Refractory Organic Substancesin the Environment
Edited byF. H. Frimmel, G. Abbt-Braun, K. G. Heumann, B. Hock,H.-D. Lüdemann and M. Spiteller
Innodata9783527614448.jpg
Refractory Organic Substancesin the Environment
Edited by
F. H. Frimmel, G. Abbt-Braun,
K. G. Heumann, B. Hock,
H.-D. Lüdemann and M. Spiteller
Related JournalActa hydrochimicaet hydrobiologica
ISSN 0323-4320www.wiley-vch.de/home/actahydro
Refractory Organic Substancesin the Environment
Edited byF. H. Frimmel, G. Abbt-Braun, K. G. Heumann, B. Hock,H.-D. Lüdemann and M. Spiteller
Editors
Prof. Dr. Fritz H. FrimmelEngler-Bunte-InstitutBereich WasserchemieUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Dr. Gudrun Abbt-BraunEngler-Bunte-InstitutBereich WasserchemieUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Prof. Dr. Klaus G. HeumannInstitut für Anorganischeund Analytische ChemieJohannes-Gutenberg-Universität MainzDuesbergweg 10�14D-55099 MainzGermany
Prof. Dr. Berthold HockLehrstuhl für BotanikTechnische Universität MünchenAlte Akademie 12D-85350 FreisingGermany
Prof. Dr. Hans-Dietrich LüdemannInstitut für Biophysikund Physikalische BiochemieUniversität RegensburgD-93040 RegensburgGermany
Prof. Dr. Michael SpitellerInstitut für UmweltforschungUniversität DortmundD-44221 DortmundGermany
This book was carefully produced. Never-theless, editors, authors and publisher donot warrant the information containedtherein to be free of errors. Readers areadvised to keep in mind that statements,data, illustrations, procedural details orother items may inadvertently be inaccurate.
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� Wiley-VCH Verlag GmbH,69469 Weinheim (Federal Republic ofGermany). 2002
All rights reserved (including those oftranslation in other languages). No part ofthis book may be reproduced in any form –by photoprinting, microfilm, or any othermeans – nor transmitted or translatedinto machine language without writtenpermission from the publishers. Registerednames, trademarks, etc. used in this book,even when not specifically marked as such,are not to be considered unprotected by law.
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ISBN 3-527-30173-9
Dedication
This volume is dedicated to the memory of Dr. Ulrich de Haar, former Secretary ofthe Senate Commission for Water Research of the Deutsche Forschungsge-meinschaft (DFG), whose brilliance, enthusiasm and creativity permeated thiswork. Dr. de Haar’s extensive geochemical background and experience in water re-search was instrumental in bridging the often difficult gap between research ideasand funding mechanisms. We are also indebted to him for the project title ROSIG(Refraktäre Organische Substanzen in Gewässern).
V
Contents
VII
Preface XIX
List of Authors XXI
List of Abbreviations XXXI
1 Setting the Scene 11.1 The Relevance of Reference Materials � Isolation and General
Characterization 11.1.1 Introduction 11.1.2 Concept of Standard and Reference Material 31.1.3 Reference Materials in the ROSIG Priority Program 41.1.4 Experimental Details 51.1.4.1 Origin of the Samples 51.1.4.2 Isolation 71.1.4.3 Analytical Methods 101.1.5 Discussion 111.1.5.1 Mass Balance of the Isolates 131.1.5.2 Spectroscopic Characterization in the UV and Visible Range 161.1.5.3 Elemental Analysis 191.1.5.4 Proton and Complexation Capacities 251.1.5.5 Size-exclusion Chromatography 281.1.6 Conclusions 33
References 36Additional References for ROS Literature 38
1.2 Element Determination and its Quality Control in Fractions of RefractoryOrganic Substances and the Corresponding Original Water Samples 39
1.2.1 Introduction 391.2.2 Description of Analytical Methods 411.2.2.1 Sample Treatment 411.2.2.2 Flame and Graphite Atomic Absorption Spectrometry
(FAAS, GF-AAS) 421.2.2.3 Inductively Coupled Plasma Mass Spectrometry (ICP-MS) 42
VIII Contents
1.2.2.4 Inductively Coupled Plasma Isotope Dilution Mass Spectrometry(ICP-IDMS) 42
1.2.2.5 Instrumental Neutron Activation Analysis (INAA) 431.2.2.6 Total Reflection X-Ray Fluorescence Spectrometry (TXRF) 441.2.3 Results of the Interlaboratory Study 451.2.3.1 Element Concentrations in ROS Fractions and their Original
Samples 451.2.3.2 Relative Enrichment Factors of Elements in Separated FA and
HA Fractions 491.2.3.3 Quality Control of Analytical Data 49
References 53
2 Structural Investigations 552.1 Heavy Metal and Halogen Interactions with Fractions of Refractory
Organic Substances Separated by Size-exclusion Chromatography 552.1.1 Introduction 552.1.2 SEC/ICP-MS System and the Isotope Dilution Technique 562.1.3 Determination of Heavy Metal�ROS Complexes in Fractions Separated
by SEC 592.1.4 Correlation of Metal�ROS Complexes with other Analytical Data 622.1.5 Kinetically Stable Cr(III) and Co(III) Complexes of ROS 642.1.6 Determination of Halogen�ROS Compounds in Fractions separated
by SEC 682.1.7 Conclusions 71
