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Determination of Polycyclic Aromatic Hydrocarbon Compounds in Sediment by Gas Chromatography/Mass Spectrometry

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Determination of Polycyclic Aromatic Hydrocarbon Compounds in Sediment by Gas Chromatography/Mass Spectrometry uses science for a changing world Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Polycyclic Aromatic Hydrocarbon Compounds in Sediment by Gas Chromatography/Mass Spectrometry Water-Resources Investigations Report 03-4318 U.S. Department of the Interior U.S. Geological Survey Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Polycyclic Aromatic Hydrocarbon Compounds in Sediment by Gas Chromatography/Mass Spectrometry By Mary C. Olson, Jana L Iverson, Edward T. Furlong, and Michael P. Schroeder Water-Resources Investigations Report 03-4318 U.S. Department of the Interior U.S. Geological Survey U.S. Department of the Interior Gale A. Norton, Secretary U.S. Geological Survey Charles G. Groat, Director U.S. Geological Survey, Denver, Colorado: 2004 For sale by U.S. Geological Survey, Information Services Box 25286, Denver Federal Center Denver, CO 80225 For more information about the USGS and its products: Telephone: 1-888-ASK-USGS World Wide Web: http://www.usgs.gov/ Any use of trade, product, or firm names in this publication is for descriptive purposes only and does not imply endorsement by the U.S. Government. Although this report is in the public domain, permission must be secured from the individual copyright owners to reproduce any copyrighted materials contained within this report. Ill Contents Abstract...........................................................................................1 Introduction........................................................................................1 Analytical method..................................................................................3 1. Scope and application....................................................................3 2. Summary of method......................................................................4 3. Interferences.............................................................................4 4. Apparatus and equipment...............................................................6 5. Reagents and consumable materials..............'...................................... .7 6. Safely precautions .......................................................................9 7. Sample preparation procedure...........................................................9 8. Instrumental analysis................................................................... 12 9. Calculation and reporting of results..................................................... 16 10. Quality assurance and quality control................................................... 17 11. Method performance................................................................... 20 Summary and conclusions....................................................................... 31 References cited................................................................................. 31 Attachment 1: Determination of polycyclic aromatic hydrocarbons in sediment by gas chromatography/mass spectrometry using selected-ion monitoring................ 33 Figures 1. Flowchart showing polycyclic aromatic hydrocarbons, organophosphate pesticides, and organochlorine pesticides............................................................5 2. Graphs showing quantitation and monitor ions in the homolog series for the isomeric parent polycyclic aromatic hydrocarbons phenanthrene/anthracene in a sample........ 18 Tables 1. Individual polycyclic aromatic hydrocarbon compounds determined using this method... 3 2. Alkylated polycyclic aromatic hydrocarbon homolog groups determined using this method and reported permanently as estimated................................4 3. Suggested gel permeation chromatography processing sequence....................... 12 4. Retention times, relative retention times, gas chromatography/mass spectrometry quantitation ions, confirmation ions, and percent relative abundance of confirmation ions for individual polycyclic aromatic hydrocarbons (PAHs) and alkylated PAH homolog groups.......................................................... 13 5. Gas chromatography/mass spectrometry analytical sequence suggested for use in this method......................................................... 15 6. Relative response factors used for the quantitation of alkylated polycyclic aromatic hydrocarbon homolog series........................................ 