Transformation Products of Emerging Contaminants in the Environment

Editors Dimitra A. Lambropoulou Department of Chemistry, Aristotle University of Thessaloniki, Greece Leo M. L. Nollet Emeritus, Faculty of Applied Engineering Sciences, University College Ghent, Belgium

Preface xiii

List of Contributors xv

VOLUME 1

PART I GENERAL CONSIDERATIONS 1

1 Classifying the Transformation Products (TPs) of Emerging Contaminants (ECs) for Prioritizing Research into their Impact on the Environment and Human Health 3
Jacek Namiesnik, Lidia Wolska, Radosaw Czernych, Grazyna Gaeziowska and Monia Cieszynska

1.1 Introduction 3

1.2 Emerging Contaminants – Emerging Problem 5

1.3 Transformation Products of ECs 41

1.4 Minimizing Environmental Risk of ECs and their TPs 43

1.5 Concluding Remarks and Future Perspectives 45

References 49

2 Transformation Products of Emerging Organic Compounds as Future Groundwater and Drinking Water Contaminants 65
Marianne E. Stuart and Dan J. Lapworth

2.1 Introduction 65

2.2 Sources and Pathways of Emerging Contaminants to Groundwater 66

2.3 Persistence in the Groundwater Environment 68

2.4 Emerging Contaminants and their Transformation Products in Groundwater 69

2.5 Toxicity and Risk Assessment 76

2.6 Conclusions 78

References 79

PART II TRANSFORMATION PROCESSES AND TREATMENT STRATEGIES 87

3 Phototransformation Processes of Emerging Contaminants in Surface Water 89
Davide Vione and Serge Chiron

3.1 Introduction 89

3.2 Direct Photolysis and Sensitised Reactions in the Transformation of Emerging Contaminants 90

3.3 The Case of Photonitration 104

3.4 Towards the Modelling of Phototransformation Kinetics in Surface Water 106

References 118

4 Transformation Products of Emerging Contaminants upon Reaction with Conventional Water Disinfection Oxidants 123
Jose Benito Quintana, Rosario Rodil and Isaac Rodr©¥guez

4.1 Introduction 123

4.2 Analytical Methodology for Transformation Products Identification 124

4.3 Factors Influencing the Kinetics of Chlorination 131

4.4 Overview of Typical Reaction Mechanisms During Free Chlorine Treatments 135

4.5 Review of Current Knowledge of Emerging Pollutant Reactions with Free Chlorine 138

4.6 Other Disinfection Agents 150

4.7 Conclusions and Outlook 155

References 155

5 Approaches to Water andWastewater Treatment for Removal of Emerging Contaminants: Ongoing Research and Recommendations for Future Work 161
Sixto Malato, P. Fernandez-Ibanez, I. Oller, L. Prieto-Rodriguez, S. Miralles-Cuevas and Alejandro Cabrera-Reina

5.1 Introduction 161

5.2 Ozonation 163

5.3 Membrane Processes 165

5.4 Membrane Bioreactors (MBR) 167

5.5 AOPs Including Solar AOPs 169

References 175

6 Transformation Products of Emerging Contaminants Formed during Advanced Oxidation Processes 179
Ioannis K. Konstantinou, Dimitra A. Lambropoulou and Maria Antonopoulou

6.1 Introduction 179

6.2 Pesticides 180

6.3 Phthalate Esters 203

6.4 Pharmaceutical Compounds 204

6.5 Others 215

6.6 Conclusion 217

Acknowledgments 218

References 218

7 Enzymatic Reactors Applied for the Biotransformation of Endocrine Disrupting Chemicals 229
J.M. Lema, M.T. Moreira, G. Eibes, T. Lu-Chau, L. Lloret, R. Taboada, A. Arca-Ramos and G. Feijoo