References 72
2.2 Characterization of Refractory Organic Substances and their MetalSpecies by Combined Analytical Procedures 73
2.2.1 Introduction 732.2.2 Size Distribution and Stability of ROS�Metal Species Assessed by
Ultrafiltration, EDTA Exchange, and Atomic Spectrometry 742.2.3 On-site Characterization of Aquatic Refractory Organic Substances and
their Metal Species by Mobile Fractionation and ExchangeTechniques 79
2.2.4 Conclusions 86References 87
2.3 Application of Nuclear Magnetic Resonance Spectroscopy to StructuralInvestigations of Refractory Organic Substances � Principles andDefinitions 89
2.3.1 Potential of Nuclear Magnetic Resonance (NMR) Spectroscopy for ROSStructure Elucidation 89
2.3.2 Quantification of Solution-state and Solid-state NMR Spectra of ROS 912.3.3 Assignment of ROS NMR Signals 92
References 94
2.4 Structural Characterization of Refractory Organic Substances bySolid-state High-resolution 13C and 15N Nuclear Magnetic Resonance 96
2.4.1 Introduction 962.4.2 Pulse Sequences Used 972.4.2.1 Cross Polarization Magic Angle Spinning (CPMAS) 972.4.2.2 Magic Angle Spinning (MAS) or Bloch-decay Spectra 972.4.2.3 Dipolar Dephasing Techniques (DD Techniques) 972.4.3 Lake Hohloh Samples 982.4.3.1 13C Solid-state Spectra 982.4.3.2 Proton Solution Spectra 1032.4.3.3 15N CPMAS Spectra 1042.4.4 Comparison of Samples from Different Locations 1072.4.4.1 13C Solid-state Spectra 1072.4.4.2 15N CPMAS Spectra 1102.4.5 Conclusions 1122.4.5.1 Methods 1122.4.5.2 Structural Results 113
References 114
2.5 Quantification of Substructures of Refractory Organic Substances byMeans of Nuclear Magnetic Resonance 115
2.5.1 Introduction 1152.5.2 Experimental Details 1162.5.2.1 Nuclear Magnetic Resonance 1162.5.2.2 Multistage Ultrafiltration 1162.5.3 Results from Solution-state NMR investigations 1172.5.3.1 General Considerations 1172.5.3.2 Aliphatic Structural Moieties 1182.3.3.3 Aromatic Structural Moieties 1182.5.4 Combination of Multistage Ultrafiltration and Two-dimensional
HMQC NMR 1252.5.5 Conclusions 127
References 128
2.6 Nuclear Magnetic Resonance Spectroscopy Investigations of SilylatedRefractory Organic Substances 129
2.6.1 Introduction 1292.6.1.1 Functional Group Analysis in Refractory Organic Substances 1292.6.1.2 Silylation of Refractory Organic Substances 1302.6.2 Materials and Methods 1312.6.3 Two-dimensional NMR Spectroscopy of Silylated Natural Organic
Matter 1322.6.3.1 Comparative Analysis of 2D NMR Spectra; Visualization of Conformity
and Variation by Calculation of Minimum and Difference Spectra 136
IXContents
2.6.4 NMR Functional Group Analysis of FA and HA Fractions Isolated fromSamples of Different Origin 137
2.6.4.1 Comparison of BS1 FA, HO10 FA, FG1 FA, HO13 FAand SUW FA 137
2.6.4.2 Comparison of BS1 HA, HO13 HA, and SUW HA 1402.6.4.3 Comparison of Results from NMR Functional Group Analysis with Data
Obtained from Complementary Methods 1412.6.5 Conclusions 143
References 144
2.7 Isotopic Evidence for the Origin and Formation of Refractory OrganicSubstances 146
2.7.1 Variations of Stable Isotope Abundances in the Course of the Synthesisand Diagenesis of Biomass 146
2.7.2 Bulk Isotope Analysis 1492.7.3 Pyrolysis-Gas Chromatography/Mass Spectrometry-Isotope-ratio
Mass Spectrometry (Py-GC/MS-IRMS) 1502.7.4 Bulk Isotopic Analyses of the Reference Samples 1512.7.4.1 Differences Between the Isotope Content of the Reference Samples 1512.7.5 Formation of Refractory Organic Substances in a Peat Profile of the
Hohlohsee 1542.7.5.1 Bulk Isotope Analyses on Hohlohsee Samples 1552.7.5.2 �13C Values of Pyrolysis Products of Sphagnum Peat and DOM from
Bog Water 156References 160
2.8 Analytical Pyrolysis of Humic Substances and Dissolved Organic Matterin Water 163
2.8.1 Introduction 1632.8.2 Methods 1642.8.3 Characterization and Differentiation of Structural Properties 1652.8.4 Pyrolysis-Field Ionization Mass Spectrometry 1722.8.5 Structural Variations as a Result of Sampling Season and Year 1752.8.6 Quality Control and Changes During Sample Storage 1762.8.7 Correlations between 13C NMR and Py-FIMS 1792.8.8 Developments of Quantitative GC/MS 1802.8.8.1 Determination of Hexose Subunits of Cellulose by Py-GC/MS 1802.8.8.2 Determination of Solvent-extracted Fatty Acids by GC/MS 1832.8.9 Conclusions 184
References 186
2.9 Characterization of Refractory Organic Substances by HPLC/MS 1882.9.1 Introduction 1882.9.2 Experimental Details 1892.9.2.1 Mass Spectrometry 189
X Contents
XIContents
2.9.2.2 Size-exclusion Chromatography (SEC) 1912.9.3 Results and Discussion 1912.9.3.1 Mass Spectra of Refractory Organic Substances 1912.9.3.2 Size-exclusion Chromatography of Refractory Organic Substances 197
References 199
