Persistent organohalogen contaminant burdens in Antarctic krill (Euphausia superba) from the eastern Antarctic sector: a baseline study.

A baseline for persistent organohalogen compound (POC) accumulation in the Antarctic keystone species, Antarctic krill (Euphausia superba) has been established for a 50 degrees longitudinal range of the eastern Antarctic sector. Samples of adult krill, caught from 12 sites distributed between 30 degrees and 80 degrees E (60-70 degrees S), were analysed for >100 organohalogen compounds including chlorinated pesticides, polychlorinated biphenyls (PCBs), polybrominated organic compounds and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). Organochlorine pesticides dominated measured krill contaminant burdens with hexachlorobenzene (HCB) as the single most abundant compound quantified. Krill HCB concentrations were comparable to those detected at this trophic level in both the Arctic and temperate northwest Atlantic, lending support for the hypothesis that HCB will approach global equilibrium at a faster rate than other POCs. Para, para'-dichlorodiphenylethene (p,p'-DDE) was detected at notable concentrations. Measurements of DDT and its degradation products provide an important baseline for monitoring the temporal and geographical influence of renewed, DDT usage for malaria-control in affected southern hemisphere countries. In contrast to the Arctic, PCBs did not feature prominently in contaminant burdens of Antarctic krill. The major commercial polybrominated diphenyl ether (PBDE) congeners -99 and -47 were quantified at low background levels with clear concentration spikes observed at around 70 degrees E , in the vicinity of modern, active research stations. The likelihood that local anthropogenic activities are supplementing low PBDE levels, delivered otherwise primarily via long range environmental transport, is discussed. The suspected naturally occurring brominated organic compound, 2,4,6-tribromoanisole (TBA), was a ubiquitous contaminant in all samples whereas the only PCDD/Fs quantifiable were trace levels of octachlorodibenzo-p-dioxin (OCDD) and 1,2,3,4,7,8/1,2,3,4,7,9-hexachlorodibenzofuran (HxCDF). With the aims of; i) Generating a robust and broadly applicable POC auditing platform for the scarcely studied eastern Antarctic sector; ii) Determining the compounds accumulating in Antarctic krill for further toxicity evaluation studies and iii) Establishing a baseline for Antarctic predator exposure to POCs, this study represents one of the most comprehensive reports of POC contamination of the Antarctic food web to date.

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples.

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho substituted biphenyls in polar bear milk from Svalbard (Norway).

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1-3 pg/g(-1) fat (0.2-1.6 pg ml(-1) milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.

Determination of levels of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and pesticides in harp seals from the Greenland Sea.

The levels of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), biphenyls (PCB) and compounds of the DDT group were determined in individual seal blubber and brain samples from ten male and one female harp seals caught in the Greenland Sea. No data from this region and from harp seals have been reported before. The age of the animals varied between 1 and 18 years. PCDD/PCDF concentrations in the blubber (4-10 pg/g TEQ wet weight (w.w.), Nordic model) were somewhat lower than in ringed seals from the Arctic. Non-ortho substituted PCB (CB 77,126 and 169) showed TEQ levels in the blubber which were about 4-10-times higher. CB 77 dominated in most samples, but in a few cases CB 169 was the most abundant congener. p,p'-DDE (average 760 ng/g w.w.) and di-ortho substituted PCB concentrations (2560 ng/g w.w. expressed as sigma PCB) in the blubber were comparable to those found in ringed seals from the European and Canadian Artic. Levels of PCDD/PCDF in brain correspond to the detection limit (about. 0.1-0.6 pg/g w.w.) for most congeners. With one exception, PCB amounts in brain (w.w.) were one to two orders of magnitude lower. A highly significant correlation was found between age, p,p-DDE and di-ortho PCB as well as between single PCDD and coplanar PCB congeners. No relationship was observed between levels of PCDD/PCDF, age and di-ortho-PCB.