7.1 Endocrine Disrupting Chemicals 229

7.2 White-Rot Fungi and Their Lignin Modifying Enzymes 234

7.3 Enzymatic Reactors 238

7.4 Determination of Transformation Products from the Enzymatic Treatment of EDCs 248

References 255

8 Biologically Mediated Chiral Inversion of Emerging Contaminants 261
Stuart J. Khan

8.1 Introduction 261

8.3 Changes in Enantiomeric Composition During Biological Transformation Processes 268

8.4 Evidence for Biologically Mediated Chiral Inversion 271

8.5 Implications and Priorities for Future Research 274

References 274

PART III ANALYTICAL STRATEGIES 281

9 Quality Issues in Water Sampling, Sample Pre-Treatment and Monitoring 283
Sara Bogialli, Stefano Polesello and Sara Valsecchi

9.1 Introduction 283

9.2 Monitoring of Transformation Products in Water Bodies 284

9.3 Sample Representativeness and Stability Issues 287

9.4 Identification of Transformation Products and Legislative Requirements 292

9.5 Conclusions 297

References 298

10 Transformation Products of Emerging Contaminants: Analytical Challenges and Future Needs 303
B. Zonja, J. Acena, A. Jelic, M. Petrovic, S. Perez and D. Barcelo

10.1 Introduction 303

10.2 Generation, Detection and Identification of Transformation Products at Lab Scale: An Analytical Challenge 305

10.3 Quantitative Analysis of TPs in the Environment 311

10.4 Evaluation of the Toxicity of TPs 318

10.5 Conclusions and Future Needs 319

Acknowledgments 320

References 320

11 Advanced Mass Spectrometry-Based Techniques for the Identification and Structure Elucidation of Transformation Products of Emerging Contaminants 325
Paola Calza and Fabbri Debora

11.1 Introduction 325

11.2 Potential and Differences Among the Different MS Systems for Determining Unknown Compounds 326

11.3 How to Proceed in the Structural Attribution 330

11.4 Accurate Mass Screening and Identification of Emerging Contaminants in Environmental Samples: Some Cases Studied 334

11.5 Conclusions 345

References 346

12 Applications of NMR Techniques for the Identification and Structure Elucidation of Emerging Organic and Other Xenobiotic Organic Contaminants 351
Alfred Preiss and Markus Godejohann

12.1 Introduction 351

12.2 Basic Techniques 353

12.3 Applications 359

12.4 Conclusions 377

List of Abbreviations 377

References 378

Index 385



VOLUME 2

PART IV OCCURRENCE, FATE AND EFFECTS IN THE ENVIRONMENT: AN OVERVIEW OF MAJOR CLASSES 385

13 Transformation Products of Pesticides in the Environment: Analysis and Occurrence 387
Ana Aguera Lopez, Marya del Mar Gomez Ramos, and Amadeo R. Fernandez-Alba

13.1 Introduction 387

13.2 Transformation of Pesticides in the Environment 388

13.3 Analytical Techniques Used in the Identification and Analysis of TPs 408

13.4 Occurrence of Pesticide TPs in the Environment 418

13.5 Concluding Remarks 419

Acknowledgments 420

References 420

14 Metabolites and Transformation Products of Pharmaceuticals in the Aquatic Environment as Contaminants of Emerging Concern 425
I. Michael, M.I. Vasquez, E. Hapeshi, T. Haddad, E. Baginska, K. Kummerer, and D. Fatta-Kassinos

14.1 Introduction 425

14.2 Human Metabolites in the Aquatic Environment 427

14.3 Biotransformation Products in the Aquatic Environment 430

14.4 Transformation of Pharmaceuticals During Photolysis and Advanced Oxidation Processes 437

14.5 Conclusions and Outlook 458

Acknowledgments 459

References 459

15 Transformation Products of Personal Care Products: UV Filters Case Studies 471
Kristina Pestotnik, Tina Kosjek, and Ester Heath