2.10 UV-Visible Spectroscopy and the Potential of Fluorescent Probes 2002.10.1 UV-Visible Absorption Spectroscopy 2002.10.2 Colorimetric Analysis 2052.10.3 Fluorescence of Refractory Organic Substances 2082.10.4 Aging of Refractory Organic Substances 2092.10.5 Complexing of Heavy Metals 211
References 214
2.11 Stationary and Time-resolved Fluorescence for Refractory OrganicSubstances Characterization 215
2.11.1 Introduction 2152.11.2 Experimental Details 2172.11.3 Results and Discussion 2182.11.3.1 Steady-state Fluorescence of Humic Substances 2182.11.3.2 Time-resolved Fluorescence of Humic Substances 2212.11.3.3 Fluorescence of Chemically Altered Humic Substances 2252.11.4 Conclusions 227
References 229
2.12 Structural Characterization of Refractory Organic Substancesby Pyrolysis-GC/FTIR 232
2.12.1 Introduction 2322.12.2 Experimental Details 2332.12.2.1 Sample Preparation 2332.12.2.2 Curie-point Pyrolysis 2332.12.2.3 Flash Pyrolysis 2342.12.2.4 GC/FTIR Spectroscopy 2342.12.3 Results and Discussion 236
References 238
2.13 X-ray Microscopy Studies of Refractory Organic Substances 2392.13.1 Introduction 2392.13.2 X-ray Microscopy 2402.13.3 Results 2432.13.3.1 Refractory Organic Substances in Soils 2432.13.3.2 Flocculation of Refractory Organic Substances by Cations 2442.13.3.3 Spectromicroscopy of Refractory Organic Substances 2442.13.4 Conclusions 246
References 247
2.14 Fractionation of Refractory Organic Substances by Electrophoresis 2492.14.1 Introduction 2492.14.2 Experimental Details 2502.14.3 Results and Discussion 2512.14.4 pH-dependence 2542.14.5 Electrophoresis with Organic Modifiers 2552.14.6 Micellar Electrokinetic Chromatography 2552.14.7 Electrophoresis in Sieving Media 2562.14.8 Isoelectric Focusing 2572.14.9 Characterization of Degradation Products of Refractory Organic
Substances 2582.14.10 Hydrothermolysis 2602.14.11 Pyrolysis 2612.14.12 Conclusions 262
References 263
2.15 Occurrence of Amino Acids, Carbohydrates, and Low-molecular-weightOrganic Acids in Refractory Organic Substances 264
2.15.1 Introduction 2652.15.2 Experimental Details 2672.15.2.1 Samples 2672.15.2.2 Determination of Amino Acids 2682.15.2.3 Determination of Carbohydrates 2682.15.2.4 Determination of Low-molecular-weight Organic Acids 2692.15.3 Results and Discussion 2702.15.3.1 Acid-hydrolyzable Amino Acids and Carbohydrates 2702.15.3.2 Enzymatically Hydrolyzable Amino Acids and Carbohydrates 2772.15.3.3 Alkaline-hydrolyzable Low-molecular-weight Organic Acids 2782.15.4 Conclusions 279
References 280
2.16 Serological Characterization of Refractory Organic Substancesby Serotyping 282
2.16.1 Introduction 2822.16.2 Experimental Details 2832.16.2.1 Material 2832.16.2.2 Antibody Production 2832.16.2.3 Precipitation Test 2842.16.2.4 Dot Blot Test 2842.16.2.5 Enzyme Immunoassay 2842.16.2.6 Fractionation of Refractory Organic Substances 2862.16.2.7 Serotyping 2872.16.3 Results 2872.16.3.1 Immunochemical Reactions of Refractory Organic Substances 2872.16.3.2 Fractionation of Refractory Organic Substances 293
XII Contents
2.16.3.3 Serotyping 2942.16.4 Discussion 297
References 301
2.17 Chemical and Spectroscopic Data of the Reference Samples �Comparison and Evaluation 302
2.17.1 Evaluation of the Isolation Procedure by Combining 13C NMR Spectrawith DOC Concentration Results 302
2.17.2 Comparison of NMR Results with Data from Other Methods ofStructural Characterization 304
2.17.2.1 NMR and UV Spectroscopy 3042.17.2.2 NMR and Analysis of the Content of Carbohydrates and Amino
Acids 3052.17.3 Complementary Results from Data Comparisons 3062.17.3.1 Carboxylic Groups Bound in Esters, Amides and Free Carboxylic Acid
Groups 3062.17.3.2 Phenolic Groups 3072.17.3.3 Exchangeable Hydrogens � Comparison of 1H and 13C NMR Data 3082.17.4 Conclusions 309
3 Biochemical and Biological Characterization 3113.1 Formation, Utilization, and Transformation of Some Refractory Organic
Substances by Aquatic Microorganisms 3113.1.1 Introduction 3113.1.2 Experimental Details 3123.1.2.1 Materials and Methods 3123.1.3 Results and Discussion 313
References 320
3.2 Effect of Microorganisms on the Formation and Transformationof Iodine Species of Refractory Organic Substances 321
3.2.1 Introduction 3213.2.2 Formation of Iodine�ROS Species from Inorganic Iodine 3223.2.3 Microbiological Influence on the Iodine�ROS Formation 3243.2.4 Transformation of Iodine�ROS Species by Aging 3263.2.5 Conclusion 328
References 329
3.3 The Influence of Refractory Organic Substances on BacterialColonization and Diversity Patterns 330
3.3.1 Introduction 3303.3.2 Materials and Methods 3313.3.2.1 Experimental Design 3313.3.2.2 Physicochemical Investigations 332
XIIIContents
XIV Contents
3.3.2.3 Microbiological Monitoring 3323.3.2.4 Molecular Methods 3333.3.2.5 Cluster Analysis 3333.3.2.6 Scanning Electron Microscopy 3343.3.3 Results 3343.3.3.1 Physicochemical Investigations 3343.3.3.2 Microbiological Monitoring 3363.3.3.3 Molecular Methods 3393.3.3.4 Cluster Analysis 3393.3.3.5 Scanning Electron Microscopy 3413.3.4 Discussion 342
