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Chlorinated Organic Contaminants in Blubber Biopsies from Northwestern Atlantic Balaenopterid Whales Summering in the Gulf of St Lawrence

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Chlorinated Organic Contaminants in Blubber Biopsies from Northwestern Atlantic Balaenopterid Whales Summering in the Gulf of St Lawrence Marine Environmental Research, Vol. 44, No. 2, pp. 201-223, 1997 0 1997 Elsevier Science Ltd All rights reserved. Printed in Great Britain PII: SOl41-1136(97)00004-4 0141-1136/97 $17.00+0.00 Chlorinated Organic Contaminants in Blubber Biopsies from Northwestern Atlantic Balaenopterid Whales Summering in the Gulf of St Lawrence J. M. Gauthier,a* C. D. Metcalfe” & R. Sear@ “Environmental and Resources Studies, Trent University, Peterborough, Ontario, Canada K9J 7B8 bMingan Island Cetacean Study (MICS), 285 Green, St. Lambert, Quebec, Canada J4P IT3 (Received 16 May 1996; revised version received 16 December 1996; accepted 29 December 1996. Published June 1997) ABSTRACT Concentrations and patterns of chlorinated biphenyls (CBS) and other persistent organochlorine compounds (OCs) were determined from small blubber biopsy samples collected from northwestern Atlantic minke (Balaenoptera acuros- trata) , fin (Balaenoptera physalus), blue (Balaenoptera musculus) , and humpback (Megaptera novaeangliae) whales summering in the Gurf of St. Lawrence, Quebec. Concentrations of CPCB (sum of 19 congeners) in biopsy samples ranged from 0.2-10 pg g-’ lipid, and congeners 52, 101, 118, 153, 138 and 180 accounted for 79% of CPCB. Mean concentration of the sum of non- ortho CB congeners in selected biopsy samples was 2 ng g-t lipid, and relative concentrations of these analytes were: 77 > 126 > 81> 169. Concentrations of XDDT ranged from 0.613 pg g-t lipid, and the average proportion of DDE to CDDT was 72%. All other organochlorine analytes were present at concentra- tions below 2 pg g-t lipid. On average, cis-nonachlor, trans-nonachlor and oxy- chlordane accounted for 27, 26 and 23%, respectively, of the chlordane-related analytes, and cl-hexachlorocyclohexane (HCH) comprised 67% of XHCH. Concentrations of CDDT were signtficantly lower and mirex concentrations were significantly higher in minke whales than in the other balaenopterid species. Concentrations of all other analytes were similar in the four whale species. Ratios of proportions of oxychlordane to trans-nonachlor were highest in fin whales. Blue whales had the lowest proportions of u-HCH but the highest proportions of DDT. Interspecies diflerences in the concentrations and patterns of certain CB *To whom correspondence should be addressed at Departement de Sciences Biologiques, Universite du Quebec a Montreal, C. P. 8888, Succ. Centre-Ville, Montreal, Quebec, H3C 3P8, Canada. E-mail: C2656Ber.ugam.ca 201 202 J. M. Gauthier et al. congeners and OC compounds may reject d@erences in diet or in metabolic capabilities. Males usually had higher mean concentrations of CBS and OCs than females, but these differences were sign$cant only for CDDT, dieldrin, CHCH and HCB. Higher proportions of lower chlorinated CB congeners were found in calves compared to adult females, indicating selective reproductive transfer. 0 1997 Elsevier Science Ltd INTRODUCTION Polychlorinated biphenyls (PCB) and other organochlorine (OC) compounds are persistent, lipophilic compounds that accumulate in the fatty tissues of biota. Whales have a lipid- rich blubber mantle that comprises most of the lipid storage tissue of the animal (Lockyer et al., 1985). The blubber layers of these animals accumulate lipophilic contaminants in utero and during post-utero development, and throughout their life-span. Most monitor- ing studies of PCB and OC contaminants in whales have been done with odontocetes. However, ppb and ppm concentrations of these persistent contaminants have been detec- ted in baleen whale blubber (Colborn & Smolen, 1996; Marsili & Focardi, 1996). Contaminant data for northwestern Atlantic balaenopterid whales in the St. Lawrence region are limited (BCland et al., 1992; Gauthier et al., 1997). Balaenopterid whales that visit the St. Lawrence region principally feed in these productive waters and in the North Atlantic (Mitchell, 1975; Borobia et al., 1995). Mysticete whales probably fast, at least partially, during their yearly migration and their winter stay in south Atlantic waters (Lockyer & Brown, 1981; Gaskin, 1982). The blubber layer deposited during feeding ensures a constant energy supply during this fasting period (Lockyer et al., 1985). Thus, balaenopterid whales mobilize lipophilic contaminants accumulated from these northern regions, including the St. Lawrence, during their migration and reproductive period. Concentrations of individual CB congeners and other persistent OCs contaminants were determined in blubber biopsy samples taken from minke (Balaenoptera acurostrata), fin (Balaenoptera physalus), blue (Balaenoptera musculus), and humpback (Megaptera novaeangliae) whales summering in the Gulf of St. Lawrence, Qutbec. Biopsies provide fresh blubber samples from presumably healthy whales, and contaminant data from biopsies were previously shown to be representative of contamination throughout the entire