15.1 Introduction 471

15.2 Main Physico-Chemical Parameters of UV Filters and their Influence on Environmental Behaviour 473

15.3 Occurrence of UV Filter Residues 477

15.4 Fate of UV Filter Residues 479

15.5 Analytical Methods for Identification of Transformation Products 490

15.6 Effects and Toxicity of UV Filters and their Transformation Products in the Environment 495

15.7 Conclusions and Future Strategies 498

Acknowledgements 499

Abbreviations 499

References 501

16 Transformation Products of Illicit Drugs 505
Dimitra A. Lambropoulou and Eleni Evgenidou

16.1 Introduction 505

16.2 Fate and Treatment of IDs and Their Metabolites/TPs 507

16.3 Analytical Methods and Detection 515

16.4 Occurrence of IDs and their Metabolites/TPs in the Environment 519

16.5 Ecotoxicity of IDs and Their Metabolites/TPs 525

16.5.1 Sewage Epidemiology 526

16.6 Concluding Remarks 527

References 527

17 Transformation Products of Artificial Sweeteners 537
Marco Scheurer, Heinz-Jurgen Brauch, and Frank Thomas Lange

17.1 Introduction 537

17.2 Processes Leading to the Formation of Artificial Sweetener Transformation Products 539

17.3 Summary and Conclusions 551

References 552

18 Transformation Products of Brominated Flame Retardants (BFRs) 557
Alin C. Dirtu, Alin C. Ionas, Govindan Malarvannan, and Adrian Covaci

18.1 Introduction 557

18.2 Transformation Products of PBDEs 558

18.3 Transformation Products of HBCDs 569

18.4 Transformation Products of TBBPA 573

18.5 Transformation Products of NBFRs 578

18.6 Concluding Remarks and Future Perspectives 580

Acknowledgements 580

References 581

19 Transformation Products of Alkylphenols 589
Montserrat Cortina-Puig, Gabino Bolyvar-Subirats, Carlos Barata, and Silvia Lacorte

19.1 Alkylphenols: Types, Properties and Uses 589

19.2 Transformation of Alkylphenols and Identification of Transformation Products 592

19.3 Occurrence of Alkylphenol Transformation Products in the Environment 603

19.4 Risks and Effects of Alkylphenols and their Transformation Products in the Environment 610

19.5 Conclusions 615

Acknowledgments 616

References 616

20 Biotic and Abiotic Transformation Processes of Benzotriazoles: Possible Pathways and Products 625
Dimitra Voutsa

20.1 Introduction 625

20.2 Biotic Degradation Processes 627

20.3 Abiotic Transformation Processes 631

20.4 Future Research Needs 634

References 634

21 Identification (Quantitative Determination and Detection) and Fate of Transformation Products of Rocket Fuel 1,1-Dimethylhydrazine 639
Bulat Kenessov, Lars Carlsen

21.1 Introduction/Background 639

21.2 Identification of Transformation Products of 1,1-Dimethylhydrazine 640

21.3 Distribution and Fate of Transformation Products of 1,1-Dimethylhydrazine in Soil at Fall Sites 646

21.4 Analytical Methods Applied in the Monitoring 647

21.5 Conclusion 656

References 657

22 Assessment of the Occurrence and Fate of Transformation Products of Endocrine Disrupting Compounds EDCs in the Environment 661
Vasiliki Boti, Vasilios Sakkas, and Triantafyllos Albanis

22.1 Introduction 661

22.2 Endocrine Disrupting Compounds (EDCs) of Concern 662

22.3 Environmental Fate and Transformation of EDCs 664

22.4 Analytical Methodology 666

22.5 Occurrence and Endocrine Disruption Effects of the TPs of Selected EDCs 672

22.6 Future Needs –Recommendations 680

References 681

23 Transformation Products of Hazardous Cyanobacterial Metabolites in Water 687
Anastasia Hiskia, Theodoros M. Triantis, Maria G. Antoniou, Armah A. de la Cruz, Kevin O'Shea, Weihua Song, Theodora Fotiou, Triantafyllos Kaloudis, Xuexiang He, Joel Andersen, and Dionysios D. Dionysiou

23.1 Introduction 688

23.2 Cyanobacterial Secondary Metabolites 688

23.3 Transformation Products of Cyanobacterial Metabolites in Water 694

23.4 Research Gaps, Recent Trends and Future Needs 710

References 711

PART V GLOBAL SPACIALITY AND ENVIRONMENTAL STATUS OF TRANSFORMATION PRODUCTS IN THE ENVIRONMENT 721

24 Occurrence of Transformation Products of Emerging Contaminants in Water Resources 723
Carlos GonScalves, Maria A.D. de Sousa, and Maria de Fatima Alpendurada

