Occurrence, distribution and behavior of hydrophilic ethers in the aquatic environment Dissertation for attaining the PhD degree of Natural Sciences submitted to the Faculty of the Johann Wolfgang Goethe-University in Frankfurt am Main by Daria Katarzyna Demers-Stępień from Gdynia Frankfurt (2013) (D 30) accepted as a dissertation by the Faculty of Geoscience/Geology of the Johann Wolfgang Goethe University Dean: Prof. Dr. Andreas Junge Expert assessors: Prof. Dr. Wilhelm Pütmann Prof. Dr. Ruprecht Schleyer Prof. Dr. Christoph Schüth Prof. Dr. Peter Cornel Date of the disputation: February 4th, 2014 Table of contents Table of Contents List of Tables .................................................................................................................................. 6 List of Figures ................................................................................................................................ 8 Abstract ........................................................................................................................................ 10 Zusammenfassung ....................................................................................................................... 14 Acknowledgements ...................................................................................................................... 21 Acronyms ...................................................................................................................................... 23 Chapter 1 Introduction .................................................................................................................. 25 1.1 Target analytes ................................................................................................................. 25 1.2 Toxicity ............................................................................................................................ 29 1.3 Formation of 1,4-dioxane as a by-product ....................................................................... 30 1.4 Focus of the research ....................................................................................................... 32 Chapter 2 Simultaneous determination of six hydrophilic ethers at trace levels using coconut charcoal adsorbent and gas chromatography/mass spectrometry .................................................. 34 2.1 Abstract ................................................................................................................................ 34 2.2 Introduction .......................................................................................................................... 35 2.3 Experimental ........................................................................................................................ 37 2.3.1 Chemical standards and reagents .................................................................................. 37 2.3.2 Sample collection .......................................................................................................... 38 2.3.3 Extraction procedure ..................................................................................................... 40 2.3.4 GC/MS analytical conditions ........................................................................................ 40 2.3.5 Quantification and quality control ................................................................................ 41 2.4 Results and discussion ......................................................................................................... 43 2.4.1 Optimization of the extraction method ......................................................................... 43 2.4.2 Precision and accuracy study ........................................................................................ 43 2.4.3 Detection and quantification limits ............................................................................... 45 2.4.4 Stability study ................................................................................................................ 46 2.4.5 Application to environmental water samples ................................................................ 49 2.5 Conclusions .......................................................................................................................... 51 Chapter 3 Behavior of organophosphates and hydrophilic ethers during bank filtration and their potential application as organic tracers. A field study from the Oderbruch, Germany. ................ 52 3.1 Abstract ................................................................................................................................ 52 3.2 Introduction .......................................................................................................................... 53 3.3 Area description and methods .............................................................................................. 56 3.3.1 Site description .............................................................................................................. 56 3 | P a g e Table of contents 3.3.2 Analytical methods ........................................................................................................ 59 3.3.3 Quality assurance .......................................................................................................... 61 3.4 Results and discussion ......................................................................................................... 62 3.4.1 Hydrochemistry ............................................................................................................. 62 3.4.2 Infiltration of OPs and ethers into the main drainage ditch .......................................... 64 3.4.3 Occurrence of OPs and ethers in the aquifer ................................................................. 66 3.4.4 Factors influencing OP and ether concentrations .......................................................... 67 3.4.5 Attenuation of OPs and ethers during bank filtration ................................................... 70 3.4.6 Organic pollutants as hydrological tracers .................................................................... 72 3.5 Conclusions .......................................................................................................................... 74 Chapter 4 Fate of 1,4-dioxane in the aquatic environment: from sewage to drinking water ........ 75 4.1 Abstract ................................................................................................................................ 75 4.2. Introduction ......................................................................................................................... 76 4.3. Materials and methods ........................................................................................................ 78 4.3.1. Chemicals and reagents ................................................................................................ 78 4.3.2 Analytical methods ........................................................................................................ 79 4.3.3. Quality assurance ......................................................................................................... 80 4.5. Site description and sampling methods .............................................................................. 81 4.5.1. Sewage treatment plants ............................................................................................... 81 4.5.2. Surface waters .............................................................................................................. 82 4.5.3. Bank filtration and drinking water treatment ............................................................... 83 4.6. Results and discussion ........................................................................................................ 86 4.6.1. 1,4-dioxane in municipal sewage treatment plants ...................................................... 86 4.6.2. Temporal and spatial distribution of 1,4-dioxane in surface waters ............................ 89 4.6.3. Occurrence of 1,4-dioxane in bank filtration and drinking water ................................ 97 4.7 Conclusions ........................................................................................................................ 101 Chapter 5 Source identification of high glyme concentrations in the Oder River ...................... 103 5.1. Abstract ............................................................................................................................. 103 5.2. Introduction ....................................................................................................................... 103 5.3. Materials and methods ...................................................................................................... 106 5.3.1. Chemicals and reagents .............................................................................................. 107 5.3.2. Analytical methods ..................................................................................................... 108 5.3.3. Quality assurance ....................................................................................................... 109 5.4. Site description and sampling methods ............................................................................ 109 5.4.1. Description of the study area .....................................................................................