Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1986 Trace analysis of volatile organic compounds in water by GC and HPLC Ikue Arikawa Ogawa Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Analytical Chemistry Commons Recommended Citation Ogawa, Ikue Arikawa, "Trace analysis of volatile organic compounds in water by GC and HPLC " (1986). Retrospective Theses and Dissertations. 8106. https://lib.dr.iastate.edu/rtd/8106 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. 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Zeeb Road, Ann Arbor, Michigan 48106 8627141 Ogawa, Ikue Arikawa TRACE ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN WATER BY GC AND HPLC Iowa State University PH.D. 1986 University Microfilms Intern&tion&l 300 N. zeeb Road, Ann Artwr, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages 2. Colored illustrations, paper or print 3. Photographs with dark background 4. Illustrations are poor copy 5. Pages with black marks, not original copy 6. Print shows through as there is text on both sides of page 7. Indistinct, broken or small print on several pages 8. Print exceeds margin requirements 9. Tightly bound copy with print lost in spine 10. Computer printout pages with indistinct print 11. Page(s) lacking when material received, and not available from school or author. 12. Page(s) seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages 15. Dissertation contains pages with print at a slant, filmed as received 16. Other University Microfilms International Trace analysis of volatile organic compounds in water by GC and HPLC by Ikue Arikawa Ogawa A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department; Chemistry Major; Analytical Chemistry Approved; Signature was redacted for privacy. In Cha Signature was redacted for privacy. Ihe'Tia^dr ^é^k^ment Signature was redacted for privacy. For the Graduate College Iowa State University Ames, Iowa 1986 ii TABLE OF CONTENTS page PREFACE 1 REFERENCES 4 REVIEW OF THE LITERATURE 5 INTRODUCTION 6 CONCENTRATION BY SOLID SORBENTS 8 Resin Sorption 8 Molecular Sieve 11 HEADSFACE ANALYSIS 14 PURGE-AND-TRAP 17 DISTILLATION 24 SOLVENT EXTRACTION 29 DIRECT GAS CHROMATOGRAPHIC ANALYSIS 31 DERIVATIZATION 36 REFERENCES 39 SECTION I. DETERMINATION OF LOW-MOLECULAR WEIGHT ALDEHYDEDS AND KETONES IN WATER BY HPLC 49 INTRODUCTION 50 EXPERIMENTAL 53 Solvents and Reagents 53 Test Solutions 53 Preparation of ZSM-5 Column 53 Chromatographic Instruments 54 Procedure for Determination of Capacity 55 Procedure for Determining Aldehydes and Ketones in Aqueous Samples 55 RESULTS AND DISCUSSION 57 Capacity Experiments 57 Elution 57 Derivatization of Carbonyl Compounds and Solvent Extraction of the 2,4-Dinitro- phenylhydrazones 60 ill Chromatography and Recovery Studies 60 Application to Drinking Water 66 CONCLUSION 71 REFERENCES 72 SECTION II. DETERMINATION OF LOW-MOLECULAR WEIGHT POLAR COMPOUNDS IN WATER BY GC 74 INTRODUCTION 75 EXPERIMENTAL 77 Solvents and Reagents 77 Instrumentation 77 Capacity Experiments 77 ZSM-5 77 ELZ-115 78 Accumulation Experiments 78 Pump Loading Method 78 Gravity Plow Method 78 Preparation of Test Solutions 79 Desorption of Test Compounds 79 RESULTS AND DISCUSSION 80 Capacity Experiments 80 Application of Concentration Method of Section I on Alcohols and Ethyl Acetate 88 Recovery 88 Gas Chromatography 90 Solvents for Desorption 98 Range of Sample Concentration 100 Diethyl Ether, Esters and Nitriles 101 Recovery 101 Sample Volume 102 Gas Chromatography 103 Aldehydes and Ketones 103 Acids 107 Recovery 107 Sample Volume 108 Baseline Problems of DBWax Column 109 Other Concentration Methods 113 CONCLUSION 120 REFERENCES 125 iv SECTION III: CONCENTRATION OF ORGANIC COMPOUNDS IN WATER BY GAS PURGING AND BOILING 126 INTRODUCTION 127 EXPERIMENTAL 130 Chemicals 130 Instrumentation 130 Columns for Concentration of Organic Compounds 133 Preparation of Tenax Column 133 Preparation of XAD Column 133 Concentration of Organic Compounds on Tenax Column' 133 Fast Heating 133 Slow Heating 134 Removal of Organic Compounds from Concentrating Column 135 Quantitation 135 Aqueous Sampling 135 RESULTS AND DISCUSSION 137 Result of Aqueous Sampling 137 Result of Gas Purging and Heating 139 Sample Concentration Range 142 Recovery 142 Gas Chromatography 142 Effect of Tenax Column Dimensions 148 Evaluation of Losses 150 Effect of pH 152 Effect of Heating Rate 154 Effect of Another Adsorbent: XAD-4 155 Correlation of Recovery with Water Solubility and Molecular Weight 158 Real Samples 166 CONCLUSION 180 REFERENCES 184 SUMMARY 186 ACKNOWLEDGEMENTS 190 1 PREFACE As in any analysis, direct measurement is the simplest. It is toward this end that an investigator strives. If this cannot be attained, then the method containing the least number of processes which gives the best results is preferred. A study of the problem of analysis of trace volatile organic compounds in water begins with existing tools and knowledge. The literature review explores the traditional methods of concentrating and analyzing volatile organic compunds in water. The division of these methods becomes obscured as the analysis becomes more demanding in terms of scope of compounds and lower amounts quantitated. While impressive gains have been noted in gas and liquid chromatography, concentration is still desirable. There are emerging, a few direct methods of analyses based on fiber optics and very selective methods of detection, such as, fluorescence detection (1) or based on multiple detection systems, such as, tandem mass spectrometry (2). Sections I and II deal with the problem of analysis low- molecular weight polar compounds in water. It has been shown that the most common method used to disinfect drinking water, chlorination, produces carcinogenic and mutagenic compounds (3). These compounds have escaped detection 2 because they are highly soluble in water and difficult to concentrate. In order to study the chemistry and the fate of these harmful compounds, an analytical method is necessary. In Sections I and II, a simple method for the analysis of these low-molecular weight polar compounds is described. Section II is more comprehensive and includes a greater variety of compounds. Section I is more limited to the class of low-molecular weight aldehydes and ketones. The analysis of aldehydes and ketones was based on the formation of the 2,4-dinitrophenylhydrazine derivatives, which resulted in high selectivity and high sensitivity. In recent years, it has been demonstrated that the dumping of toxic wastes have caused these toxic compounds to percolate through various geological rock formations and contaminate the ground and surface waters which are the main sources of drinking water. As a consequence, legislation (4) has been introduced which will affect 50,000 public water supply systems in the USA. These water systems must have their water supplies analyzed within four years by chemists certified by the US Environmental Protection Agency for 8 volatile organic compounds using the prescribed method of purge-and-trap with suitable detection. Section III describes changes that can be made in the purge-and-trap method, so that a greater variety of organic compounds can be analyzed by a single experiment. A single experiment