Direction ………………………………… 15
4.2.2 Uncertainty in Fugacity Ratios ……………………………………………. 15
4.2.3 Rate of Gas Exchange: The Modified Two Film Model …………………. 15
4.3. Chemical Tracers of Exchange Processes
4.3.1. Isomer and Parent-Metabolite Pairs …………………………………….. 17
4.3.2. Chiral Compounds ………………………………………………………. 17
4.3.3. a -HCH Enantiomers …………………………………………………….. 18
4.3.4. Cyclodiene Enantiomers ………………………………………………… 20
4.3.5. Enantiomers in Source Identification and Exchange Processes ………… 21

Chapter 5: MATERIALS AND METHODS
5.1. Sampling Locations ………………………………………………………………… 22
5.2. Air Sampling ………………………………………………………………………... 22
5.3. Water Sampling……………………………………………………………………... 24
5.4. Samples Extraction and Cleanup/Fractionation ……………………………………. 24
5.5. Analysis Methods, Quantitative and Chiral ………………………………………... 24
5.6.Quality Control ……………………………………………………………………… 25

Chapter 6: SOURCES, TRANSPORT AND ENVIRONMENTAL OCCURRENCE
6.1. Southern Sources and Transport
6.1.1. Toxaphene ………………………………………………………………... 25
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6.1.2. Cyclodienes ………………………………………………………………. 37
6.1.3. HCHs ……………………………………………………………………... 29
6.2. Great Lakes
6.2.1. Air ………………………………………………………………………… 29
6.2.2. Water ……………………………………………………………………… 31
6.2.3. Air-Water Gas Exchange …………………………………………………. 32
6.2.4. Chiral Tracers of Gas Exchange ………………………………………….. 37
6.3. Arctic
6.3.1. Air …………………………………………………………………………. 37
6.3.2. Water ……………………………………………………………………… 39
6.3.3. Air-Water Gas Exchange …………………………………………………. 41

REFERENCES …………………………………………………………………………………… 43
Original Papers
1 Jantunen, L.M., Bidleman, T.F. 2006. Henry’s Law constants for hexachlorobenzene,
p,p’-DDE and components of technical chlordane and estimates of gas exchange for
Lake Ontario. Chemosphere 62, 1689-1696. ……………………………………………….. 61

2 Jantunen, L.M., Bidleman, T.F., Harner, T. 2000. Toxaphene, chlordane
and other organochlorine pesticides in Alabama air. Environmental Science
and Technology 34, 5097-5105. ………………………………….………………………… 73

3 Jantunen, L.M., Helm, P.A., Bidleman, T.F. 2008. Air-water gas exchange of
chiral and achiral pesticides in the Great Lakes. Atmospheric Environment 42,
8533-8542 ………………………………………………………………………………... 91

4 Jantunen, L.M., Bidleman, T.F. 2003. Air-water gas exchange of toxaphene
in Lake Superior. Environmental Toxicology and Chemistry 22, 1229-1237……………. 117

5 Jantunen, L.M., Bidleman, T.F. 1996. Air-water gas exchange of hexachlorocyclohexanes
(HCHs) and the enantiomers of a -HCH in Arctic regions. Journal of Geophysical
Research 101, 28837-28846, corrections ibid. 1997, 102, 19279-19282…………………… 135

6 Jantunen, L.M., Helm, P.A., Bidleman, T.F., Kylin, H. 2008. Hexachlorocyclohexanes
(HCHs) in the Canadian archipelago, 2. Air-water gas exchange of a , and g -HCHs.
Environmental Science and Technology 42, 465-470 and Supporting Information. ……… 158

7 Jantunen, L.M., Bidleman, T.F. 1998. Organochlorine pesticides and enantiomers
of chiral pesticides in Arctic Ocean water. Archives of Environmental
Contamination and Toxicology 35, 218-228………………………………………………. 177

