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Applied Water Science Volume 1
Scrivener Publishing
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Fundamentals and Applications
Edited by
Inamuddin,
Mohd Imran Ahamed,
Rajender Boddula,
and
Tauseef Ahmad Rangreez
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Contents
Preface xix
1 Sorbent-Based Microextraction Techniques for the Analysis
of Phthalic Acid Esters in Water Samples 1
Miguel Ángel González-Curbelo, Javier González-Sálamo,
Diana A. Varela-Martínez and Javier Hernández-Borges
1.1 Introduction 2
1.2 Solid-Phase Microextraction 6
1.3 Stir Bar Sorptive Extraction 25
1.4 Solid-Phase Extraction 26
1.5 Others Minor Sorbent-Based Microextraction Techniques 48
1.6 Conclusions 52
Acknowledgements 53
References 53
2 Occurrence, Human Health Risks, and Removal of
Pharmaceuticals in Aqueous Systems: Current Knowledge
and Future Perspectives 63
Willis Gwenzi, Artwell Kanda, Concilia Danha,
Norah Muisa-Zikali and Nhamo Chaukura
2.1 Introduction 64
2.2 Occurrence and Behavior of Pharmaceutics
in Aquatic Systems 65
2.2.1 Nature and Sources 65
2.2.2 Dissemination and Occurrence in Aquatic Systems 67
2.2.3 Behaviour in Aquatic Systems 71
2.3 Human Health Risks and Their Mitigation 73
2.3.1 Human Exposure Pathways 73
2.3.2 Potential Human Health Risks 74
2.3.3 Human Health Risks: A Developing World Perspective 81
2.3.4 Removal of Pharmaceuticals 82
v
vi Contents
2.3.4.1 Conventional Removal Methods 83

2.3.4.2 Advanced Removal Methods 85
2.3.4.3 Hybrid Removal Processes 88
2.4 Knowledge Gaps and Future Research Directions 88
2.4.1 Increasing Africa’s Research Footprint 88
2.4.2 Hotspot Sources and Reservoirs 89
2.4.3 Behavior and Fate in Aquatic Systems 89
2.4.4 Ecotoxicology of Pharmaceuticals and Metabolites 89
2.4.5 Human Exposure Pathways 89
2.4.6 Human Toxicology and Epidemiology 90
2.4.7 Removal Capacity of Low-Cost Water Treatment
Processes 90
2.5 Summary, Conclusions, and Outlook 90
Author Contributions 91
References 91
3 Oil-Water Separations 103
Pallavi Jain, Sapna Raghav and Dinesh Kumar
3.1 Introduction 103
3.2 Sources and Composition 106
3.3 Common Oil-Water Separation Techniques 106
3.4 Oil-Water Separation Technologies 107
3.4.1 Advancement in the Technology of Membrane 111
3.4.1.1 Polymer-Based Membranes 111
3.4.1.2 Ceramic-Based Membranes 111
3.5 Separation of Oil/Water Utilizing Meshes 113
3.5.1 Mechanism Involved 113
3.5.2 Meshes Functionalization 114
3.5.2.1 Inorganic Materials 115
3.5.2.2 Organic Materials 115
3.6 Separation of Oil-Water Mixture Using Bioinspired Surfaces 116
3.6.1 Nature’s Lesson 116
3.6.2 Superhydrophilic/Phobic and Superoleophilic/Phobic
Porous Surfaces 117
3.7 Conclusion 118
Acknowledgment 118
References 119
4 Microplastics Pollution 125
Agnieszka Dąbrowska
4.1 Introduction and General Considerations 125
Contents vii
4.2 Key Scientific Issues Concerning Water and

