For the 1983 nesting season, Forster's tern (Sterna forsteri) reproductive success was significantly impaired on organochlorine contaminated Green Bay, Lake Michigan compared to a relatively uncontaminated inland location at Lake Poygan, Wisconsin. Compared with tern eggs from Lake Poygan, eggs from Green Bay had significantly higher median concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), other polychlorinated dibenzo-p-dioxins (PCDDs), total polychlorinated biphenyls (PCBs), total (three congeners) non-ortho, ortho' PCBs, five individual PCB congeners known to induce aryl hydrocarbon hydroxylase (AHH) and several other organochlorine contaminants. Conversions of analytical concentrations of TCDD and PCB congeners based on relative AHH induction potencies allowed for estimation of total 2,3,7,8-TCDD equivalents. Two PCB congeners, 2,3,3',4,4'- and 3,3',4,4',5-pentachlorobiphenyl (PeCB) accounted for more than 90% of the median estimated TCDD equivalents at both Green Bay and Lake Poygan. The median estimated TCDD equivalents were almost 11-fold higher in tern eggs from Green Bay than in eggs from Lake Poygan (2175 and 201 pg/g). The hatching success of Green Bay sibling eggs from nests where eggs were collected for contaminant analyses was 75% lower at Green Bay than at Lake Poygan. Hatchability of eggs taken from other nests and artificially incubated was about 50% lower for Green Bay than for Lake Poygan. Among hatchlings from laboratory incubation, those from Green Bay weighed approximately 20% less and had a mean liver weight to body weight ratio 26% greater than those from Lake Poygan. In both field and laboratory, mean minimum incubation periods were significantly longer for eggs from Green Bay compared to Lake Poygan (8.25 and 4.58 days, respectively). Mean minimum incubation time for Green Bay eggs in the field was 4.37 days longer than in the laboratory. Hatchability was greatly improved when Green Bay eggs were incubated by Lake Poygan adults in an egg-exchange experiment, but was sharply decreased in Lake Poygan eggs incubated in Green Bay nests. Nest abandonment and egg disappearance were substantial at Green Bay but nil at Lake Poygan. Thus, not only factors intrinsic to the egg, but also extrinsic factors (parental attentiveness), impaired reproductive outcome at Green Bay. The epidemiological evidence from this study strongly suggested that contaminants were a causal factor. AHH-active PCB congeners (intrinsic effects) and PCBs in general (extrinsic effects) appeared to be the only contaminants at the concentrations measured in eggs, capable of producing the effects that were observed at Green Bay.

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Registry No. H2S04, 7664-93-9. (1) La Mer, V. K.; Inn, E. C. Y.; Wilson, 1. B. J . Collo/d Scl. 1950, 5 . (2) Spurnq, K.; Hampl, V. Collect. Czech. Chem. Commun. 1965, (3) Coutarel, L.; Matljevlc, D.; Kerker, M.; Huang, C. J . Colloid Interface (4) Rapaport, E.; Weinstock, S. E. (7) Juhos, L. T.; Evans, M. J.; Mussenden-Harvey, R.; Furiosi, N. J.; Lapple, C. E.; Freeman, G. Mckenzie, R.; Vermeersch, M.; Dorman, F.; Pul, D.; Linne, M.; Lui, 6.; Whkby, K. Afmos. Environ. 1978, 12, 105-111. 86 1-865. 38, 493-497.

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A technique Is proposed for the quantitative determination of constituents In complex mixtures characterized by gas chromatography data. The technique Is partial least squares In latent variables (PLS) and the data to which It Is applied are gas chromatograms of the Aroclors 1242, 1248, 1252, and 1260. In addition the problem Is formulated as one of classification and calibration and a sample of used transformer oil from a waste dump Is classified as to Its origin.

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We developed an integrated analytical procedure for organochlorine contaminants that enables quantitation of toxaphene residues as low as 0.1 gg/g in fish tissue. Preparation of the sample requires extraction of ground tissue with dichloromethane, cleanup of the extract by gel permeation chromatography, and fractionation by Florisil and silica gel chromatography. Toxaphene residues are then characterized and quantified by capillary-column gas chromatography with electron capture. An automated data system is used to select and quantitate peaks and to eliminate interference from the high-resolution chromatograms. Selected components are then confirmed by gas chromatography-negative-ion mass spectrometry (NIMS).This procedure consistently yields results within 1% of spike concentrations. Substitution of conventional packed-column gas chromatography into the procedure reduces accuracy slightly; values average 7% below spiked concentrations. We also evaluated several confirmation techniques and other methods for eliminating analytical interferences. Nitration of the toxaphene-containing fraction before gas chromatography successfully eliminated interferences from the DDT complex but not from chlordane components. This procedure also altered the composition of the toxaphene mixture. Among the gas chromatography-mass spectrometry confirmation procedures evaluated, NIMS proved superior to the more conventional electron-impact mass spectrometry because toxaphene components were far more sensitive to NIMS.