Determination of Halogenated Natural Products in Passive Samplers Deployed along the Great Barrier Reef, Queensland/Australia

Halogenated natural products (HNPs) have been increasingly reported to occur in marine wildlife from all oceans. Several HNPs, Such as 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) and 4,6-dibromo-2-(2',4'-dibromo)phenoxyanisole (2'-MeO-BDE 68 or BC-2), were detected at particularly high concentrations in dolphins from Queensland/Australia. About half of the coastline of Queensland (similar to 2500 km) is covered by the Great Barrier Reef, a rich ecosystem hosting a huge variety of species, many of which are known to produce natural compounds. In this study, semipermeable membrane devices (SPMDs) were deployed as passive samplers for about 30 days at 12 marine and 2 nonmarine sites (i.e., rivers) along the Great Barrier Reef as part of a routine monitoring program during November 2007 and May 2008. Q1 and 2'-MeO-BDE 68 were detected at the marine sites with frequencies of about 65% but not in any sample from the two rivers. Further HNPs (2,4,6-tribromophenol, TB P; 2,4,6-tribromoanisole, TBA; 2,2'-dimethoxy-3,3'5,5'-tetrabromobiphenyl, 2,2'-diMeO-BB 80 or BC-1; 3,5-dibromo-2-(2',4'-dibromo)phenoxyanisole, 6-MeO-BDE 47 or BC-3; and 3,5-dibromo-2-(3',5'-dibromo,2'-methoxy)phenoxyanisole, 2',6-diMeO-BDE 68 or BC-11) were detected as well with frequencies of 18-97% in the marine samples, but no polybrominated flame retardants were detected. The highest amount of a single HNP, 2.3 mu g/SPMD, was determined for TBP, which had a frequency of detection of only 46%. The maximum (average) amount in the SPMDs from marine sites was 44 ng (12 ng) for Q1 and 115 ng (20 ng) for 2'-MeO-BDE 68. A first order kinetic model was used to estimate concentrations of the HNPs in the water phase. Based on the depuration of performance reference Compounds obtained at one of the sites, we assumed a sampling rate of 16 L/day. We used this sampling rate to estimate that the highest and average available concentrations of Q1 in the water during the deployment of the SPMD were 97 and 25 pg/L, respectively. The estimated maximum water concentrations of 2'-MeO-BDE 68, 2,2'-diMeO-BB 80, 6-MeO-BDE 47, and 2',6-diMeO-BDE 68 were on average 2-5.5 fold higher than that of Q1. The results confirm that the HNPs are produced throughout the Great Barrier Reef, which appears to be a significant source of these compounds.