Microplastics Pollution 126
4.3 Marine Microplastics: From the Anthropogenic Litter
to the Plastisphere 131
4.4 Social and Human Perspectives: From Sustainable
Development to Civil Science 133
4.5 Conclusions and Future Projections 134
References 134
5 Chloramines Formation, Toxicity, and Monitoring Methods
in Aqueous Environments 139
Rania El-Shaheny and Mahmoud El-Maghrabey
5.2 Inorganic Chloramines Formation and Toxicity 140
5.3 Analytical Methods for Inorganic Chloramines 143
5.3.1 Colorimetric and Batch Methods 144
5.3.2 Chromatographic Methods 148
5.3.3 Membrane Inlet Mass Spectrometry 150
5.4 Organic Chloramines Formation and Toxicity 151
5.5 Analytical Methods for Organic Chloramines 154
5.6 Conclusions 156
References 156
6 Clay-Based Adsorbents for the Analysis of Dye Pollutants 163
Mohammad Shahadat, Momina, Yasmin, Sunil Kumar,
Suzylawati Ismail, S. Wazed Ali and Shaikh Ziauddin Ahammad
6.1.1 Biological Method 165
6.1.2 Physical Method 165
6.1.3 Why Only Clays? 165
6.1.4 Clay-Based Adsorbents 166
6.1.4.1 Kaolinite 166
6.1.4.2 Rectorite 168
6.1.4.3 Halloysite 169
6.1.4.4 Montmorillonite 170
6.1.4.5 Sepiolite 170
6.1.4.6 Laponite 171
6.1.4.7 Bentonite 171
6.1.4.8 Zeolites 172
6.2 Membrane Filtration 180
6.3 Chemical Treatment 181
viii Contents
6.3.1 Fenton and Photo-Fenton Process 182

6.3.2 Mechanism Using Acid and Base Catalyst 182
6.4 Photo-Catalytic Oxidation 186
6.5 Conclusions 188
Acknowledgments 188
References 188
7 Biochar-Supported Materials for Wastewater Treatment 199
Hanane Chakhtouna, Mohamed El Mehdi Mekhzoum,
Nadia Zari, Hanane Benzeid, Abou el kacem Qaiss
and Rachid Bouhfid
7.2 Generalities of Biochar: Structure, Production,
and Properties 201
7.2.1 Biochar Structure 201
7.2.2 Biochar Production 203
7.2.2.1 Pyrolysis 204
7.2.2.2 Gasification 204
7.2.2.3 Hydrothermal Carbonization 205
7.2.3 Biochar Properties 205
7.2.3.1 Porosity 205
7.2.3.2 Surface Area 207
7.2.3.3 Surface Functional Groups 207
7.2.3.4 Cation Exchange Capacity 210
7.2.3.5 Aromaticity 210
7.3 Biochar-Supported Materials 212
7.3.1 Magnetic Biochar Composites 212
7.3.2 Nano-Metal Oxide/Hydroxide-Biochar Composites 214
7.3.3 Functional Nanoparticles-Coated Biochar
Composites 216
7.4 Conclusion 220
References 222
8 Biological Swine Wastewater Treatment 227
Aline Meireles dos Santos, Alberto Meireles dos Santos,
Patricia Arrojo da Silva, Leila Queiroz Zepka
and Eduardo Jacob-Lopes
8.2 Swine Wastewater Characteristics 228
8.3 Microorganisms of Biological Swine Wastewater Treatment 231
8.4 Classification of Biological Swine Wastewater Treatment 235
Contents ix
8.5 Biological Processes For Swine Wastewater Treatment 236

8.5.1 Suspended Growth Processes 237
8.5.1.1 Activated Sludge Process 237
8.5.1.2 Sequential Batch Reactor 237
8.5.1.3 Sequencing Batch Membrane Bioreactor 238
8.5.1.4 Anaerobic Contact Process 238
8.5.1.5 Anaerobic Digestion 238
8.5.2 Attached Growth Processes 239
8.5.2.1 Rotating Biological Contactor 239
8.5.2.2 Upflow Anaerobic Sludge Blanket 240
8.5.2.3 Anaerobic Filter 240
8.5.2.4 Hybrid Anaerobic Reactor 241
8.6 Challenges and Future Prospects in Swine Wastewater
Treatment 241
References 242
9 Determination of Heavy Metal Ions From Water 255
Ritu Payal and Tapasya Tomer
9.2 Detection of Heavy Metal Ions 256
9.2.1 Atomic Absorption Spectroscopy 257
9.2.2 Nanomaterials 257
9.2.3 High-Resolution Surface Plasmon Resonance
Spectroscopy with Anodic Stripping Voltammetry 258
9.2.4 Biosensors 259
9.2.4.1 Enzyme-Based Biosensors 260
9.2.4.2 Electrochemical Sensors 261
9.2.4.3 Polymer-Based Biosensors 261
9.2.4.4 Bacterial-Based Sensors 262
9.2.4.5 Protein-Based Sensors 262
9.2.5 Attenuated Total Reflectance 262
9.2.6 High-Resolution Differential Surface Plasmon
Resonance Sensor 262
9.2.7 Hydrogels 263
9.2.8 Chelating Agents 264
9.2.9 Ionic Liquids 265
9.2.10 Polymers 266
9.2.10.1 Dendrimers 266
9.2.11 Macrocylic Compounds 266
9.2.12 Inductively Coupled Plasma Mass Spectrometry 267
x Contents
9.3 Conclusions 267

