Fluorescent Whitening Agents Natural Waters

Diss. ETH No. 12355 Fluorescent Whitening Agents • ID Natural Waters A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH for the degree of Doctor of Natural Sciences presented by JEAN-MARC ALAIN STOLL Dipl. Chem., University of Zurich born on November 9, 1966 citizen of Schaftbausen and Osterfingen (SH) accepted on the recommendation of Prof. Dr. Walter Giger, examiner Dr. Robert P. Eganhouse, co-examiner Dr. Markus M. Ulrich, co-examiner Zurich 1997 The following chapters have been published or submitted for publication: Chapter 2 Stoll J. M. A. and Giger W. (1997). Determination of Detergent-Derived Fluorescent Whitening Agent Isomers in Lake Sediments and Surface Waters by Liquid Chromatogra- phy. Anal. Chem., 69, 2594-2599. Chapter 3 Stoll J. M. A. and Giger W. Mass Balance for Detergent- Derived Fluorescent Whitening Agents in Surface Waters of Switzerland. Water Res. (in press). Chapter 4 Stoll J. M. A., Ulrich, M. M., and Giger W. Dynamic Behavior of Fluorescent Whitening Agents in Greifensee: Field Measurements Combined with Mathematical Modeling of Sedimentation and Photolysis. Submitted to Environ. Sci. Technol. Chapter 5 Stoll J. M. A., Poiger T. F ., Lotter A. F ., Sturm M., and Giger W. (1997). Fluorescent Whitening Agents as Molecular Markers for Domestic Waste Water in Recent Se- diments of Greifensee, Switzerland. In: Molecular Markers in Environmental Geochemistry (Eganhouse R. P. ed.), ACS Symposium Series 671, American Chemical Society: Washington, DC. pp. 231-241. I Table of Contents Abstract ........................................................................................IV Z usammenfassung ........................................................................ VI 1 ll'J'fliOI>UCTIOl'l........................................................ 1 1.1 Clean Clothing ......................................................................... 1 1.2 White Clothing ........................................................................ 3 1.3 Environmental Aspects of Laundry Detergents ............................ 6 1.4 Environmental Aspects of Sewage Sludge ................................... 8 1.5 Scope of this Work ...................................................................9 1.6 Outlook ..... "'························-··················································IO 1.7 Literature Cited ..................................................................... 11 2 ANALYTICAL METHODS ......................................... 15 2.1 Introduction .......................................................................... 17 2.2 Experimental Section .............................................................. 20 2.2.1 Reagents ......................................................................... 20 2.2.2 Standard Solutions ........................................................... 20 2.2.3 Samples .......................................................................... 21 2.2.4 Enrichment from Aqueous Samples ................................... 21 2.2.5 Liquid Extraction of Solid Samples .................................... 22 2.2.6 High-Performance Liquid Chromatography ........................ 22 2.2. 7 Quality Assurance ............................................................ 23 2.3 Results and Discussion ............................................................ 25 2.3.1 Separation ....................................................................... 25 2.3.2 Detection and Quantitation ................................................ 26 2.3 .3 Applications .................................................................... 30 2.4 Conclusions ........................................................................... 32 2.5 Literature Cited ..................................................................... 33 II 3 RIVER MONITORING ............................................... 35 3.1 Introduction .......................................................................... 37 3.2 Sampling Locations and Analytical Methods .............................. 39 3 .3 Results and Discussion ............................................................ 42 3.3.1 FWA Concentrations and Loads in Swiss Rivers ................. .42 3.3.2 FWA Mass Balance for Switzerland ................................... 48 3.3.3 FWAs as Molecular Markers for Production Wastewater ..... 50 3.3.4 Elimination of FWAs in Lakes .......................................... 52 3.4 Conclusions ........................................................................... 53 3.5 Literature Cited ..................................................................... 54 4 LAKE MOI>EL ......................................................... 57 4.1 Introduction .......................................................................... 59 4.2 Experimental Section .............................................................. 61 4.2.1 Greifensee, the Study Site ................................................. 61 4.2.2 Sampling and Chemical Analyses ....................................... 63 4.2.3 Chemicals ....................................................................... 64 4.2.4 Mathematical Simulation Model. ........................................ 64 4.3 Results and Discussion ............................................................ 65 4.3.1 Evaluation of FWA Inputs from STP Effluents ................... 65 4.3.2 Evaluation of Sorption/Sedimentation ................................ 67 4.3.3 Evaluation of Photocheinical Degradation .......................... 68 4.3. 4 Seasonal V aria ti on of Measured FWAs in Greifensee ........... 69 4.3.5 Computer Simulation, Model Validation ............................. 73 4.3.6 Computer Simulation, Transport by Sedimenting Particles ... 76 4.3.7 Computer Simulation, Photodegradation in Greifensee ........ 77 4.3.8 Limits of the Model ............................................................. 78 4.4 Literature Cited ..................................................................... 78 S LAKE SEDIMENT .................................................... 81 5.1 Introduction .......................................................................... 83 5.2 Study Site .............................................................................. 86 5 .3 Experimental ......................................................................... 88 5.3.1 Samples .......................................................................... 88 III 5 .3 .2 Reagents ......................................................................... 88 5.3.3 Liquid Extraction ............................................................ 89 5 .3 .4 High-Performance Liquid Chromatography ........................ 89 5 .4 Results and Discussion ............................................................ 92 5. 4.1 FWAs as Molecular Markers for Domestic Waste Water ...... 92 5 .4.2 Sedimentary Archive and Emission History of FWAs .......... 94 5.5 Conclusions ........................................................................... 95 5 .6 Literature Cited ..................................................................... 96 Appendix ....................................................................................... 99 IV Abstract Detergents for laundry washing are among the classic chemicals of ci- vilization polluting surface waters. Their relevance for the aquatic environment is on the one hand due to their application with water and subsequent discharge to sewers. On the other hand the amounts used are large: A total of 70,000 tons, consisting of about 20 detergent com- ponents, were consumed in Switzerland in the year 1995. In order to evaluate the risk of laundry detergents, it is important to know the fate and behavior of every individual component in the aquatic environment. One component was chosen for this study whose behavior in the aquatic environment is known only to a limited extent: the fluorescent whitening agents (FWAs). The three most important detergent-FWAs were investigated: DAS 1 (a diw:nino£tilbene), DSBP (a di£tyrylhinhenyl) and BLS (a bleach~table compound). An analytical method for the FW As was developed as a prere- quisite for the investigation of the aquatic environment. This method con- sists of the extraction of FW As from both solid and aqueous samples with subsequent separation with reversed-phase HPLC. Limits of quantitation were 1 - 11 µg kg·1 and 0.2 - 3 ng L- 1 for dry sediment and aqueous samples, respectively. Recoveries ranged from 87 to 100 % with an analytical precision of 1 to 12 % (relative standard deviation). The method was then used to investigate the behavior and fate of detergent-derived FWAs in natural waters. The investigation was divided into three parts: 1. Occurrence and substance fluxes, 2. Transformation processes, 3. Enrich- ment in the benthos of a lake. The occurrence and the substance fluxes of the FWAs were investigated in the first part of this study. For this purpose, a monitoring program was conducted in Swiss rivers during one year. Concentrations of both DAS 1 and DSBP measured in the rivers were mostly between 10 1 1 and 120 ng L- , with maximum values of up to 1 µg L- • On the basis of these measurements, a mass balance was developed, indicating that 13 % of the FW As being used are discharged to surface waters. With an annual 1 consumption of 60 t in 1995 this corresponds to 8 t y· • The transformation processes of the FW As in Greifensee, a small lake in Switzerland, were investigated in the

Load more