Lewis T. Gauthier

Isomers of Dechlorane Plus flame retardant in the eggs of herring gulls (Larus argentatus) from the Laurentian Great Lakes of North America: temporal changes and spatial distribution.

Dechlorane Plus (DP) is a chlorinated flame retardant (FR) comprised of two major structural isomers, syn and anti. For the Laurentian Great Lakes of North America, reports on DP have been limited to sediment and fish, not known for birds, and regardless temporal trends in Great Lakes wildlife is unknown. In the present study, syn- and anti-DP isomers were detected in egg pools spanning 1982-2006 of a Great Lakes biomonitoring species, the herring gull (Larus argentatus), from seven colonies in the five Laurentian Great Lakes. The sum (Sigma) of syn- and anti-DP concentrations were generally <15 ng g(-1) wet weight (ww) and variable depending on the colonial site and year, although Sigma-DP concentrations were generally higher post mid-1990s for all sites. Syn- and anti-DP concentrations ranged from 3.1 x 10(2) to 1.4 x 10(3)pg g(-1)ww and 1.3 x 10(2) to 4.4 x 10(3)pg g(-1)ww, respectively. There was a weak but significant (r(S)=-0.31, p<0.001) negative relationship between the Sigma-DP concentration and the distance for the only DP production facility in North America at Niagara Falls, New York. However, the fraction of the anti-DP to the Sigma-DP concentration (f(anti)) was 0.69+/-0.08 (for all seven colonies and years, n=101 pools), and there was no significant (r(S)=-0.18, p=0.07) negative relationship of f(anti) with increasing distance from the production facility at Niagara Falls, New York, which indicated that there was no temporal or spatial enrichment of either isomer relative to the commercial DP mixture. Over the past 25 years, it is clear that DP isomers have accumulated in the food web of female herring gulls with subsequent transfer during ovogenesis.

Biochemical tracers reveal intra-specific differences in the food webs utilized by individual seabirds

Food web structure regulates the pathways and flow rates of energy, nutrients, and contaminants to top predators. Ecologically and physiologically meaningful biochemical tracers provide a means to characterize and quantify these transfers within food webs. In this study, changes in the ratios of stable N isotopes (e.g., δ15N), fatty acids (FA), and persistent contaminants were used to trace food web pathways utilized by herring gulls (Larus argentatus) breeding along the shores of the St Lawrence River, Canada. Egg δ15N values varied significantly among years and were used as an indicator of gull trophic position. Temporal trends in egg δ15N values were related to egg FA profiles. In years when egg δ15N values were greater, egg FA patterns reflected the consumption of more aquatic prey. Egg δ15N values were also correlated with annual estimates of prey fish abundance. These results indicated that temporal changes in aquatic prey availability were reflected in the gull diet (as inferred from ecological tracer profiles in gull eggs). Analysis of individual eggs within years confirmed that birds consuming more aquatic prey occupied higher trophic positions. Furthermore, increases in trophic position were associated with increased concentrations of most persistent organic contaminants in eggs. However, levels of highly brominated polybrominated diphenyl ether congeners, e.g, 2,2′,3,3′,4,4′,5,5′,6,6′-decabromoDE (BDE-209), showed a negative relationship with trophic position. These contrasting findings reflected differences among contaminant groups/homologs in terms of their predominant routes of transfer, i.e., aquatic versus terrestrial food webs. High trophic level omnivores, e.g., herring gulls, are common in food webs. By characterizing ecological tracer profiles in such species we can better understand spatial, temporal, and individual differences in pathways of contaminant, energy, and nutrient flow.

Retrospective analysis of organophosphate flame retardants in herring gull eggs and relation to the aquatic food web in the Laurentian Great Lakes of North America.

