Chlorinated Dioxin Trends between 1987 and 1993 for Samples of Crab Hepatopancreas from Pulp and Paper Mill and Harbour Sites in British Columbia
M. B. YUNKER' and W. J. CRETNEy 2
Department of Fisheries and Oceans Institute of Ocean Sciences Sidney, British Columbia
1995
Canadian Technical Report of Fisheries and Aquatic Sciences 2082 Canadian Technical Report of Fisheries and Aquatic Sciences
Technical reports contain scientific and technical information that contributes to existing knowledge but which is not normally appropriate for primary literature. Technical reports are directed primarily toward a worldwide audience and have an .international distribution. No restriction is placed on subject matter and the series reflects the broad interests and policies ofthe Department of Fisheries and Oceans, namely, fisheries and aquatic sciences. Technical reports may be cited as full publications. The correct citation appears above the abstract of each report Each report is abstracted in Aquatic Sciences and Fisheries Abstracts and indexed in the Department's annual index to scientific and technical publications. Numbers 1-456 in this series were issued as Technical Reports of the Fisheries Research Board of Canada Numbers 457-714 were issued as Department ofthe Environment, Fisheries andMarine Service, Research and Development Directorate Technical Reports. Numbers 715-924 were issued as Department of Fisheries and the Environment, Fisheries and Marine Service Technical Reports. The current series name was changed with report number 925. Technical reports are produced regionally but are numbered nationally, Requests for individual reports will be filled by the establishment listed on the front cover and title page. Out-of-stock reports will be supplied for a fee by commercial agents.
Rapport technique canadien des sciences halieutiques et aquatiques
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M. B. YUNKER1 and W. J. CRETNEy 2
Department of Fisheries and Oceans Institute of Ocean Sciences Sidney, British Columbia
1995
Canadian Technical Report of Fisheries and Aquatic Sciences 2082
"' 2 Contaminants Science Section, Institute of Ocean Sciences, Box 6000, Sidney, B.C., Canada V8L 4B2
© Minister of Supply and Services Canada 1995 Cat. No. Fs 97-6/2082E ISSN 0706-6457
Correct citation for tbis publication:
Yunker, M. B., and W. J. Cretney. 1995. Chlorinated dioxin trends between 1987 and 1993 for samples of crab hepatopancreas from pulp and paper mill and harbour sites in British Columbia. Can. Tech. Rep. Fish. Aquat. Sci. 2082: xiii + 138 p.
ii ABSTRACT
Yunker, M. B., and W. 1. Cretney. 1995. Chlorinated dioxin trends between 1987 and 1993 for samples of crab hepatopancreas from pulp and paper mill and harbour sites in British Columbia. Can. Tech. Rep. Fish. Aquat. Sci. 2082: xiii + 138 p.
Principal components analysis (PCA) has been applied to a large data set of the concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans in samples of crabhepatopancreas from British Columbia (B.C.), Canada. These samples have been collected since 1987 from locations in the vicinity of B.C. coastal mills and the principal B.C. harbours. PCA distinguishes harbour samples from mill samples, reveals differences between individual mill sites and reliably classifies the dioxin and furan congener patterns according to chlorine bleaching, digested polychlorinated phenol and pentachlorophenol wood preservative sources. PCA is also used to assign sources to individual crab samples.. In most cases changes in mill process chemistry since 1987 have produced dramatic reductions in both the proportion of toxic 2,3,7,8-chlorinated congeners and the overall chlorinated dibenzo-p-dioxin and dibenzofuran concentrations. The mill related tetrachlorodibenzofurans have been removed faster than the hexachlorodibenzo-p-dioxins, with the result that composition profiles and PCA projections for the mill sites have become more similar over time. Crab hepatopancreas samples from B.Co's harbours have lower proportions of the toxic 2,3,7,8-chlorinated congeners, but have shown less change over time.
Keywords: chlorinated dibenzo-p-dioxins,chlorinated dibenzofurans, crab hepatopancreas.principal components analysis
111 I~ RESUME
Yunker, M. B., and W. 1. Cretney. 1995. Tendances de la distribution des dioxines chlorees entre 1987 et 1993 dans des echantillons d'hepatopancreas de crabes provenant de sites d'usines de pates et papier et de ports de Colombie-Britannique. Can. Tech. Rep. Fish. Aquat. Sci. 2082: xiii + 138 p.
L' analyse en composantes principales (ACP) a 6te appliquee a un vaste ensemble de donnees sur les concentrations de dibenzo-p-dioxines et de dibenzofurannes chloreespresentes dans les echantillons d'hepatopancreas de crabes preleves en Colombie-Britannique (C.-B.), Canada. Ces echantillons ont ete recueillis depuis 1987 a proximite des usiries de pates et papier de la cote et des ports importants. L' analyse permet de distinguer les echantillons recueillis a proximite de ports de ceux recueillis a proximite des usines. Elle revelo egalement les differences entre les sites de collecte a proximite des usines et classe de facon assez sure les distributions descongeneres dioxines et furannes en fonction du blanchiment au chlore, des phenols polychloresdigeres et des sources d'agents de protection du bois a base de pentachlorophenol. L'ACP peut egalement servir a determiner les sources odes differents echantillons de crabes. Dans la majorite des cas, les modifications apportees au procede chimique des usines depuis 1987 ont induit des reductions drastiques ala fois dans la proportiondes congeneres toxiques, 2,3,7,8-dibenzo-p-dioxines, et de l'ensemble des congeneres ainsi que des concentrations des dibenzofurannes. Les tetrachloro-dibenzofurannes provenant de ces usines ont diminue a un rythme plus rapide que celui des hexachloro-dibenzo-p-dioxines, faisanten sorte que les profils de composition et les previsions de I' ACP sont graduellement devenus plus similaires a proximite des usines. Les echantillons d'hepatopancreas provenant des ports de C.B. montraient des proportions plus faibles de congeneres tetrachlorees (2,3,7,8)mais un changement temporel plus lent que Ies autres congeneres.
Mots-des: dibenzo-p-dioxines chlorees, dibenzofurannes chlorees, hepatopancreas de crabe, analyse en compos antes principales
iv ===-_____c~=_==___---_____c---~~~~~-~~------
TABLE OF CONTENTS
ABSTRACT 111 RESUME IV
TABLE OF CONTENTS V LIST OF MAPS vii LIST OF TABLES V111 LIST OF FIGURES ix ACKNOWLEDGMENTS xiii
1. INTRODUCTION 1
2. PCA MODEL BUILDING 5
3. OVERVIEW OF PCA RESULTS 11
THE PCA MODEL 11 APPLICATION OFPCATO B.C. COASTAL SITES 14 COMPARISON OF DIFFERENT CRAB SPECIES 15
4. HARBOURS AND REMOTE AREAS 25
HARBOURS 25 REMOTE AREAS 26 Baseline Locations 26 Quatsino Sound and Phillips Arm 27
5. HOWE SOUND 35
SAMPLES FROM OUTSIDE HOWE SOUND 36
6. CROFTON 47
7. CAMPBELL RIVER 57
8. GOLD RIVER 67
9.NANAIMO 75
10. PORT ALBERN! 85
V I~ 11. POWELL RIVER· 93
12. PRINCE RUPERT 101
13. KITIMAT 111
14. CONCLUSIONS 121
15. REFERENCES 123
16. BIDLIOGRAPHY OF DATA REPORTS 125
Howe Sound 125 Strait of Georgia 126 Crofton 127 Campbell River 128 Gold River 131 Nanaimo 131 Port Alberni 132 Powell River 134 Prince Rupert 135 Kitimat 137
vi LIST OF MAPS
Map 1-1. Map ofthe British Columbia coast showing the pulp mills and the principal harbours. 3
Map 5-1. Crab sampling locations in Howe Sound. 38
Map 5-2. Crab sampling locations between Howe Sound and Powell River. 39
Map 6-1. Crab sampling locations near Crofton. 49
Map 7-1. Crab sampling locations near Campbell River. 60
Map 8-1. Crab sampling locations near Gold River. 69
Map 9-1. Crab sample locations near Nanaimo, 77
Map 10-1. Crab sampling locations near Port Alberni. 86
Map 11-1. Crab sampling locations near Powell River. 94
Map 12.,.1. Crab sampling locations near Prince Rupert. 103
Map 13-1. Crab sampling locations near Kitimat. 113
Vll LIST OF TABLES
Table 1-1. Coastal B.C. sampling sites, their physical environment and the pulping process used by th~ different mills. 2
Table2-1. PCA model abbreviations, percent of samples for which the congeners used in the PCA model were undetectable, 2,3,7,8-toxic equivalent factors for the peA congeners and the variables used to calculate a normalizationfactor. 7
Table2-2. Samples with too few congeners detectable to be included in the PCA data set. 8
Table 3-1. Dungeness crab hepatopancreas congener total and TEQaverages obtained using samples with similar PCA projections. 16
Table 3-2. Congener totals and calculated TEQs for the samples of Dungeness, Red Rock and Box crab used in the species comparison. 17
Table 4-1. Samples from B.C. harbours and remote areas of the B.C. coast. 28
Table 5-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Howe Sound. 37
Table 6-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Crofton. 48
Table 7-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Campbell River. 59
Table 8-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Gold River. 68
Table 9-1. Dungenesscrab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Nanaimo Harbour and the Harmac mill site. 76
Table 10-1. Dungenesscrab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Port Alberni. 85
Table 11-1. Dungenesscrab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Powell River. 93
Table 12-1. Dungenesscrab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Prince Rupert. 102
Table 13-1. Dungenesscrab hepatopancreas congener total and TEQ averages for samples with similarPCA projections from Kitimat. 112
viii LIST OF FIGURES
Figure 2-1. Samples from the Central Coast and Queen Charlotte Islands in 1991 (n=2). 9
Figure 2-2. Samples C IO (1990) and C1 (1991) from the Nanaimo area (11=2). 9
Figure 2-3. Prince Rupert (1991) samples SC4, SC5 and SC6 (n=3), 10
Figure 3-1. Varimax rotated variable (loadings) plot for PCnDIF congener projections in the first and second PCs. 18
Figure 3-2. Varimax rotated sample (scores) plot for crab hepatopancreas samples in the first and second PCs. 19
. Figure 3-3. Crab sample congener profiles and PCA projections for the earliest sampling times available. 20
Figure 3-4. Crab sample congener profiles and PCA projections for the most recent sampling times. 21
Figure 3-5. Dungeness and RedRock crab samples from Nanaimo, the Sechelt peninsula, Campbell Riverand Powell River. 22
Figure 3-6. Dungeness and Box crab samples from Campbell River, Powell River and Howe Sound. 23
Figure 4-1. PCA projections for samples from the B. C. harbours. 29
Figure 4-2. Vancouver Harbour/Burrard Inlet in 1987 (n=l) and 1992 (n=7). 30
Figure 4-3. The Fraser River estuary in 1987 (n=l) and 1993 (n=4). 30
Figure 4-4. Victoria and Esquimalt harbours in 1987 (n=1)' and 1994 (n=6). 31
Figure 4-5. Chemanius harbour in 1987 (ne l), 31
Figure 4-6. PCA projections for samples from remote areas. 32
Figure 4-7. Samples collected from remote areas of the B. C. coast in 1993. 33
Figure 4-8. Congener profile for a crab sample from Nootka Sound in 1993 (nel), 33
Figure 4-9. Samples from Quatsino Sound (n=5). 34
Figure 4-10. Samples from Phillips Arm (n=4). 34
ix i~ Figure5-1. Howe Sound congener profiles for 1987 (n=2) and 1989 (n=6). 40
Figure5-2. Congenerprofiles for Port Mellon (n=6) and Woodfibre(n=2) mills in19~3. 40
Figure5-3. PCAprojections for samples from Howe Sound in 1987 and 1989. 41
Figure5-4. PCA projections for samples from Howe Sound in 1990. 42
Figure 5-5. PCA projections for samples from Howe Sound in 1991. 43
Figure5-6. PCA projections for samples from Howe Sound in 1992. 44
Figure 5-7. PCA projections for samples from Howe Sound in 1993. 45
Figure 6-1. Crofton congener profiles for 1987 (n=2) and 1990 (n=5). 50
Figure 6-2. CowichanBay congener profiles for 1990 (n=4). 50
Figure 6-3. Croftoncongener profiles for 1993 (n=3). 51
Figure 6-4. PCA projections for samples from Crofton in 1987 and 1990 and CowichanBay in 1990. 52
Figure 6-5. PCA projections for samples from Crofton in 1991. 53
Figure 6-6. PCA projections for samples from Crofton in 1992. 54
Figure 6-7. PCA projections for samples from Crofton in 1993. 55
Figure 7-1. Congenerprofiles for stations in the CampbellRiver estuary in 1990 (n=1 for both). 61
Figure 7-2. CampbellRiver congener profiles for 1990 (n=3). 61
Figure 7-3. CampbellRiver congener profiles for 1993 (n=3). 62
Figure 7-4. PCA projections for samples from CampbellRiver in 1990. 63
Figure 7-5. PCA projections for samples from CampbellRiver in 1991. 64
Figure 7-6. PCA projections for samples from CampbellRiver in 1992. 65
Figure 7-7. PCA projections for samples from CampbellRiver in 1993. 66
Figure 8-1. Gold River congener profiles for 1990 (n=5). 70
x Figure 8-2. Gold River congener profiles for 1993 (n=4). 70
Figure 8-3.PCA projections for samples from Gold River in 1990. 71
. Figure 8-4. PCA projections for samples from Gold River in 1991. 72
Figure 8-5. PCA projections for samples from Gold River in 1992. 73
Figure 8-6. PCA projections for samples from Gold River in 1993. 74
Figure 9-1. Nanaimo Harbour congener profiles for 1987 (ne l) and 1990 (n=2). 78
Figure 9,..2 Nanaimo Harbour congener profiles for 1992 (n=4). 78
. Figure 9-3. Nanaimo/Harmac mill congener profiles for 1987 (n=l) and 1990 (n=5). 79
figure 9-4. NanaimolHarmac mill congener profiles for 1993 (n=3). 79
Figure 9-5. PCAprojectipns for samples from Nanaimo in 1990. 80
Figure 9-6. PCA projections for samples from Nanaimo in 1991. 81
Figure 9-7. PCA projections for samples from Nanaimo in 1992. 82
Figure 9-8. PCA projections for samples from Nanaimo in 1993. 83
Figure 10-1. Port Alberni congener profiles for 1990 (n=6). 87
Figure 10-2. Port Alberni congener profiles for 1993 (n=4). 87
Figure 10-3. PCA projections for samples from Port Alberni in 1990. 88
Figure 10-4. PCA projections for samples from Port Alberni in 1991. 89
Figure 10-5. PCA projections for samples from PortAlberni in 199~. ,90
Figure 10-6. PCA projections for samples from fort Alberni in 1993. 91
Figure 11-1. Powell River congener profiles for 1990 (n=5). 95
Figure 11-2. Powell River congener profiles for 1993 (n=2). 95
Figure 11-3. PCA projections for samples from Powell River in 1990. 96
Figure 11-4. PCA projections for samples from Powell River in 1991. 97
xi IF Figure 11-5. PCA projections for samples from Powell River in 1992. 98
Figure 11-6.PCA projections for samples f~om Poweli River in 1993. 99
Figure 12-1. Prince Rupert congener profiles for 1987 (n=l) and 1989 (n=3). 104
Figure12-2. Prince Rupert congener profiles for 1993 (n=4). 104
Figure 12-3. PCA projections for samples from Prince Rupert in 1987 and 1989. 105
Figure 12-4. PCA projections for samples from Prince Rupert in 1990. 106
Figure 12-5. PCA projections for samples from Prince Rupert in 1991. 107
Figure 12-6. PCA projections for samples from Prince Rupert in 1992.. 108
Figure 12-7. PCA projections for samples from Prince Rupert in 1993. 109
Figure 13-1. Congener profiles for Eurocan pulp mill sludge and Minette Bay sediment. 114
Figure 13-2. Congener profiles for soil and sludge samples from the Alcan smelter. 114 r
Figure 13-3. Congener profiles for roof dust from the casting area ofthe Alcan smelter. 115
Figure 13-4. Kitimat congener profiles for 1989 (n=8). 115
Figure 13-5. Kitimat congener profiles for 1991 (n=7). 116
Figure 13-6. Kitimat congener profiles for 1992 (n=41). 116
Figure 13-7. PCA projections for samples from Kitimatin 1989. 117
Figure 13-8. PCA projections for samples from Kitimat in 1991. 118
Figure 13-9. PCA projections for samples from Kitimat in 1992. 119
xii ACKNOWLEDGMENTS
Collection and data analysisfor the pulp mill sites which constitute most of the samples in this study was performed by Hatfield Consultants Ltd., Beak Consultants Ltd., G3 Consulting Ltd. and Norecol Ltd. with chemical analyses done by Axys Analytical Ltd., Envirotest Laboratories Ltd. and Wellington Laboratories Ltd. All of this work was funded directly by the operators of the B.C. mills. Samples from remote areas and the B.C. harbours were collected by the Departments ofFisheries and Oceans and Environment and were primarily analysed by government laboratories.
D. C. Muir, R. F. Addison, D. A. KellYl H. Rogers and 1. W. Dwernychuk provided helpful comments on an earlier draft of this report. Their assistance is gratefully acknowledged.
W. Knapp, M. Sullivan and M. Hagen assisted in assembling the data set. W. Knapp also provided maps, reports etc., plus electronic copy of the majority ofthe Bibliography in Section 16. H. Rogers, MiIkonomou, M. Whittle and J. Thompson provided unpublished data from the harbours and remote areas. R. Norstrom is thanked for providing access to the unpublished 1987 data. J. Van Oostdam is also thanked for providing access to unpublished data from the Alcan site. J. C. Cosgrove of the Royal British Columbia Museum recounted his observations ofcrab feeding behaviour and provided a current reference. E. Pelletier and C.Picard translated the abstract into French. Funding for this multivariate interpretation was provided by the Department of Fisheries and Oceans Toxic Chemicals Program.
xiii 1. INTRODUCTION
. Chlorinated contaminants produced and discharged by pulp mills were documented in British Columbia, Canada (B.C.) coastal waters more than a decade ago (e.g., Voss and Yunker 1983). More recently the presence of chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ecologically significant concentrations in sediments, shellfish and groundfish was described by .Norstrom et al. (1988), both in the vicinity of B.C. mills and in the principal B.C. harbours. As one result, harvesting of prawn, shrimp and crab was restricted near pulp mills in late 1988 more extensive fisheries closures have followed as the extent of contamination has been more fully delineated.
The major processes that produced PCDDlFs in pulp mill effluent in the past were the chlorination of dibenzo-p-dioxin precursors during bleaching and the condensation of polychlorinated phenols during pulp digestion (Luthe and Prahacs 1993; Luthe et al. 1993). The elimination of dibenzo-p-dioxin precursors from defoamer products, exclusion of chlorophenol-contaminated wood chips and introduction of chlorine dioxide bleaching have dramatically reduced mill-related contamination (Whitehead et al, 1992; Luthe et al, 1992). The introduction of PCDDlFs from combustion (both from the mill and ambient deposition) into mill effluent is a more minor process, but has proved to be more difficult to eliminate (Hites 1990; Luthe and Prahacs 1993).
Monitoring programs were initiated in 1989 to document the sources and concentrations of PCDDlFs in B.C. harbours and pulp mill sites. These. programs were designed to assess ecosystem impact, address human health concerns due to contamination of the fishery and assist in the formulation of regulations for fisheries management. Aspects such as.the geographical 'extent of contamination, persistence of PCDDlFs over time, and trends in the congener composition and proportion of toxic congeners were also important considerations. However, translation of these aspects into monitoring programs has produced a very large data set. For crab hepatopancreas alone research and monitoring activities since the late 1980s in the vicinity of 10 coastal mills and the principal harbours (Table 1-1; Map 1-1) had produced chlorinated dibenzo-p-dioxin and dibenzofuranconcentrations for nearly 500 samples. A data set this size can only be effectively interpreted with multivariate analysis techniques.
In this work we employ Principal Components Analysis (PCA)to explore the interrelationships and trends in both the chlorinated dibenzo-p-dioxin and dibenzofuran patterns and the toxic congener composition among B.c. mill sites and between harbours and mill sites. The integration of toxic-equivalency into the interpretation provides a mechanism for addressing both ecosystem effects and potential health risks to humans. An abbreviated account of this workhas appeared in Yunker and Cretney (1996).