References 344
3.4 Influence of Refractory Organic Substances on Enzyme Activity in-vivoand DNA Damage of Aquatic Microorganisms 346
3.4.1 Introduction 3463.4.2 Methods 3483.4.2.1 Detection and Evaluation of Microbial Enzyme Activity in Batch
Experiments 3483.4.2.2 Flow Injection Analysis of Microbial Enzyme Activity (FAME) 3483.4.2.3 Detection of Genotoxicity by Use of the umu Test 3493.4.2.4 Detection of Genotoxicity by Use of the Comet Assay 3503.4.2.5 Origin of Water Samples and Microorganisms 3503.4.2.6 Refractory Organic Substances 3503.4.2.7 Spiking of Refractory Organic Substances and Pollutants 3513.4.2.8 Influence of pH and Conductivity on Refractory Organic Substances 3513.4.3 Results 3513.4.3.1 Effects of Different Concentrations of Refractory Organic Substances
on Enzyme Activities in Batch Experiments 3513.4.3.2 Interaction of Refractory Organic Substances with Pollutants in Batch
Experiments 3533.4.3.3 Application of the FAME System Looking for Effects of Different
Refractory Organic Substances on Enzyme Activity 3543.4.3.4 Addition of HgCl2 and its Influence on Peroxidase Activity Using the
FAME System 3543.4.3.5 Detection of Genotoxic Effects by Use of the umu Test 3563.4.3.6 Detection of Genotoxic Effects by Use of the Comet Assay 3573.4.4 Discussion 3583.4.4.1 ROS as Nutrients or Toxicants or as a Trap for Nutrients and
Toxicants 3583.4.4.2 Interactions of ROS with Added Toxicants 3593.4.4.3 Do pH and Electrical Conductivity Influence the Effects of ROS and
Toxicants? 3593.4.4.4 Are ROS Genotoxic or Can They Mask Genotoxins? 359
References 360
3.5 Effects of Dissolved Organic Matter on the Bioconcentration of OrganicContaminants and on Reproduction in Aquatic Invertebrates 361
3.5.1 General Introduction 3613.5.2 Influence of Dissolved Organic Matter on the Bioconcentration of
Hydrophobic Organic Contaminants � Quantitative Aspects 3623.5.2.1 Introduction 3623.5.2.2 Influence of the Concentration of Dissolved Organic Matter 3633.5.2.3 Influence of the Origin of Dissolved Organic Matter 3653.5.2.4 Influence of the Type of Contaminant 3693.5.2.5 A General Model for Describing the Effect of Dissolved Organic Matter
on the Bioconcentration of Hydrophobic Organic Contaminants 3703.5.3 Effect of Refractory Organic Substances on the Reproduction of a
Nematode (Caenorhabditis elegans) 3723.5.3.1 Introduction 3723.5.3.2 Experimental Details 3733.5.3.3 Results 3733.5.3.4 Discussion 3763.5.3.5 Ecological Implications 377
References 378
4 Molecular Interactions 3834.1 Sorption of Dissolved Organic Matter on Soil Particles and its
Dependence on their Surface-charge Properties 3834.1.1 Introduction 3834.1.2 Materials and Methods 3844.1.2.1 Samples 3844.1.2.2 Methods 3854.1.3 Results and Discussion 3864.1.3.1 Charge of Dissolved Organic Matter 3864.1.3.2 Charge of the Soil Samples 3874.1.3.3 Sorption of Dissolved Organic Matter 3884.1.4 Conclusions 392
References 393
4.2 Dissolved Organic Carbon in Seepage Water �Production and Transformation During Soil Passage 394
4.2.1 Introduction 3954.2.2 Materials and Methods 3964.2.2.1 Experiment (1) � Laboratory Experiments with Forest Soils � DOC
Production as a Function of Litter Quality and Ash Addition 3964.2.2.2 Experiment (2) � DOC Production in Agricultural Soils � Continuous
Rye and Silage Maize Fields 3984.2.2.3 Experiment (3) � Field and Laboratory Studies with Forest Soils �
Transformation of DOC in Seepage Water During Passage ThroughSoil 399
XVContents
4.2.3 Results and Discussion 4004.2.3.1 Experiment (1) � Laboratory Experiments with Forest Soils � DOC
Production as a Function of Litter Quality and Ash Addition 4004.2.3.2 Experiment (2) � DOC Production in Agricultural Soils – Continuous
Rye and Silage Maize Fields 4034.2.3.3 Experiment (3) � Field and Laboratory Studies with Forest Soils �
Transformation of DOC in Seepage During Soil Passage 406References 409
4.3 Refractory Organic Substances in Aggregated Forest Soils � Retentionversus Translocation 411
4.3.1 Introduction 4114.3.2 Materials and Methods 4134.3.2.1 Sorption Experiments with Homogenized Soil Samples and Intact
Soil Cores 4134.3.2.2 Field Experiment on Dissolved Organic Matter in Slightly Developed,
Shallow Forest Soils 4164.3.3 Sorption of Dissolved Organic Matter in Aggregated Forest Soils 4174.3.3.1 Sorption of Dissolved Organic Matter to Homogenized Soil Samples
and Intact Cores 4174.3.3.2 Ionic Strength and Competitive Inorganic Anions Effects on the
Sorption of Dissolved Organic Matter 4214.3.3.3 Competition of Dissolved Organic Matter Constituents During
Sorption 4224.3.3.4 Dissolved Organic Matter Adsorption to Surface and Interior Material
of Soil Aggregates 4234.3.3.5 Sorption of Dissolved Organic Matter in Aggregated Soils �
Synopsis 4244.3.4 Dissolved Organic Matter in Slightly Developed,