With the phase-out and regulation of some flame retardant chemicals, the production and usage of organophosphate triester flame retardants (OPFRs) has increased in recent years. In the present study, 14 OPFRs (either chlorinated, brominated or non-halogenated) were analyzed in egg pools of 10-13 individual herring gull eggs from five colonial nesting sites for 11 years spanning 1990-2010, (for a total of n=55 egg pools) in the Laurentian Great Lakes of North America (Chantry Island, Fighting Island, Agawa Rocks, Toronto Harbour and Gull Island). OPFR profiles varied slightly between colony sites and collection years. For all five sites tris(2-chloroisopropyl) phosphate (TCIPP), tris(2-chloroethyl) phosphate (TCEP) and tris(2-butoxyethyl) phosphate (TBOEP) were detected, while triphenyl phosphate (TPHP) was only quantifiable in eggs from Chantry Island and Gull Island collected in 2008 and 2010. For the 2010 egg pools, the ΣOPFR concentrations were generally low and ranged from 2.02 to 6.69 ng/g wet weight (ww). ΣOPFR concentrations in 2010 were significantly higher (p<0.05) than they were between 1990 and 2004 (4.06 vs. 1.55 ng/g ww, respectively). In a pilot examination of Great Lakes aquatic food webs, 2010-collected alewife and rainbow smelt (major herring gull fish prey) and lake trout from western Lake Erie and Ontario, only contained TBOEP at low to sub ng/g ww concentrations. These results demonstrate that low to sub-ppb concentrations of at least three OPFRs, TCIPP, TCEP and TBOEP, have been persistent in herring gull eggs from the Great Lakes for at least the past 20 years, probably bioaccumulate mainly via the fish diet, and are transferred to the eggs of exposed herring gulls.

Liquid chromatography-electrospray-tandem mass spectrometry method for determination of organophosphate diesters in biotic samples including Great Lakes herring gull plasma.

Environmentally relevant organophosphate (OP) triester flame retardants are known to degrade to OP diester phosphoric acids. In this study, a quantitatively sensitive method was developed for OP diesters in biological samples of varying complexity, bovine serum, chicken egg homogenate and pork liver. Fortified with 1ng or 10ng each of the six OP diester and six OP triester standards, samples were extracted by accelerated solvent extraction that completely separated OP diesters and triesters. OP diester fractions were cleaned up using weak anion exchange solid phase extraction and eluted with high ionic strength ammonium acetate buffer. Optimal analysis of chlorinated OP diesters was via decamethonium hydroxide dicationic reagent derivatization and by LC-ESI(+)-MS/MS, and for all non-chlorinated OP diesters by non-derivatized LC-ESI(-)-MS/MS. Except for derivatization LC-ESI(+)-MS/MS analysis of liver, at the 10ng spiking level for the three matrices, recovery efficiencies, matrix effects and method limits of quantification (MLOQs) of OP diesters ranged from 55-116%, 92-119%, and 0.02-0.31ng/g wet weight (ww) respectively. Plasma samples of n=6 herring gulls (2010, Chantry Is., Laurentian Great Lakes) contained triphenyl phosphate and tris(1-3-dichloro-2-propyl) phosphate ranging from 1.3 to 4.0ng/g ww and <MLOQ to 0.41ng/g ww respectively. The OP diesters bis(1,3-dichloro-2-propyl) phosphate, bis-(2-butoxyethyl) phosphate and di(2-ethylhexyl) phosphate ranged from 0.7 to 3.5ng/g ww, 0.08 to 29.4ng/g ww and <MLOQ to 0.18ng/g ww respectively, and thus OP triester to diester metabolism occurs in exposed wild herring gulls.

The flame retardant β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane: fate, fertility, and reproductive success in American kestrels (Falco sparverius).

Captive American kestrels (Falco sparverius) were exposed via diet during reproduction to an environmentally relevant concentration of β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (β-TBECH). The β-TBECH isomer was injected into the food source at a daily dosing concentration of 0.239 ng/g kestrel/day (22 pairs); control birds were exposed via diet to the safflower oil vehicle only (24 pairs). Eight pairs in each group were exposed for four weeks and sacrificed for tissue analysis; the remaining pairs completed their breeding cycle, with exposure ceasing at the end of incubation (82 days). α- and β-TBECH appeared to be rapidly metabolized and/or eliminated from fat, liver, and plasma; both isomers and potential hydroxylated metabolites of β-TBECH (plasma) were undetected. Notwithstanding, compared to controls, pairs exposed to β-TBECH laid fewer eggs (p = 0.019) and laid lighter eggs (successful eggs: p = 0.009). Exposed pairs also demonstrated poorer egg fertility (p = 0.035) although testis mass and histology were similar among males. Reductions in egg production and fertility resulted in decreased hatchling success (p = 0.023). The β-TBECH-exposed pairs also produced fewer males overall (p = 0.009), which occurred concurrently with increased estradiols maternally deposited in eggs (p = 0.039). These findings demonstrate that β-TBECH may be detrimental for breeding in wild birds receiving similar exposure levels.