1 Table 1-1. Coastal B.C. sampling sites, their physical environment and the pulping process used by the different mills. Site Geographical Physical Primary Location Environment Mill Process Pulp mill sites Port Alberni Fjord Restricted circulation Bleached Kraft Crofton Channel Well flushed BleachedKraft Campbell River (Elk Falls Mill) Channel Well flushed Bleached Kraft Gold River Fjord Restricted circulation Bleached Kraft Howe Sound (port Mellon and Woodfibre Mills) Fjord Restricted circulation Bleached Kraft Kitimat " Fjord Restricted circulation Unbleached Kraft Nanaimo (Harmac Mill) Channel Well flushed Bleached Kraft Powell River Strait Well flushed Bleached Kraft Prince Rupert Narrow Channel Restricted circulation ~ . Bleached Kraft Harbours and industrialized areas Vancouver Harbour (Burrard Inlet) Fjord Restricted circulation Nanaimo Harbour Bay Restricted circulation VictorialEsquimalt Harbours Bay Restricted circulation Fraser River mouth Estuary Well flushed
a Kitimat is also a major harbour and is the site of an aluminum smelter and a methanol production plant (see Section 13).
2
"f" 51° i I e:::;...
CD
Quatsino Sound
50 0
54"
52" I- Queen Charlotte Is
50" • Pac i fie
o c e a n ~c;,i;I;'1 1260 1250 1240 1230 1220 48" t , ,,,,, 134" 130" 126" 122" Map 1-1. Map ofthe British Columbiacoast showing the pulp mills and the principal harbours.
3 TillS PAGE IS BLANK 2. peA MODEL BUILDING
Data for the concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans in 469 samples of crab hepatopancreas were obtained primarily in electronic form from the Federal Departments of Fisheries and Oceans and Environment. Samples from a few mill sites from 1988 and 1989 were not analyzed for the full suite of congeners and could not be included in the data set. All data were then reverified against original laboratory reports. Data were primarily for Dungeness crab (Cancer magister) hepatopancreas, although 13 hepatopancreas samples from Red Rock crabs (Cancer productus), six from Box crabs (Lopholithodes spp) and one sample from a Kelp crab (Pugettia producta) were also included.
The data set included 11 benchmark samples from 1987 (i.e. prior to any mill process changes) which were obtained from a Canadian Wildlife Service unpublished report (Norstrom et al. 1988). Post 1987 monitoring data for the mill sites included 378 samples analyzed by Axys Analytical Ltd. of Sidney B.C. (formerly Seakem Analytical Ltd.), 15 samples analyzed by Envirotest Ltd. of Edmonton Alberta and eight samples analyzed by Wellington Laboratories Ltd. of Guelph Ontario. The 1989 and 1993 samples from Kitimat and Nanaimo respectively were analyzed by Envirotest and the 1993 samples from Gold River were analyzed by Wellington Laboratories. Data for samples from remote locations have principally been produced by the Department of Fisheries and Oceans, with 30 samples from the Great Lakes Laboratory for Fisheries and Aquatic Sciences in Burlington Ontario and 25 samples from the Institute of Ocean Sciences in Sidney B.C.
Consistent collection, dissection, extraction and analysis procedures have been maintained for the crab samples analyzed by Axys Analytical (more than 80% of the data set). All samples were collected and dissected by Hatfield Consultants and were all SUbjected to the same extraction protocol by Axys Analytical (e.g., Dwernychuk 1993). All samples were spiked with nC_ labelled surrogate standards for the 2,3,7,8-tetra- to octachlorodibenzo-p-dioxins plus 2,3,7,8 tetrachlorodibenzofuran; as a minimum 13C-Iabelled 1,2,3,4-tetrachlorodibenzo-p-dioxin was added as a recovery standard. For samples analyzed by high resolution GC/MS (i.e. 1991 onwards), 13C-Iabelled 2,3,7,8-penta- to heptachlorodibenzofuran surrogates and 1,2,3,7,8,9 hexachlorodibenzo-p-dioxin and ],2,3,4,6,7,8-heptachlorodibenzo-p-dioxin recovery standards were also added. Minor method differences occurred with the other laboratories, but all analyses employed l3C-Iabelledstandards.
Unsupervised principal components analysis was performed using the nonlinear iterative partial least squares (NIPALS) algorithm in a program which allowed a detailed examination of both crab sample and variable (congener) projections (respectively scores and loadings; software was provided by the Chemometrics Clinic, Seattle WA). Congeners and congener totals which were undetected (ND) were replaced by the limit of detection. Values with questionable ion ratios (NDR) were used only if the concentration was reasonable in the context of similar samples from the site.
5 For most PCA variables the limit of detection was used to estimate the concentration for less than 15% of the samples (Table 2-1). The more chlorinated congeners, particularly OCDD, OCDP and the HpCDFs, were undetectable in higher percentages of samples and were used only when it was verified that their presence did not skew the model. The congeners 1,2,3,4,7,8 HxCDD and 1,2,3,4,7,8,9-HpCDF were undetectable in most samples and were removed. Because the 2,3,7,8-substituted HxCDFs were only detectable in a few samples, an average of the detection limits or concentrations for the individual congeners was used. For each congener series a non-2,3,7,8 congener total was obtained by subtracting the 2,3,7,8-substituted congener(s) from the homologue total; if a value of zero resulted for these "other" dioxins, the detection limit for the homologue total was substituted.
Normalization of each sample was employed before PCA, because: 1) concentrations differed by orders of magnitude, particularly between years and 2) a primary goal was to examine trends in the chlorinated dibenzo-p-dioxin and dibenzofuran congeners with a "mill" pattern. Log transformation was also evaluated, but the resulting PCAmodel was more sensitive to detection limit artifacts. Negative correlations due to closure of the largest variables were avoided during normalization by using a subset of the variables with mid-range standard deviations and means (Johansson et al. 1984; Yunker et al. 1995). The subset of congeners used. to calculate normalization factors for each sample is listed in Table 2-1. Data were then autoscaled (mean centered and divided by the variance on a variable-by-variable basis) before PCA.
The use of the limit of detection as an estimation of the actual concentration proved to be a problem for 18 low concentration samples that either were from remote areas or were earlier (1989-91) samples with high detection limits (Table 2-2). These samples had only 2-6 congeners detectable out of 20 (average 4), and the limit of detection (and hence apparent concentration) was usually noticeably higher for the higher chlorine-numbered congeners (e.g., Figure 2-1 to Figure 2-3). The resulting dominance of hepta- and octachlorinated congeners produced a . spurious separation of these samples from all other samples in the first principal component (PC). When these samples were excluded the hepta- and octachlorinated congeners became much less important to the PCA model (see following). To simplify source interpretation a Varimax axis rotation was then applied to the first three PCs,
6 Table 2-1. PCA model abbreviations, percent of samples for which the congeners used in the PCA model were undetectable, 2,3,7,8-toxic equivalent factors for the PCA congeners and the variables used to calculate a normalization factor. Congener PCA Percent TEF Normalizing Abbrev. Undetectable Variables 2,3,7,8-TCl)D 4D 8.1 1.0 4D Non-2,3,7,8 TCDD 4DO ·5.8 0 1,2,3,7,8-PnCDD 5l) 11.1 0.5 SD Non-2,3,7,8 PnCDD 5DO 9.2 0 5DO 1,2,3,6,7,8-HxCDD 6D2 1.1 0.1 1,2,3,7,8,9-HxCDD 6D3 12.2 0.1 6D3 Non-2,3,7,8 HxCDD 6DO 0.4 0 1,2,3,4,6,7,8-HpCDD 7D 15.4 0.01 7D Non-2,3,7,8 HpCDD 7DO 12.8 a 7DO OCDD 8D 39.2 0.001 8D 2,3,7,8-TCDF 4F 0.6 0.1 Non-2,3,7,8 TCl)F 4FO 0.6 a 1,2,3,7,8-PnCDF 5F1 29.9 0.05 5F1 2,3,4,7,8-PnCl)F 5F2 14.1 0.5 5F2 Non-2,3,7,8 PnCDF 5FO 7.2 a SFO 2,3,7,8-HxCDF mean 6F 66.3 0.1 Non:'2,3,7,8 HxCDF 6FO 23.0 a 6FO 1,2,3,4,6,7,8-HpCDF 7F1 41.2 0.01 7F1 Non-2,3,7,8 HpCDF 7FO 39.4 a OCl)F 8F 87.2 0.001
7 Table 2-2. Samples with too few congeners detectable to be included in the PCA data set. ArealYear Sample Site Location Species Congeners .. Calculated Date Number Detectable TEQ pg/g Queen Charlotte Is. 91 19-Mar-91 Government Creek Dungeness Crab 4 0.2 Central Coast 91 19-Mar-91 Burke Channel Dungeness Crab 4 0.2 Crofton 90 14-Aug-90 C14 Satellite Channel Dungeness Crab 4 2.0 Crofton 90 16-Aug-90 C15 Satellite Channel Dungeness Crab 4 7.1 Crofton 90 20-Aug-90 C16 Houston Channel Dungeness Crab 6 7.6 Crofton 90 20-Aug-90 C16A Houston Channel Dungeness Crab 6 21.1 Crofton 90 15-Aug-90 C19 Saanich Inlet Dungeness Crab 4 4.9 Crofton 90 16-Aug-90 C21 SaanichPeninsula - North Red RockCrab 4 1.7 Nanaimo 90 24-Aug-90 ClO Hammond Bay Dungeness Crab 4 4.4 Port Alberni 90 04-Jul-90 C6 Sproat Narrows Dungeness Crab 5 3.1 Powell R. 90 07-Sep-90 C7 Savary Is. - North Dungeness Crab 4 9.4 Powell R. 90 04-Sep-90 C8 Savary Is. - South Red Rock Crab 2 0.9 Powell R. 90 05-Sep-90 cn Algerine Passage Dungeness Crab 4 5.1 Prince Rupert 90 06-Jun-90 SCIA Morse Basin Dungeness Crab 5 16.6 Prince Rupert 91 22-Mar-91 SC4 Kitson Island - West Dungeness Crab 6 7.9 Prince Rupert 91 22-Mar..:91 SC5 Coast Island - South Dungeness Crab 6 6.9 Prince Rupert 91 22-Mar-91 SC6 Kinahan Islands Dungeness Crab 4 1.5 Kitimat Arm 89 16-Dec-89 S4 Gobeil Bay Dungeness Crab 2 0.8
8
.., 12
Mean TEQ=0.2 pg/g 10 10
00 --~ 8 d' o ...... tl 6 I:: II) g o U 4
2
4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F
• Measured Concentrations ~ Detection Limit
Figure 2-1. Samples from the Central Coast and Queen Charlotte Islands in. 1991 (n=2). '. -~,
80
Mean TEQ=9.1 pg/g 67 60 '00 bb p., d' .9..... ro ...... 40 I:: II) U I:: 0 U 20
4D 5D 6D2 6DO 7DO 4F 5F15FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7F 1 8F
• Measured Concentrations ~ Detection Limit
Figure 2-2. Samples ClO (1990) and Cl (1991) from the Nanaimo area (n=2).
9 35
30 Mean 1EQ=5.4 pg/g 29 co bb 25 c... d' 0 OJ:! 20 cd ...... ~ a.> o 15 ~ 0 U 10
5
0 4D 50 602 600 700 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 70 8D 4FO 5F2 6F 7Fl 8F
• Measured Concentrations ~ Detection Limit
Figure 2-3. Prince Rupert (1991) samples SC4, SC5 and SC6 (n=3).
10 ------~------
3. OVERVIEW OF peA RESULTS
The utility of this data set for the interpretation of trends in congener composition both between sites and over time is greatly enhanced by having more than 80% of the samples analyzed by one laboratory. Furthermore, the normalization of samples before PCA removed potential concentration biases and allowed samples from different laboratories to be added to the model. Concentration profiles and PCA projections for the non-Axys Analytical samples were entirely consistent with the Axys samples from similar sites or the same site in different years.
THE peA MODEL
PCA is invaluable for classifying chlorinated dibenzo-p-dioxin and dibenzofuran congener variables according to their primary source (e.g., chlorine bleaching, pentachlorophenol) and for identifying congeners that covary. PCA separates a data matrix into the product of two matrices (one each for samples and variables) with the PCs comprising individual column or row vectors in their respective matrix. Each PC provides interrelated information concerning trends in the samples and the variables. The PCA model is calculated with no a priori assumptions about the data structure and completely unbiased projections result. A very readable explanation of the application ofPCA to chemical data has been published by Meglen (1992).
The crab hepatopancreas PCA model used throughout this report includes 451 samples and employs 20 PCDDIF variables. Before Varimax axis rotation the variance accounted for by the model in respectively the first, second and third PCs was 27.4%, 17.4% and 14.6%, for a total of 59.4%. The firstfive PCs all had eigenvalues greater than 1.0, and thus represented real (as opposed to random) variation in the data set (Meglen, 1992). After axis rotation of the first three PCs the variance in the three PCs was redistributed to 22.1%, 18.8% and 18.5%.
Variable and sample projections for the PCA model are given in Figure 3-1 and Figure 3-2. General features of the model are discussed in this section. In the area by area discussion that follows PCA sample plots are presented that show subsets of the larger model to illustrate, for example, the trends in samples from a given location in a given year. Hence these subset sample plots are only visual simplification not a newPCA model based on a smaller number of samples, and the general discussion in this section applies to every PCA plot shown in this report.
In Figure 3-1 the PCDDIF variables project together according to source. Congeners that are produced primarily by chlorination of'dibenzo-p-dioxin precursors during pulp mill chlorine. bleaching project to the far right and include 2,3,7,8-TCDFI the non-2 1317,8 TCDFs and the two 2,3,7,8-PnCDF isomers (e.g., Luthe and Prahacs 1993). Dibenzo-p-dioxins that are produced by the condensation of polychlorinated phenols during pulp digestion cluster in the bottom ofFigure 3-1, close to the y-axis, and include 1,2,3,7,8-PnCDD, 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD and the non-2,3,7,8 HxCDD isomers (Luthe et al. 1993). 2,3,7,8-TCDDprojects midway between these two groups, which suggests mixed sources. Congeners that are present in
11
--_~_----_._._--- pentachlorophenol wood preservative but are removed during the pulping process project at the top of Figure 3-1 and include 1,2,3,4,6,7,8-HpCDF, the non-2,3,7,8 TCDFs and HxCDFs, and to a lesser extent the non-2,3,7,8 HpCDFs (Hagenmaier and Brunner 1987; Luthe et al. 1993). With the exception of 1,2,3,4,6,7,8-HpCDF, all of the above congeners have significant loadings only in the first two PCs.
Congeners at or near the limit of detection (Table 2-1), such as 2,3,7,8-HxCDF, OCDF, OCDP and the HpCDDs project close to the origin in the first two PCs but make a strong contribution to the third PC. Thus the contributions of detection limit artifacts and/or combustion have been largely shifted to the third Pc. The remaining variable, non-2,3,7,8 PnCDD,makes a contribution to all three PCs and is apparently present in all sample types.