Shallow Forest Soils 4244.3.4.1 Release of Dissolved Organic Matter from the Forest Floor 4244.3.4.2 Dissolved Organic Matter in the Mineral Soil 4264.3.4.3 Fluxes of Organic Matter and Nutrients � Rainstorm Events 4284.3.4.4 Chemical Characteristics of Leached Organic Matter 4294.3.4.5 Dissolved Organic Matter in Slightly Developed Shallow Soils �
Synopsis 430References 432
4.4 Refractory Organic Substances Derived from Organic Amendmentsin Soil � Formation, Translocation, and Interaction withXenobiotics 435
4.4.1 Introduction 4354.4.2 Material and Methods 4364.4.2.1 Crop Residues 4364.4.2.2 Xenobiotics 436
XVI Contents
4.4.2.3 Soil-column Experiments 4374.4.2.4 Sampling and Analysis 4384.4.2.5 Extraction of the Soil Samples 4394.4.2.6 Calorimetric Studies of the Interaction of Refractory Organic Substances
and Methabenzthiazuron 4404.4.2.7 Biosurfactant Properties of Refractory Organic Substances from Crop
Residues 4404.4.3 Results and Discussion 440
References 445
4.5 Analysis of the Binding of Amitrole and Anilazine to Aquatic andTerrestrial Refractory Organic Substances 446
4.5.1 Introduction 4464.5.2 Materials and Methods 4484.5.2.1 Chemicals 4484.5.2.2 Synthesis 4484.5.2.3 Refractory Organic Substances and Dissolved Organic Matter 4504.5.2.4 Chromatographic Methods 4514.5.2.5 NMR Spectroscopy 4524.5.2.6 Selective Reaction Monitoring (SRM) of Bound Residues 4524.5.2.7 Formation and Clean-up of Dissolved Organic Matter�Amitrole
Complexes 4524.5.2.8 Formation of Bound Residues 4544.5.2.9 Interaction of Anilazine with Dissolved Organic Matter 4544.5.2.10 Determination of kf Values According to the Freundlich Equation for
Amitrole and Dissolved Organic Matter 4554.5.2.11 Incubation of Amitrole with Five Different Soils 4554.5.2.12 Water � Sediment Systems with Anilazine and Dihydroxyanilazine
456
4.5.2.13 Water � Sediment Systems with Amitrole 4574.5.2.14 Quantification of Mineralization 4574.5.2.15 Release of Amitrole from DOM�Amitrole Complexes 4574.5.2.16 Extraction Methods for Purified Bound Residues 4584.5.2.17 Extraction of Soil Samples 4584.5.2.18 Silylation of Soil Samples 4584.5.2.19 Matrix Effects 4584.5.2.20 Biotests 4594.5.3 Results and Discussion 4594.5.3.1 Pesticides in Soil 4594.5.3.2 Pesticides in Water � Sediment Systems 4604.5.3.3 Pesticides and Dissolved Organic Matter 462
References 472
XVIIContents
4.6 Sorption and Chemical Reactions of Polycyclic Aromatic Hydrocarbonswith Dissolved Refractory Organic Substances and Related ModelPolymers 475
4.6.1 Introduction to the Problems 4754.6.2 The Solid-phase Microextraction Technique 4774.6.3 Kinetics of the Interaction of Dissolved Organic Matter and PAH 4844.6.4 Reversibility of Sorptive Interactions in the Aqueous Domain 4894.6.5 Relationships between Structural Properties of HOC and their Sorption
Affinity 4914.6.6 The Modified Flory-Huggins Concept 4924.6.7 Relationships between Properties of Dissolved Organic Matter and their
Sorption Potential 4974.6.8 Poly(Acrylic Acid) Esters as Surrogates of Dissolved Organic Matter
for Sorption Studies 4994.6.9 Long-term Interactions between Dissolved Organic Matter and PAH
under Strictly Abiotic Conditions 5064.6.10 Summary 510
References 512
4.7 Investigation of the Interactions between Polycyclic AromaticCompounds and Refractory Organic Substances with Stationary andTime-resolved Fluorescence and Absorption Spectroscopy 516
4.7.1 Introduction 5164.7.2 Experimental Details 5184.7.2.1 Samples 5184.7.2.2 UV-Visible and Fluorescence Spectroscopy 5194.7.3 Results and Discussion 5214.7.3.1 Absorption and Fluorescence Spectroscopic Characterization of
Refractory Organic Substances 5214.7.3.2 Interactions between Refractory Organic Substances and Pyrene in
Electronic Singlet States 5244.7.3.3 Interactions between Refractory Organic Substances and Polynuclear
Aromatic Components in Electronic Triplet States 5274.7.3.4 Strong Interactions of Refractory Organic Substances and Polycyclic
Aromatic Compounds � Triplet Quenching of Methylene Blue 5294.7.4 Conclusions 531
References 532
Index 535
Author index 545
XVIII Contents
Preface
The research described herein is the result of six years of cross-disciplinary scien-tific study of the properties of a uniform set of samples of refractory organic sub-stances (ROS). Sources sampled included a brown water lake, soil seepage water,ground water, a secondary effluent from a waste water treatment plant, and awaste water lake from a brown coal processing plant. Each source was sampled sea-sonally, and the ROS from each sample were isolated by use of a common tech-nique before being made available to the cross-disciplinary research teams.Thus, this work comprises a unique data base in addition to providing new insightsinto the structures, transformations, and interactions of ROS in the environment.
