Recent advances in ultratrace analysis of dioxins and related halogenated hydrocarbons

Abstract

Can. J. Chem. 65, 1086Chem. 65, (1987.Analytical methodology for polychlorinated dioxins and furans (PCDDs and PCDFs) in environmental samples is not standardized. Many variations exist for the extraction, cleanup, quantitation, and confirmation of these compounds and reported detection limits and recoveries vary over several orders of magnitude. This paper describes research carried out at the Canada Centre for Inland Waters over the past seven or eight years to develop reliable methodology at ultratrace levels (10-'2-10-l 5 g/g) applicable to a wide range of environmental samples. Extraction techniques are described for biological tissue (fish, clams, leaches, eggs), fly ash, sediments, and water. Detailed cleanup procedures for the various matrices consist of most or all of the following: gel permeation chromatography liquid/liquid extraction with Na3P04, liquid/liquid extraction with H2S04, basic alumina chromatography, and carbon fibre chromatography. Preliminary screening of the cleaned extracts is achieved by gas chromatography equipped with a mass selective detector and positive identification by gas chromatography /mass spectrometry operated in electron impact and chemical ionization modes and with full scan and multiple ion detection. Custom software permitting the analysis of a wide range of compounds in a single run by gc/ms is reported. The presence of specific isomers of PCDDs and PCDFs is confirmed by high resolution gas chromatography /mass spectrometry. A radioimmunoassay screening procedure for PCDDs in environmental samples is also described. Les mtthodes d'analyse des dioxinnes et des furannes polychlorts (DPC et FPC) ne sont pas standardisees. Plusieurs variations existent pour l'extraction, le nettoyage, la quantification et la confirmation de la prtsence de ces composCs; de plus, les limites de dttection ainsi que les taux de rtcuptration rapportCs varient par plusieurs ordres de grandeur. Dans ce travail, on dtcrit les etudes effectukes au cours des 7 a 8 dernikres anntes au centre canadien des eaux inttrieures dans le but de dtvelopper une mtthodologie applicable a des niveaux d'ultratraces (lo-" h 10-g/g) et a un grand Cventail d'tchantillons prtlevts dans I'environnement. On dtcrit des techniques d'extraction pour des tissus biologiques (poissons, moules, eaux de lessivage et oeufs), des suies, des sediments et des tchantillons d'eau. Les diverses mCthodes dCtaillCes proposCes pour le nettoyage de diverses matrices comportent la plupart ou toutes les techniques suivantes: chromatographie par permCation de gel; extraction liquide/liquide avec du Na3P04; extraction liquide/liquide avec du &So4; chromatographie standards sur de l'alumine ou des fibres de charbon.On a effectut des essais prtliminaires sur des extraits IavCs en faisant appel a la chromatographie en phase gazeuse couplte h un dttecteur sClectif de masses; on a proctdC I'identification positive par chromatographie en phase gazeuse couplCe la spectromCtrie de masse, optrCe soit dans le mode d'impact Clectronique ou d'ionisat...

Determination of polychlorinated dibenzo‐p‐dioxins, dibenzofurans, and biphenyls by gas chromatography/mass spectrometry in the negative chemical ionization mode with different reagent gases

“…H 2 as reagent gas. According to Afghan et al (1987), hydrogen was used as a reagent gas for PCDD analysis for the first time in 1986 by a Canadian group. The authors noted, ''it is difficult to dry hydrogen.''…”

Effects of Bleached Kraft Mill Effluent on Fish in the St. Maurice River, Quebec

“…After X rays, a small number of whole and gutted fish were homogenized for lipid and isomer-specific analysis of chlorinated dioxins and furans by a method adapted from Afghan et al [31]. The main differences were the substitution of a column extraction for the acid digestion and reduction of the number of solvents for cleanup of the carbon fiber column from five to three.…”

Determination of dissolved-phase pesticides in surface water from the Yakima River Basin, Washington, using the Goulden large-sample extractor and gas chromatography/mass spectrometry

“…Conventional methods applied to the trace analysis of organics in water, through, for example, U.S. Environmental Protection Agency (U.S. EPA) method 625 (1), can be modified to incorporate largesample preconcentration techniques. The Goulden largesample extractor (GLSE), a continuous-flow liquid-liquid extractor, can effectively preconcentrate trace organic substances, including many pesticides, from large volumes of water providing very low MDLs (2)(3)(4)(5)(6)(7)(8).…”