The projection of the toxic 2,3,7,8-substituted TCDD, TCDP and PnCDDs on the right side of Figure 3-1 produces a correlation between samples and their toxicity in Figure 3-2. The log of the 2,3,7,8-TCDD toxic equivalents (TEQ) is highly correlated (r2=0.42; p There is a direct source correspondence between the positions of the variables in Figure 3-1 and the positions of the samples in Figure 3-2. In Figure 3-2 samples with similar distributions of the 20 PCDDIF congeners and congener totals cluster or project together. Samples that are far apart have a different "fingerprint" of the 20 congeners and the crabs collected for these samples have been exposed to a different suite of PCDDIFs. Crab samples projecting to the far right in Figure 3-2 have the highest proportion of congeners characteristic of pulp mill chlorine bleaching, while samples in the lower centre have been most strongly influenced by polychlorinated phenol condensation. Samples in between these two areashave been exposed to varying amounts of these two inputs. Crab samples projecting in the upper left of Figure 3-2 have been exposed to pentachlorophenol wood preservatives and are from the major B.C. harbours. These samples have low proportions of the toxic congeners, but have high proportions of the non-2,3,7,8 congeners _. principally the PnCDFs and HxCDFs and the HxCDDs. Samples collected in different years project together indicating little or no change in composition over time. Crabs do not appear to take up hepta- and octachloro dibenzo-p-dioxins and dibenzofurans to any great extent: these congeners were generally only detectable when concentrations were very high. One important consequence is that the contribution of atmospheric combustion (the typical pattern is predominant OCDD with lesser amounts of HpCDD and HpCDF; Hites 1990) can not be evaluated based solely on crab data. 12 APPLICATION OF PCA TO B.C. COASTAL SITES Crabs from the vicinity of nine B.C. coastal Kraft mills at eight sites have been exposed to chlorine bleach plant effluents (Table 1-1). The tenth mill at Kitimat does not use chlorine bleaching. Crabs from the principal harbours have all been exposed to chlorophenols from wood treatment facilities as well as to PCDD/Fs from combustion. Crabs from reference locations, which include Sidney Island (north of Victoria), the Queen Charlotte Islands and the B.C. Central Coast, were expected to have received minimal exposure to PCDDlFs. Each area is discussed individually in the sections that follow. Averaged congener profiles for crab samples with similar PCA projections that are from locations geographically close to each mill site provide a direct connection between congener composition and the PCA results. Congener profiles are presented for the earliest and most recent samplingtimes in Figure 3-3 and Figure 3-4; the specific samples used for each profile are tabulated in the individual sections. In each case the tip of the arrow indicates the mean projection of the samples that have been used to define each profile. In all cases where 1987 and 1989/90 samples have been averaged there was little or no change in either composition profile or PCA projection over the time interval shown. For Campbell River (Elk Falls) and Powell River the crab sample collected closest to the mill site sometimes had a PCA projection similar to that of the harbours (see Sections 7 and 11). Because this likely indicates the presence of pentachlorophenol wood preservatives, these samples were not included in the profiles. Examination of Figure 3-3 and Figure 3-4 reveals striking differences between the chlorinated dibenzo-p-dioxin and dibenzofuran profiles of different mill sites. At Gold River, for example, the 1990 profile is made up almost entirely of TCDFs. In contrast, the 1989 profile from Kitimat shows a pattern consistent with polychlorinated phenol condensation, without any inputs from chlorine bleaching. This condensation was likely a result of heating pentachlorophenol contaminated wood chips during the Kraft pulping process (Luthe etal: 1993). In 1987/90 locations such as Nanaimo (Harmac Mill), Port Alberni and Campbell River contained equal proportions of the TCDFs and the non-2,3,7,8 HxCDDs. The mill at Crofton had a lower proportion ofthe HxcbDs and the mills at Powell River, Howe Sound and Prince Rupert were similar to the Gold River mill in having only small proportions of the HxCDDs. The composition of Gold River samples indicates either that very few pentachlorophenol contaminated chips were used in the bleach plant, or less likely, that digester conditions did not favour HxCDD formation. Over the four or five years since the mills introduced changes to control the discharge of PCDD/Fs, the TCDFs have been removed faster than the HxCDDs at the mill sites, while the harbour profiles have shown little change over time (Figure 3-4). At each mill site an increase in the proportion of the HxCDDs has been accompanied by a corresponding decrease in the TCDFs, While the mill sites have maintained much of their individual character, the overall effect has been for the composition profiles and PCA projections to become more similar over time. Examination of profile and PCA results for the Nanaimo area illustrates that different PCDDIF fingerprints can be obtained for locations which are only ca. 5 km apart (Figure 3-3 and Figure 3- 13 4; Section 9). In general crab samples from the Harmac mill site project with similar mill samples (close to the y-axis), while samples from Nanaimo Harbour project close to the Victoria and Vancouver Harbour samples. Nanaimo Harbour samples have a slightly higher proportion of the TCDFs than the larger harbours, and some contribution of chlorine bleaching effluents from the mill is likely. At a few locations from the boundary area just outside Nanaimo Harbour, crab samples had a mill pattern one year and a harbour pattern in another year - this highlights the utilityof PCA in assigning a contaminant source to individual crab samples. , In general 1987 samples had the highest concentrations of toxic congeners (Table 3-1). In subsequent years both lower proportions of the toxic 2,3,7,8-chlorinated congeners and a decreasein overall PCnDIF concentrations have been observed. The result has been a decrease in the TEQ at B.C. mill sites. Mills located on a fjord (where the bottom water exchanges very slowly) or in an area with restricted circulation had the highest proportion of toxic congeners in the earliest years of sampling, but have shown the largest TEQ reduction over time (Table 1-1 and Table 3-1). The Howe Sound and Gold River mills provide good examples. In quiescent areas burial plays an important role in the removal of the particulate associated dioxins and furans (cf. Macdonald et aI. 1992). Within Howe Sound the reduction in TEQ has been more rapid adjacent to the Woodfibre mill; here the large amount of sediment delivered by the Squamish River is the most likely reason for the difference. Hence, the amount of sediment available for burial at each mill site is an important factor in contaminant removal. In contrast, samples from locations which are well flushed by tidal currents had lower initial proportions of the toxic congeners than samples from inlets but have exhibited a smaller decrease in TEQ over time. The Crofton and Campbell River locations illustrate this trend. In this case burial rates are either too low or resuspension processes are too active for effective removal of contaminants by burial. The high current rates offCampbell River facilitate sediment transport and dispersal mayplaya more important role in contaminant removal in this area. The principal harbours have been less intensively studied, but they would appear to present a different situation. These locations are adjacent to metropolitan areas, with the potential for chronic inputs. Furthermore sedimentation and burial rates are likely to be lower in harbours than they are in fjords that are fed by a major river (e.g., the Squamish River in Howe Sound). It has proven to be difficult to define a background pattern for crabs on the B.C. coast. Earlier samples from remote areas were analyzed by low resolution mass spectrometry, with too few congeners detectable to provide a reliable PCA projection. Subsequent samples have generally been collected from locations away from the mill monitoring areas, but they may have been impacted by mill discharges (see Section 4). However, even samples from areas more removed from mills and harbours have PCA projections and composition profiles different from the usual atmospheric pattern (cf. Hites 1990).' This topic requires further study. 14 COMPARISON OF DIFFERENT CRAB SPECIES The different crab species that are included in this data set feed in different ecological niches. Dungeness crabs are bottom scavengers; their diet consists primarily of clams, but they also feed on smaller crustaceans and fish and will feed opportunistically on fish carcasses (Jensen, 1995). Although smaller in size, Red Rock crabs have a similar diet, but tend to frequent rocky habitats 'in. shallower water, and are likely to scavenge on smaller animals. Box crabs feed on sea urchins and other echinoderms; they are one of the few crab species that feed on anemones. Kelp crabs are situated further down the food chain; they feed mostly on vegetation, but will feed opportunistically on jellyfish. These differences in diet, and in some cases trophic level, result in exposure to different concentrations and proportions of PCDDIFs for the different crabs. To test for a relationship between species and PCDDIF congener composition, the PCA projections of Red Rock and Box crabs are compared to the projections of Dungeness crabs that were collected at the same time from the same environment (i.e. areas at a similar distance from the mill, with the same circulation pattern, etc.). In each case arrows are used to highlight the difference in PCA projection relative to the most suitable Dungeness crab sample (Figure 3-5 and Figure 3-6; Table 3-2). For a number of samples (e.g., Red Rock crabs from Lasqueti Island or a number of the Box crabs from around Quadra Island; Sections 5 and 7) no concurrent samples are available. Dungeness crab samples are also not available for comparison to the one sample of Kelp crab (Section 7). PCA projections of the Red Rock crab samples shift in a number of different directions relative to the Dungeness crab samples, which suggests an overall similarity in the congener compositions (Figure 3-5). However, on balance the Red Rock crabs appear to have a lower proportion of the most toxic congeners. In agreement, congener totals and calculated TEQs are consistently lower for samples of Red Rock crab (Table 3-2). Fewer sample pairs are available for the Box crabs, but the Box crabs consistently project to the lower left of the Dungeness crabs, and in most cases have a lower congener total and TEQ (Figure 3-6; Table 3-2). While these differences in composition may in part be due to differences in sampling location and hence the amount of exposure to mill effluent experienced by the crabs, the PCA results suggest that differences in feeding behavior have resulted in a reduction in the toxic load for both of the non Dungeness species. Given these interspecies differences in PCA projections and TEQs, it is evident that whenever possible a single species - Dungeness crab - should be used for the mill monitoring programs. The use of a single species is also preferable for statistical evaluation of trends. In addition, because the Dungeness crabs apparently ingest among the highest proportions of toxic congeners of any crab species, they provide a useful and highly defensible indicator for both fishery closures and openings. 15 Table 3-1. Dungeness crab hepatopancreas congener total and TEQ averages obtained using samples with similar peA projections. Sampling Location 1987 1989/90 1992/94 Congener Calculated n b Congener Calculated n b Congener Calculated n b Totala TEQa Totala TEQa Total a TEQa pg/g wet weight pg/g wet weight pg/g wet weight Principal Harbours 1700 77 3 - -- 770 23 17 Nanaimo Harbour 470 27 1 300 15 2 360 18 4 Port Albemi - -- 450 23 6 230 11 4 Crofton 4300 420 2 1700 130 5 1500 94 3 Campbell River (Elk Falls) - - - 1200 100 3 800 53 3 Gold River - - - 13,000 1100 5 1200 99 4 Howe Sound 30,000 2900 2 9900 850 6 1000 95 8 Kitimat - - - 570 68 8 110 7.2 41 Nanaimo (Harmac) Mill 1100 82 1 810 65 5 290 14 3 Powell River - -- 620 57 5 160 12 2 Prince Rupert 18,000 1900 1 2900 260 3 1000 53 4 a The specific samples used for these calculations are detailed in tables that are included in each of the individual sections. b n is the number of samples. 16 '.- Table 3-2. Congener totals and calculated TEQs for the samplesofDungeness, Red Rock and Box crab used in the species comparison. SamplelYear Station Location a Congener Calculated Station Location a Congener Calculated Total TEQ Total TEQ pg/g pg/g Dungeness Crab RedRock Crab Campbell R. 90 C5 Gowlland Harbour 1800 130 C2 May Island 210 21 Nanaimo 90 C5 Pylades Channel 440 44 C4 Northumberland Ch. 99 6.8 Nanaimo 90 C6 Ruxton Is. 210 20 C7 Stuart Channel 200 11 Nanaimo 91 C4 North Mudge Is. 480 36 C4 North Mudge Is. 170 14 Nanaimo 91 C4 North Mudge Is. 460 35 SecheIt 93 b C303 Secret Cove 220 10 C302 Secret Cove 33 1.4 Powell R. 93 C16 HemandoIs. 120 9.6 C15 Copeland Is. 30 2.2 Dungeness Crab Box Crab PowellR.90 C2 Harwood Is. 690 64 C3 Scuttle Bay 1600 140 Campbell R. 92 C15 Marina Island 320 25 C9 Sutil Channel 180 14 Howe Sound 93 C21 Gower Point 670 45 C23 Offshore Gower Pt. 260 16 Howe Sound 93 C21 Gower Point 690 47 a Station locations are given on maps in each individual section. b See Map 5-2. 17 0.4 I .r-- _ I I PCP Wood 0.3 Preservative 7Ft 0.2 Chlorine 0.1 I- ~7FO 7D Bleaching 7DO ,,-.... ~ I .._- SD 00 0.0 00 ...-i '--" I SF 6F C'l -0.1 I ~ -0.2 5DO 4D Mixed Sources -0.3 Polychlorophenol 6DO 5D -0.4 Condensation 6D3 6D2 -0.5 I ! ! I I I I ! -0.3 -0.2 -0.1 o 0.1 0.2 0.3 0.4 0.5 pl (22.1%) Figure 3-1. Varimax rotated variable (loadings) plot for PCDDIF congener projections in the first and second PCs. 18 -T ·5 Harbours ." . 4 0" ':. 0 .':.- . • °°- •.. 0 •• 0 • .. • 3 .. . . 2 o • a 0 0.-0 • 8,p ., • o -.; .:.,. 0 •• 0 0 'i o 8. ~.: o .. :: :0 0 .., .. Cl Bleaching ,,-... 1 OliO 00 • 0r/"O.,,. ·0 . .,p . ~ o· .. o. 0 II' 00 :;0 0 00 0 oOlrt 00 "0000 0 0°0 00 ~ .. <;» .. 000 0 N . o • .. 'lo .. ., 0 .. +-' o. -1 II II., • J' ' 0", 00 DOD 0 'lo·t·· o _0 ., 0' o • .CJ··o. _II' 0•.•.• .,. • eaOos a., Kitimat 00 :. 0 : 0 ., : •. r. . . .., 0 0 No Cl ·--.0 e .0 -2 • " ., ., It • 0 ..., .,., a . . .. . More Cl -3 Polychlorophenol -4 I- Condensation More PCP -2 o 2 4 6 8 10 tl (22.1 %) Figure 3-2. Varimax rotated sample (scores) plot for crab hepatopancreas samples in the first and second pes. 19 Harbours - 1987 Nanaimo Harbour ..87/89 Nanaimo Mill - 87/90 Powell River - 1990 ~m_~~~m~__ ~m~~~~m~_~ ~m~~~~m~_~ ~m~~~~m~_~ ~500~IDBD~5~WWIBF ~~~IDm_m~m~ ~~~mw_m~m~ 4oo~~mRD~~6F~I~ Port Alberni - 1990 Gold River - 1990 4 ---:~ ~ 2 " 00 ~m~~~.m~__ ~m~~~~m~_~ 00 ~~~IDw_m~m~ ,...... 0 ~~~m8D4rom~mw <;» N Kitimat - 1989 ..... 10 ~_ID~~~4Fm~~~ ~~~mw~~.m8F Campbell River - 1990 Crofton ..1987/89 Prince Rupert- 1987/89 Howe Sound- 1987/89 ~m~~~~m~-~ ~ma~~~m~_~ ~m~~~~m~__ ~m~~~~m~ __ ~~~mw_m~m~ ~~~IDw_m~m~ ~~_~w_m.m~ ~~~mm_ill~m~ Figure 3-3, Crabsample congener profiles and PCA projections for the earliest sampling times available, 20 'f Harbours - 1992/94 NanmmoHarbour-1992 Nanaimo Mill - 1993 Powell River - 1993 4DSD~~7004F5F15ffi~~ 40m~~700~~1~~~ 4DID~~~~~I~~~ 400500~mRD4M~~W18F 40 50 602600 700 4F SFt SPO 6FO 7FQ 4OO~~IDrn~~.Wt8F 400500Q7D8D4ro~W~18F 400 500 603 7D 80 4FO SF2 6F 7FI 8F Port Alberni - 1993 Gold River - 1993 40 50 602 600 700 4F 5F! 5RJ 6FO 7FO 4DID~~~4Fm~6ro~ 400 500 601 - 70· 80 4FO SF2 6F 7FI 8F 400~~7D8D4ffi~W7Fl~ Kitimat - 1992 .' -4 -2 o 2 10 4Dm~~~~~I~~'~ ~5oo~m8D4ro~.Wl~F Campbell River - 1993 Crofton - 1993 Prince Rupert - 1993 Howe Sound - 1993 4D~~~~~m~~~ 40 S06D2 600 7004F 5Fl· 5PO 6FO 7Fo IDSD~~~4F~1~~~ ~5D~~~4F~1~~~ ~SOO~IDm~5n§m~ 400 500 70 SO 4FO SF2 6F 7Fl 8F '603 ~~bIDID~m~Wl~ ~500~7D8D~~~~lBF Figure 3-4. Crab sample congener profiles and PCA projections for the most recent sampling times. 21 Comparison of Dungeness (D) and Red Rock (R) Crabs 6 4 2 r: Sechelt 93 rr». ~ o 00. 00 ,.....-I <:» Nanaimo 90/91 C'l -2 ..j-J -4 Campbell River 90 -6 -8 -5 o 5 10 t1 (22.1 %) Figure 3-5. Dungeness andRed Rock crabsamples from Nanaimo, theSechelt peninsula, Campbell River andPowell River. 22 Comparison of Dungeness (D) and Box (B) Crabs 6 4 - f---- 2 C21D ,-..... Howe Sound 93 I ~ C23B C2D 00. /' 00 0 ...... C15D <;» Campbell River 92 JI ~'URiv"90 N C9B ~ f- C3B I -2 I , -4 f---- -6 I-- ! j -8 I· -5 o 5 10 t1 (22.1%) Figure 3-6. Dungeness and Box crab samples from Campbell River, Powell River and Howe Sound. 