Preparation and certification of a reference material on PCBs in pig fat and its application in quality control in monitoring laboratories during the Belgian "PCB-crisis".

In this article, the production and validation of a new certified reference material "PCBs in animal fat" for the control of the maximum level of 200 ng/g setup by the European Communities for veterinary products from Belgium is described. Three materials are established: a blank, one material with about 100 ng/g and one with about 200 ng/g (sum of seven PCBs). Data on the production and certification are given. Additionally, this material was used as an unknown test material in the quality assurance program of the Belgium meat monitoring system (before the certification of the material). While the certification was performed with an uncertainty of less than 10%, the round robin exhibited larger deviations. However, these deviations were less than 20% for most of the 30 participating laboratories. Only two had significantly higher deviations.

The synergistic binding of anions and Fe3+ by transferrin. Implications for the interlocking sites hypothesis.

The finding that transferrin does not bind Fe3+ at the specific metal binding sites in the absence of carbonate and synergistic anions emphasizes the fundamental importance of the anion binding site to the chemistry of Fe3+-transferrin-CO32-. An important question regards the chemical and structural requirements for carbonate substitution. This has been, however, an area of some dispute in the literature. We have utilized four synthetic routes for the preparation of Fe3+-transferrin-anion complexes. The products have been examined with regard to spectral properties, and reaction with: (a) NaHCO3, (b) Fe3+-nitrilotriacetic acid in NaHCO3, and (c) sodium citrate under CO2-free conditions. The results provide information as to which anions are synergistic, and the basic properties of the Fe3+-transferrin-anion complexes that are formed. The 6 inorganic anions that were tested were all found to be nonsynergistic. Dihydroxyacetone and glyceraldehyde were also nonsynergistic. Dicarboxylic acids were found to form stable Fe3+-transferrin-anion complexes which were only slowly displaced by carbonate. Several monocarboxylic acids with proximal aldehyde, ketone, alcohol, amino, or thiol functional groups proved to be synergistic. CPK molecular model studies suggested the functional group and the carboxylic acid must be able to fit within a site between 6.3 and 7.0 A in maximal length. One large substituent could be accommodated by the site, however, two methylgroups on the alpha carbon to a carboxylate group could not be accommodated. Chloroacetate and monocarboxylic acids were nonsynergistic. The results are interpreted in terms of an interlocking sites hypothesis which envisions the synergistic anion as interacting with the protein via its its carboxyl group and bonding with the Fe3+ via its proximal functional group.

The nonspecific binding of Fe3+ to transferrin in the absence of synergistic anions.

An obligatory role for barbonate (or other synergistic anions) in the specific binding of Fe3+ by transferrin has been a point of controversy for two decades. There are an equal number of confirmatory and negative reports of specific Fe3+-transferrin binary complexes. A criticism of previous studies is the use of only one synthetic route, and limited product testing. This study reports the development of several preparative routes aimed at the formation of a specific Fe3+-transferrin complex, and the characterization of the products by spectrophotometry and chemical reactivity. The preparative routes described include: (a) displacement of carbonate from Fe3+-transferrin-CO32- at low pH followed by removal of CO2 by several techniques; (b) addition of FeCl3 to apotransferrin under CO2-free conditions; (c) oxidation of Fe2+ in the presence of apotransferrin under CO2-free conditions; (d) reaction of apotransferrin with nonsubstituting Fe3+ complexes in the absence of CO2; and (e) attempts to displace anions from weak Fe3+-transferrin-anion complexes. The product were examined with regard to their visible spectra, and their examined with regard to their visible spectra, and their reactivity with: (a) NaHCO3, (b) Fe3+-nitrilotriacetic acid in NaHCO3, and (c) citrate. The results are compared with the characteristics of Fe3+-transferrin-anion complexes and nonspecific Fe3+, transferrin mixtures. The data indicate that in the absence of synergistic anions the affinity of the specific metal binding sites of transfe-rin for Fe3+ is so low as to not compete favorably with hydrolytic polymerization and nonspecific binding effects.