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List of Tables

Chapters 3-6

Table 1 Toxaphene nomenclature ………………………………………………………… 7
Table 2 Physical-chemical data for OCPs ………………………………………………… 12
Table 3 Distribution of OCPs EFs in background soils, % of total samples ……………. 21
Table 4 Atmospheric concentrations of OCPs in the Great Lakes and Arctic ……………. 35
Table 5 Water concentrations of OCPs in the Great Lakes and Arctic …………………… 36

B. Original Papers
Paper I
Table I-1. Parameters of log H=m/T +b and enthalpies of water-air transfer (D H ) ………… 77
wa
Table I-2. Comparison of Henry’s Law constants, Pa m3 mol-1 ………………………………. 78
Table I-3. Air (C, pg m-3) and water (C , pg L-1) concentrations from Lake Ontario,
a w
July 1998 used to calculate fugacity ratios. ……………………………………….. 79

Paper II
Table II-1. OCs in Alabama air, January to October 1996 and May 1997, pg m-3 ± SD. ……… 87

Table II-2. Ratios of chlordane compounds in air, soil and technical chlordane. ……………… 92
Table II-3. Mean atmospheric concentrations (pg m-3) of OCs in the southern U.S.
and Great Lakes regions. ………………………………………………………….. 95

Table II-4. Regression parameters of log P/Pa versus 1/T plots. ………………………………. 97

Paper III
Table III-1. Concentrations of gas phase organochlorine pesticides in air, pg m-3. ………….. 108

Table III-2. Concentrations of dissolved organochlorine pesticides in surface water,
pg L-1. ……………………………………………………………………………. 110
Table III-3. Comparison to other Great Lakes air measurements (pg m-3). ………………….. 113

Table III-4. Fugacity and flux calculations for the Great Lakes. ……………………………. 120

Table III-5. Enantiomer fractions of chiral organochlorine pesticides in surface water and air. 122

Paper IV
Table IV-1. Water concentrations of dissolved toxaphene in Lake Superior, Great Lakes,
pg L-1 ……………………………………………………………………………… 135

Table IV-2. Atmospheric concentrations of toxaphene over the Great Lakes, August 1996
and May 1997, pg m-3, see Figure 1 for sample locations. ………………………… 136

Table IV-3. Fugacity ratio and flux calculations for cruises and annual predictions, see
Figure 1 for sample locations. …………………………………………………… 140

Paper V
Table V-1. Hydrographic information, concentration of a - and g -HCHs and enantiomeric
Ratio (ER) of a -HCH in water ……………………………………………………. 157

Table V-2. HCH concentrations in surface water in sub-arctic and arctic regions …………….. 159

Table V-3. Concentrations of HCHs and enantiomeric ratio (ERs) of a -HCH in air ………….. 160

Table V-4. Fugacity ratio and flux calculations ………………………………………………. 162

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Paper VI
Table VI-1. Atmospheric concentrations of HCHs during TNW-99 and at Resolute
Bay (RB)a, pg m-3 ………………………………………………………………. 175

Table VI-2. Air and water concentrations of a - and g -HCH on TNW-99 …………………… 176

Table VI.3. Atmospheric concentrations and fluxes of a - and g -HCH at Resolute Bay ……. 179

Table VI-4. Water concentrations of HCHs by zone, fugacity ratios and net fluxes ............... 180

Table VI-5. Fugacity and flux calculations for TNW-99 …………………………………….. 181

Paper VII

Table VII-1. Hydrographic information and concentrations (pg L-1) of dissolved pesticides …… 195
in surface water.
Table VII-2. Average regional concentrations of pesticides in surface water (pg L-1) ………….. 201

Table VII-3. Enantiomeric ratios of chiral pesticides in surface water …………………………. 206