References 268
10 The Production and Role of Hydrogen-Rich Water
in Medical Applications 273
N. Jafta, S. Magagula, K. Lebelo, D. Nkokha and M.J. Mochane
10.2 Functional Water 275
10.3 Reduced Water 275
10.4 Production of Hydrogen-Rich Water 277
10.5 Mechanism Hydrogen Molecules During Reactive
Oxygen Species Scavenging 279
10.6 Hydrogen-Rich Water Effects on the Human Body 280
10.6.1 Anti-Inflammatory Effects 280
10.6.2 Anti-Radiation Effects 281
10.6.3 Wound Healing Effects 282
10.6.4 Anti-Diabetic Effects 284
10.6.5 Anti-Neurodegenerative Effects 285
10.6.6 Anti-Cancer Effects 285
10.6.7 Anti-Arteriosclerosis Effects 285
10.7 Other Effects of Hydrogenated Water 285
10.7.1 Effect of Hydrogen-Rich Water
in Hemodialysis 285
10.7.2 Effect on Anti-Cancer Drug Side Effects 286
10.8 Applications of Hydrogen-Rich Water 286
10.8.1 In Health Care 286
10.8.2 In Sports Science 288
10.8.3 In Therapeutic Applications and Delayed
Progression of Diseases 289
10.9 Safety of Using Hydrogen-Rich Water 290
10.10 Concluding Remarks 291
References 292
11 Hydrosulphide Treatment 299
Marzie Fatehi and Ali Mohebbi
11.1.1 Agriculture 302
11.1.2 Medical 307
11.1.3 Industrial 315
11.2 Conclusions 325
References 326
Contents xi
12 Radionuclides: Availability, Effect, and Removal Techniques 331

Tejaswini Sahoo, Rashmirekha Tripathy, Jagannath Panda,
Madhuri Hembram, Saraswati Soren, C.K. Rath,
Sunil Kumar Sahoo and Rojalin Sahu
12.1.1 Available Radionuclides in the Environment 333
12.1.1.1 Uranium 333
12.1.1.2 Thorium (Z = 90) 334
12.1.1.3 Radium (Z = 88) 335
12.1.1.4 Radon (Z = 86) 336
12.1.1.5 Polonium and Lead 336
12.1.2 Presence of Radionuclide in Drinking Water 337
12.1.2.1 Health Impacts of Radionuclides 338
12.1.2.2 Health Issues Caused Due to Uranium 338
12.1.2.3 Health Issues Caused Due to Radium 339
12.1.2.4 Health Issues Caused Due to Radon 339
12.1.2.5 Health Issues Caused Due to Lead
and Polonium 339
12.2 Existing Techniques and Materials Involved in Removal
of Radionuclide 340
12.2.1 Ion Exchange 340
12.2.2 Reverse Osmosis 340
12.2.3 Aeration 341
12.2.4 Granulated Activated Carbon 341
12.2.5 Filtration 342
12.2.6 Lime Softening, Coagulation, and Co-Precipitation 342
12.2.7 Flocculation 343
12.2.8 Nanofilteration 343
12.2.9 Greensand Filteration 344
12.2.10 Nanomaterials 344
12.2.10.1 Radionuclides Sequestration by MOFs 344
12.2.10.2 Radionuclides Removal by COFs 345
12.2.10.3 Elimination of Radionuclides by GOs 346
12.2.10.4 Radionuclide Sequestration by CNTs 346
12.2.11 Ionic Liquids 347
12.3 Summary of Various Nanomaterial and Efficiency
of Water Treating Technology 348
12.4 Management of Radioactive Waste 348
12.5 Conclusion 350
References 350
xii Contents
13 Applications of Membrane Contactors for Water Treatment 361