Most of the results were obtained in the course of a priority research programfunded by the Deutsche Forschungsgemeinschaft (DFG), to whom we are deeplyindebted. Two members of the DFG were particularly influential in obtaining sup-port for this program, Dr. Ulrich de Haar (see Dedication) and Professor Fritz Führ,a member of the Senate of the DFG, both of whom effectively advocated support ofthis research. Such advocacy was vital to this research, because economic condi-tions at the time placed constraints upon funding and competition among manydisciplines was intense.
Cross-disciplinary interest and support for this program was extraordinaryamong German scientists and without the generous and thoughtful time commit-ments of many individuals this work would not have been possible. Notable amongthese are the project referees who assisted in numerous proposal reviews andoffered valuable suggestions at annual workshops. This group was chaired withgentle authority by J. Schwoerbel, and included K.-H. Ballschmiter, U. Förstner,K. Haider, G. Matthess, K. Cammann, H. J. Knackmuss, J. Reichert, A. Schäfer,and C. J. Soeder. The principal contributors to the work of this project were, ofcourse, the individual scientists who wrote the proposals and wrote the chapterscontained herein.
Steady contributions were made by Axel Heidt and Dr. Gudrun Abbt-Braun inrunning the sampling campaigns and organizing two international symposia. Inaddition, Dr. Abbt-Braun handled the day-to-day tasks of project managementwith extraordinary effectiveness and sensitivity. Dagmar Schirner supervised the fi-nancial management of the project, and Dr. Claudia Boukis, Markus Delay, SabrinaLehringer, and Carola Neidhardt assisted in the organization of symposia and in
XIX
the onerous tasks associated with preparation of this book. I am grateful to otherpersonnel of the DFG for skillful administration of this project, notably Dr. UteWeber, Dr. Susanne Faulhaber, and Frau Michels. Special thanks are due to Dr.Pauly of Wiley-VCH, for expertise with this publication and for understandingthe tight schedules of research scientists, and to Professor Russ Christman foreditorial assistance.
As a part of our project, two international symposia were held at the Universityof Karlsruhe under the name of ROSE (Refractory Organic Substances in the En-vironment). In these settings, project scientists were able to discuss their findingswith each other and with invited experts from around the world. Two books ofextended abstracts of symposia presentations are available. In addition, a selectionof peer-reviewed papers appeared in two special issues of Acta hydrochimica ethydrobiologica.
On behalf of the project editorial group, I am happy to present this unique col-lection of scientific reports which represents the most important findings of ourproject. It is my hope that this book will find many interested readers and thatit will provide an encouraging platform for young scientists who wish to devotetheir careers to addressing the many fascinating and unanswered questionsabout the properties and roles of refractory organic substances in the environment.
Karlsruhe, Fritz FrimmelJanuary 2002
XX Preface
List of Authors
Dr. Gudrun Abbt-BraunEngler-Bunte-InstitutDivision of Water ChemistryUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermanyTel.: �49-(0)721-6084309Fax: �49-(0)721-6087051e-mail: [email protected]
Professor Fritz BeeseInstitute of Soil Scienceand Forest NutritionUniversität GöttingenBüsgenweg 2D-37077 GöttingenGermanyTel.: �49-(0)551-399765Fax: �49-(0)551-393310e-mail: [email protected]
Dipl.-Chem. Kai BehrensInstitut für Anorganischeund Angewandte ChemieUniversität HamburgMartin-Luther-King-Platz 6D-20146 HamburgGermany
Dipl.-Chem. Stefan BrandtIm Kleinfeld 9D-67227 Frankenthal
Dipl.-Chem. Thomas BrinkmannEngler-Bunte-InstitutDivision of Water ChemistryUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Professor Joachim BuddrusInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11Postfach 10 13 52D-44139 DortmundGermanyTel.: �49-(0)231-1392214Fax: �49-(0)231-1392120e-mail: [email protected]
XXI
XXII List of Authors
Dr. Peter BurbaInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11Postfach 10 13 52D-44139 DortmundGermanyTel.: �49-(0)231-1392181Fax: �49-(0)231-1392120e-mail: [email protected]
Dr. B. Kent BurnisonCanada Center of Inland Waters867 Lakeshore RoadP. O. Box 5050Burlington Ontario L7R 4A6Canada
Dr. Frank ButtchereitInstitut für BodenkundeUniversität HannoverHerrenhäuser Str. 2D-30419 HannoverGermany
Dr. Harald ClausUmweltbundesamtDienstgebäude LangenPaul-Ehrlich-Str. 29D-63225 LangenGermany