23 rms PAGE IS BLANK 4. HARBOURS AND REMOTE AREAS HARBOURS Crab samples from Burrard Inlet (Vancouver Harbour), the Fraser River Estuary, Victoria Harbour and Chemanius Harbour were collected by the Environmental Protection Service in July 1987 and analyzed by the Canadian Wildlife Service (Norstrom et al. 1988; see Map 1-1 for area locations). The remaining harbour samples were collected by the Department of Fisheries and Oceans or, in a few cases, by the Environmental Protection Service. Samples were obtained from Burrard Inlet in June, October and November 1990 and January 1992, the Fraser River estuary in February 1992 and March 1993 and Victoria and Esquima1t Harbours in March of 1991, 1992 and 1994. Analytical laboratories are detailed in Table 4-1. All harbour samples were Dungeness crab. Harbour samples from all years and all locations project together in a single cluster (Figure 4-1). This cluster comprises samples from Vancouver Harbour (including Burrard Inlet, False Creek, Port Moody and Indian Arm), the Fraser River estuary, Victoria Harbour (including also Esquimalt Harbour and Esquimalt Lagoon) and Chemainus Harbour (Figure 4-2 to Figure 4-5; Table 4-1). Samples from Nanaimo Harbour and Prince Rupert Harbour also project in or near to the cluster (see Sections 9 and 12). There are no apparent differences in PCA projections between years or between locations in each area - e.g., Indian Arm, Burrard Inlet and False Creek all have similar compositions. Hence crabs from the harbours must have been exposed to PCDDlFs with a similar composition and/or a similar source; likely candidates include pentachlorophenol wood preservatives and combustion processes. Two samples collected in 1987 from locations outside of the major harbours have slightly different projections. The sample to the lower right of the cluster (F87) was obtained from lona Island, near the Fraser River estuary; a subsequent sample from this location in 1992 projected with the other harbour samples. The sample just below the centre of the cluster (Ch87) was obtained from Chemainus Harbour; this sample has a composition that is different from samples obtained from just outside the harbour in the Crofton mill receiving environment (Figure 4-5; Map 6-1 and Section 6). Composition profiles for the major harbours have not changed dramatically over the five to seven years between the earliest and most recent samples (Figure 4-2 to Figure 4-4). Changes in composition which do occur are primarily for congeners that do not make a strong contribution to projections in the first two PCs; this contributes to the lack of change observed in the harbour PCA projections over time (Figure 4-1). However, congener totals and TEQs have decreased in all of the major harbours, both at individual sampling locations and in the harbours as a whole (Table 4-1). In all three locations the most noticeable change in composition is an increase in the proportions of non-2,3,7,8 substituted congeners for the HpCDDs and the TCDFs, PnCDFs and HxCDFs. Proportions of the other hepta- and octachlorinated congeners have also increased 25 noticeably in most cases. These congeners are prominent constituents in samples of soil and sludge and in some samples of roof dust from the Alcan aluminum smelter site in Kitimat- a linkage of these congeners to combustion processes is implied (see Section 13 and Figure 13-2). Accordingly, the increase in the proportion of these congeners suggests that combustion byproducts are providing an increasingly important contribution to contaminant profiles for the harbours. Data are not available to distinguish whether the input of these congeners has increased since 1987, or whether they were present all along and are only becoming apparent as concentrations of the non-combustion congeners decrease. REMOTE AREAS Baseline crab samples from remote areas of the B.C. coast, including the Queen Charlotte Islands, the CentralCoast andPhillips Arm, were collected by the Department of Fisheries and Oceans in March 1991 and analyzed by the Burlington Ontario laboratory (see Map 1-1 for area locations). Samples collected on the Central Coast and in the Queen Charlotte Islands had too few congeners detectable to be retained in the PCA model (Table2-2). Subsequently Fisheries and Oceans resampled Phillips Arm and collected crab samples from Quatsino Sound in December 1992 and Sidney Island (near Sidney on Vancouver Island) in March 1993. Samples were also obtained from commercial catches in locations near Nootka Sound and the Queen Charlotte Islands in May 1993, Clayoquot Sound in June 1993 and the Prince Rupert area in August 1993 (the latter sample is discussed in Section 12). Analytical laboratories are detailed in Table 4-1. All remote area samples were Dungeness crab. Baseline Locations Samples from Clayoquot Sound, Sidney Island and Nootka Sound have similar PCA projections and congener compositions (Figure 4-6 to Figure 4-8). While these samples have been collected in locations awayfrom the mill monitoring sites, the presence ofnon-2,3,7,8 HxCnDs and ofthe two TCOFs as the major congeners indicates that these areas may have been impacted by mill discharges. The Nootka Sound sample has a higher congener concentration and TEQ· and may have been influenced by discharges from the Gold River mill (Section 8). The sample from Graham Island in the Queen Charlotte Islands has a noticeably higher proportion of potential combustion congeners (e.g. the non-2,3,7,8 substituted congeners for the HpCODs and the TCDFs, PnCDFs and HxCDFs; see above), but the presence of asubstantial HxCOD component may indicate additionalinput from pentachlorophenol wood preservatives. It is unlikely that any of these samples represent a background/atmospheric input pattern for crabs on the B.C. coast. One may have to sample even moreremote locations (e.g. a seamount) to find an area that has not been impacted by mill effluents or wood preservatives. To facilitate interpretation of PCA results for the mill sites, samples from baseline locations (QC and SI for the Queen Charlotte and Sidney Islands, respectively) and the three major B.C. harbours (V, Band F for Victoria, Vancouver and the Fraser Estuary, respectively) are shown in a smaller point size on the PCA plots in the sections which follow. 26 Quatsino Sound and Phillips Arm Quatsino Sound has a pulp mill at Port Alice on Neroutsos Inlet and a large copper mine which discharges tailings into Rupert Inlet. The pulp mill uses sulphite bleaching with mild chlorination in a process that is unique to British Columbia and Canada (Hatfield Consultants Ltd., 1994). Samples have both congener profiles and PCA projections that are the same as the major harbours (Figure 4-1, Figure 4-6 and Figure 4-9). Congener concentrations and TEQs are low and comparable to other remote locations around Vancouver Island. Hatfield Consultants Ltd. (1994) have attributed the low levels of dioxins and furans in the mill effluent to a lack of dioxin precursors and the combination of a relatively mild chlorination treatment and the low lignin content unbleached sulphite pulps. As with the Gold River samples (Section 3), the congener pattern also indicates either that very few pentachlorophenol contaminated chips were used or that pulping conditions did not favour HxCDD formation. Samples from Phillips Arm have a different PCA projection and congener profile than other remote areas (Figure 4-6 and Figure 4-10). Congener concentrations and TEQs are also much higher than expected for a remote area. This location is presently the site of a logging camp and has apparently been contaminated by chemicals with an unknown source. 27 Table 4-1. Samples from B.C. harbours and remote areas of the B.C. coast. Samples Averaged Laboratory a Congener Calculated Total TEQ pg/g wet weight Harbours - Earliest Samples Burrard Inlet, 1987 (n=l) CWS 650 27 Fraser River Estuary, 1987 (n=l) CWS 860 73 Victoria Harbour, 1987 (n=l) CWS 3600 130 Chemanius Harbour, 1987 (neeL) CWS 1200 69 Harbours - Most Recent Samples Burrard Inlet, 1992 (n=7) BUR 380 14 . Fraser River Estuary, 1993 (n=4) AXYS 430 16 Victoria Harbour, 1994 (n=6) lOS 1500 38 Remote Areas Graham Is., Clayoquot Sound., Sidney Is., 1993 (n=4) IOS,AXYS 21 1.2 Nootka Sound, 1993 (n=l) lOS 82 5.4 Quatsino Sound, 1992 (n=5) lOS 33 1.1 Phillips Arm, 1991 and 1992 (n=4) BUR,IOS 480 24 "Laboratories are the Department ofFisheries and Oceans at the Institute of Ocean Sciences in Sidney B.C. (lOS), Axys Analytical Ltd. (AXYS), the Great Lakes Laboratory for Fisheries and Aquatic Sciences in Burlington Ontario (BUR) and the Canadian Wildlife Service (CWS). 28 . " ... ,.;: Harbour Samples 6 r:---~""·_·_-_···--·i ! V92 ! i V92 i Vancouver B ~B90B90.! 4 I- I F93 i 90 I Fraser R. Estuary F ~2 IB92v91Mif I Victoria V i F93! ~....-:...,. :..._ ..... __.__._...... _.1 Chemainus Ch ,.-... 2 I- / ..../ Ch87 ( \ F87 ~ ;, ".o. 00 00 \,~.:::\----_ .-l o f •••••_ ....l.__..._ ....--.....l I "-" C"l V92 i ~ V92 I -2 I- I F93 V91 lifO ! I B87 I I v!W2 ~~o B90 I ..4 I- ! vJ3 9lB92 ! Area I B92 ~3V94M'9¥ i i V91 B92 V94 j Expanded I B92 i I B9h7 F92 F92 I -6 I- I I I F93 i L·..··..__··..·__······__······__ _._. -_ __ J -8 T I -5 o 5 10 t1 (22.1 %) Figure 4-1. PCA projections forsamples from the B. C. harbours. 29 '. 200 80 1992 Mean TEQ=14 pg/g 1987 TEQ=30 pg/g \- 170 bO 0.0 "- eo 150 60 0.0 e, --P< d d 0 0 '.;:l ...... cd cd .l:i .l:i 1=1 1=1 Q.) 100 40 Q.) c.l o 1=1 1=1 0 0 U U r- C"J 00 0\ 0\ 0\ ..... 50 20 ..-< o 0 4D SD 6D2 .6DO 7DO 4FSFI. SFO 6FO 7FO 4DO SDO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F _1987 ~ 1992 Figure 4-2. Vancouver Harbour/Burrard Inlet in 1987 (n=1) and 1992 (n=7). 80 1994 Mean TEQ=16 pg/g 300 1987 TEQ=70 pg/g 60 0.0 ~ 60 bb c, Po< d d .S: .8 "-' ...... cd 200 ....cd "-' ..... t: 1=1 G) Q.) o 40 o t: 1=1 0 0 U U r- C'<"l 00 0\ 0\ 100 0\ ..-< 20 .-< 4D SD 6D2 6DO 7DO 4F SFI SFO 6FO 7FO 4DO SDO 6D3 7D 8D 4FO SF2 6F 7Fl 8F -1987 ~ 1993 Figure 4-3. The Fraser River estuary in 1987 (n=1) and 1993 (n=4). 30 1200 1994 Mean TEQ=38 pg/g .. 1987 TEQ=130 pg/g 300 .....O/J O/J O/J 1000 bo l:l.. l:l.. c .S=- .S '-' 800 '-' cd I-< 200 cd '-' l:: ~ ll) ll) o u· l:: 600 l:: 0 o U U r- oo 400 0'\ ,.....0'\ 100 ,.....0'\"'" 200 0 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F _1987 ~ 1994 Figure 4-4. Victoria and Esquimalt harbours in 1987 (n=1) and 1994 (n=6). 400 TEQ=70 pg/g 300 ~ c, .S= '-' ti 200 c ll) U ol:: U 100 o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 4-5. Chemanius harbour in 1987 (n=1). 31 Samples from the Outer Coast and Remote Areas 6 4 i- @W2 Q92 Q92 Q92 QC Cl 3 I- SISI t 093 R93 . It I- pp Quatsino Sound Q PA Sidney Island SI Nootka Sound No -4 I- Prince Rupert R Clayoquot Sound Cl Phillips Arm PA -6 l- I -8 -5 o 5 10 tl (22.1 %) Figure4-6. peA projections for samples fromremote areas. 32 .; ~ 9r------'-----,------, 5 Clayoquot & Sidney TEQ=105 pg/g 8 Graham I. TEQ=006 pglg 705 4.1 4 7 OJ) OJ) ."Sb 6 "Sb P< P< d' 3 d' .9 5 .9...... cd § 1§ ~ 4 lU u c 2 g o o U 3 U 2 o L-__"""'- o 4D 5D 6D2 6DO 7DO 4F 5Ft 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Ft 8F Figure 4-7. Samples collected from remote areas of the B. C. coastin 1993. Figure 4-8. Congener profile for a crab sample from Nootka Soundin 1993 (J}=1). 33 7,------'------. Mean TEQ=l.l pg/g 6 bO 5 bb Q.< d' o 4 "z:j <:d ...... t: 8 3 ot: U .2 o 4D 5D 6D2 6DO 7DO 4F 5:r:;'1 5FO 6fO .7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 4-9. Samples from Quatsino Sound (n=5). 250 , Mean TEQ=24 pg/g 200 ~ en c, d' 150 0 .z:j <:d. J:j t: Q) CJ t: 100 0 U 50 o 1-----.....- 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 4-10. Samples from Phillips Ann (n=4). 34 5. HOWE SOUND Two pulp mills are located on Howe Sound: the Howe Sound Pulp and Paper Limited mill in Port Mellon and the Western Pulp Limited Partnership mill in Woodfibre, near Squamish (Map 5-1). These mills will be referred to as the Port Mellon and Woodfibre mills, respectively. Crab samples were collected near the Port Mellon and Woodfibre mills by the Department of Fisheries and Oceans in the winter of 1987-1988 and analyzed by the Canadian Wildlife Service (Norstrom et al. 1988). Subsequent samples were collected by Hatfield Consultants Ltd. in both late January/early February and November of 1989, in September 1990, and then annually in February or March from 1991 to 1993 (Map 5-1). These mill monitoring program samples were all analyzed by Axys Analytical Ltd. In March 1993 additional samples were collected by G3 Consulting Ltd. between the Howe Sound and Powell River mill sampling areas and analyzed by the Institute of Ocean Sciences (Map 5-2). All samples [Tom Howe Sound were Dungeness crab except for Box crab from Station C23 in 1993. Samples from outside Howe Sound in 1993 were Dungeness crab from Stations C301 and C303 but were Red Rock crabs from Stations C302, C304, C306 and C309. Congener profiles and PCA projections for the earliest sampling times indicate only a small change in congener composition between 1987 and January/February 1989 (Figure 5-1 and Figure 5-3). Samples collected close to the Port Mellon mill (P87, C10, C11 and C 12) had essentially the same PCA projections in both years while Woodfibre samples (W87, C3, C4 and C5) showed only a small difference in projection (Figure 5-3). The -change between years was principally due toa modest decrease in the proportion of 2,3,7,8-TCDF with a small increasein the non..,2,3,7,8 TCDFs and the HxCDDs. The change in congener profile apparently accelerated between January/February and November 1989; this is reflected in a much larger shift to the upper left in individual PCAprojections during this time (Figure 5-3). While this second change apparently represents a larger decrease in the proportion of TCDFs than had occurred between 1987 and early 1989, part of thechange could be due to differences in season. A progressive shift to the upper left in PCA projections, indicating a progressive increase in the HxCDD proportion,' occurs for samples collected between 1989 and 1993 (Figure 5-3 to Figure 5-7). By 1993 the HxCDD proportion was roughly one-half of the size of 2,3,7,8-TCDF (Figure 5-2). The change in composition over time must have proceeded uniformly throughout Howe Sound because PCA projections indicate that the congener composition has remained relatively consistent at any given time (Figure 5..3 to Figure 5-7). The uniformity in composition extended to samples collected well outside Howe Sound in 1993 (see following). Over the six years of sampling in Howe Sound, the relatively small change in congener profile has been accompanied by a large decrease in both concentration and TEQ (Table 5-1; Figure 5 2). Despite the relatively uniform congener composition that has persisted throughout Howe Sound in each year, samples collected from locations adjacent the Woodfibre mill have 35 '" maintained a consistently lower congener total and TEQ than samples from locations adjacent to the Port Mellon mill (Map 5-1). SAMPLES FROM OUTSIDE HOWE SOUND The 1993 PCA projections for Dungeness crab samples from Stations C21 (two samples) and. C23 at the mouth of Howe Sound are identical to the PCA projections for Station C301 (Trail Bay; two samples) and nearby Station C24 (Roberts Creek) located to the west of Howe Sound (Figure 5-7; Map 5-2). At a further distance from Howe Sound, the Dungeness crab sample from C303 (Secret Cove) has a composition closer to that of the principal B.C. harbours, which suggests some contribution from a non-mill source. The Red Rock crab from Station C309 (Halibut Bank) projects further to the right and much closer to the Dungeness crab samples from within Howe Sound (Figure 5-7). While the change in species may contribute to a shift in congener profile to a higher proportion of the most toxic congeners (i.e. a shift to the right in PCA projection; see Section 3), the PCDDlFs in the C309 crab sample likely have primarily a mill source, and geography would suggest that the Howe Soundmills are the most probable candidates (Map 5-2). In support, positions of the Dungeness crab samples C301 and C303 and the Red Rock crab sample C309 are unchanged relative to the Howe Sound samples in the third PC (not shown). This congruence in three PCs strengthens the assertion that these sampleshave the same PCDDIF sources as the Howe Sound samples. The Red Rock crab sample from Station C302 (Secret Cove), and the samples from Stations C304 and C306 (Nelson Island and Lasqueti Island respectively) project near to the Dungeness crab sample C303 (Secret Cove; Figure 5-7; Map 5-2). The 1993 Dungeness crab sample from Powell River that is closest to Howe Sound also projects with this group of samples (powell River C13; Map 5-2 and Section 11). However, all of these samples are shifted relative to both the Howe Sound and Powell River samples in the third PC. Projections of these samples in the third PC indicate a higher proportion of the hepta- and octachlorinated congeners than other samples from the Howe Sound region. This shift could be due to either a decrease in mill influencein the region betweenthe two mills and/or an additional source of PCDD/Fs. 36 Table 5-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Howe Sound. Samples Averaged Congener Calculated Total TEQ pg/g wet weight Earliest Samples Port Mellon and Woodfibre mills, 1987 (n=2) 30,000 2900 Howe Sound C3, C4, C5, ClO, Cll and C12, JanlFeb 1989 (n=6) 9900 850 Howe Sound, 1987 (n=2) plus 15,000 1400 C3, C4, C5, ClO, Cll and C12, 1989 (n=6) Most Recent Samples Port Mellon ClO and C14, 1993 (n=6) 1300 120 Woodfibre C3 and C5, 1993 (n=2) 79 7.0 Port Mellon ClO and C14 (0=6) plus 1000 95 Woodfibre C3 and C5, 1993 (n=2) 37 .. FISHERY CLOSURES -NOV: 1994 C2~ '-'..-. I~':'j Closed toall crab, shrimp and prawn fisheries I2J Closed to commercia! crab fishery C3 Health advisory to recreational and native crab fisheries on the consumption ofcrab hepatopancreas (Note: crab C5 C4 hepatopancreas not to be consumed) N C9 A ------C7 \ C17 Port Mellon Pulp Mill C18 ~ C24 C14 Burrard C22 C20 Inlet o 10 km Map 5-1. Crab sampling locations in Howe Sound. 38 ~ '/~'t),\," ~ Powell~pMllJ!.iver ,'\' -. ..) . o 20km <, Jm., "" D K . GI2 : ( C4 .. '..J / \'\ f\~~~ N"SOr((~") //) Woodfibre I .-~'" G13,,~Sla,n, Island '" ~<> PUlpMiJ.s ~Sland"Texada '\ r} ( Peninsul~cSechelt \ ~~ C10 ~----,~, C?o ' Howe ':::::' C307'~~X7 "'-- Sound C305 C306 Lasqueti C301 ~ Island "", C24 ~-...... Strait~f .."-----,, GeorgIa /_ C21 I ~.~ Burrard ~ /' C309 Inl~ N 2~~~ . C20 '~ VANCOUVER A ) ( r,,·. \~J'~~ NANAIMO r Map 5-2. Crab 'sampling locations between Howe Sound and PowellRiver. 39 21000 20 1989 TEQ=850 pg/g 1987 TEQ=2900 pg/g 6 OJ) 5700 OJ) bb OJ) 0.. --P. d' 15 d' .9 ...... 0 "'-' ..... d d I-< ~ 4 "0'" I-< "'-' ..... c= ;j ;j c= ll:J ::l'" ::l'" ll:J U o c= 0 0 c= 0 J9 10 J9 0 U U t- 01 00 00 .....01 2 .....01 5 ___"'-""- --1 0 o 4D 5D 6D2 6DO 1DO 4F 5F1 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F _1987 ~ 1989 Figure 5-1. Howe Sound congener profiles for 1987 (n=2) and 1989 (n=6). 800 40 Port Mellon TEQ=120 pglg Woodfibre TEQ=7.0 pglg OJ) OJ) ""- --OJ) OIl P. Po< d' 600 30 d' ...... 0 "'-' .9 d ..... I-< d "'-'c= .....I-< Q) c= c.l ll:J c= c=c.l 0 400 20 0 U U c= Q.) .....0 I-< Q) 1§ :g -e 0 t 200 10 0 0 p., ~ o 4D 5D 6D2 6DO 7DO 4F 5Fl SFO 6FO 7FO 4DO SDO 6D3 7D 8D 4FO ,SF2 6F 7Fl 8F • Port Mellon ~ Woodfibre Figure 5-2. Congener profiles for Port Mellon (n=6) and Woodfibre (n=2) mills in 1993. 40 Howe Sound - 1987/89 6 v v F v BB .~li3 Port Mellon 87 P87 4 f- ""B B B v B ~VB Woodfibre 87 W87 BV F F F Jan/Feb89 en QC Nov 89 en - 51 2 51 Q2 .c.4 r-t o o Cl. ('l C2 ~ .cJ.1.c.l -2 f- cs C12 P87 W87 CII CIO C5 (:4 C3 Cl7 -4 - Cl7 -6 - I -8 -5 o 5 10 tl Figure 5-3. peA projections for samples from Howe Sound in 1987 and 1989. 41 Howe Sound - 1990 6 v V VBB ,.... F B 4 vB ~IB B B v, B ~VB - By FF F QC - 81 2 81 ( 19 C1:. C2 o C"l C17 C3 C5 ~ 'iii' C14 C4 C 16 -2 - C9 'ClO Cll -4 '- -6 ~ I -8 -5 o 5 10 t1 Figure5-4. peA projections for samples from Howe.Sound in 1990. 42 Howe Sound - 1991 6 V V F V ',BB ~Ill BB 4 B VB ~./ BV FF B F QC 2 Sl Sl C3 o C12 -C'l ClO C9 C1itC12 ~ C5 11 -2 -4 -6 -8 -5 o 5 10 t1 Figure 5-5. peA projections for samples from Howe Sound in 1991. 43 Howe Sound - 1993 6 y yy B F ~ B 4 B B B vB ~VB YBFF By F C30f?83Q'@, 2 C306 C3 01 C302 C24 C23 o ~ ~ C14 -2 -4 -6 -8 -5 o 5 10 t1 Figure 5-7. peA projections for samples from Howe Sound in 1993. 45 TillS PAGE IS BLANK 6. CROFTON Crab samples adjacent to the Fletcher Challenge Canada Limited Crofton Pulp and Paper mill were collected by the Environmental Protection Service in July 1987 and analyzed by the Canadian Wildlife Service (Norstrom et al. 1988). The next samples were collected north and south of the Crofton mill by Hatfield Consultants Ltd. in January 1990 and at the head of Cowichan Bay by Envirochem Ltd. in January and March 1990 (Map 6-1). The sampling range was extended further to the north above Thetis Island and to the south into Saanich Inlet by Hatfield Consultants Ltd. in August 1990; six of these samples (C14, CIS, C16, C16A, C19 and C21) had too few congeners detectable to be retained in the PCA model (Table 2-2). Subsequent. Crofton mill monitoring samples were collected by Hatfield Consultants Ltd. in April 1991,· February 1992 and March 1993. Axys Analytical Ltd. analyzed all mill monitoring program samples from 1990 to 1993 except for the two 1990 Envirochem samples from Cowichan Bay that were analyzed by B.C. Research. All samples from the Crofton vicinity have been Dungeness crab. Between 1987 and 1990 the calculated TEQ decreased markedly for stations closest to the mill (Table 6-1). Congener profiles and PCA projections both indicated a decrease in the proportion of toxic congeners over this time (Figure 6-1 and Figure 6-4). The change in composition between years was principally due to a decrease in the TCDFs coupled with an increase inthe HxCDDs. PCA results indicate that PCDDlFs with a pulp mill origin were present in 1990 as far north as Ladysmith and as far south as Saanich Inlet (Figure 6-4). From 1990 through to 1993 samples close to the Crofton mill exhibited only a small decrease in the congener total and calculated TEQ (Table 6-1). PCA projections and congener profiles also showed only a small change from year to year, with the major change being a decrease in the proportion of the TCDFs (Figure 6-3; Figure 6-5 to Figure 6-7)~ In 1993 samplesfrom Thetis Island (C22) in the north, to the Crofton mill (C3and C4), to Cowichan Bay (C13) in the south had the same congener composition (Figure 6-7), indicating that PCDDlFs from the Crofton mill have persisted in the region. Sources ofPCDDlFs other than the Crofton mill become potentially more important at the edges of the Crofton monitoring area {Map 6-1). Inthe north, PCA projections of crabs from Crofton Stations C22 and C18 and Nanaimo/Harmac Station CIS (see Section 9) overlap - projections are consistent with either mill as a source or with mixed inputs. To the south, samples C12, C13, DB2 and WB1 from within Cowichan Bay in 1990 exhibited congener profiles and PCA projections that were distinct from the Crofton and Saanich Inlet samples (Figure 6-2 and Figure 6-4). The presence of non-2,3,7,8-substituted furans in the Cowichan Bay samples (Figure 6-2) is consistent with the input of pentachlorophenol wood preservatives into Cowichan Bay as a result of sawmill and lumber transshipment activities. In subsequent years samples from Station ClO at the mouth of Cowichan Bay always had a Crofton mill pattern, while Stations C13 and C14 from further back in the bay were similar to the pulp mill in some years, and Cowichan Bay 47 in others. The results suggest that Crofton mill effluent has made only a partial contribution to . the congener profiles exhibited by crabs from Cowichan Bay. Table 6-1. Dungeness crab hepatopancreas congener total andTEQ averages for samples with similar PCA projections from Crofton. . Samples Averaged Congener .Calculated• Total TEQ pg/g wet weight I Earliest Samples Crofton, 1987 (n=2) 4300 420 Crofton C4, C5, C6, C7 and C8, 1990 (n=5) 1700 130 Crofton 1987 (n=2) plus C4, C5, C6, C7 and C8, 1990 (n=5) 2400 220 Cowichan Bay C12, C13, DB2 and WEI; 1990 (n=4) 470 27 Most Recent Samples Crofton C3, C4 and C7, 1993 (n=3) 1500 94 48 N A ------. o 10 km [1 ------C19 FISHERY CLOSURES - NOV. 1994 Closedto commercial crab fishery _ Healthadvisory to recreational and nativecrabIisherieson the consumption of crabbcpatopancrc3.s Map 6-1. Crab sampling locations near Crofton. 