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Analytical methods for unique and rare samples, such as marine mammal tissue, strive to reduce opportunities for analyte loss and contamination. Historically, analytical methodologies for marine mammal tissues required an extraction followed by multiple cleanup and concentration steps. These steps increase the opportunity for analyte loss and sample contamination. Selective pressurized liquid extractions (SPLE; an analytical technique that combines PLE with in-cell adsorbent cleanup) have the potential to reduce and/or eliminate the number of steps. A SPLE method was developed for the simultaneous extraction of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) from bowhead whale blubber. This SPLE utilized acidic silica with a fat-to-fat retainer ratio of 0.02 as well as eliminated post-extraction cleanup steps, such as size-exclusion chromatography step. In addition, neutral silica was placed beneath the acidic silica as an acid buffer, thereby preventing acid from contaminating the extraction system. Analysis was performed using gas chromatography/mass spectrometry in electron capture negative ionization mode. PBDE, PCB and OCP triplicate recoveries averaged 84±1%, 83±3%, and 76±11%, respectively. Overall, measurements of NIST Whale Blubber SRM 1945 were within±30% of certified values. PBDEs were measured for the first time in bowhead whale blubber; average concentrations ranged from 0.2 to 1.4 ng g(-1) wet weight (ww). Average OCPs and PCBs concentrations ranged from 0.4 to 37 ng g(-1)ww and 0.1 to 3.0 ng g(-1)ww, respectively, which were within one order of magnitude lower than those previously reported in bowhead whale blubber.

Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0–12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels.

Muscle samples were collected from pup, juvenile and adult Weddell seals (Leptonychotes weddellii) near McMurdo Sound, Antarctica during the austral summer of 2006. Blubber samples were collected from juvenile and adult seals. Samples were analyzed for emerging and legacy persistent organic pollutants (POPs) including current and historic-use organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Of the 41 target analytes, 28 contaminants were recovered from the Weddell seal blubber, in this order of prevalence: p,p'-DDE, p,p'-DDT, trans-nonachlor, mirex, cis-nonachlor, PCB 153, PCB 138, dieldrin, heptachlor epoxide, nonachlor III, PCB 187, oxychlordane, cis-chlordane, PCB 118, PBDE 47, PCB 156, PCB 149, PCB 180, PCB 101, PCB 170, PCB 105, o,p'-DDT, PCB 99, trans-chlordane, PCB 157, PCB 167, PCB 189, and PCB 114. Fewer POPs were found in the muscle samples, but were similar in the order of prevalence to that of the blubber: p,p'-DDE, o,p'-DDT, trans-nonachlor, nonachlor III, oxychlordane, p,p'-DDT, dieldrin, mirex, cis-nonachlor, PCB 138, and PCB 105. Besides differences in toxicant concentrations reported between the muscle and blubber, we found differences in POP levels according to age class and suggest that differences in blubber storage and/or mobilization of lipids result in age class differences in POPs. To our knowledge, such ontogenetic associations are novel. Importantly, data from this study suggest that p,p'-DDT is becoming less prevalent temporally, resulting in an increased proportion of its metabolite p,p'-DDE in the tissues of this top predator. In addition, this study is among the first to identify a PBDE congener in Weddell seals near the McMurdo Station. This may provide evidence of increased PBDE transport and encroachment in Antarctic wildlife.