Ashish Kapoor, Elangovan Poonguzhali,
Nanditha Dayanandan and Sivaraman Prabhakar
13.2 Characteristics of Membrane Contactors 362
13.3 Membrane Module Configurations 365
13.4 Mathematical Aspects of Membrane Contactors 366
13.5 Advantages and Limitations of Membrane Contactors 367
13.5.1 Advantages 367
13.5.1.1 High Interfacial Contact 368
13.5.1.2 Absence of Flooding and Loading 368
13.5.1.3 Minimization of Back Mixing
and Emulsification 368
13.5.1.4 Freedom for Solvent Selection 368
13.5.1.5 Reduction in Solvent Inventory 368
13.5.1.6 Modularity 369
13.5.2 Limitations 369
13.6 Membrane Contactors as Alternatives to Conventional
Unit Operations 370
13.6.1 Liquid-Liquid Extraction 370
13.6.2 Membrane Distillation 370
13.6.3 Osmotic Distillation 372
13.6.4 Membrane Crystallization 372
13.6.5 Membrane Emulsification 372
13.6.6 Supported Liquid Membranes 373
13.6.7 Membrane Bioreactors 373
13.7 Applications 374
13.7.1 Wastewater Treatment 374
13.7.2 Metal Recovery From Aqueous Streams 375
13.7.3 Desalination 375
13.7.4 Concentration of Products in Food
and Biotechnological Industries 375
13.7.5 Gaseous Stream Treatment 376
13.7.6 Energy Sector 376
13.8 Conclusions and Future Prospects 377
References 378
14 Removal of Sulfates From Wastewater 383
Ankita Dhillon, Rekha Sharma and Dinesh Kumar
Contents xiii
14.2 Effect of Sulfate Contamination on Human Health 384

14.3 Groundwater Distribution of Sulfate 384
14.4 Traditional Methods for Sulfate Removal 385
14.4.1 Treatment With Lime 385
14.4.2 Treatment With Limestone 386
14.4.3 Wetlands 387
14.5 Modern Day’s Technique for Sulfate Removal 387
14.5.1 Nanofiltration 387
14.5.2 Electrocoagulation 388
14.5.3 Precipitation Methods 389
14.5.4 Adsorption 391
14.5.5 Ion Exchange 392
14.5.6 Biological Treatment 393
14.5.7 Removal of Sulfate by Crystallization 394
14.6 Conclusions and Future Perspective 394
Acknowledgment 395
References 395
15 Risk Assessment on Human Health With Effect
of Heavy Metals 401
Athar Hussain, Manjeeta Priyadarshi, Fazil Qureshi
and Salman Ahmed
15.2 Toxic Effects Heavy Metals on Human Health 403
15.3 Biomarkers and Bio-Indicators for Evaluation
of Heavy Metal Contamination 406
15.3.1 Hazard Quotient 407
15.3.2 Transfer Factor 407
15.3.3 Daily Intake of Metal 408
15.3.4 The Bioaccumulation Factor 409
15.3.5 Translocation Factor 410
15.3.6 Enrichment Factor 410
15.3.7 Metal Pollution Index 412
15.3.8 Health Risk Index 412
15.3.9 Pollution Load Index 412
15.3.10 Index of Geo-Accumulation 413
15.3.11 Potential Risk Index 413
15.3.12 Exposure Assessment 414
15.3.13 Carcinogenic Risk 415
References 417
xiv Contents
16 Water Quality Monitoring and Management: Importance,

Applications, and Analysis 421
Abhinav Srivastava and V.P. Sharma
16.1 Qualitative Analysis: An Introduction to Basic Concept 422
16.2 Significant Applications of Qualitative Analysis 422
16.2.1 Water Quality 424
16.2.2 Water Quality Index 426
16.3 Qualitative Analysis of Water 427
16.3.1 Sampling Procedure 428
16.3.2 Sample Transportation and Preservation 429
16.3.3 Some Important Physico-Chemical Parameters
of Water Quality 431
16.4 Existing Water Quality Standards 434
16.5 Quality Assurance and Quality Control 435
16.6 Conclusions 437
References 437
17 Water Quality Standards 441
Hosam M. Saleh and Amal I. Hassan
17.2 Chemical Standards for Water Quality 443
17.2.1 Physical Standards 443
17.2.2 Chemical Standards for Salt Water Quality 445
17.2.3 Biological Standards 446
17.2.4 Radiation Standards 447
17.2.5 Wastewater and Water Quality 447
17.3 Inorganic Substances and Their Effect on Palatability
and Household Uses 451
17.3.1 Aluminum 451
17.3.2 Calcium 451
17.3.3 Magnesium 452
17.3.4 Chlorides 452
17.4 The Philosophy of Setting Standards for Drinking Water
(Proportions and Concentrations of Water Components) 457
17.5 Detection of Polychlorinated Biphenyls 458
17.6 The Future Development of Water Analysis 459
17.7 Conclusion 460
References 460
Contents xv
18 Qualitative and Quantitative Analysis of Water 469