49 600 2500 2500 540 1987 TEQ=400 pg/g i:lIl 1989 TEQ=130 pg/g 01) ""- bb 01) Po< 2000 P< d 400 d' 0 .8 'J:l "cd . ~ ...... 1:1 1500 c:: Q) Q) u o 1:1 c:: 0 0 U U 1000 r- 200 0'1 00 00 0'1 0'1 M ,...., 500 ___~.ea-_~L-c=--__-....lo 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D '8D 4FO 5F2 6F ,TFI 8F • 1987 ~ 1989 Figure 6-1. Crofton congener profiles for 1987 (n=2) and 1990 (n=5). Mean TEQ=27 pg/g 150 ~ eo c, C .~.... 100 ~ l:i ::: ll) :::C,,) o U 50 o '---...... - 4D 5D 6D2 6DO 7DO 4F 5F! 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 6-2. Cowichan Bay congener profiles for 1990 (n=4). 50 600 Mean TEQ=94 pg/g OJ) t;:o 400 Co d' .S ...e '=Q) g o U 200 o L.-_~" 40 50 602 600 700 4F 5Fl 5FO 6FO 7FO 400 500 603 70 80 4FO 5F2 6F 7Ft 8F Figure 6-3. Crofton congener profiles for 1993 (n=3). 51 Crofton and Cowichan Bay - 1987/90 6 v VV B B Cowichan.Bay 90 WEI, DB2 4 F B'ill B Crofton 87 87 ,p ~'"\ B v " FF DB2 VF Crofton 90 Cn QC 2 WB1 51 51 Cl3 o C12 C'l ~ C~~O CI0 I C283 -2 18 87 C7C5 C17 87 -4 C -6 -8 -5 o 5 10 t1 Figure 6-4. PCA projections for samples from Crofton in 1987 and 1990 and Cowichan Bay in 1990. 52 Crofton - 1991 6 V V F V 4 VJB Jtlll BB v ~\ B B ~ \v F F F QC 2 SI S1 o C"'l ~ -2 C3 -4 .:.6 -8 -5 '0 5 10 tl Figure 6-5. PCA projections for samples from Crofton in 1991. 53 Crofton - 1992 6 v v F BVBB l- 4 V! ~\ B B V 'v F~"\ F QC ,- 2 C13s1 SI C13 Cr!~f16A o cc'io C'l ..j..l C3 , C~fl -2 I- C4 C8 C7 -4 ,- -6 >- -8 I -5 o 5 10 t1 Figure 6-6. PCA projections for samples from Crofton in 1992. 54 Crofton - 1993 6 v v F V B B 4 l- \IlB ~,IB B B v B \l!\~ V FF F QC ,- 2 SI SI o C13 3 N cc?:f ...j..) c~ -2 I- -4 l- -6 I- -8 I -5 o 5 10 - tl Figure 6-7. PCA projections for samples from Crofton in 1993. 55 rms PAGE IS BLANK 7. CAMPBELL RIVER Two mills are located near to Campbell River: the Fletcher Challenge Canada Limited Elk Falls Pulp and Paper mill and the Campbell River Mills Limited Raven Lumber sawmill (Map 7-1). These mills will be referred to as the Elk Falls and Raven Lumber mills, respectively, Crab samples were collected in the Campbell River area by Hatfield Consultants Ltd. in 1990, with most samples collected in January and a few supplementary samples collected in August and September 1990. From 1991 to 1993 mill monitoring program samples were collected annually by Hatfield Consultants Ltd. in February or March (Map 7-1). Axys Analytical Ltd. / analyzed all Campbell River samples from 1990 to 1993. Crab samples from the Campbell River area had the highest proportion of non-Dungeness species of any area. In 1990 Red Rock crabs Were obtained at Stations C2, C10 and C11. In 1991 and 1992 all samples were Dungeness crab except for Box crab from Station C9 in 1992. In 1993 Box crabs were obtained again at Station C9, as well as Stations C15and C17A, while Kelp crab was sampled at Station C17B. The Campbell River area is also notable for the number of samples with distinct congener profiles and PCA projections. Crab sample C7 from 1990 has a composition very different from all other crab samples from the Campbell River area. The sample contains high proportions of TCDFs; its congener profile and PCA projection (Figure 7-1 and Figure 7-4) is more reminiscent of the Gold River samples (Section 8) than of the Campbell River samples. By including this sample in the 1990 congener total, TEQ average and congener profile (Table 7-1; Figure 7-1 and Figure '7-4), the contribution of the TCDFs and the magnitude of the TEQ may be overestimated. However, because this sample may be indicative of pre-1990 discharges from the Elk Falls mill, it has been retained in the 1990 averages. The Raven Lumber crab sample CR-Cl from 1990 and the Elk Falls mill monitoring program crab samples collected in 1990, 1991 and 1993 from Station C4 had PCA projections similar to that of the harbours (Section 4; Figure 7-4 to Figure 7-7). Because these samples were located close to the mills, they very likely had been influenced by pentachlorophenol wood preservative from contaminated wood chips. Samples C3 from 1990, C4 from 1992 and CT from 1992 and' 1993 had PCA projections slightly further removed from the harbour samples; these samples most likely had also been exposed to contaminated wood chips. Accordingly, these samples were not included in the congener total and TEQ averages for the Elk Falls mill. Ifonly Dungeness crab samples are considered, and if the unusual samples enumerated above are excluded, the PCA projections of the two Dungeness crab samples Cl and C5 may be considered to be representative of the pulp mill profile in 1990 (Figure 7-4). The 1990 congener total and calculated TEQ for just these two samples is only slightly different from the totals that include C7 (Table 7-1). Relative to a 1990 baseline, the Dungeness crab samples collected between Quadra Island and Vancouver Island in general exhibit only small changes in PCA composition and TEQ between 1991 and 1993 (Figure 7-5 to Figure 7-7; Table 7-1). A good example is 57 Station C2, located on Quadra Island directly across from the Elk Falls mill, which exhibits almost no change in PCA projection from 1991 to 1993. From the PCA results it is evident that PCDDlFs with a pulp mill composition were present in crab samples from Kanish Bay (CI3) in 1992 and 1993 and from the north end of Quadra Island (CI9, C20) in 1993 (Figure 7-6 and Figure 7-7). These samples exhibit a composition pattern that is indistinguishable from the pattern of Stations Cl, C2, C5, CI0 and C12. Samples from Station C9 on the southeast corner of Quadra Island (Francisco Point) are more difficult to categorize. The change in PCA projection between 1991 and 1992 at Station C9 could be due to the species change from Dungeness crab to Box crab, but sample C7 consisted of Dungeness . crab in both years and went through a similar shift (Figure 7-5 and Figure 7-6). There was no. further change in the composition of the two Box crab samples collected at Station C9 in 1992 and 1993. When considered in the context of a relatively constant mill-related PCA composition, it is likely that the Box crab samples from Station C9 and Mitlenatch Island (CI7A) in 1993 reflect PCDDlFs with a pulp mill origin. Sample C15 from Marina, Island, on the east side of Quadra Island, had a composition identical to the pulp mill samples in 1992, but had a composition intermediate between the mill samples and harbour samples in 1993 (Figure 7-6 and Figure 7-7). The composition change between years may be due to a species change from Dungeness crab to Box crab. The 1992 Dungeness crab sample from Station C16 in Heriot Bay also projected between the mill samples and harbour samples and has apparently received PCDD/Fs from non-mill sources. Sample C17B consisted of Kelp crabs from Oyster River, which is located south of Quadra Island along the coast of Vancouver Island. The TEQ for this sample (0.3 pg/g) was much lower ' than any of the TEQ values for the samples of Dungeness crab or Box crab. Because this is the only sample of kelp crab in the data set, no conclusions can be reached about the PCA projection: of this sample. Since a comparison of trends in TEQ data is questionable when different species are involved" the collection and analysis of crab species other than Dungeness crab is of dubious value in the current mill monitoring program. It is recommended that an effort be made to relocate Elk Falls sampling stations that are located to the east and south of Quadra Island (C9, CI5 and C17) to nearby areas where the habitat is suitable for the collection ofDungeness crabs. Because Heriot Bay (CI6) may have received PCDD/Fs from non-mill sources it is unsuitable as a substitute for C9. 58 Table 7-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Campbell River. Samples Averaged Congener Calculated Total TEQ pg/g wet weight Earliest Samples Elk Falls C1, C5 and C7, 1990 (n=3) 1240 100 Elk Falls C1 and C5, 1990 (n=2) 1200 90 Elk Falls C7, 1990 (n=l) 1300 120 Raven Lumber CR-C1, 1990 (n=l) 3900 130 Most Recent Samples Elk Falls C2 and C12, 1993 (n=3) 800 53 59 C10 C3.----"." C4 -----l..ol'L" Elk Falls Pulp Mill CR-C1 <, Raven Lumber C15 CAMPBELL RIVER C9 CB ----¥.<6:::l_ Willow Point C17A 10 km o Mitlenatch Island FISHERYCLOSURES - NOV: 1994 [2] Closed to commercial crab fishery Health advisory to recreational and , C17B N native crab fisheries on the consumption ofcrab hepatopancreas A Map 7-1. Crab sampling locations near Campbell River. 60 1000 1000 Stn Cl TEQ=130pg/g Stn C7 TEQ=120pglg 900 800 .. ,".:: 800 ...... OIl 800 OIl OIl 'Bb 0.. P< d' 600 d' .....0 .....0 "-' 600 "-' ~ ~ c=1-< ~ 0 0 C,) 400 C,) l:::: l:::: 0 400 0 U U 200 200 o 0 40 50 602 600 700 4F 5Fl 5FO 6FO 7FO ,\ 400 . 500 603 70 80 4FO 5F2 6F· 7Fl 8F • Stn C7 ~Stn CR-Cl Figure 7-1. Congener profiles for stations in the Campbell River estuary in 1990 (n=1 for both). 250 TEQ=47 pglg 220 200 OIl 'Bb 0.. d' 150 .S2..... ~ .....~ l:::: 0 C,) l:::: 100 0 U 50 a 40 50. 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 7-2. Campbell River congener profiles for 1990 (n=3). 61 250 T,EQ=53 pglg 200 b.ll bb P< l:f 0 'l:l cd t: c ILl t) c 100 0 U :50 o 4D 5D 6D2 6DO 7DO 4F 5F! 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure7"'3. Campbell River congener profiles for 1993 (n=3). 62 'Campbell River - 1990 6 I 1 CR"fl v F v B B 4 r- B ¥!~\ B B 'jl v IS \ V FF F QC 2 r 51 51 C4 o C3 C7 C'l ~ rIO -2 r- Cl C5 CI e -4 r -6 r -8 -5 o 5 10 tl Figure 7-4. PCA projections for samples from Campbell River inJ990. 63 Campbell River - 1991 6 v v F V B B 4 B~ B B Vi '.Il\"h v \ FF VF QC 2 81 51 o N +-l C5 -2 C9 -4 -6 -8 ~5 o 5 10 t1 Figure 7-5. PCAprojections for samples from Campbell River in 1991. 64 ~ Campbell River - 1992 6 v v F B VB B ~ 4 V3. ~ B B V III ,~ V FF F QC C4 I- 2 SI SI ( 7. C16 o Ccj C'l ~ C9 C5fJ- C13 C -2 I- C13 C12 -4 I- -6 ~ -8 I -5 o 5 10 t1 Figure 7-6. PCA projections for samples from Campbell River in 1992. 65 Campbell River - 1993 6 v V F VBB B r- 4 V1 ~\ B C4 B v \ V FF' F QC ~ 2 51 51 CI7B [.7 CI5 o N CI ~ CIC~ij 2 C9 ~2 -2 -- CI:b9 -4 ~ -6 -- -8 I -5 o 5 10 t1 Figure 7-7. PCAprojections for samples from Campbell River in 1993. 66 .,.. 'J ------~ 8. GOLD RIVER Crab samples were collected in the vicinity of the Canadian Pacific Forest Products Limited (now Avenor Inc.) Gold River Pulp Mill by Beak Consultants Ltd. in 1990, with most samples collected in January and February and a few supplementary samples collected in September and October. Subsequent mill monitoring program samples were collected by Beak Consultants Ltd. in March 1991, February 1992 and April 1993 (Map 8-1). Axys Analytical Ltd. analyzed all Gold River mill monitoring program samples from 1990 to 1992. Wellington Laboratories Ltd. of Guelph Ontario analyzed the 1993 samples. In May 1993 an additional commercial fishery crab sample was collected in the Nootka SoundiNutchaliz Inlet area by the Department of Fisheries and Oceans and analyzed by the Institute of Ocean Sciences. All samples from the Gold River area were Dungeness crab. PCA projections and PCDDIF congener profiles for crab hepatopancras samples collected near to the Gold River mill in 1990 are unusual because the samples are made up almost entirely of TCDFs (Figure 3-3, Figure 8-1 and Figure 8-3). This is the composition that would be expected if very few pentachlorophenol contaminated chips had been used in the bleach plant at the mill (see Section 3). PCA results indicate that PCDDlFs with a pulp mill origin were present throughout Muchalat Inlet in 1990 (Figure 8-3 to Figure 8-6; Map 8-1). Samples collected outside the inlet through 1993 indicate that mill PCDDlFs are present as far north as Netsook Bay and as far west as Marvinas Bay. The commercial fishery sample from outside the mill monitoring area whose location wasrecorded as Nootka SoundlNutchaliz Inlet (Section 4) also has a congener profile and PCA projection that may indicate influence by discharges from the Gold River mill (Figure 4-8 and Figure 8-6). Between 1990 and 1993 the calculated TEQ decreased by more than an order of magnitude for stations closest to the mill (Table 8-1). Congener profiles and PCA projections both indicated a decrease in the proportion of toxic congeners over this time (Figure 8-1, Figure 8-2, Figure 8-3 and Figure 8-6). The change in composition between years principally has been reflected as an increase in the HxCDDs. PCA projections remained relatively consistent within each year, which indicates that the change in congener composition has proceeded uniformly overtime. 67 .···1 Table 8-1. Dungenesscrab hepatopancreas congener total and TEQ averages for samples with similar peA projections from GoldRiver. Samples Averaged Congener Calculated Total TEQ pg/g wet weight Earliest Samples Gold RiverS3,S4,S5, 56 and 88,1990 (11=:=5) 13,000 1100 Most Recent Samples Gold River53, 55 andS6, 1993 (n=4) . 1200 99 'NootkaSound,1993 (n=l) , 82 5.4 68 FISHERY CLOSURES - NOV. 1994 o 5km CSI Closed to all crabfisheries N iLj Closed to commercial crabfishery Health advisory to recreational and native crabfisheries ontheconsumption A of crabhepatopancreas '7 isn it . Inlet / 83 81~ ~<, , /rY}J.fI 85 "-.- -, Go/dRiver ~~. 86 Pulp Mill 88 Ji. 814\ ., ) :~~ . ?i " Marvinas '\' , ~~~. a fr-_\ Bay. . '" r ~bif /) 82 C-t " iJ / 81 Map 8-1. Crab sampling locationsnear Gold River. 69 10 r------, 9000 Mean TEQ=1100 pg/g 8 , 2 o 4D SD 6D2 6DO 7DO 4F SFt SFO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO SF2 6F 7Ft 8F Figure 8-1. Gold River congener profiles for 1990 (n=5). 800 Mean TEQ=99 pglg 690 600 ~ bO Q., " C .9.... <1:1 ....1-0 400 c: II) c:CJ 0 U 200 o I...-__.....-.J_...... 4D SD 6D2 6DO 7DO 4F SFt SFO 6FO 7FO 4DO SDO 6D3' 7D 8D 4FO SF2 6F . 7Ft 8F Figure 8-2. Gold River congener profiles for 1993 (n=4). 70 T Gold River- 1990 6 v v v Il B 4 FB ¥! B VJ ""\'\ B v ~v FFF QC 2 51 51 S4 S8 o S5 S9 N S6S3 ~ SI SID S12 S11 -2 -4 -6 -8 -5 o 5 10 t1 Figure 8-3. peA projections for samplesfrom GoldRiver in 1990. 71 Gold River - 1991 6 - - I v V F BVB 4 l- VI Ilf1l B B V , ~\~ v FF F QC L- 2 51 51 514 o l- 5654 C'l 51 53 ~ 513 512 55 512 59 -2 L- 57 -4 l- -6 I-- I -8 I I ~ -5 o 5 10 tl Figure 8-4. peA projections for samples from Gold RiveriI11991. 72 -1.. Gold River - 1992 6 v - v F BV -B 11 4 I- VJ ~\ B B V \ _ "\ V FF F QC I- 2 SI SI o SIS S5 N ~ S13 S9 SI S12 S6 -2 l- -4 I- -6 - -- I -8 I -5 o 5 10 tl Figure 8-5. peA projections for samplesfrom Gold Riverin 1992. 73 - Gold River - 1993 6 v v F BVBB Nootka Sound Nt 4 f- VI ~ B B Gold River Sn V 'il \'\ v FF F QC 2 f- 51 51 Nt o ~1j Sg3~5 N SIS ~ S6 , S9S12 -2 f- - -4 - -6 f- -8 I -5 o 5 10 tl Figure 8-6. PCAprojections for samples from Gold River-in 1993. 74 ":}II .. 9. NANAIMO Crab samples were collected in Nanaimo Harbour and near the Harmac Pacific Inc. Pulp Mill by the Environmental Protection Service in July 1987 and analyzed by the Canadian Wildlife Service (Norstrom et al. 1988). Subsequent samples were collected in Nanaimo Harbour and near the Harmac mill by Hatfield Consultants Ltd. in January 1990 (Map 9-1). The sampling range was extended further to the north and to the south in August 1990; one of these samples (ClO) had too few congeners detectable to be used in: the PCA model (Table 2-2). Nanaimo and Harmac mill monitoring samples were then collected by Hatfield Consultants Ltd. in March 1991 and February 1992 and by G3 Consulting Ltd. in March 1993. Axys Analytical Ltd. analyzed all mill monitoring program samples from 1990 to 1992. Envirotest Laboratories Ltd. of Edmonton Alberta analyzed the 1993 samples. Crab.species other than Dungeness crab have been obtained at a few locations in the Nanaimo area; Red Rock crabs were obtained at Stations C4 and C7 in 1990, at Station C4 in 1991 and at Station C5 in 1993. Interpretation of the PCA results for the Nanaimo area illustrates the different PCDDIF fingerprints of Nanaimo Harbour and ofthe Harmac mill and highlights the utility of PCA in ascribinga source to individual crab samples (Section 3; Figure 3-3 and Figure 3-4)..Samples N87, Cl and C9 from Nanaimo Harbour project with the Victoria and Vancouver Harbour samples and change only slightly in composition profile between 1987 and 1992 (Figure 9-1, Figure 9-2; Figure 9-5 to Figure 9-7). Nanaimo Harbour samples have a slightly higher proportion of the TCDFs than the larger harbours; this suggests that chlorine bleaching effluents , from the mill have also made a contribution. At a few locations from the boundary area just outside Nanaimo Harbour (C1 and Cll; Map 9-1), crab samples had a harbour pattern in one year and a mill pattern in another year. Over the six years of sampling in the Nanaimo area, a smaller decrease in both concentration and TEQ has occurred in the harbour samples than in the mill samples (Table 9-1). Crab samples from the vicinity of the Harmac mill project with mill samples from other areas and have a composition that has remained distinct from the harbours through to 1993 (Figure 9-3 and Figure 9-4; Figure 9-5 to Figure 9-8). Congener profiles andPCA projections for the earliest sampling times indicate that only a small change had occurred in congener composition between 1987 and January 1990. However, a progressive shift to the upper left in PCA projections, indicating a progressive increase in the HxCDD proportion, occurs for samples collected between 1990 and 1993. The change in composition has proceeded uniformly over time and congener compositions and PCA projections have remained relatively consistent in each year. In 1993 crab samples ranging from Lock Bay (C13) in the north, on the outside of Gabriola Island, to the Harmac mill (C2), to Kulleet Bay (CIS) in the south had the same congener composition (Figure 9-8; Map 9-1). Hence PCDDlFs from the Harmac mill have dispersed and persisted throughout the region. In the south, the 1992 and 1993 PCA projections for Nanaimo/Harmac Station CIS overlap with Crofton Station C22 (see Section 6) - projections are consistent with either mill as a source or with mixed inputs. 