Tetradecabromodiphenoxybenzene Flame Retardant Undergoes Photolytic Debromination

Highly brominated flame retardant compounds have relatively low bioavailability, but some of these compounds have been shown to be of environmental concern. Tetradecabromodiphenoxybenzene (TDBDPB) contains 14 bromine atoms and is the major component of commercial flame retardant mixtures such as the recently phased out SAYTEX 120. The chemical stability of TDBDPB has not been reported. We demonstrated that TDBDPB can photolytically undergo stepwise reductive debromination that follows first-order kinetic degradation models when exposed to UV or natural sunlight radiation and when dissolved in the solvents tetrahydrofuran, methanol, or n-hexane. Photolytic degradation half-lives of TDBDPB ranged from 98 to 169 min, 0.78 to 0.83 min, 1.0 to 1.8 min, and 4.9 to 7.4 min when exposed to UV-A, -B, and -C, and natural sunlight, respectively. However, the TDBDPB half-lives when exposed to UV-B and especially UV-C are likely underestimated since solutions were in borosilicate glass vials during irradiation resulting from increasingly lower % transmittance of λ < 300 nm. Neat technical TDBDPB powder exposed to UV-B and -C radiation also produced less brominated products, although the rate was much slower as compared to when in solution. Exposure of TDBDPB solutions to natural sunlight generated a number of polybrominated diphenoxybenzene (PBDPB) photolysis products, among which the Br(4)- to Br(7)-PBDPBs were the most frequently observed and estimated to be most concentrated. As evidenced by the TDBDPB half-lives and the degree of debrominated byproduct formation, the findings showed that the fraction of the absorbed irradiation that was of sufficient energy to break C-Br bonds of TDBDPB and lesser brominated PBDPBs increased from UV-B or -C to UV-A. Coincidentally, we recently reported on the presence of several Br(4) to Br(6) methoxylated PBDPBs in the Great Lakes herring gull eggs, which may be linked to a TDBDPB source via photolytic degradation to more bioavailable and persistent debromination products.

Alpha and Beta Isomers of Tetrabromoethylcyclohexane (TBECH) Flame Retardant: Depletion and Metabolite Formation In Vitro Using a Model Rat Microsomal Assay

The metabolism of α- and β-isomers of the flame retardant chemical tetrabromoethylcyclohexane (TBECH) was investigated using a model in vitro enzyme-mediated biotransformation assay based on rat liver microsomes. In enzymatically active assays, concentrations of both α- and β-TBECH isomers were equally depleted by about 40% and in a time-dependent fashion over a 60-min assay incubation period, and determined by GC-MS(ECNI) analysis. No such depletion was observed in nonenzymatically active control assays. After the full 60-min assay incubation period, debrominated TBECH metabolites were not detected by GC-MS(ECNI), and suggested that enzyme-mediated debromination of TBECH did not occur via cyctochrome P450 enzyme-mediated catalysis or that the rate of TBECH metabolism in vitro was too slow. In the enzymatically active assays, but not in the nonezymatically active control assays, α- and β-monohydroxy-TBECH (OH-TBECH), dihydroxy-TBECH ((OH)(2)-TBECH), and some additional compounds with molecular formulas of C(8)H(13)Br(3)O(2) and C(8)H(11)Br(3)O(2) were identified by LC-Q-ToF-MS. Two unique sets of OH-TBECH and (OH)(2)-TBECH metabolites were derived from both α- and β-TBECH isomers. The LC-ESI(-)-MS/MS peak areas of all four OH-TBECH and (OH)(2)-TBECH metabolites increased at a comparable rate in a time-dependent manner over a 60-min assay incubation period. This study demonstrated that metabolism via hydroxylation can occur in vitro for α- and β-TBECH. These results underscore the importance of understanding the biological fate of TBECH and the possible implications on the health and TBECH levels in exposed wildlife and in the environment.

Quantitation of hydroxylated byproduct formation in a Saccharomyces cerevisiaeΔ9 desaturating system

The distribution of products obtained from stearoyl CoA Delta9 desaturase-mediated oxidation in Saccharomyces cerevisiae has been measured directly for the first time using an omega-fluorinated fatty acid substrate.