Accumulation of environmental contaminants in wood duck (Aix sponsa) eggs, with emphasis on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

We measured polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), organochlorine pesticides, and mercury in wood duck (Aix sponsa) eggs collected near a North Carolina (USA) bleached kraft paper mill. Samples were taken a decade after the mill stopped using molecular chlorine. Using avian toxic equivalency factors, 2,3,7,8-tetrachlorodibenzo-p-dioxin toxicity equivalent (TEQ) concentrations were 1-30 pg/g fresh wet weight in eggs (n = 48) collected near the mill in 2002-2005 and were significantly higher than those from a reference site (<1 pg/g) 25 km away. Geometric mean wood duck egg TEQs (6 pg/g) were one-fifth those measured at this site prior to the cessation of molecular chlorine bleaching. Concentrations of mercury in wood duck eggs from nests of the Roanoke River sites ranged from 0.01 to 0.14 microg/g (geometric mean, 0.04 microg/g) and were significantly higher than those from the reference site, where concentrations did not exceed 0.04 microg/g (geometric mean, 0.02 mug/g). All concentrations were lower than those associated with adverse effects in birds. The congener profiles, lack of contamination in reference site eggs, and decline in contaminant concentrations after process changes at the mill provide strong evidence that mill discharges influenced contamination of local wood duck eggs. Collectively, the results indicate that the wood duck is an effective sentinel of the spatial and temporal extent of PCDD, PCDF, and mercury contamination.

Considerations involved with the use of semipermeable membrane devices for monitoring environmental contaminants.

Semipermeable membrane devices (SPMDs) are used with increasing frequency, and throughout the world as samplers of organic contaminants. The devices can be used to detect a variety of lipophilic chemicals in water, sediment/soil, and air. SPMDs are designed to sample nonpolar, hydrophobic chemicals. The maximum concentration factor achievable for a particular chemical is proportional to its octanol-water partition coefficient. Techniques used for cleanup of SPMD extracts for targeted analytes and for general screening by full-scan mass spectrometry do not differ greatly from techniques used for extracts of other matrices. However, SPMD extracts contain potential interferences that are specific to the membrane-lipid matrix. Procedures have been developed or modified to alleviate these potential interferences. The SPMD approach has been demonstrated to be applicable to sequestering and analyzing a wide array of environmental contaminants including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polychlorinated dioxins and dibenzofurans, selected organophosphate pesticides and pyrethroid insecticides, and other nonpolar organic chemicals. We present herein an overview of effective procedural steps for analyzing exposed SPMDs for trace to ultra-trace levels of contaminants sequestered from environmental matrices.

Organochlorine contaminants in double-crested cormorants from Green Bay, WI: I. Large-scale extraction and isolation from eggs using semi-permeable membrane dialysis.

A 41.3-kg sample of double-crested cormorant (Phalacrocorax auritus) egg contents was extracted, yielding over 2 L of egg lipid. The double-crested cormorant (DCC) egg extract, after clean-up and concentration, was intended for use in egg injection studies to determine the embryotoxicity of the organic contaminants found within the eggs. Large-scale dialysis was used as a preliminary treatment to separate the extracted contaminants from the co-extracted sample lipids. The lipid was dialyzed in 80x5 cm semi-permeable membrane devices (SPMDs) in 50-ml aliquants. After the removal of 87 g of cholesterol by freeze-fractionation, the remaining lipid carryover (56 g) was removed by 100 routine gel permeation chromatography (GPC) operations. A 41,293-g sample was thus extracted and purified to the extent that it could easily be placed at a volume of 5 ml, the volume calculated to be necessary for the egg injection study. Analyses were performed comparing contaminant concentrations in the final purified extract to those present in the original egg material, in the extract after dialysis and cholesterol removal, and in the excluded materials. Recoveries of organochlorine pesticides through dialysis and cholesterol ranged from 96% to 135%. Total polychlorinated biphenyls in the final extract were 96% of those measured in the original egg material. Analysis of excluded lipid and cholesterol indicated that 92% of the polychlorinated dibenzo-dioxins and -furans were separated into the final extract.