75 Table 9-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Nanaimo Harbour and the Harmac mill site. SamplesAveraged Congener Calculated Total·,' TEQ pg/gwet weight . Nanaimo Harbour-s- Earliest to Most Recent Samples Nanaimo Harbour, 1987 (n=l) 470 27 Nanaimo Harbour Cl and C9, 1990 (n=2) 300 15 Nanaimo Harbour, 1987 (n=l); C1 and C9, 1990 (n=2) 360 19 Nanaimo Harbour C1, C9 and C12, 1992 (n=4) 360 18 Harmac Pulp Mill- Earliest to Most Recent Samples Hannac Mill, 1987 (n=l) 1100 82 Hannac Mill C2, C3, C5, C6 and C8, 1990 (n=5) 810 65 Hannac Mill, 1987 (n=l); C2, C3, C5, C6 and C8, 1990 (n=5) 860 68 HannacMillC2 and C3, 1993 (n=3) 290 14 76 o 5km I.)Entrance Island -- C12 C13 C4 Gabriola NANAIMO Island \ __. '-I r-Harmac 1IIm/ '-\Pulp Mill // , / C3 \ ~_---"T- C6 N Ai C7--~ C15 Miami Islet FISHERY CLOSURES· NOV. 1994 o Crofton I Healthadvlsory to recreational and Q'"-, native crab fisheries on the Consumption .... '..'."\". . pfcrab hepatopancreas ' .. LADYSMITH \J Map 9-1. Crab sample locations near Nanaimo. 77 ._-_._----- 120 120 1987 lEQ=27 pg/g 1990 lEQ=15 pg/g 100 100 ~ 0.0 en ~ c, 0.. C 80 80 a .9...... 0 cd cd l:2 .....I-< d d 0 60 60 Q) ·0 o d d 0 0 U U r- 40 0 00 40 0\ ....0\ ....0\ 20 .20 ...... "---' 0 4D 5D 6D2 6DO 7DO 4F SFl 5FO 6FO 7FO 4DO SDO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F .1987 ~ 1990 Figure 9-1. Nanaimo Harbour congener profiles for 1987 (n=1) and 1990 (n=2). Mean TEQ=18 pg/g 80 80 eo 60 eoc, a ....o ~ ~ 40 o od U 20 o 4D SD 6D2 6DO 7DO 4F SFl SFO 6FO 7FO 4DO SDO 6D3 7D 8D 4FO SF2 6F 7Fl 8F Figure 9-2 Nanaimo Harbour congener profiles for 1992 (n=4). 78 400 400 1987 TEQ=80 pg/g 350 eo 320 1990 TEQ=65 pg/g eo bb 300 300 en 0- --0- s:: ci 0 0 '<:,l '<:,l cd cd .l::i .b c:: c:: II) II) u 200 200 u c:: c:: 0 0 U U r- O 00 0\ 0\ 0\ ..... 100 100 ..... 4D 5D 6D2 6DO 7DO 4F 5F15FO 6FO 7FO' 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F,' .1987 ~ 1990 Figure 9-3. NanaimolHarmac mill congener profiles for 1987 (n=1) and 1990 (n=5). 120 110 Mean TEQ=14 pg/g 100 eo bb 80 0- s:: o ...... ~ 60 i:: II) c::u o U 40 20 o L-._....-.J-'---- 4D . 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 9-4. NanaimolHarmac mill congener profiles for 1993 (n=3). 79 Nanaimo - 1987/90 6 v v Nanaimo Mill 87 H87 VBB 4 FB 1M!> B Nanaimo Harbour 87 N87 VI V~IlyCl. BV \ N87F B C9 Nanaimo 90 Cn F QC 2 81 81 0 N +-l I H87 C7 C8 -2 C3 \ r- cs C6 -4 C2 -6 l -8 -5 o 5 10 t1 Figure 9-5. PCA projections for samples from Nanaimo in 1990. 80 ~ .. Nanaimo - 1991 - 6 I I C9 F ~B ~ 4 '- BBB B v , ~\~ V FF F 2 L- BN 51 Cl C4 o L- """Clr - - C C"l C7 -.+-J C4 C3 C4 -2 - C2 -4 ,.- .,.6 'L- I I -8 L - -5 '0 5 10 tl Figure 9-6. peA projections for samples from Nanaimo in 1991. 81 Nanaimo - 1992 6 V F CICI B B 4 I- B IlfIj B B ~ ~" V \ "fi8 V FF F C12 C9 QC '. 2 r- Sl : C8 Cll ClttsC3 o 14 f-.13 C't ~ C15 ( 4 -2 t-- -4 l- -6 f- -8 I -5 o 5 10 tl Figure 9-7. peA projections for samples from Nanaimo in 1992. 82 6 Nanaimo - 1993 6 v V F BVBB 4 - .Jl ~1Iy B B V '\ Y!v FF F QC 2 r- 51 51 .' C2 C3 C13 C2 C5 CIS o CI5 N ~ -2 - "- '" -4 ,.- -6 f-- -8 I -5 o 5 10 tl Figure 9-8. peA projections for samples from Nanaimo in 1993. 83 rms PAGE IS BLANK 10. PORT ALBERNI Crab samples were collected in Alberni Harbour and Alberni Inlet by Hatfield Consultants Ltd. in July 1990 (Map 10.:.1); one ofthese samples (C6) had too few congeners detectable to be retained in the PCA model (Table 2-2). Subsequent samples for the MacMillan Bloedel Limited Alberni Pulp and Paper Division mill monitoring program were collected by Hatfield Consultants Ltd. in March 1991, January 1992 and April 1993. Axys Analytical Ltd. analyzed all Port Alberni mill monitoring program samples from 1990to 1993. All samples from Port Alberni were Dungeness crab. Samples from Alberni Inlet have a higher proportion of the PnCDFs, HxCDFs and HpCDFs than most mill site samples, but a much lower proportion of these furans than any of the major harbours (FigureIfl-I and Figure 10-2; cf. Figure 3-3). Over the four years of the monitoring program the dibenzo-p-dioxins (with non-2,3,7,8 HxCDDs predominant) and the PnCDFs, HxCDPs and HpCDFs have persisted in the Alberni samples while the TCDFs have been largely • ' J removed. As a result congener totals and TEQs had decreased to one-half of the 1990 levels by 1993 (Table 10-1). ' PCA projections for samples obtained throughout Alberni Inlet indicate a uniform composition that has remained distinct from the major B.C. harbours and that has changed, little since 1990 (Figure 10-3 to Figure 10-6). In a few cases crab samples from Alberni Harbour (Cl and Clb) have varied from this composition. In 1991 and 1992 these samples had a PCA composition identical to the major harbours, but were indistinguishable from other AlberniInlet samples in 1990 and 1993. ' ,•... Table 10-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Port Alberni. " Samples Averaged Congener Calculated Total TEQ pg/g wet weight Earliest Samples Port Alberni ci, C2, C4,C5, C6, C7, 1990 (n=6) 450 23 Most RecentSamples Port Alberni Cl, C5, C6, C7, 1993 (n=4) 230 .11 85 PortAlbemi Pulp Mill . C1 Albemi Harbour ---:--~-_. C1b . . Polly Point C2 N C3 ------+..... A C4----rw . C5 C6 C7 NahmintBay o 5km Map 10-1. Crab sampling locations near Port Alberni. 86 120 Mean TEQ=23pg/g 100 OJ) ""- OJ) 80 c, c:: ,9.... ctl 10< 60 1:: lU U t:: 0 U 40 20 o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Ft 8F Figure 10-1. Port Alberni congener profiles for 1990 (n=6). 80 ,------,.----,------,------.-:....,., 70 Mean TEQ=II pg/g 60 OJ) ""- 'OJ) ~ c:: ,9.... ~ 40 t:: lU U ot:: U 20 o L..-__L 4D 5D' 6D2 6DO 7DO 4F 5Fl5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 10-2. Port Alberni congener profiles for 1993 (n=4). 87 Port Alberni - 1990 6 v .F V -1\ B:!Rt BB -4 B ·V:-B B v , \F'~ VFF C4 F 2 Cl C6 E~C5 Sl sr o C'l ~ -2 -4 -6 -8 -5 o 5 10 t1 Figure 10-3. PCA projections for samples from Port Alberni in 1990. 88 Port Alberni - 1991 6 v V F VB B 4 ,pB~\~ B vClb v FF Cl QC 2 C2 SI SI C4 C5 o N ~ -2 -4 -6 -8 -5 o 5 10 tl Figure 10-4. peA projections for samples from Port Alberni in 1991. 89 Port Alberni - 1992 6 v V F BVBB 4 - V!~B B V rn \, v FF Cl F QC 2 - ~ SI S[ / 7 IC4,C4,C5,C6,C7 I o ~ ~ -2 '- - -4 ..... -6 - -8 I -5 o 5 10 t1 Figure 10-5. peA projections for samples from Port Alberni in 1992. 90 Port Alberni - 1993 6 v v F V B B 4 B Jlv'l! B B VI "f!\~ v 'l! FF VF QC 2 Cl 51 51 1!6 o C5 C'l ~ -2 -4 ~ -6 -8 -5 o 5 10 tl Figure 10-6. peAprojections for samples from Port Alberni in 1993. 91 TillS PAGE IS BLANK 11 . POWELL RIVER Crab samples were collected in the Powell River area by Hatfield Consultants Ltd. in 1990, with five samples collected in the vicinity of the MacMillan Bloedel Limited Powell River Division Pulp and Paper mill in January and February and five supplementary samples collected further afield in September (Map 11-1). Three of these latter samples (C7, C8 and C11) had too few congeners detectable to be retained in the PCA model (Table 2-2). Subsequent mill monitoring program samples were collected by Hatfield Consultants Ltd. in March 1991, February 1992 and March 1993. Axys Analytical Ltd. analyzed all Powell River samples from 1990 to 1993. All PCA samples from the Powell River area were Dungeness crab except for samples of Box crab from Station C3 in 1990 and Red Rock crab from Stations C14 and C15 in 1993. Between 1990 and 1993 the congener total and calculated TEQ decreased by approximately a factor of four for stations closest to the mill (Table 11-1). Congener profiles and PCA projections both indicated a decrease in the proportion of toxic congeners over this time (Figure 11-1 to Figure 11-6). The change in composition between years has been principally due to a decrease in the TCDFs, with an increase in the PnCDDs, HxCDDs, PnCDFs and HxCDFs. From the PCA results it is evident that PCDD/Fs with a mill composition are present in crab samples ranging from Hernando and Cortes Islands (C16 to C18) in the northwest to Lang Bay (CI4) and possibly Saltery Bay (C13) in the southeast (Figure 11-3 to Figure 11-6). PCA projections indicate that the congener composition has remained relatively consistent throughout the region in each year, indicating that the change in composition has proceeded uniformly over time. The Saltery Bay sample C13 from 1993 is very similar in PCA projection to samples that were collected between Howe Sound and Powell River in 1993 (Section 5). The sample collected adjacent to the mill at Station C4 had PCA projections close to that of the harbours in 1993 (Section 4). Samples from this location were also shifted towards the harbour ,samples in 1991 and 1992. Because these samples were located closest to the mill, they very likely have been influenced by pentachlorophenol from contaminated wood chips. Table 11-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Powell River. . Samples Averaged GongenerCalcnlated Total TEQ pg/g wet weight Earliest Samples Powell River Cl, C2, C4, C5 and C9, 1990 (n=5) 620 57 Most Recent Samples Powell River Cl and C5, 1993 (n=2) 160 12 93 018 / Campbell RiverC15 01 N C3 A Mitlenelch Island 05 FISHERY CLOSURES - NOV. 1994- C14 C12 lS1 Closed to all crab fisheries o Closed to commercial crab fishery Health advisory to recreational and native crab fisheries on the consumption ) of crab hepatopancreas I ( . Texada ~ L Island. c;s-j- to "-\ o 10km ~ "\ .•. 'Ud\ \ Map 11-1. Crab sampling locations near Powell River. 94 500 Mean TEQ=57 pg/g 440 400 bI) -.eo Q.. d 300 .9.... 100 o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 11-1. Powell River congener profiles for 1990 (n=5). 80 Mean TEQ=12 pg/g 80 -.bI) eo 60 Q.. d .8.... 20 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 11-2. Powell River congener profiles for 1993 (n=2). 95 Powell River - 1990 6 .., r I v v F v B B 4 f- B ~lll B B 'J! "'\\ y \y FF F QC 2 - 51 C13 C4 ~5 C2 ,.." o .. . .. C"I ~ Cl -2 - C3 -4 - .. -6 I- -8 L I i J -5 o 5 10 tl Figure 11-3. peA projections for samples from Powell River in 1990. 96 " Powell River - 1991 6 V V F ~ll 4 \1iI BB B v , ~'yB V FF B F C4 QC 2 51 51 C5 C5 Cl C2 o N ~ -2 -4 -6 -8 -5 o 5 10 t1 Figure 11-4. peA projections for samples from Powell River in 1991. 97 Powell River - 1992 6 V V F BVBB 4 i- V!~B B V , V FF"lfJ F C4 QC 2 ~ 51 C16 C14 816 C5 rl o Cl ~ ~ -2 >- -4 - -6 ~ -8 I -5 o 5 10 tl Figure 11-5. peA projections for samples fromPowell River in 1992. 98 't ~ "" -- ---_.,_._.-._._.. _~.~~~-~~--~~-~--,-----_._-_._-._--- Powell River - 1993 6 v v F V B 4 B VI! B B VJ ~\"\ v \ FF VF QC 2 cn CS o N ~ -2 -4 -6 -8 -5 o 5 10 t1 Figure 11-6. peA projections for samples from Powell River in 1993. 99 TIDS PAGE IS BLAJ\TJ( 12. PRINCE RUP'ERT Crab samples were collected near the Skeena Cellulose Inc. pulp mill in Prince Rupert by the Department of Fisheries and Oceans in the winter of 1987-1988 and analyzed by the Canadian Wildlife Service (Norstrom et al. 1988). Subsequent crab samples were collected in the vicinity of the mill by Hatfield Consultants Ltd. in January 1989, with more wide-ranging sampling .instituted in June 1990 (Map 12-1). Mill monitoring program samples were then collected annually by Hatfield Consultants Ltd. in March or April from 1991 to 1993. One of the 1990 samples (SC1A) and three of the 1991 samples (SC4, SC5 and SC6) had too few congeners detectable to be retained in the PCA model (Table 2-2). Axys Analytical Ltd. analyzed all mill monitoring program samples from 1990 to 1993. In August 1993 an additional commercial fishery crab sample was collected in Chatham Sound by the Department of Fisheries and Oceans and analyzed by the Institute of Ocean Sciences. All samples were Dungeness crab. Congener profiles and PCA projections indicate that only a small change in congener composition had occurred between 1987 and March 1991 for the crab samples collected closest to the mill (Figure 12-1; Figure 12-3 to Figure 12-5). These samples were principally from the narrow channels to the south and east of Kaien Island - Porpoise Harbour, Wainwright Basin and Morse Basin (samples SCI, SC2, SC3 and SC5; Map 12-1). The small change that did occur between years was principally due to an increase in the proportion of HxCDDs. Crab samples collected outside this enclosed area in 1990 and 1991 had a distinctly different composition that was closer to the pattern exhibited by the principal B.C. harbours. These samples included the 1990 samples SC4 and SC6 that were collected from islands to the west in Hecate Strait and the 1991 sample SC1A from the north side of Kaien Island in Prince Rupert Harbour (Figure 12-4 and Figure 12-5; Map 12-1). By 1992 PCA projections for the crab samples collected close to the mill had shifted to a cluster just right of axis centre (Figure 12-6). This shift towards the upper left indicated a larger decrease in the proportion of TCDFs between 1991 and 1992 than had occurred up to 1991. Samples collected in Prince Rupert Harbour and to the north and west of Kaien Island in 1992 formed a separate cluster of samples that projected closer to samples from the major harbours. The progressive shift to the upper left in PCA projections, indicating a progressive increase in the HxCDn proportion, generally continued for most of the 1993 mill samples (Figure 12-7). One sample collected adjacent to the mill (SC2) had shifted in the opposite direction (toward the lower centre). This sample contained one of the highest proportions ofnon-2,3,7,8 HxCDDs in entire crab data set, as well as significant amounts of the TCDFs (not shown). By 1993 the HxCDD proportion was roughly twice the size of the individual TCDFs in the averaged mill samples (Figure 12-2). Samples from Prince Rupert Harbour in 1993 (SC1A, SClo, SC11) projected very close to samples from Victoria andVancouver Harbours (Figure 12-7). Samples collected to the north and west again formed a distinct cluster between the harbour samples and the mill samples. The commercial fishery crab sample from Chatham Sound projected with this latter cluster. 101 ------_.._-----_._------As in other mill areas, peA projections have remained relatively consistent at any given time in the channels adjacent to the mill; this indicates that the change in congener composition has proceeded uniformly over time. Between 1987 and 1993 the congener total and calculated TEQ have decreased by more than anorder ofmagnitude for stations closest to the mill (Table 12-1). Table 12-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar peA projections from Prince Rupert. Samples Averaged Congener Calculated Total TEQ pg/g wet weight Earliest Samples Weststar Pulp a, 1987 (n=l) . 17,600 1900 Prince Rupert SCI, SC3 and SC5, 1989 (n=3) 2900 260 Prince Rupert, 1987 (n=1) plus SCI, SC3 and SC5, 1989 (n=3) 6500 670 Most Recent Samples Prince Rupert SCI, SC2 and SC7, 1993 (n=4) 1000 53 a Since 1987 the name ofthe mill has changed from Weststar Pulp to Skeena Cellulose. 102 FISHERY CLOSURES- NOV: 1994 ~ Osborne .0+'~ ~"-. SC9 ~'~> EJ Closed to all crab fisheries ~" Cove .?; ""-..\ r2'J Closed to commercial crab fishery Health advisory to recreational and native crab fisheries on the consumption of crab hepatopancreas "<~ SC10 SC15 ~ .!> • .4 .,/ / SC1A • 4 SC1 / > SC1 SC13 SC7 SC11 N SC2 A SG12 SCB SC3 CHATHAM SOUND o 5km Map 12-1. Crab sampling locations near Prince Rupert. 103 1600 12000 1987 TEQ=1900 pg/g 1400 1989 TEQ=260 pg/g 10 O/J ~ 1200 ~ t:l< 0.. c=- d' ...... 0 .S..... ~ t'::S J:: ~ .....I-< ~ a ~ d) a.l :I'" 800 o 0 o ~ c: 0 P 0 U 5 U r- 0\ 00 00 ...... 0'1 0\ 400 - o 0 4D 5D 6D2 6})0 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 12-1. Prince Rupert congener profiles for 1987 (n=l) and 1989 (n=3). 600 ....------.. Mean 1EQ=53 pg/g 540 bIl bll 400 c, c=- ....o ~ a.l o2l U 200 o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 12-2. Prince Rupert congener profiles for 1993 (n=4). 104 Prince Rupert - 1987/89 6 v v F BVBB 1987 sample 87 4 ~ ~ "Ill B B 1989 sample SCn v ~'"'I! Iv FF F QC ~ 2 51 51 o C'l ~ -2 - SC3 87 -4 ~ SCI SC5 -6 ~ -8 I -5 o 5 10 t1 Figure 12-3. PCA projections for samples from Prince Rupertin 1987 and 1989. 105 C~l' Prince Rupert - 1990 6 v v - F' BVBB 4 - VJ~B B V , ,,~ Y FF F QC 2 "- 51 51 SC4 o ,,~o C'l t ..;..l -2 - • SC3 Sc§f5 -4 - SCI SC2 -6 I- , -8 I -5 o 5 10 t1 Figure 12-4. peA projections for samples from Prince Rupertin1990. 106 ;'/;0 ------~------~ ----~------. Prince Rupert - 1991 6 " " v V FB V B' B 4: t- , VI ~Ilv B B V" "iJ V FF F " ~ QC 2 t- SClA SI SI , 0 .. <:'I' . ~ .. , , -2' r SCl SC3 - SG2 -4 l- -6 :- E -8 I -5 o 5 10 tl ' Figure 12-5. peA projections for samples from Prince Rupert in 1991. 107 Prince Rupert - 1992 6 v V F V B B 4 ,.... 'i!B "iii B B V ""~ 'v FF F SC9 2 I- SC1A SCS SC8 SC9 SCll SClO o ~ C7 ?8~C4 ~ S 1 -2 - SC2 -4 ,.... -6 - -8 I -5 o 5 10 tt- Figure 12-6. PCA projections for samples from Prince Rupert in 1992. 108 '" '" Prince Rupert - 1993 6 v I v F V B B 4 r- B Jl¢i! B B 'J! 'o/lllv V" "h I v FF I sCIA SClO SCll 2 r- SI SC9 SSeeSSC ~1\.93 o 'r"'I':l SC3 - C'l SCI ~ SClC7 -2 r- -4 - -6 r- SC2 -8 - .L J -5 o 5 10 tl Figure 12-7. peA projections for samples from Prince Rupertin1993. 109 THIS PAGElS BLAl\TK ." 