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List of Figures

Chapters 3-6
Figure 1 Structures of toxaphene congeners ……………………………………………….. 5
Figure 2 Structures of cyclodiene OCPs …………………………………………………… 9
Figure 3 Structure of HCH ………………………………………………………………… 10
Figure 4 Triangular relationship between K , K and K …………………………… 11
OA OW AW
Figure 5 Henry’s Law apparatus …………………………………………………………… 14
Figure 6 Enantiomers of a -HCH …………………………………………………………... 18
Figure 7 Enantiomers of trans-chlordane ………………………………………………… 20
Figure 8 Sample collection sites, AOS-94, Great Lakes 1996-2000 and TNW-99 ……… 23
Figure 9 Toxaphene chromatograms, showing air and soil from Alabama compared
to a standard …………………………………………………………………….. 28
Figure 10 a -HCH in air: EF versus air concentration for Lake Superior, August
1996 and May 1997 ……………………………………………………………… 34
Figure 11 EF with depth in the Arctic Ocean at four stations ……………………………… 42
Figure 12 EF of a -HCH in air from AOS-94 ………………………………………………. 43

B. Original Papers

Paper I
Figure I-1. Bubble stripping experiment at 10oC, for trans-chlordane (--▲--), ……………… 75
cis-chlordane (--■--) and trans-nonachlor((cid:3)●(cid:3)).

Figure I-2. Plots of Eq. (5) for HCB (a), trans-chlordane (b), trans-nonachlor (c) …………… 76
and p,p’-DDE (d).

Figure I-3. Fugacity ratios for trans-chlordane, calculated with the HLCs determined in
this study, in comparison to literature values. The error bars are derived
from propagation of errors (as in Sahsuvar et al., 2003) for this study only. ……… 79

Paper II
Figure II-1 Concentration in pg m-3 (a) g -HCH, (b) heptachlor, (c) trans-chlordane (TC)
and trans-nonachlor (TN), (d) cis-chlordane (CC) and heptachlor
exo-epoxide (HEPX), (e) dieldrin and oxychlordane (OXY), (f) p,p’-DDE
and (g) total toxaphene calculated using single and multiple response factors
(SRF, MRF). Scales on the right pertain to the open bars. ………………………… 88

Figure II-2. Chromatograms of total toxaphene and Cl-7 to Cl-9 homologue groups in
NW Alabama air. Top = standard, middle = soil and bottom = air.
Peak 1 = B8-1413 (T2, P26), 2 = B8-1412, 3 = B8-1945, 5 = B8-806/809,
6 = B8-229, 7 = B9-1679 (T12, P50) and 8 = B9-2206. …………………………. 90

Figure II-3. Plots of log P (partial pressure, Pa) versus 1/T (ambient temperature, K)
TC = trans-chlordane, CC = cis-chlordane, TN = trans-nonachlor,
tox = toxaphene, dieldrin and g -HCH. The solid line is the linear regression
using all data points; the dashed line is the linear regression after 1-2 points
(shaded) are removed. ……………………………………………………………. 95

Paper III
Figure III-1. HCH concentrations with depth: a) Lake Superior, b) Lake Ontario …………. 116

Figure III-2. Decline of HCHs in Lake Ontario water ……………………………………….. 117
.
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Figure III-3. Enantiomer fractions of chiral OCPs in water and air ……………………. 121

Figure III-4. Plot of a -HCH enantiomer fraction (EF) versus a -HCH air concentrations
(pg m-3), dashed lines are the corresponding average EF of a -HCH in water ….. 125

Paper IV
Figure IV-1. Cruise track on Lake Superior showing station numbers (Table 1) …………….. 133

Figure IV-2. Chromatograms of total toxaphene and Cl-7 to Cl-9 homolog groups,
top = air, middle = water and bottom = standard. Peak 1 = P26,
2 = B8-1412 [22] (no Parlar number), 3 = P39, 4 = P40+P41, 5 = P42,
6 = P44, 7 = P50 and 8 = P63. P26 appears lower than actually present
in air and water samples because it splits between silicic acid fractions
1 and 2. Fraction 2 is shown here ……………………………………………… 141