blubber mantle of balaenopterid whales (Gauthier et al., 1997). Interspecific differ- ences in contaminant concentrations and patterns are discussed in relation to feeding ecology and metabolic capabilities of balaenopterid species. Gender differences in con- tamination and contaminant data for adult females and calves of humpback whales are discussed in terms of reproductive transfer to the offspring. MATERIALS AND METHODS Study area and biopsy sampling Biopsies were collected in the summer and fall of 1991 and 1992 from 50 free-ranging northwestern Atlantic balaenopterid whales in the northwestern portion of the Gulf of St. Lawrence, QuCbec, Canada (Fig. 1) by personnel at the Mingan Island Cetacean Study Chlorinated organic contaminants in blubber biopsies 203 (MICS). In 199 1, a total of 46 biopsy samples were taken from 21 minke whales (Godbout region: 1; Mingan region: 20), 15 fin whales (Godbout: 1; Mingan: 14), two blue whales (Sept-Iles: 1; Mingan: l), and eight humpback whales (Mingan: 8). In 1992, four samples were collected from blue whales in the Mingan area. Whales were approached with five-meter hard-bottom inflatable boats equipped with 70 or 90 hp Yamaha outboard motors using an approach method described previously (Sears et al., 1990). All whales, except for minke whales, were photographed (Sears et al., 1990) and identification features were recorded to identify individuals so that whales were not biopsied twice in this study. Biopsy samples were taken from a distance of 620 m using a small stainless steel biopsy tip fired from a 76cm long, 1.8 kg Barnett Wildcat bow. The cross-bow and biopsy tip used in this study were similar to equipment described by Pals- boll et af. (1991). The arrow was kept afloat after it became dislodged from the whale blubber with a buoyant, aerodynamic, cone-shaped stop collar designed to limit the penetration of the biopsy tip in the whale. The tip was cleaned with ethanol between each shot to minimize wound infection and cross-contamination of the samples. Following biopsy, skin was cut from the blubber, placed in a dimethyl sulphoxide (DMSO)/saline solution and stored at 4°C. Skin samples were flown to Denmark for sex determination by Per Palsboll and Martine B&rub&at the University of Copenhagen using the polymerase chain reaction (PCR) with SRY gene primers (Palsbsll et al., 1992). Blubber samples were wrapped in solvent-washed aluminium foil and frozen at -15°C until forwarded to Trent University, Peterborough, Ontario for analysis. Biopsy samples yielded an average of 0.25 g (0.035-0.582 g) of blubber. A f/antic Ocean Fig. 1. Map of study area - biopsies were taken from balaenopterid whales in three regions of the northwestern Gulf of St. Lawrence, QuCbec: Mingan region (shaded), Godbout region (x), and Sept-Iles region (x). 204 J. M. Gauthier et al. Contaminant analysis Procedures for preparation of blubber samples for analysis were similar to those described by Gauthier et al. (1997). Briefly, samples were extracted with hexane in a Soxhlet appa- ratus and lipids were removed from the extracts by GPC on Biobeads SX-3. Lipid content of the sample was estimated by gravimetric analysis of the lipid fraction from the GPC column. After GPC, extracts were subfractionated by silica-gel column chromatography. Silica-gel Fraction A contained CBS, aldrin, hexachlorobenzene (HCB), heptachlor, mirex, and the majority of p,p’-DDE, while Fraction B contained the remainder of the DDE, heptachlor epoxide, isomers of hexachlorocyclohexane (HCH), chlordane com- pounds, dieldrin, p,p’-DDT, p,p’-DDD and methoxychlor. Non-ortho CB congeners were isolated from the silica gel Fraction A prepared from six selected minke whale samples using a carbon column (AX-21) subfractionation technique described previously (Gau- thier et &1997). The or&-substituted CBS and the other OC compounds were analyzed by HRGC- ECD using a Varian model 3500 GC with a 30 m DB-5 column (0.25 mm ID, 0.25 pm film thickness) using GC conditions described previously (Janz et al., 1992). CB congeners 3 1, 52, 49, 44, 66, 101, 87, 110, 151, 118, 153, 105, 138, 180, 170, 201, 195, 194 and 209 were quantified against a CLB-1 standard purchased from the National Research Council, Halifax, Canada. Quantification of other OC compounds was done by comparison with standards obtained from the Canadian Wildlife Service, Hull, Quebec. Chromatograms of silica-gel Fractions A and B from a male fin whale blubber biopsy sample (BP9131), as analyzed by HRGC-ECD with a 30m DB-5 column, are shown in Fig. 2. Non-ortho CB congeners 8 1, 77, 126 and 169 were analyzed by GC-ECD on a 60 m DB-5 as descri- bed for ortho CBS, with an analytical standard prepared from CB congeners purchased from Ultra Scientific, Rhode Island. Non-o&o CB congeners were not confirmed by CC-MS. DDE A B Fig. 2. Chromatograms of silica-gel Fractions A and B from a male fin whale blubber biopsy sample (BP9131), as analyzed by HRGC-ECD with a 30m DB-5 column. Major CB congeners (IUPAC number) and OC compounds are indicated on Fraction A and Fractions A and B, respectively. Chlorinated organic contaminants in blubber biopsies 205 Procedural blank samples were run during the course of this study.
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