Amita Chaudhary, Ankur Dwivedi and Ashok N Bhaskarwar
18.2 Sources of Water 470
18.3 Water Quality 472
18.3.1 Physical Parameters 472
18.3.2 Chemical Parameters 472
18.3.3 Biological Parameters 474
18.3.4 Water Quality Index 474
18.4 Factors Affecting the Quality of Surface Water 476
18.5 Quantitative Analysis of the Organic Content of the
Wastewater 477
18.5.1 Biochemical Oxygen Demand 477
18.5.1.1 DO Profile Curve in BOD Test 478
18.5.1.2 Significance of BOD Test 479
18.5.1.3 Nitrification in BOD Test 480
18.5.2 Chemical Oxygen Demand 480
18.5.3 Theoretical Oxygen Demand (ThOD) 482
18.6 Treatment of Wastewater 483
18.6.1 Primary Treatment Method 484
18.6.1.1 Pre-Aeration 484
18.6.1.2 Flocculation 484
18.6.2 Secondary Treatment 485
18.6.2.1 Aerobic Biological Process 485
18.6.2.2 Anaerobic Biological Treatment 485
18.6.2.3 Activated Sludge Process 487
18.6.3 Tertiary Treatment 488
18.6.3.1 Nutrients Removal 488
18.6.3.2 Phosphorus Removal 490
18.6.3.3 Ion-Exchange Process 490
18.6.3.4 Membrane Process 491
18.6.3.5 Disinfection 491
18.6.3.6 Coagulation 491
18.7 Instrumental Analysis of Wastewater Parameters 492
18.7.1 Hardness 492
18.7.2 Alkalinity 492
18.7.3 pH 493
18.7.4 Turbidity 493
xvi Contents
18.7.5 Total Dissolved Solids 494

18.7.6 Total Organic Carbon 494
18.7.7 Color 495
18.7.8 Atomic Absorption Spectroscopy 495
18.7.9 Inductive Coupled Plasma–Mass Spectroscopy 496
18.7.10 Gas Chromatography With Mass Spectroscopy 497
18.8 Methods for Qualitative Determination of Water 497
18.8.1 Weight Loss Method 497
18.8.2 Karl Fischer Method 498
18.8.3 Fourier Transform Infrared Spectroscopy
Method 499
18.8.4 Nuclear Magnetic Resonance Spectroscopy
Method 499
18.9 Conclusion 500
References 500
19 Nanofluids for Water Treatment 503
Charles Oluwaseun Adetunji, Wilson Nwankwo,
Olusola Olaleye, Olanrewaju Akinseye, Temitope Popoola
and Mohd Imran Ahamed
19.2 Types of Nanofluids Used in the Treatment of Water 505
19.2.1 Zero-Valent Metal Nanoparticles 505
19.2.1.1 Silver Nanoparticles (AgNPs) 505
19.2.1.2 Iron Nanoparticles 506
19.2.1.3 Zinc Nanoparticles 507
19.2.2 Metal Oxides Nanoparticles 507
19.2.2.1 Tin Dioxide (TiO2) Nanoparticles 507
19.2.2.2 Zinc Oxide Nanoparticles (ZnO NPs) 508
19.2.2.3 Iron Oxides Nanoparticles 508
19.2.3 Carbon Nanotubes 509
19.2.4 Nanocomposite Membranes 509
19.2.5 Modes of Action of These Nanofluids 509
19.2.5.1 Carbon-Based Nano-Adsorbents (CNTs)
for Organic Expulsion 509
19.2.5.2 Heavy Metal Removal 510
19.2.5.3 Metal-Based Nano-Adsorbents 510
19.2.5.4 Polymeric Nano-Adsorbents 511
19.2.5.5 Nanofiber Membranes 511
19.2.5.6 Some Applications of Nanofluids
in the Treatment of Water 512
Contents xvii
19.2.5.7 Informatics and AI Nanofluid-Enhanced