17 7. Bias and precision data of polycyclic aromatic hydrocarbon spike recoveries for seven replicates using full-scan acquisition with compound concentrations of 4.8, 1ZO, and 24.0 micrograms per kilogram in three matrices.................................22 IV 8. Polycyclic aromatic hydrocarbon matrix background concentrations in full-scan acquisition......................................................................25 9. Recovery of semivolatile organic compounds from Evergreen Lake sediment samples spiked at 800 micrograms per kilogram...............................26 10. Recovery of semivolatile organic compounds from Evergreen Lake sediment samples spiked at 2,000 micrograms per kilogram........................................27 11. Recovery of semivolatile organic compounds from Mississippi River sediment samples spiked at 400 micrograms per kilogram...............................28 12. Polycyclic aromatic hydrocarbon concentrations certified bythe National Institute of Standards and Technology for Standard Reference Material 1941b and determined using this method........................................29 13. Alkylated polycyclic aromatic hydrocarbon homolog group concentrations detected in Standard Reference Material 1941 b not reported bythe National Institute of Standards and Technology and determined using this method ...........................................................29 14. Polycyclic aromatic hydrocarbon concentrations certified bythe National Institute of Standards and Technology for Standard Reference Material 1944 and determined using this method.........................................30 15. Alkylated polycyclic aromatic hydrocarbon homolog group concentrations detected in Standard Reference Material 1944 not reported bythe National Institute of Standards and Technology and determined using this method ...........................................................30 16. Bias and precision data of polycyclic aromatic hydrocarbon spike recoveries for seven replicates using selected-ion monitoring acquisition with compound concentrations of 4.8,12.0, and 24.0 micrograms per kilogram in three matrices...........................................................................36 17. Polycyclic aromatic hydrocarbon matrix background concentrations in selected-ion monitoring..................................................................39 18. Polycyclic aromatic hydrocarbon method spike recoveries using selected-ion monitoring at a concentration of 24 micrograms per kilogram for year 2000...............40 19. Polycyclic aromatic hydrocarbon concentrations certified bythe National Institute of Standards and Technology for Standard Reference Material 1941 band determined using selected-ion monitoring...............................................41 20. Alkylated polycyclic aromatic hydrocarbon homolog groups detected in Standard Reference Material 1941 b not reported bythe National Institute of Standards and Technology and determined using selected-ion monitoring............41 21. Polycyclic aromatic hydrocarbon concentrations certified bythe National Institute of Standards and Technology for Standard Reference Material 1944 and determined using selected-ion monitoring ..........................................42 22. Alkylated polycyclic aromatic hydrocarbon homolog groups detected in Standard Reference Material 1944 not reported bythe National Institute of Standards and Technology and determined using selected-ion monitoring............43 23. Polycyclic aromatic hydrocarbon concentrations detected in Certified Reference Material 354 using selected-ion monitoring for year 2001......................43 24. Statistics for selected-ion monitoring and full-scan acquisition data fortified at 12.0 micrograms per kilogram.................................................44 Conversion Factors Multiply By To obtain Length centimeter (cm) 3.94X10'1 inch meter (m) 3.28 x 10'° foot micrometer (um) 3.94 x 10'5 inch millimeter (mm) 3.94X10'2 inch nanometer (nm) 3.94 xlO'8 inch Mass gram (g) 3.53 x lO'2 ounce, avoirdupois microgram (jig) 3.53 x 10'8 ounce, avoirdupois nanogram (ng) 3.53 xlO'11 ounce, avoirdupois picogram (pg) 3.53 xlO'14 ounce, avoirdupois Volume liter (L) 3.38 x 10'1 ounce, fluid microliter (uL) 3.38 xlO'5 ounce, fluid milliliter (mL) 3.38 x 10'2 ounce, fluid Pressure kilopascal (kPa) 1.45X10'1 pounds per square inch Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows: °F = (1.8x°C) ABBREVIATED WATER-QUALITY UNITS ABBREVIATIONS AND ACRONYMS °C degree Celsius ACS American Chemical Society °C/min degree Celsius per minute amu atomic mass unit g/mole gram per mole ASMB Alberta Sweet Mix Blend ug/kg microgram per kilogram (parts per billion) CAS Chemical Abstracts Service mg/kg milligram per kilogram CRM Certified Reference Material mg/L milligram per liter CCV continuing calibration verification solution mL/min milliliter per minute DFTPP decafluorotriphenylphosphine ng/uL nanogram per microliter dPAH perdeuterated polycyclic aromatic hydncarbon pg/uL picogram per microliter dPAHIS perdeuterated
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