Dr. Andrea DankwardtLehrstuhl für BotanikTechnische Universität MünchenAlte Akademie 12D-85350 FreisingGermany
Dr. Antony N. DaviesInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11D-44139 DortmundGermanyTel.: �49-(0)231-1392218Fax: �49-(0)231-1392120e-mail: [email protected]
Dr. Ralf DunkelStraße der Jugend 6AD-06179 LangenbogenGermany
Dipl.-Biol. Monika ErbesMeixlerstraße 4D-55120 MainzGermany
Professor Zdenek FilipUmweltbundesamtInstitut für Wasser-, Boden-und LufthygieneDienstgebäude LangenPaul-Ehrlich-Str. 29D-63225 LangenGermanyTel.: �49-(0)6103-704160Fax: �49-(0)6103-704147e-mail: [email protected]
Professor Walter R. FischerInstitut für BodenkundeUniversität HannoverHerrenhäuser Str. 2D-30419 HannoverGermanyTel.: �49-(0)511-7622623Fax: �49-(0)511-7625559e-mail: [email protected]
XXIIIList of Authors
Dr. Heiner FlessaInstitute of Soil Scienceand Forest NutritionUniversität GöttingenBüsgenweg 2D-37077 GöttingenGermany
Dr. Dieter FreitagGSF-Forschungszentrum für Umweltund GesundheitInstitut für Ökologische ChemieSchulstraße 10D-85356 Freising/AttachingGermany
Professor Fritz H. FrimmelEngler-Bunte-InstitutDivision of Water ChemistryUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermanyTel.: �49-(0)721-6082580Fax: �49-(0)721-699154e-mail: [email protected]
Professor Fritz FührForschungszentrum Jülich GmbHInstitut für RadioagronomiePostfach 19 13D-52425 JülichGermany
Dr. Anett GeorgiUFZ � Center for EnvironmentalResearch Leipzig-HallePermoserstr. 15D-04318 LeipzigGermany
Dr. Gerd GleixnerMax-Planck-Institut für BiogeochemiePostfach 100 164D-07701 JenaGermanyTel.: �49-(0)3641-643707Fax: �49-(0)3641-643710e-mail: [email protected]
Dr. Annette GünzlLeopoldstr. 8D-85399 HallbergmoosGermany
PD Dr. Georg GuggenbergerLehrstuhl für Bodenkundeund BodengeographieUniversität BayreuthD-95440 BayreuthGermany
Dr. Stephan HaiberInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11Postfach 10 13 52D-44139 DortmundGermany
Dr. Markus Haitzer(since 2000) US Geological Survey3215 Marine StreetBoulderColorado 80303USA
Dipl.-Biol. Ines HeiberNaheweinstr. 37D-55452 LaubenheimGermany
XXIV List of Authors
Dr. Bálint HeilInstitute of Soil Scienceand Forest NutritionBüsgenweg 2D-37077 GöttingenGermany
Dr. Norbert HertkornGSF-Forschungszentrumfür Umwelt und GesundheitInstitut für Ökologische ChemieIngolstädter Landstr. 1D-85764 NeuherbergGermanyTel.: �49-(0)89-31874248Fax: �49-(0)89-31873371e-mail: [email protected]
Dipl.-Ing. Helmut HerzogInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11Postfach 10 13 52D-44139 DortmundGermany
Professor Klaus Gustav HeumannInstitut für Anorganischeund Analytische ChemieJohannes-Gutenberg-Universität MainzDuesbergweg 10�14D-55099 MainzGermanyTel.: �49-(0)6131-3925882Fax: �49-(0)6131-3923369e-mail: [email protected]
Dr. Wieland HillInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11D-44139 DortmundGermany
Professor Bertold HockLehrstuhl für BotanikTechnische Universität MünchenAlte Akademie 12D-85350 FreisingGermanyTel.: �49-(0)8161-713396Fax: �49-(0)8161-713044e-mail: [email protected]
Dr. Sebastian Höss(since 2000) Boden und SedimentBewertung(BSB)Thierschstr. 43D-80538 MünchenGermany
Dipl.-Biol. Svenja HonschoppParkstr.D-28209 BremenGermany
Dr. Jutta JahnelEngler-Bunte-InstitutDivision of Water ChemistryUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Dr. Brit Jakubowski (née Aster)Institut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11Postfach 10 13 52D-44139 DortmundGermany
XXVList of Authors
Dr. Gerald JandlInstitut für BodenkundeUniversität RostockJustus-von-Liebig-Weg 6D-18051 RostockGermany
Oliver Janssen-WeetsPappelstr. 88D-28199 BremenGermany
Dr. Klaus KaiserLehrstuhl für Bodenkundeund BodengeographieUniversität BayreuthD-95440 BayreuthGermanyTel.: �49-(0)921-552178Fax: �49-(0)921-552246e-mail: [email protected]
Dipl.-Ing. agr. Matthias KaniaLehrstuhl für BotanikTechnische Universität MünchenAlte Akademie 12D-85350 FreisingGermany
Professor Martin KaupenjohannInstitut für Bodenkundeund Standortslehre (310)Fachgebiet BodenchemieUniversität HohenheimD-70599 StuttgartGermany
Professor Antonius KettrupGSE-Forschungszentrum für Umweltund GesundheitInstitut für Ökologische ChemieIngolstädter Landstr. 1D-85764 NeuherbergGermanyTel.: �49-(0)89-31874047Fax: �49-(0)89-31873371
Dr. Uwe KlausInstitut für UmweltforschungUniversität DortmundD-44221 DortmundGermany
Professor Arndt KnöchelInstitut für Anorganischeund Angewandte ChemieUniversität HamburgMartin-Luther-King-Platz 6D-20146 HamburgGermanyTel.: �49-(0)40-428383982Fax: �49-(0)40-428382893e-mail: [email protected]
