title: Radiocarbon evidence for a naturally produced, bioaccumulating halogenated organic compound.
abstract: Halogenated organic compounds (HOCs) such as 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole (DBP-Br4Cl2) and heptachloro-1'-methyl-1,2'-bipyrrole (Q1) have been detected worldwide, sometimes at high levels in Antarctic air, seabird eggs, the blubber of marine mammals, and, most notably, even human milk. To date, it has been difficult to determine whether these compounds are natural products or derived from industrial synthesis. Molecular-level 14C analysis of these compounds is particularly appealing because most industrial compounds are manufactured from petrochemicals (14C-free) and natural compounds should have "modern" or "contemporary" 14C levels. To investigate the source of DBP-Br4Cl2, we isolated 600 microg of this compound (150 microg of carbon) from marine animal extracts by employing gel permeation chromatography, Florisil column chromatography, and two-dimensional preparative capillary gas chromatography. The purified DBP-Br4Cl2 was split into two samples (75 microg of carbon each) and analyzed by accelerator mass spectrometry for 14C content. The delta14C values were -449 percent per thousand and -467 percent per thousand, corresponding to conventional 14C ages of 4740 and 5000 years before present (BP), respectively. The presence of detectable 14C in the DBP-Br4Cl2 strongly points to at least a natural or biogenic source. However, these delta14C values for DBP-Br4Cl2 are more depleted than expected for a recently synthesized natural product. Several explanations are discussed, but additional samples
authors.affiliation: Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543, USA. creddy@whoi.edu
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Reddy
authors.forename: Li
authors.initials: L
authors.lastname: Xu
authors.forename: Gregory W
authors.initials: GW
authors.lastname: O'Neil
authors.forename: Robert K
authors.initials: RK
authors.lastname: Nelson
authors.forename: Timothy I
authors.initials: TI
authors.lastname: Eglinton
authors.forename: D John
authors.initials: DJ
authors.lastname: Faulkner
authors.forename: Ross
authors.initials: R
authors.lastname: Norstrom
authors.forename: Peter S
authors.initials: PS
authors.lastname: Ross
authors.forename: Sheryl A
authors.initials: SA
authors.lastname: Tittlemier
mesh_terms: D000818:Animals; D001682:Biological Availability; D002250:Carbon Radioisotopes / Q000032:analysis; D004784:Environmental Monitoring; D004785:Environmental Pollutants / Q000493:pharmacokinetics*; D020387:Food Chain; D006219:Halogens / Q000493:pharmacokinetics*; D009930:Organic Chemicals / Q000493:pharmacokinetics; D011758:Pyrroles / Q000493:pharmacokinetics*; D014018:Tissue Distribution
chemical_list: D002250:Carbon Radioisotopes; D004785:Environmental Pollutants; D006219:Halogens; D009930:Organic Chemicals; D011758:Pyrroles