Figure IV-3. Averaged relative proportions of Parlar congeners Peak 3, Peak 5
and Peak 6 normalized to Peak 4 (=1.00) for air and water samples ……………. 141

Figure IV-4. Monthly fugacity ratios (bars), air and water temperatures (solid and
dashed lines) for Lake Superior ………………………………………………….. 144

Figure IV-5. Monthly toxaphene fluxes (bars) and wind speed (solid line) for Lake Superior .. 144

Paper V
Figure V-1. Sampling and Cruise Track, from BERPAC-93 (—) and Arctic Ocean
Section-94 (---). Small numbers indicate locations of some sampling stations.
Extent of ice cover for August 1994 (---) ………………………………………… 152

Figure V-2. Figure 2: Latitudinal trends of HCHs on AOS-94 and BERPAC-93.
Bering Sea to the North Pole = increasing numbers; Pole to the
Greenland Sea = decreasing numbers.
a) a - and γ-HCH concentrations in water
b) α- and γ-HCH concentrations in air
c) α/γ-HCH ratio in air and water
d) Fugacity ratios of α- and γ-HCH ……………………………………… 155

Figure V-3. Potential and actual net fluxes of α- and γ-HCH at different latitudes.
Actual flux = potential flux x fraction of open water. Positive
flux = volatilization, negative flux = deposition …………………………………… 164

Figure V-4. Enantiomeric ratios (ERs) of α-HCH in air and water at different latitudes.
ER = (+)α-HCH/(–)α-HCH ......................................................................................... 165
Figure V-5. Chromatograms (BSCD column) showing enantioselective degradation
of α-HCH with depth at stations AOS-37 and 38 …………………………………. 166

Paper VI
Figure VI-1. Map of TNW-99 cruise track …………………………………………………… 174

Figure VI-2. Arctic ice maps, June and August, 1999 ………………………………………… 182

Figure VI-3. Clausius-Clapeyron plots for a - and g -HCH at RB and TNW-99 ………………. 184
Figure VI-4. EF of a -HCH and concentration of g -HCH at Resolute ……. 186
Bay (pg m-3). Arrow indicates ice break up.
Figure VI-5. EF in the water versus EF in the air, showing a correlation when >90% open
water (r2= 0.68), but no correlation when 0-50% open water …………….. 187

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Paper VII
Figure VII-1. Cruise track of AOS-94. Dots running from the Chukchi Sea to the
Greenland Sea correspond to station numbers on Table 1 ………………………… 193

Figure VII-2. Concentration of OCs in the upper 40-60 m of the water column , summarized
by latitude (N) HCHs: 65-69 = station 1 + BERPAC-93 data; 70-74 =
station 2 + BERPAC-93 data; 75-79 = stations 7,11,13,16; 80-84 =
stations 18,19,20,24,25,26; 85-89 = stations 28,29,30,31; 90= station 35;
84-80= stations 37,38; 75 = station 39. Other OCs: 65-69 = station 1;
70-74 = station 2; 75-79 = stations 11,13,16; 80-84 = stations 20,24,25;
85-89 = stations 28,29,31; 90 = station 35; 84-80 = station 37; 75 = station
39. Bar shades are: a -HCH (black) and g -HCH (white), CHBs: single
response factor (black) and multiple response factor (white), heptachlor epoxide
(black), trans-chlordane (black) and cis-chlordane (white), endosulfan-I
(black) and endosulfan-II (white), trans-nonachlor (black) and cis-nonachlor
(white) …………………………………………………………………………… 200

Figure VII-3. Chromatograms of the 7-, 8- and 9-chlorinated CHBs in surface water at
station 37 ………………………………………………………………………… 203

Figure VII-4. Enantiomeric ratios (ERs) of a -HCH in the dissolved (–) and particulate (---)
Phases ……………………………………………………………………………. 205

Figure VII-5. Chromatograms of heptachlor exo-epoxide (HEPX), cis-chlordane and
trans-chlordane enantiomers in the dissolved phase at station 35 ……………… 205

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