Dr. Thomas KochKurfürstenallee 29D-28211 BremenGermany
Professor Frank-Dieter KopinkeUFZ � Center for EnvironmentalResearch Leipzig-HallePermoserstr. 15D-04318 LeipzigGermanyTel.: �49-(0)341-2353264Fax: �49-(0)341-2352492e-mail: [email protected]
XXVI List of Authors
Dr. Oliver KrachtMax-Planck-Institut für BiogeochemiePostfach 100 164D-07701 JenaGermany
Dipl.-Ing. Rüdiger KuckukInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundBunsen-Kirchhoff-Str. 11D-44139 Dortmund
Professor Jussi KukkonenUniversität JoensuuDepartment of BiologyP. O. Box 11180101 JoensuuFinnland
Dr. Michael Kumke(since 2000) Institut für Physikalischeund Theoretische ChemieUniversität PotsdamKarl-Liebknecht-Str. 24�25D-14476 GolmGermanyTel.: �49-(0)331-9775209Fax: �49-(0)331-9775088e-mail: [email protected]
Dr. Jörg LambertInstitut für Spektrochemieund Angewandte Spektroskopie (ISAS)Universität DortmundPostfach 10 13 52D-44139 DortmundGermany
Professor Heinz LanghalsInstitut für Organische ChemieUniversität MünchenButenandtstr. 5�13 (Haus F)D-81377 MünchenGermanyTel.: �49-(0)89-21807699Fax: �49-(0)89-21807640e-mail: [email protected]
Dr. Ulrich Lankes(since 2000) Engler-Bunte-InstitutDivision of Water ChemistryUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Professor Peter LeinweberInstitut für BodenkundeUniversität RostockJustus-von-Liebig-Weg 6D-18051 RostockGermanyTel.: �49-(0)381-4982088Fax: �49-(0)381-4982159e-mail: [email protected]
Professor Hans-Gerd LöhmannsröbenInstitut für Physikalischeund Theoretische ChemieUniversität PotsdamKarl-Liebknecht-Str. 24�25Haus 25D-14476 GolmGermanyTel.: �49-(0)331-9775222Fax: �49-(0)331-9775088e-mail: [email protected]
XXVIIList of Authors
PD Dr. Bernard LudwigInstitute of Soil Scienceand Forest NutritionBüsgenweg 2D-37077 GöttingenGermanyTel.: �49-(0)551-393506e-mail: [email protected]
Professor Hans-Dietrich LüdemannInstitut für Biophysikund Physikalische BiochemieUniversität RegensburgD-93040 RegensburgGermanyTel.: �49-(0)941-9432492Fax: �49-(0)0941-9432479e-mail: [email protected]
Dr. Katrin MackenzieUFZ � Center for EnvironmentalResearch Leipzig-HalleSektion SanierungsforschungPermoserstr. 15D-04318 LeipzigGermany
Dr. Gieselher MarxInstitut für Anorganischeund Analytische ChemieJohannes-Gutenberg-Universität MainzDuesbergweg 10–14D-55099 MainzGermany
Dr. Jörg MielckeEngler-Bunte-InstitutBereich WasserchemieUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Dr. Rommy Müller-StarckLehrstuhl für BotanikTechnische Universität MünchenAlte Akademie 12D-85350 FreisingGermany
Professor Alexander NehrkornHeinrichsweg 1D-26209 HattenGermany
PD Dr. Ursula ObstForschungszentrum Karlsruhe GmbHITC-WGTPostfach 3640D-76021 KarlsruheGermanyTel.: �49-(0)7247-826806Fax: �49-(0)7247-826858e-mail: [email protected]
Dr. Thomas PfeiferInstitut für UmweltforschungUniversität DortmundD-44221 DortmundGermany
Dr. Thomas PützForschungszentrum Jülich GmbHInstitut für RadioagronomiePostfach 1913D-52425 JülichGermanyTel.: �49-(0)2461-616182Fax: �49-(0)2461-612518e-mail: [email protected]
XXVIII List of Authors
Dr. Gunther RädlingerInstitut für Anorganischeund Analytische ChemieJohannes Gutenberg UniversitätMainzDuesbergweg 10�14D-55099 MainzGermany
Dr. Hans-Hermann RüttingerInstitut für Pharmazeutische ChemieFachbereich PharmazieMartin-Luther-Universität HalleWolfgang-Langenbeck-Str. 4D-06120 HalleGermanyTel.: �49-(0)345-5525182Fax: �49-(0)345-5527028e-mail: [email protected]
Dr. Claudia SchmidtInstitut für RöntgenphysikGeorg-August-Universität GöttingenGeiststr. 11D-37073 GöttingenGermany
Professor Hanns-Ludwig SchmidtPrielhofweg 2D-84036 LandshutGermanyTel.: �49-(0)871-44497Fax: �49-(0)871-44497
Professor Hans-Rolf SchultenInstitut für BodenkundeUniversität RostockJustus-von-Liebig-Weg 6D-18051 RostockGermanyTel./Fax: �49-(0)381-4982137e-mail: [email protected]
Dr. Ute Schultze (née Zimmermann)Institut für Physikalischeund Theoretische ChemieUniversität Erlangen-NürnbergEgerlandstr. 3D-91058 ErlangenGermany
Professor Ernst-Detlef SchulzeMax-Planck-Institut für BiogeochemiePostfach 100 164D-07701 JenaGermanyTel.: �49-(0)3641-643702Fax: �49-(0)3641-643710e-mail: [email protected]
Dr. Thomas SkrivanekInstitut für Physikalischeund Theoretische ChemieUniversität Erlangen-NürnbergEgerlandstr. 3D-91058 ErlangenGermany
Dipl.-Ing. Christian SpechtEngler-Bunte-InstitutDivision of Water ChemistryUniversität KarlsruheEngler-Bunte-Ring 1D-76131 KarlsruheGermany
Professor Michael SpitellerInstitut für UmweltforschungUniversität DortmundD-44221 DortmundGermanyTel.: �49-(0)231-7554080Fax.: �49-(0)231-7554085e-mail: [email protected]