13. KITIMAT Crab samples were collected in: Kitimat Arm by Norecol Ltd. in December 1989 and by the Department of Fisheries and Oceans in January 1991 and November 1992 (Map 13-1). A few locations to the south outside Kitimat Arm were also sampled in 1991. The 1989 sample from Gobeil Bay (S4) had too few congeners detectable to be retained in the PCA model (Table 2-2). Envirotest Ltd. of Edmonton Alberta analyzed the 1989 samples from Kitimat. The Burlington Ontario laboratory of the Department of Fisheries and Oceans analyzed the 1991 samples. Axys Analytical Ltd. analyzed the 1992 samples. All samples from Kitimat were Dungeness crab. The Eurocan Pulp and Paper mill at Kitimat uses a Kraft pulping process, but it differs from the B.C. mills previously discussed because the mill does not use any chlorine bleaching. Accordingly, the TCDFs and PnCDFs that are characteristic of chlorine bleaching are almost completely absent in the Eurocan settling lagoon (Figure 13-1 and see following). Kitimat also has a major harbour, two other large industries - the Alcan aluminum smelter and the Methanex methanol production plant - and had a sawmill with a wood treatment facility from 1969 through 1981. Furthermore, pentachlorophenol treated lumber from another sawmill at nearby Terrace was apparently shipped from the docks at Kitimat through 1989 (Kelly, pers. commun., 1995). Hence high temperature processes at the aluminum smelter and pentachlorophenol used for wood treatment are both likely to have contributed.additional PCDDlFs to Kitimat fjord. A number of samples are available to help characterize potential PCDDIF sources in the Kitimat area. Samples of sludge from five areas ofthe Eurocan Pulp and Paper Co. aeration lagoon were obtained by Norecol, Dames and Moore Inc. in 1993 and analyzed by Axys Analytical Ltd (congener profiles for each area were normalized before calculation of the average profile shown in Figure 13-1). A striking feature of the sludge samples is the almost complete absence of PCDFs. OCDD and the non-2,3,7,8 HxCDDs are major constituents in all sludge samples, but most of the PnCpps in the averaged profile are due to one area of the lagoon. The non.;.2,3,7,8 I HxCDDs&lso predominate in a sediment core collected by Environment Canadafrom Minette Bay in May 1990 (Figure 13-1). With the exception of OCDD, the averaged congener profiles for the lagoon and the sediment core are almost identical. Samples of roof dust, soil and'sludge from the Alcan smelter site were collected by B.C. Environment in 1991 and also analyzed by Axys Analytical Ltd (Figure 13-2 and Figure 13-3). The HpCDDs, OCDD and the PCDFs that are the main constituents in the Alcan samples are only minor constituents in the sediment core. Congener profiles for the 1989 crab samples from Kitimat Arm contain mainly HxCDDs with only minor amounts. of the TCDFs; this pattern is consistent with polychlorinated phenol condensation, with little or no chlorine bleaching (Figure 13-4; cf. Section 3). The H~CDD,and to a lesser extent PnCDD, profile in crabs is mirrored in the sediment core from Minette Bay (Figure 13-1). Between 1989 and 1992 the absolute concentrations of PnCDD and the HxCDDs (i.e. the congeners most characteristic ofpolychlorophenol condensation) and the TEQ have decreased by 111 nearly an order ofmagnitude in Kitimat crab samples (Figure 13-4, Figure 13-5 and Figure 13-6; Table 13-1). Over this time period congener profiles have also shown an increase in the proportion of the non-2,3,7,8 substituted HpCDDs, as well as the TCDFs, PnCDFs and HxCDFs. These congeners were present in varying proportions in samples of soil and sludge and in some samples of roof dust collected on the Alcan aluminum smelter site in 1991 (Figure 13-2 and Figure 13-3). Again the match is not exact; the hepta- and octachlorinated congeners in particular were present in major amounts in the smelter samples, but are apparently not available to the crabs. The presence of the non-2,3,7,8 substituted congeners at the Alcan smelter site and in Kitimat Arm may not be due to recent contamination. It may be that these congeners were present in low levels in the 1989 crab samples, and are only becoming apparent as analytical detection limits improve. The absence of chlorine bleaching and the presence of a novel suite of non-2,3,7,8 substituted congeners produces PCA projections for the Kitimat crab samples that are different from other regions of the B.C. coast (Figure 13-7 to Figure 13-9)..Samples form a tight cluster on the peA plot with only one sample from Bish creek in 1992 (sample 196) outside the cluster (Figure 13 9). While the overall peA projections have changed little from 1989 to 1992, projections have generally shifted to the upper left as the HxCDD proportion has decreased (Figure 13-8 and Figure 13-9). From the PCA projections of the 1991 samples it is evident that PCDDlFs with the Kitimat .Estuary composition are present in Gobeil Bay on Kildlala Arm (Map 13-1) and in Douglas and Sue channels at least as far as Foch Lagoon and Hawkesbury Island (Figure 13-8). Table 13-1. Dungeness crab hepatopancreas congener total and TEQ averages for samples with similar PCA projections from Kitimat. Samples Averaged Congener Calculated Total TEQ pg/g wet weight Earliest Samples Kitimat EC1, EC2, EC3 and EC5, 1989 (n=8) 570 68 Kitimat 1991, (n=7) 130 12 . Most Recent Samples Kitimat 1992, (n=41) 110 7.2 112 ----~-----~------ -FISHERY CLOSURES - NOV 1994 Closed to commercial crab fishery Health advisory to recreational and . native crab fisheries on the consumption of crab hepatopancreas S1 - S5 are 1989 Noreco1 Sample Sites K1 - K5 are 1992 DFO Sample Sites K3,83 K4~· K5 ~ Kitimat Arm 85 Emsley Cove N A (~ Coste , . Island / I ./ .' / / / / c _ ~/' Foch Lagoon / Hawkesbury Is. Hilton Point // ;:/ - ~\ o .Map 13-1. Crabsampling locations near Kitimat. 113 0.4 200 4) lL'l I-< t;::- 0 0 U I-< ..... p.. 0.3 150 I:::: c: lL'l 0 0 .5 OIl '0 'I:d lL'l ~ Cf.l "'Cl 0.2 100 >- 4) cd N ~ .. """ -I:d .....lL'l § lL'l 0 .5 Z 0.1 50 ;:g o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F -Eurocan Settling Lagoon Sludge (n:=5) m'§lMinette Bay Sediment Core (n=7) Figure13-1. Congener profiles for Eurocan pulp mill sludge and Minette Bay sediment. 1500 500 -.b1J 400 b1J Pol OIl ..... a.i OIl b1J ~ 1000 "0 .... .E -0 300 Cf.l tr.l 4) I-<>- ...... I:d tr.l .S.., c: I-< I:d 200 ~ o I:::: 500 cd -<- U --< 100 o 0 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F • Soil (n=3) JE1l Sludge (n=2) Figure 13-2. Congener profiles for soil and sludge samples from theAlcan smelter. 114 2000 100 OJ) OJ) OJ) --P; OJ) --P; 80 ..J' ..J' 1500 lJ) lJ) ;::3 ;::3 0 0 ...... 0 0 60 0 0 ~ ~ I-< 0 ell 1000 ..... Q) ell I-< .S -< 40 o CO -ell .S..... U en Q) ell 500 ~ U 0 20 U _____L-IL- I-J --IIGL---lO 40 50 602 600 7DO 4F 5F! 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7F! 8F • Casting Area (n=2) ~ Calcinator (n=2) Figure 13-3. Congener profiles for roof dust from the casting area of the Alcan smelter. 250 TEQ=68 pglg 220 200 co bb P; r:: 150 .S:...... ~ I=: Q) u I=: 100 0 U 50 o 4D 5D 6D2 6DO 7DO 4F 5F! 5FO 6FO 7FO 4DO 5DO 6D37D 8D 4FO 5F2 .6F 7Ft 8F Figure 13-4. Kitimat congener profiles for 1989 Cn=8). 115 50 1EQ=12 pg/g 40 b1J b1J --Q; a 30 ...... 0 cd l-< ....c:: ll.l U c:: 20 0 U 10 o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 13-5. Kitimat congener profiles for 1991 (n=7). 30 28 Mean TEQ=7.2 pg/g b1J ~ 20 Q; a ..;::o cd .l:J c:: ll.l c::U o U 10 o 4D 5D 6D2 6DO 7DO 4F 5Fl 5FO 6FO 7FO 4DO 5DO 6D3 7D 8D 4FO 5F2 6F 7Fl 8F Figure 13-6. Kitimat congener profiles for 1992 (n=41). 116 2 Kitimat - 1989 6 v v F V B B 4 B "Iil B B \6 v!!tv V \v FF B F QC 2 51 51 o C'l ~ ~ 55 52 -2 ~l -4 -6 -8 -5 o 5 10 t1 Figure 13-7. PCAprojections for samplesfrom Kitimatin 1989. 117 Kitimat - 1991 6 y y F BYB B Hawkesbury Island HB 4 """- VI· ~ B B Y '.!J\, Foch Lagoon FL \y FF F QC 2 f-. 51 51 o S2 N K3 +-l 1 S4 -2 f- pt .. HE S5 -4 f- -6 f- -8 I -5 o 5 10 tl Figure 13-8. PCA projections for samples from Kitimat in 1991. 118 r .. ---_..---_.------_.-_._.~~-_._-- Kitimat - 1992 6 v v ~1iIVBB 4 FB B \Il Vl!~VB BV ~V FF F QC 2 51 51 ·0 C'" +-I 5 -2 -4 -6 -8 -5 o 5 10 t1 Figure 13-9. PCA projections for samples from Kitimat in 1992. 119 rms PAGE IS BLANK 14. CONCLUSIONS PCA is a valuable method for exploring trends and defining relationships in the large sample set of chlorinated dibenzo-p-dioxin and dibenzofuran data for samples of crab hepatopancreas that have been collected from B.C. coastal sites. PCA has proven to be particularly useful for classifying samples according to principal source. • Variations in the proportions of TCDFs from chlorine bleaching and HxCDDs derived from pentachlorophenol have produced striking differences between the PCDDIF profiles of crabs from different mill sites. • Changes in mill process chemistry since 1987 have produced dramatic improvements. In most cases both the proportion of the toxic 2,3,7,8-chlorinated congeners and the overall chlorinated dibenzo-p-dioxin anddibenzofuran concentrations have decreased markedly in crabs collected from the mill sites. • Mill related TCDFs have been removed faster than the HxCDDs: one effect is that crab composition profiles and PCA projections have become more similar over time at the mill sites. • Crab samples from RCo's harbours have lower proportions of the toxic 2,3,7,8-chlorinated congeners, but have shown less changeover time. • PCA results suggest that differences in feeding behavior may have reduced the toxic load for crab species other than Dungeness crab. It is suggested that whenever possible a single species - Dungeness crab - should be used for the mill monitoring programs. 121 rms PAGE IS BLANK 15. REFERENCES Dwernychuk,L. W. 1993. Dioxinlfuran trend monitoring program. Howe Sound 1992. Report prepared for Howe Sound Pulp and Paper, Port Mellon B.c. and Western Pulp Ltd., Squamish B.C. by Hatfield Consultants Ltd., West Vancouver B.C. Hagenmaier, H. and H. Brunner. 1987. Isomer specific analysis of pentachlorophenol and sodium pentachlorophenate for 2,3,7,8-substituted PCDD and PCDP at sub-ppb levels. Chemosphere 16: 1759-1764. Hatfield Consultants Ltd. 1994. Port Alice environmental effects monitoring pre-design reference document. Report prepared for Western Pulp Limited Partnership, Port Alice B.C. by Hatfield Consultants Ltd., West Vancouver B.C. Hites, R. A.· 1990. Environmental behavior of chlorinated dioxins and furans. Acc. Chern. Res. 23: 194-201. Jensen, G. C. 1995. Pacific coast crabs and shrimps. Sea challengers. Monterey, CA, USA. Johansson, E., S. Wold and K. Sjodin. 1984. Minimizing effects of closure on analytical data. Anal. Chern. 56: 1685-1688. Kelly, D. A. 1995. Eurocan Pulp and Paper Co., personal comniunication. Luthe, C. E., R. M. Berry and R. H. Voss. 1993. Formation of chlorinated dioxins during production of bleached Kraft pulp from sawmill chips contaminated with polychlorinated phenols. Tappi J. 76(3): 63-69. Luthe, C., and S. Prahacs. 1993. Dioxins from pulp mill combustion processes: implications and control. Pulp Paper Can. 94(8): 37-46. Luthe, C. E., P. E. Wrist and R. M. Berry. 1992. An evaluation of the effectiveness of dioxins control strategies on organochlorine effluent discharges from the Canadian bleached chemical pulp industry. Pulp Paper Can. 93(9): 40-49. Macdonald, R. W., W. J. Cretney, N. Crewe and D. Paton. 1992. A history of octachlorodibenzo-p-dioxin, 2,3,7,8-tetrachlorodibenzofuran, and 3,3',4,4' tetrachlorobiphenyl contamination in Howe Sound, British Columbia. Environ. Sci. Technol. 26: 1544-1550. '\ Meglen, R. R. 1992. Examining large databases: a chemometric approach using Principa\\ components analysis. Mar. Chern. 39: 217-237. \\ Norstrom, R. L, M. Simon, P. E. Whitehead, R. Kussat and C. Garrett. 1988. Levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDPs) in biota and 123 \ sediments near potential sources of contamination in British Columbia, 1987. Canadian Wildlife Service Analytical report CRD-88-5, 26 pp. Voss, R. H. and M. B. Yunker. 1983. A study of the potential persistence of chlorinated phenolics discharged into Kraft mill receiving waters. Report prepared for the B.C. Council of Forest Industries Technical Advisory Committee. Vancouver, B.C. 131 pp. Whitehead, P. E., R. J. Norstrom and J. E. Elliott. 1992. Dioxin levels in eggs of great blue herons (Ardea herodias) decline rapidly in response to process changes in a nearby Kraft pulp mill. In Dioxin 92. 12th International Symposium on Dioxins and Related . Compounds. Tampere, Finland. pp. 325-328. Yunker, M. B., R. W. Macdonald, D. 1. Veltkamp and W. J. Cretney. 1995. Terrestrial and marine biomarkers in a seasonally ice-covered Arctic estuary Integration Of multivariate and biomarker approaches. Mar. Chern. 49:1-50. Yunker, M. B. and W. J. Cretney. 1996. Dioxins and furans in crab hepatopancreas: use of principal components analysis to classify congener patterns and determine linkages to contamination sources. In: Environmental Fate and Effects of Pulp and Paper Mill Effluents. M. R. Servos, K. R. Munkittrick, J. H. Carey and G. J. Van Der Kraak Ed:;. St. Lucie Press, Delray Beach, Florida. pp.315-325. 124 16. BIBLIOGRAPHY OF DATA REPORTS Howe Sound Dwernychuk, L.W. 1989. Bottom sediments and biological tissues: a baseline organochlorine contamination survey in Howe Sound, JanuarylFebruary 1989. Prepared for: Howe Sound Pulp and Paper Ltd. and Western Pulp Partnership by Hatfield Consultants Ltd., West Vancouver, B.C. May 1989. Dwernychuk, L.W. 1989. Marine receiving environment studies in Howe Sound, 1990, Status Report. Prepared for: Howe Sound Pulp and Paper Ltd. and Western Pulp Partnership by Hatfield Consultants Ltd., West Vancouver, s.c August 1989. Dwernychuk, L.W. 1990. Hepatopancreas and leg muscle of Howe Sound Dungeness crabs dioxin/furan analyses, November 1989. Prepared for: Western Pulp Ltd. Partnership, Squamish, B.C. by Hatfield ConsultantsLtd., West Vancouver, B.c. March 1990. Dwernychuk, L.W. 1990. Mill activities and the marine environment: Howe Sound Pulp. and Paper Ltd., Port Mellon, B.c. Submitted to: Environmental Protection on behalf of Howe Sound Pulp and Paper Ltd., Port Mellon, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. June 1990. Dwernychuk, L.W. 1991. Dioxin/furan trend monitoring program. Status Report, ·Howe Sound, February/March 1991. Prepared for: Howe Sound Pulp and Paper Ltd., Port Mellon, B.c. and Western Pulp Ltd. Partnership, Woodfibre Pulp Operations, Squamish, B.C. by Hatfield ConsultantsLtd., West Vancouver,B.C. May 1991. Dwernychuk, L.W., G.S. Bruce, B. Gordon and G.P. Thomas, 1991. Comprehensive organochlorine survey of the receiving environment of Howe Sound, 1990 (effluent, water, sediment, biological organisms). Tables, figures/data submission only. Prepared for: Howe Sound Pulp and Paper Ltd., Port Mellon, B.c. and Western Pulp Ltd. Partnership, Woodfibre Pulp Operations, Squamish, B.c. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W.; G.S. Bruce, B. Gordon and G.P. Thomas. 1991. Organochlorine trend monitoring, Howe Sound, 1991 (sediments, shrimp, prawn, crab). Prepared for: Howe Sound Pulp and Paper Ltd., Port Mellon, B.C. and Western Pulp Ltd. Partnership, Woodfibre Pulp Operations, Squamish, B.c. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W., G S. Bruce, B. Gordon and G P. Thomas. 1991. Organochlorine contaminants/monitoring study, Howe Sound, 1990. (Volume 1: report/tables/figures/ plates/appendices AI-AS; Volume 2: appendices A6-AlO.) Report for: Howe Sound Pulp 125 and Paper Ltd., Port Mellon; B.C. and Western Pulp Ltd. Partnership, Squamish, B.C. by Hatfield Consultants Ltd., West Vancouver, B.c. December 1991. Dwemychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring program, Howe Sound, 1992 (sediment/crab/shrimp/prawn). Prepared for: Western Pulp Ltd. Partner, Woodfibre Pulp Operations, Squamish, B.C. and Howe Sound Pulp and Paper Ltd., Port Mellon, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. May 1992. Dwemychuk, L.W. 1992. Data submission: 1992 Dioxin trend monitoring (sediment/crab/prawnlshrimp) Howe Sound. Prepared for: Howe Sound Pulp and Paper, Port Mellon, B.C. and Western Pulp Ltd Partnership, Squamish, B.C. by Hatfield ConsultantsLtd. West Vancouver, B.C. December 1992. Dwemychuk, L.W. 1993. Dioxin/furan trend monitoring program, Howe Sound, 1992. Trend graphics/data submission (sediment/crab/prawn/shrimp). Prepared for: Howe Sound Pulp and Paper, Port Mellon, B.C. and Western Pulp Ltd. Partnership, Squamish, B.C. by Hatfield ConsultantsLtd., West Vancouver, B.C. January 1993. Dwernychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Howe Sound, 1992 (sediment/crab/prawn/shrimp). Prepared for; Howe Sound Pulp and Paper, Port Mellon, B.C. and Western Pulp Ltd. Partnership, Squamish, B.C. by Hatfield Consultants Ltd., West Vancouver, B.c. March 1993. Dwernychuk, L.W., T.G. Boivin and J.A. Sartori. 1993. Status Report: Dioxin/furan trend monitoring program, Howe Sound, 1993 (sediment/crab/shrimp/prawn). Prepared for: Howe Sound Pulp and Paper, Port Mellon, B.C. and Western Pulp Ltd. Partnership, Squamish,B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1993. Dwemychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Data Submission Report: Dioxin/furan trend monitoring program, Howe Sound, 1993 (sediment/crab/shrimp/prawn). Prepared for: Howe Sound Pulp and Paper, Port Mellon, B.c. and Western Pulp Ltd. Partnership, Squamish,B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. October 1993.. Dwernychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Howe Sound, 1993 (sediment/crab/shrimp/prawn). Prepared. for: Howe Sound Pulp and Paper, Port Mellon, B.C. and Western Pulp Ltd. Partnership, Squamish,B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1993. Strait of Georgia Thomas, G.P. and B. Gordon. 1993. 1993 Strait of Georgia organochlorine program. Prepared for: Department of Fisheries and Oceans (pacificRegion), by G3 Consulting Ltd., Burnaby, B.C. Apri11993. 126 Crofton Dwemychuk, L.W. 1990. Effluent, receiving water bottom sediments and biological tissues: a baseline organochlorine contamination survey, JanuarylFebruary 1990. Prepared for: Fletcher Challenge Canada, Crofton Pulp and Paper. Hatfield Consultants Ltd., West Vancouver, B.C. May 1990. Dwemychuk, L.W. 1990. Baseline organochlorine contamination study near Fletcher Challenge Canada, Crofton Pulp and Paper mill, interim data submission. Prepared for: Fletcher Challenge Canada by Hatfield Consultants Ltd., West Vancouver, B.C. March 1990. Dwemychuk, L.W. 1990. Baseline organochlorine contamination study near Fletcher Challenge Canada, Crofton Pulp and Paper mill, Status Report: supplementary sampling, August 1990. Prepared for: Fletcher Challenge Canada by Hatfield Consultants Ltd., West Vancouver, B.C. October 1990. Konasewich, D. 1990. Baseline contamination study, nearshore area of Cowichan Bay, Westcan Terminals Ltd. Prepared for: DOEIDFO by Envirochem Special Projects Inc. North Vancouver, B.C. April 1990. Envirochem 1990. Baseline contamination study, nearshore area of Cowichan Bay, Doman Forest Products Ltd. Cowichan Bay Division. Prepared for: DOEIDFO byEnvirochem Special Projects Inc. North Vancouver, B.c. April 1990. Dwemychuk; L.W. 1991. Baseline organochlorine contamination study near Fletcher Challenge Canada, Crofton Pulp and Paper. Supplementary Sampling, August 1990. Prepared for: Fletcher Challenge Canada Ltd., Crofton Pulp and Paper by Hatfield Consultants Ltd., West Vancouver, B.c. January 1991. Dwemychuk, L.W. 1991. Dioxinlfuran trend monitoring program, Crofton Pulp and Paper, Status Report, April 1991. Prepared for: Fletcher Challenge Canada Ltd., Crofton Pulp and Paper, Crofton, s.c by Hatfield Consultants Ltd., West Vancouver, B.C:. May 1991. Dwemychuk, L.W;, G.S. Bruce, B. Gordon and G.P. Thomas. .1991. Organochlorine trend monitoring, Crofton Pulp and Paper, 1991. Graphics/data submission only (sediment, crab, oyster). Prepared for: Fletcher Challenge Canada Ltd., Crofton Pulp and Paper, Crofton, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwemychuk, L.W., G. S. Bruce. B. Gordon and G.P. Thomas. 1992. Organochlorine trend monitoring; Crofton Pulp and Paper, 1991 (sediments, crabs, oysters). Prepared for: Fletcher Challenge Canada Ltd., Crofton Pulp and Paper, Crofton, B.c. by Hatfield Consultants Ltd., West Vancouver, B.C. January 1992. Dwemychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring program. Crofton Pulp and Paper, 1992 (sediment/crab/oyster). Prepared for: Fletcher 127 Challenge Canada, Crofton Pulp and Paper, Crofton, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. June 1992. Dwemychuk, L.W. 1993. Dioxin/furan trend monitoring program, Crofton, 1992. Trend graphics/data submission (sediment/crab/oyster). Prepared for: Fletcher Challenge, Crofton, B.c. by Hatfield Consultants Ltd., West Vancouver, B.C. February 1993. Dwemychuk, L.W., T.G. Boivin, D. Levy and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Crofton, 1992 (sediment/crab/oyster). Prepared for: Fletcher Challenge Canada Ltd, Crofton Pulp and Paper Division, Crofton, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. April 1993. Dwemychuk, L.W., T.G. Boivin and lA. Sartori. 1993. Status Report: Dioxinlfuran trend monitoring program, Crofton, 1993 (sediment/crab/oyster). Prepared for: Fletcher Challenge Canada Ltd! Crofton Pulp and Paper Division, Crofton, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. May 1993. Dwemychuk, L.W., T.G. Boivin and G. S. Bruce. 1993. Data Submission Report: Dioxin/furan trend monitoring program, Crofton, 1993 (sediment/crab/oyster). Prepared for: Fletcher Challenge Canada Ltd, Crofton Pulp and Paper Division, Crofton, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. October 1993. Dwernychuk, L.W., T.G. Boivin and G. S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Crofton, 1993 (sediment/crab/oyster). Prepared for: Fletcher Challenge Canada Ltd, Crofton Pulp and Paper Division, Crofton, B.c. by Hatfield Consultants Ltd. West Vancouver, B.C. December 1993. Campbell River Dwernychuk, L.W. 1990. Effluent, receiving water, bottom sediments and biological tissues: a baseline organochlorine contamination survey, January/February 1990. Prepared for: Fletcher Challenge Canada, Elk Palls Pulp and Paper by Hatfield Consultants Ltd., West Vancouver, B C. May 1990. Dwernychuk, L.W. 1990. Baseline organochlorine contamination study near Fletcher Challenge Canada, Elk Palls Pulp and Paper mill, interim data submission 1990. Prepared for: Fletcher Challenge Canada by Hatfield Consultants Ltd., West Vancouver, B C. March 1990. Dwernychuk, L.W. 1990. Baseline organochlorine contamination study near Fletcher Challenge Canada, Elk Palls Pulp and Paper mill, Status Report: supplementary sampling, August 1990. Prepared for: Fletcher Challenge Canada by Hatfield Consultants Ltd., West Vancouver, B C. October 1990. 