Water Treatment 513
19.3 Conclusion and Recommendation to Knowledge 516
References 516
Index 525
Preface
Applied Water Science

I-Fundamentals and Applications
Inamuddin1, Mohd Imran Ahamed2, Rajender Boddula3
and Tauseef Ahmad Rangreez4
1
Department of Applied Chemistry, Zakir Husain College of Engineering and
Technology, Faculty of Engineering and Technology, Aligarh Muslim University,
Aligarh, India
2
Department of Chemistry, Faculty of Science, Aligarh Muslim University,
Aligarh, India
3
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication,
National Center for Nanoscience and Technology, Beijing, China
4
Department of Chemistry, National Institute of Technology, Srinagar,
Jammu and Kashmir, India
Water is one of the precious and basic needs of life for all living beings and
is a precious national asset. Without it, the existence of life cannot be imag-
ined. Availability of pure water is decreasing day by day, and water scarcity
has become a major problem that is faced by our society for the past few
years. Hence, it is essential to find and disseminate the key solutions for
water quality and scarcity issues. The inaccessibility and poor water qual-
ity continue to pose a major threat to human health worldwide. Around
billions of people lacking to access drinkable water. The water contains the
pathogenic impurities, which are responsible for water-borne diseases. The
concept of water quality mainly depends on the chemical, physical, biolog-
ical, and radiological measurement standards to evaluate the water quality
and determine the concentration of all components and then to compare
the results of this concentration with the purpose for which this water is
xix
xx Preface
used. Therefore, awareness and a firm grounding in water science are the
primary needs of readers, professionals, and researchers working in this
research area.
This book explores the basic concepts and applications of water sci-
ence. It provides an in-depth look at water pollutants’ classification, water
recycling, qualitative and quantitative analysis, and efficient wastewater
treatment methodologies. It also provides occurrence, human health
risk assessment, strategies for removal of radionuclides, and pharma-
ceuticals in aquatic systems. The book chapters are written by leading
researchers throughout the world. This book is an invaluable guide to
students, professors, scientists, and R&D industrial specialists working
in the field of environmental science, geoscience, water science, physics,
and chemistry.
Chapter 1 provides a general overview of different analytical method-
ologies that have been proposed for the analysis of phthalic acid esters in
water samples. Special attention has been given to methods based on the
application of sorbent-based microextraction techniques (i.e., solid-phase
microextraction and micro solid-phase extraction magnetized or not,
among others).
Chapter 2 discusses the occurrence, dissemination, and behavior of
pharmaceuticals in aquatic environments. Human exposure pathways and
health risks, including the emergence of antimicrobial resistance are sum-
marized. Risk factors promoting human exposure in developing countries
are discussed. Methods for removal of pharmaceuticals and future research
directions are also highlighted.
Chapter 3 focuses on the latest developments in the methods for the oil/
water separation through filtration of the membrane using distinct materi-
als with surface properties that are super wetting.
Chapter 4 presents the fundamental studies on the interdisciplinary
issue of microplastic-based pollution of water environments; the scientific
approach and roadmap to this complex problem are discussed.
Chapter 5 summarizes the routes of formation of organic and inorganic
chloramines upon chlorination disinfection. Chloramine’s possible health
risks to humans including mutagenicity and hemolytic anemia are dis-
cussed. Further, the analytical methods for their control in aqueous envi-
ronments are summarized. Selective methods including chromatographic
and pH-controlled colorimetric techniques are highlighted.
Chapter 6 highlights the removal of industrial dyes using different
approaches such as clay-based adsorbents, membrane filtration, and chem-
ical treatment with special focus on clay-based low-cost adsorbents. The
Preface xxi
results of dyes’ adsorption study are discussed and compared with other
reported wastewater treatment technologies.
Chapter 7 provides a general description of biochar material from the
preparation (synthetic methods) to its application as a powerful adsor-
bent in the wastewater treatment field. Recent advancements of biochar-
supported materials with a focus on their applications for different
contaminants’ removal and the underlying mechanisms are also discussed.
Chapter 8 focuses on biological processes for swine wastewater treat-
ment. Therefore, it details the swine wastewater characteristics, microor-
ganisms, metabolic pathways involved, and biological processes in swine
wastewater treatment. Besides, challenges and prospects in this research
field are also presented.
Chapter 9 discusses various imperative techniques to detect hazardous
metal ions in various water reservoirs. The toxicological effects of various
metal ions on living beings and atmosphere along with their detection lim-
its, in addition to future perspectives of these procedures, are highlighted.
Chapter 10 discusses the production of hydrogen-rich water and its
role in medical applications. Firstly, a concise discussion of two of the pro-
duction methods of hydrogen-rich water is provided. Lastly, the medical
benefits, medical applications, and the safety of hydrogen-rich water are
discussed in detail.
Chapter 11 focuses on the application of hydrosulfide treatment in med-
icine, agriculture, and industry fields. Hydrosulfide anion is considered as
an innovative gaseous signaling molecule and plays significant biologi-
cal roles in the organisms. Its performance is discussed in detail for the
improvement of biotic/abiotic stress tolerance of cells.
Chapter 12 discusses the properties of available radionuclides including
uranium, lead, polonium, cesium, strontium, thorium, radon, and radium.
Moreover, the health problem caused due to these radionuclides contam-
inated water is also highlighted. Techniques involved in the removal of
radionuclides including ion exchange, aeration, filtration, nanofiltration,
and flocculation are summarized.
Chapter 13 reviews the developing applications of membrane contactors
in water treatment and desalination demonstrating their ability to substi-
tute or supplement the conventional separation processes. The advantages
and limitations of membrane contactors are discussed and their potential
for value recovery from spent streams of small and medium industries are
highlighted.
Chapter 14 comprehensively reviews all the sulfate remediation tech-
nologies and also lists various methods involved in tackling the sulfate
xxii Preface
problem from wastewater. Both conventional methods and modern-day

