Chlorinated Dioxin Trends Between 1987 and 1993 for Samples of Crab Hepatopancreas from Pulp and Paper Mill and Harbour Sites in British Columbia
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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. 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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. 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.