128 Dwernychuk, L.W. 1990. Baseline organochlorine contaminants study, Raven Lumber Ltd. Prepared for: Raven Lumber, Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, s.c March 1990. Dwernychuk, L.W. 1990. Surface runoff, receiving water, bottom sediments and biological tissues: a baseline organochlorine contamination survey, JanuarylFebruary 1990. Prepared for: Raven Lumber Ltd. by Hatfield ConsultantsLtd., West Vancouver, B.C. May 1990. Dwernychuk, L.W. 1991. Baseline organochlorine contamination study near Fletcher Challenge Canada, Elk Falls Pulp and Paper. Supplementary sampling, AugustlSeptember 1990. Prepared for: Fletcher Challenge Canada Ltd., Elk Falls Pulp and Paper by Hatfield Consultant Ltd., West Vancouver, s.c. January 1991. Dwernychuk, L.W. 1991. Dioxin/furan trerid monitoring program Status Report, March 1991, Elk Falls. Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1991. Dwernychuk, L.W. 1991. Organochlorine trend monitoring, Elk Falls 1991, graphics/data submission only (sediment, crab). Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W. 1991. Dioxin/furan trend monitoring program Status Report, March 1991, Raven Lumber. Prepared for: Raven Lumber Ltd., Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1991. Dwernychuk, L.W. 1991. Organochlorine trend monitoring, Raven Lumber, 1991, graphics/data submission (sedimentlcrab). Prepared for: Raven Lumber Ltd., Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring program, Campbell River Mills, Campbell River, B.C. (sediment/crab). Prepared for: Campbell River Mills Ltd., Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. July 1992. Dwernychuk, L.W., G.S. Bruce, B, Gordon and G.P. Thomas. 1992. Organochlorine trend monitoring (sediments/crabs), Campbell River Mills, 1991. Prepared for: Campbell River Mills, Campbell River, B.c. by Hatfield Consultants Ltd., West Vancouver, B.C. September 1992. Dwernychuk, L.W. 1992. Data submission: 1992 dioxin trend monitoring (sedimentlcrab), Campbell River Mills Ltd., Campbell River, B.C. Prepared for: Campbell River Mills Ltd., Campbell River, B.C. by Hatfield Consultants Ltd" West Vancouver, B.C. December 1992. . Dwernychuk, L.W., G.S. Bruce, B. Gordon and G.P. Thomas. 1992. Organochlorine trend monitoring, Elk Falls Pulp and Paper, 1991 (sediments, crabs). Prepared for: Fletcher 129 Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.c. by Hatfield Consultants Ltd., West Vancouver, B.c. July 1992. Dwernychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring program, Fletcher Challenge Canada, Elk Falls 1992 (sediment, crab). Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.c. by Hatfield Consultants Ltd. West Vancouver, B.C. July 1992. Dwernychuk, L.W. 1992. Data submission: 1992 dioxin trend monitoring (sediment/crab), Fletcher Challenge Canada Ltd., Elk Falls Pulp and Paper. Prepared for: Fletcher Challenge Canada Ltd., Elk Falls Pulp and Paper, by Hatfield Consultants Ltd. West Vancouver, B.C. December 1992. Dwernychuk, L.W. 1993. Dioxin/furan trend monitoring program, Campbell River Mills, 1992. Trend graphics/data submission (sediment/crab). Prepared for: Campbell River Mills Ltd., Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. February 1993. Dwernychuk, L.W., D. Archibald and T.G. Boivin. 1993. Final Report: Dioxin/furan trend monitoring program, Campbell River Mills, 1992 (sediment/crab). Prepared for: Campbell River Mills Ltd., Campbell River, B.C. by Hatfield Consultants Ltd. West Vancouver, B.c. April 1993. Dwernychuk, L.W. 1993. Dioxin/furan trend monitoring program, Elk Falls, 1992. Trend graphics/data submission (sediment/crab). Prepared for: Fletcher Challenge Canada Ltd. Campbell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. February 1993. Dwernychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Dioxin/furan trend monitoring program final report: Elk Falls, 1992 (sediment/crab). Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.C. by Hatfield Consultants, West Vancouver, B.C. April 1993. Dwemychuk, L.W., T.G. Boivin and I.A. Sartori. 1993. Status Report: Dioxin/furan trend monitoring program, Elk Falls, 1993 (sediment/crab). Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.c. by Hatfield Consultants, West Vancouver, B.C. May 1993. Dwemychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Data Submission Report: Dioxin/furan trend monitoring program, Elk Falls, 1993 (sediment/crab). Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.C. by Hatfield Consultants, West Vancouver, B.C. October 1993. Dwernychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Elk Falls, 1993 (sediment/crab). Prepared for: Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.C. by Hatfield Consultants, West Vancouver, B.c. December 1993. 130 Gold River Beak Associates Consulting. 1990. Baseline organochlorine monitoring program, Gold River Mill. Prepared for: Canadian Pacific Forest Products Ltd., by Beak Associates Consulting, Richmond, s.c May 1990. Beak Associates Consulting. 1990. Baseline organochlorine monitoring program, addendum report, Gold River Mill. Prepared for: Canadian Pacific Forest Products Ltd., by Beak Associates Consulting, Richmond, B.C. November 1990. Beak Consultants Ltd. 1991. Baseline organochlorine monitoring program, draft report. Prepared for: Canadian Pacific Forest Products Ltd., Gold River Mill by Beak Consultants Ltd., Richmond, B.C. October 1991. Beak Consultants Ltd. 1991. Baseline organochlorine monitoring program, addendum report 2. Prepared for: Canadian Pacific Forest Products Ltd., Gold River Mill by Beak Consultants Ltd., Richmond, B.C. October 1991. Beak Consultants Ltd. 1992. Baseline organochlorine monitoring program, addendum report 3. Prepared for: Canadian Pacific Forests Products Ltd., Gold River Mill by Beak Consultants Ltd., Richmond, B.C. September 1992. . Beak Consultants Ltd. 1993. Baseline organochlorine monitoring program, addendum report 4. Prepared for: Canadian Pacific Forests Products Ltd., Gold River Mill by Beak Consultants Ltd., Richmond, B.C. December 1993. Nanaimo Dwemychuk, L.W. 1990. Effluent, receiving water, bottom sediments and biological tissues: a baseline organochlorine contamination survey, January/February 1990. Prepared for: MacMillan Bloedel Ltd., Harmac Division by Hatfield Consultants Ltd., West Vancouver, s.c May 1990. Dwernychuk, L.W. 1990. Baseline organochlorine contamination study near MacMillan Bloedel Harmac Division. Interim data submission, 1990. Prepared for: MacMillan Bloedel Ltd., Harmac Division by Hatfield Consultants Ltd., West Vancouver, B.C. October 1990. Dwemychuk, L.W. 1990. Baseline organochlorine contamination study near MacMillan Bloedel Harmac Division. Status Report: Supplementary sampling, August 1990, Prepared for: MacMillan Bloedel Ltd., Harmac Division by Hatfield Consultants Ltd., West Vancouver, B.C. October 1990. Dwemychuk, L.W. 1991. Baseline organochlorine contamination study near MacMillan Bloedel Ltd., Harmac Division. Supplementary sampling, August 1990. Prepared for: MacMillan 131 Bloedel Ltd., Hannac Division by Hatfield Consultants Ltd., West Vancouver, B.C. January 1991. Dwernychuk, L.W. 1991. Dioxin/furan trend monitoring, Harmac 1991. Status Report, March/April, 1991. Prepared for: MacMillan Bloedel Ltd., Harmac Division, Nanaimo, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1991. Dwernychuk, L.W. 1991. Organochlorine trend monitoring, Harmac 1991, graphics/data submission (sediment, crab). Prepared for: MacMillan Bloedel Ltd., Harmac Division, Nanaimo, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring, MacMillan Bloedel Harmac, 1992 (sediments, crab). Prepared for: MacMillan Bloedel, Harmac, Nanaimo,B.C. by Hatfield Consultants Ltd., West Vancouver, B.c. July 1992. Dwernychuk, L.W., B. Gordon and G.P. Thomas. 1992. Organochlorine trend monitoring; MacMillan Bloedel Ltd., Harmac Division, 1991 (sediments, crabs). Prepared for: MacMillan Bloedel Harmac Division, Nanaimo, RC. by Hatfield Consultants Ltd., West Vancouver, B.C. August 1992. Dwernychuk, L.W. 1992. Data submission: 1992 dioxin trend monitoring (sediment/crab), MacMillan Bloedel Ltd., Harmac Division. Prepared for: MacMillan Bloedel Ltd., Harmac Division, Nanaimo B.c. by Hatfield Consultants Ltd. West Vancouver, RC. December 1992. Dwemychuk, L.W. 1993. Dioxin/furan monitoring program, Harmac, 1992. Trend graphics/data submission (sediment, crab). Prepared for: MacMillan Bloedel Ltd. Harmac Division, Nanaimo, B.c. by Hatfield ConsultantsLtd., West Vancouver, RC. February 1993. Dwernychuk, LoW., T.G. Boivin, D. Levy and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Harmac, 1992 (sediment/crab). Prepared for: MacMillan Bloedel Ltd. Harmac Division, Nanaimo, B.C. by Hatfield Consultants Ltd., West Vancouver,B.C. April 1993.' Thomas, G.P. and B. Gordon. 1993. Status Report: Organochlorine trend monitoring program, 1993 Harmac, Prepared for: MacMillan Bloedel Ltd. Harmac Division, by G3 Consulting Ltd., Burnaby,B.C. March 1993. Thomas, G.P. and B. Gordon. 1993. Final Report: Organochlorine trend monitoring program, 1993 Harmac. Prepared for: MacMillan Bloedel Ltd. Hannac Division, by G3 Consulting Ltd., Burnaby,s.c September 1993. Port Alberni Dwernychuk, L.W. 1990. Baseline organochlorine contamination study near MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, 1990 Status Report. Prepared for: MacMillan 132 Bloedel Ltd., Alberni Pulp and Paper Division by Hatfield Consultants Ltd., West Vancouver, B.C. October 1990. Dwernychuk, L.W. 1990. Effluent organochlorine contamination survey, June/July 1990. Volume 1: Reports/tables/ figures/plates; Volume 2: appendices. Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division by Hatfield Consultants Ltd., West Vancouver, B.C. October 1990. Dwemychuk, L.W., G.S. Bruce. B. Gordon and G.P. Thomas. 1991. Dioxin/furan trend monitoring program: Status Report, Alberni Inlet, March 1991. Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1991. Dwemychuk, L.W. 1991. Baseline organochlorine trend monitoring: Albemi Inlet, 1991 (sediments/crab) graphics/data submission. Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.C. by Hatfield Consultants Ltd., West Vancouver, s.c. November 1991. Dwernychuk, L.W., G.S. Bruce. B. Gordon and G.P. Thomas. 1991. Organochlorine trend monitoring: Alberni Inlet, 1991 (sediments/crab). Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.c. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwemychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring program, Alberni Inlet, 1992 (sediment/crab/shrimp/prawn). Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.c. by Hatfield Consultants Ltd., West Vancouver, n.c. May 1992. Dwemychuk, L.W. 1992. Data submission: 1992 dioxin trend monitoring (sediment/crab)· MacMillan Bloedel Ltd., Alberni Pulp and Paper Division. Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. December 1992. Dwemychuk, L.W. 1993. Dioxin/furan trend monitoring program, Port Albemi, 1992. Trend graphics/data submission (sediment/crab). Prepared for: MacMillan Bloedel, Alberni Pulp and Paper Division, Port Alberni, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. February 1993. Dwemychuk, L.W. T.G. Boivin, D. Levy and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Port Alberni, 1992 (sediment/crab). Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. March 1993. Dwemychuk, L.W. T.G. Boivin and G.S. Bruce. 1993. Final Report: Dioxin/furan trend monitoring program, Port Alberni, 1993 (sediment/crab). Prepared for: MacMillan Bloedel Ltd., Alberni Pulp and Paper Division, Port Alberni, B.C. by Hatfield Consultants Ltd. West Vancouver, B.C. October 1993. 133 Powell River Dwernychuk, L.W. 1989. The marine receiving environment near MacMillan Bloedel Ltd., Powell River Division: A study on the physical, chemical and biological components of intertidal and subtidal systems. Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. July 1989. Dwemychuk, L.W. 1990. Effluent, receiving water, bottom sediments and biological tissues: a baseline organochlorine contamination survey, January/February 1990. Prepared for: MacMillan Bloedel Ltd., Powell River Division by Hatfield Consultants Ltd., West Vancouver, s.c May 1990. Dwemychuk, L.W. 1990. Baseline organochlorine contamination study near MacMillan Bloedel Ltd., Powell River Division, interim data submission 1990. Prepared for: MacMillan Bloedel Ltd., Powell River Division by Hatfield Consultants Ltd., West Vancouver, B.C. March 1990. Dwemychuk, L.W. 1990. Baseline organochlorine contamination study near MacMillan Bloedel Ltd., Powell River Division, Status Report: supplementary sampling, August 1990. Prepared for: MacMillan Bloedel Ltd., Powell River Division by Hatfield Consultants Ltd., West Vancouver, B.c. October 1990. Dwernychuk, L.W. 1991. Baseline organochlorine trend monitoring, Powell River, 199 L Graphics/data submission (sediment, crab) supplementary sampling, September 1990. Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. January 1991. Dwernychuk, L.W. 1991. Baseline organochlorine contamination study near MacMillan Bloedel Ltd., Powell River Division, supplementary sampling, September 1990. Prepared for: MacMillan Bloedel Ltd., Powell River Division by Hatfield Consultants Ltd., West Vancouver, B.C. January 1991. Dwemychuk, L.W. 1991. Dioxinlfuran trend monitoring program status report, Powell River, March /ApriI1991. Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1991. Dwernychuk, L.W. 1991. Organochlorine trend monitoring, Powell River 1991, graphics/data submission (sediment/crab). Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W. 1992. Status Report: comprehensive organochlorine trend monitoring program, MacMillan Bloedel Ltd., Powell River Division. Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. July 1992. 134 Dwernychuk, L.W., B. Gordon and G.P. Thomas. 1992. Organochlorine trend monitoring, MacMillan Bloedel Ltd., Powell River Division, 1991 (sediments, crabs, oyster). Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. August 1992. Dwernychuk, L.W. 1992. Data submission: 1992 dioxin trend monitoring (sediment/crab/oyster), MacMillan Bloedel Ltd., Powell River Division. Prepared for: MacMillan Bloedel Ltd, Powell River Division by Hatfield Consultants Ltd. West Vancouver, B.C. December 1992. Dwernychuk, L.W. 1993. Dioxin/furan trend monitoring program, Powell River, 1992. Trend graphics/data submission (sediment/crab/oyster). Prepared for: MacMillan Bloedel, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. February 1993. Dwernychuk, L.W., D.A. Levy, T.G. Boivin and G.S. Bruce. 1993. Final Report: Dioxinlfuran trend monitoring program, Powell River, 1992 (sediment/crab/oyster). Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. March 1993. Dwemychuk, L.W., T.G. Boivin and lA. Sartori. 1993. Status Report: Dioxinlfuran trend monitoring program, Powell River, 1993 (sediment/crab/oyster). Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1993. Dwernychuk, L.W., T.G. Boivin and G.S. Bruce. 1993. Final Report: Dioxinlfuran trend monitoring program, Powell River, 1993 (sediment/crab/oyster). Prepared for: MacMillan Bloedel Ltd., Powell River Division, Powell River, B.c. by Hatfield Consultants Ltd., West' Vancouver, B.C. September 1993. Prince Rupert Dwemychuk, L.W. 1989. Bottom sediments and biological tissues: a baseline organochlorine contamination survey in the marine environment near Skeena Cellulose Inc., JanuarylFebruary 1989. Prepared for: Skeena Cellulose Inc. by Hatfield Consultants Ltd., West Vancouver. B.C. May 1989. Dwernychuk, L.W. 1990. Status Report: Receiving environment studies near Skeena Cellulose, 1990. Prepared for: Skeena Cellulose Inc., Prince Rupert,B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. August 1990. Dwemychuk, L.W.' 1991. Dioxinlfuran trend monitoring program, Status Report, March 1991, Skeena Cellulose. Prepared for: Skeena Cellulose Inc., Prince Rupert, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. May 1991. 135 Dwernychuk, L.W. 1991. Organochlorine trend monitoring, Skeena Cellulose, 1991, graphics/ data submission (sediment/crab). Prepared for: Skeena Cellulose Inc., Prince Rupert, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. November 1991. Dwernychuk, L.W., O.S. Bruce, B. Gordon' and G.P. Thomas. 1991. Comprehensive organochlorine survey of the receiving environment of the vicinity of Skeena Cellulose 1990/91, (effluent/water/sediment/ biological organisms), (tables, figures/ data submission). Prepared for: Skeena Cellulose Inc., Prince Rupert, B.c. by Hatfield Consultants Ltd., West Vancouver, B.c. December 1991. Dwernychuk, L.W., O.S. Bruce, B. Gordon and G.P. Thomas. 1992. Comprehensive organochlorine survey of the receiving environments in the vicinity of Skeena Cellulose 1990/91 (effluent/water/sediment/ biological organisms); Volume 1: report/tables/figures; .Volume 2: appendices. Prepared for: Skeena Cellulose Inc., Prince Rupert, B.C. by Hatfield Consultants Ltd., West Vancouver, B.c. July 1992. Dwernychuk, L.W. 1992. Status Report: Comprehensive organochlorine trend monitoring program, Skeena Cellulose Inc., Prince Rupert (sediment/crab/shrimp). Prepared for: Skeena Cellulose Inc., Skeena Pulp Operations, Prince Rupert, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. August 1992. Dwernychuk, L.W., O.S. Bruce, B, Gordon and O.P. Thomas. 1992. Organochlorine trend monitoring (sediments/shrimp/prawn/crab), Skeena Cellulose, 1991. Prepared for: Skeena Cellulose Inc., Prince Rupert, BiC, by Hatfield Consultants Ltd., West Vancouver, B.C. September 1992. Dwernychuk, L.W. 1992. Data Submission: 1992 Dioxin trend monitoring (sediment, crab), Skeena Cellulose Inc., Prince Rupert, B.C. Prepared for: Skeena Cellulose Inc., Skeena Pulp Operations, Prince Rupert, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. December 1992. Dwernychuk, L.W. and O.S. Bruce. 1992. Dioxin and Furan Levels in marine biota near eight coastal mills relative to Totino, Queen Charlotte, Port Hardy, Victoria and Vancouver Harbours. Prepared for: Western Pulp Ltd. Partnership, Squamish, B.C., Howe Sound Pulp . and Paper, Port Mellon, B.C., MacMillan Bloedel Ltd., Alberni Pulp. and PaperDivision, Port Alberni, B.C., MacMillan Bloedel Ltd., Harmac Division, Nanaimo, B.C., MacMillan Bloedel Ltd., Powell River Division, Powell River, B.C., Skeena Cellulose., Prince Rupert, B.C., Fletcher Challenge Canada, Elk Falls Pulp and Paper, Campbell River, B.C., Fletcher Challenge Canada, Crofton, Pulp and Paper, Crofton, B.C. by Hatfield Consultants Ltd., West Vancouver, s.c November 1992. Dwernychuk, L.W. 1993. Dioxin/furan levels (sediments/crab), Prince Rupert Harbour region, 1992. Prepared for: Skeena Cellulose Inc., Skeena Pulp Operations, Prince Rupert, B.c. by Hatfield ConsultantsLtd., West Vancouver, B.C. February 1993. 136 Dwemychuk, L.W. and T.G. Boivin. 1993. Dioxin and furan levels in the Prince Rupert Harbour region, 1992 (sediment/crab). Prepared for: Skeena Cellulose Inc., Prince Rupert, B.C. by Hatfield Consultants Ltd., West Vancouver, B.C. 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