Are ingested plastics a vector of PCB contamination in northern fulmars from coastal Newfoundland and Labrador?

While marine animals are exposed to environmental contaminants via their prey, because plastic pollution in the aquatic environment can concentrate some chemicals, ingested plastics are thought to increase the exposure of biota to contaminants. Currently, in the literature there are contradictory results relating to how higher levels of ingested plastics by birds may lead to higher levels of polychlorinated biphenyl (PCBs). To date none of these have incorporated known Toxic Equivalency Factors (TEFs) for non-ortho and mono-ortho congeners of PCB which is critical to assessing the potential effects from PCBs. We examined northern fulmars (Fulmarus glacialis) from the Labrador Sea region Canada, and the ingested plastics from these same birds for comparative PCB concentrations. We found no significant correlations between the PCB concentrations in the birds and the mass or number of retained ingested plastic pieces in the stomach, this held true when PCBs were considered by a number of different ways, including ∑4PCB, ∑PCB, lower-chlorinated, high-chlorinated, non-ortho PCB, and mono-ortho congeners. PCB concentrations were lower in plastics as compared with livers. We found significant differences in congener profiles between the ingested plastics and seabird livers suggesting that while plastics do not contribute to the PCB concentrations, there may be some interactions between plastics and the chemicals that the birds are exposed to via ingested plastics.

Stereoselective biosynthesis of chloroarylpropane diols by the basidiomycete Bjerkandera adusta.

Previously we have shown that 1-arylpropane-1,2-diols are catabolic products of L-phenylalanine during idiophasic metabolism of B. adusta that are stereoselectively biosynthesized from a C(7)-unit (ring+benzylic carbon) and a C(2)-unit as predominantly erythro 1R, 2S enantiomers.In order to probe the mechanism of 1-arylpropane-1,2-diol formation, the products of the incubation of isotopically labelled aromatic aldehydes as substrates with Bjerkandera adusta (DAOM 215869) have been characterized. The aromatic aldehydes were benzaldehyde (ring D(5)) and 4-methoxy- and 4-hydroxybenzaldehydes (ring 13C(6)). These aldehydes were all stereoselectively incorporated into the corresponding 1-arylpropane-1,2-diols, including the chloro analogues, as well as into the corresponding alpha-ketols (phenyl acetyl carbinols (PAC's) and 2-hydroxy propiophenones (2-HPP's)) the presumed precursors of the diols. Benzoic acid (ring D(5)) was likewise incorporated into the diols, chlorodiols and alpha-ketols. These results lead us to conclude that the aromatic aldehydes benzaldehyde, 4-hydroxybenzaldehyde and 4-methoxybenzaldehyde are likely C(7)-unit precursors in the carboligation reaction(s) that leads to 1-arylpropane-1,2-diol biosynthesis. The metabolic role of the diols remains to be elucidated but they may be important intermediates in CAM (chlorinated anisyl metabolite) aldehyde-alcohol cycling and also act as substrates for the chlorination/hydroxylation enzymes yet to be identified in white rot fungi.

Chlorometabolite production by the ecologically important white rot fungus Bjerkandera adusta.

Two strains of the basidiomycete, Bjerkandera adusta (DAOM 215869 and BOS55) produce in static liquid culture, phenyl, veratryl, anisyl and chloroanisyl metabolites (CAM's) (alcohols, acids and aldehydes) as well as a series of compounds not previously known to be produced by Bjerkandera species: 1-phenyl, 1-anisyl, 1-(3-chloro-4-methoxy) and 1-(3,5-dichloro-4-methoxy) propan-1,2-diols, predominantly as erythro diastereomers with IR, 2S absolute configurations. 1-Anisyl-propan-1,2-diol and 1-(3,5-dichloro-4-methoxy)-propan-1,2-diol are new metabolites for which the names Bjerkanderol A and B, respectively, are proposed. Experiments with static liquid cultures supplied with 13C6- and 13C9-L-phenylalanine showed that all identified aromatic compounds (with the exception of phenol) can be derived from L-phenylalanine. For the aryl propane diols, the 13C label appeared only in the phenyl ring and the benzylic carbon, suggesting a stereoselective re-synthesis from a C7 and a C2-unit, likely aromatic aldehyde and decarboxylated pyruvate, respectively. Other compounds newly discovered to be derived from phenylalanine by this white rot fungus include phenylacetaldehyde and phenylpyruvic, phenylacetic, phenyllactic, mandelic and phenyl glyoxylic (benzoyl formic) acids. For both strains, cultures supplied with Na37Cl showed incorporation of 37Cl in all identified chlorometabolites. Veratryl alcohol and the CAM alcohols, which occur in both strains and can be derived from L-phenylalanine (all 13C-labelled), have reported important physiological functions in this white rot fungus. Possible mechanisms for their formation through the newly discovered compounds are discussed.