1. HOLD TIME, STORAGE, AND SAMPLE CONTAINER CONSIDERATIONS FOR ANALYTICAL METHODS TO DETERMINE HIGHLY FLUORINATED COMPOUNDS IN ENVIRONMNTAL MATRICES Mary A. Kaiser 1, Million Woudneh 2, Barbara S. Larsen 1, Michael D. Aucoin 3, Kelly A. Rinehimer 3, and Richard Grace 2 1 DuPont Company, P.O.Box 80402, Wilmington, DE, 19880-0402; 2 AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, B.C. V8L 5X2, Canada, 3 URS Corporation, Barley Mill Plaza 19, Wilmington, DE 19805 USA ABSTRACT A comprehensive panel of fluorotelomer alcohols, perfluorocarboxylic acids, and perfluorinated sulfonates were stored in three types of storage containers: polypropylene, high-density polyethylene (HDPE), and amber glass at common laboratory storage conditions. Results were measured at intervals from 0 to 90 days to determine hold time guidance and compatible container types. Results indicate that when stored in appropriate containers and standard laboratory storage conditions, sample results are not affected for periods up to 90 days. Amber glass or HDPE containers were determined to be the best storage containers. Polypropylene containers were deemed to be incompatible with some perfluorinated carboxylic acids. INTRODUCTION Fluorotelomer alcohols, perfluorocarboxylic acids and perfluorinated sulfonates are important highly fluorinated raw materials that have attracted considerable attention in the last eight years. Many of these compounds have been found in a variety of environmental matrices and have been reported in many locations. These compounds have presented considerable analytical challenges. While considerable analytical work has focused on providing increasingly reliable results, limited information is available on key issues that affect sample results such as hold times, storage conditions and sample containers. EXPERIMENTAL DESIGN Fluorotelomer alcohols Hold time study: Matrix = methanol and filter Container types = amber glass jar with polypropylene caps. Hold time intervals = 0, 2, 7, 14, 28, 60 and 90 Days. # of samples analyzed = 3 samples per hold time interval. Storage temperature = -20 o C CONCLUSIONS USES OF HIGHLY FLUORINATED MATERIALS Aerospace Materials Hydraulic tubing Wire & Cabling Flares Chemical Processing Valves, Lined Piping, Tanks Semiconductor Manufacture Health Care Fire Fighting Carpet & Textiles MATERIALS Perfluorocarboxylates F(CF2) n CO 2 - Fluorotelomer alcohols F(CF 2 ) n CH 2 CH 2 OH Perfluoroalkyl sulfonates F(CF2) n SO 3 - Note that there is a “perfluorinated” part and an organic functional group. Very different physical-chemical properties from each other. EXPERIMENTAL DESIGN Method validation for both perfluorinated acids and fluorotelomer alcohols: two matrices three concentrations triplicate three different days Perfluorinated acids Hold time study: Matrix = reagent water Container types = polypropylene, amber glass, and high- density polyethylene. Hold time intervals = 0, 2, 7, 14, 28, 60 and 90 Days. # of samples analyzed = 3 samples per hold time interval. Storage temperature = 4 o C METHOD OUTLINE Fluorotelomer alcohols Quantitative recovery achieved for 8:2 to 16:2 fluorotelomer alcohols spiked and stored in closed amber glass jars. Perfluorinated carboxylic and sulfonic acids Mean percent recovery values of all acid analytes were > 90% after 60 days of storage in amber glass containers. Mean percent recovery values of all acid analytes were > 80% after 90 days of storage in amber glass containers Mean percent recovery values of all acid analytes were > 70% after 60 days of storage in HDPE containers. Mean percent recovery values of all acid analytes were > 68% after 90 days of storage in HDPE containers. Up to 28% PFUnA and 34% PFDoA were recovered from polypropylene containers that were used for storing water samples in contact with these perfluorinated acids. Polypropylene containers are therefore not suitable for sample collection for C 11 and C 12 perfluorocarboxylic acids.