24.1 Brief Introduction on the Sources of Transformation Products of Emerging Contaminants 723

24.2 Transformation Products in Natural Waters: From Contamination Sources to Drinking Water Production 725

24.3 Wastewaters as a Major Source of Transformation Products 744

24.4 Origin and Presence of Transformation Products in Drinking Water 750

24.5 Ubiquity and Regio-Specificity of Transformation Products 752

24.6 Transformation Products of Emerging Contaminants: Fate and Behavior 753

24.7 Conclusions 756

References 758

25 Occurrence of Transformation Products of Emerging Contaminants in Water Resources of the United States 763
Imma Ferrer and E. Michael Thurman

25.1 Introduction: Emerging Contaminants 763

25.2 State-of-the-Art Techniques for the Identification of Emerging Contaminants and Their Transformation Products 764

25.3 Use of Accurate Mass Tools for the Identification of Emerging Contaminants 768

25.4 Occurrence of Transformation Products in Environmental Waters in the US 779

References 782

26 Spatial Modeling for Elucidation of Perfluorinated Compound Sources and Fate in a Watershed 787
Yasuyuki Zushi and Shigeki Masunaga

26.1 Introduction 787

26.2 Source Identification of PFCs Using GIS 792

26.3 Spatial Distribution of PFOS and PFOA Contributed by Nonpoint Sources 798

26.4 Conclusion 804

Acknowledgments 805

References 805

27 Global Distribution of Polyfluoroalkyl and Perfluoroalkyl Substances and their Transformation Products in Environmental Solids 809
Holly Lee and Scott A. Mabury

27.1 Introduction 809

27.2 Global Contamination of PFASs in Environmental Solid Matrices 813

27.3 Fate of PFASs in Environmental Solids 821

27.4 Uptake into Vegetation 827

27.5 Summary and Future Outlook 829

References 830

PART VI RISK ASSESSMENT, MANAGEMENT AND REGULATORY FRAMEWORK 839

28 Toxicity and Risk of Transformation Products of Emerging Contaminants for Aquatic Organisms: Pharmaceutical Case Studies 841
Marina DellaGreca, Marina Isidori, Fabio Temussi

28.1 Introduction 841

28.2 Photolysis in the Environment: Pharmaceutical Case Studies 844

28.3 Effect-Driven Approach 844

28.4 Exposure-Driven Approach 853

28.5 Conclusion 867

References 868

29 Quantitative Structure–Activity Relationship/Quantitative Structure– Toxicity Relationship (QSAR/QSTR) Modeling as Tools for Assessing Effects and Predicting Risks of Transformation Products of Emerging Contaminants 871
Lars Carlsen and Bulat Kenessov

29.1 Introduction 871

29.2 The Toolbox 873

29.3 Environmental Behavior 876

29.4 Ecotoxicological Effect 879

29.5 Effects on Humans 880

29.6 Conclusions 885

References 885

30 Steps Toward a Regulatory Framework for Transformation Products in Water 889
Maria D. Hernando Guil, Maria J. Martýnez-Bueno, Laura Duran, Jose M. Navas and Amadeo R. Fernandez-Alba

30.1 Introduction 889

30.2 Scientific Advances and Technical Knowledge of Transformation Products. Relevant Cases of Study 891

30.3 Toxicological Considerations in Assessing Mixtures of Chemicals and Significance of Transformation Products in EU Regulations. Interaction Between Regulatory Frameworks 906

References 908

31 NORMAN Association: A Network Approach to Scientific Collaboration on Emerging Contaminants and their Transformation Products in Europe 915
Jaroslav Slobodnik and Valeria Dulio

31.1 Introduction 915

31.2 The NORMAN Network as a Science-to-Policy Interface 917

31.3 Effect-Directed Analysis for Identification of Relevant Emerging Contaminants and their Transformation Products in Complex Environmental Samples 921

31.4 Quality Control Aspects 924

31.5 Conclusions 925

Acknowledgements 926

References 926

PART VII OUTLOOK 929

32 Outlook 931

32.1 General Remarks 931

32.2 Gaps, Recommendations and Future Needs 933

Index 937