technologies are covered in this chapter for sulfate removal.
Chapter 15 discusses the various sources and pathways of heavy met-
als’ movement and accumulation in the environment. The toxicity effects
of these heavy metals on human health are also presented. Various bio-
indicators and biomarkers generally used for the assessment of heavy
metal-based pollution about intake, hazard, toxicity, and transfer factor are
discussed. Also, details of various indices associated with health risk, car-
cinogenic risk, and exposure assessment are focused and recommended.
Chapter 16 emphasizes that the analysis of water is an important multi-
step process and vital for surveillance and management. The monitoring
should be a dynamic procedure with the adoption of techno-economic and
state-of-art techniques. We need to improve water quality, minimize pol-
lutants, conserve for the generations, and upgrade awareness levels. Every
drop of water counts and has the hidden story of life.
Chapter 17 deals with chemical standards for water quality and explains
the philosophy of establishing these standards. In addition to the effect
of inorganic substances on water quality, it takes into account the future
development of water analysis to make water clean and suitable for human
use.
Chapter 18 describes the different approaches used to measure water
both quantitatively and qualitatively. The dischargeable and acceptable
limits are also tabulated in this chapter as per WHO and BIS guidelines.
The simulation equations for estimating the water quality index are pre-
sented. Additionally, wastewater treatment techniques are also explained
in three stages.
Chapter 19 discusses the application of nanofluids as one of the sustain-
able bioremediation techniques for the treatment and purification of heav-
ily contaminated water. Different types of nanofluids used in the treatment
of water such as zero-valent metal nanoparticles, metal oxides nanoparti-
cles, carbon nanotubes, and nanocomposites are also highlighted.
1
Sorbent-Based Microextraction
Techniques for the Analysis of Phthalic
Acid Esters in Water Samples
Miguel Ángel González-Curbelo1, Javier González-Sálamo2,3,
Diana A. Varela-Martínez1,2 and Javier Hernández-Borges2,3*
Departamento de Ciencias Básicas, Facultad de Ingeniería, Universidad EAN,

1
Bogotá D.C., Colombia

2
Departamento de Química, Unidad Departamental de Química Analítica,
Facultad de Ciencias, Universidad de La Laguna (ULL). Avda. Astrofísico
Fco. Sánchez, San Cristóbal de La Laguna, España
3
Instituto Universitario de Enfermedades Tropicales y Salud Pública de Canarias,
Universidad de La Laguna (ULL). Avda. Astrofísico Fco. Sánchez, San Cristóbal de
La Laguna, España
Abstract
Current society is living in a world in which it is exposed to a broad spectrum of
contaminants that can pose different risks for health. In this sense, we are daily
bombarded with news related to pollution by plastic residues (especially in the
oceans), being one of the main issues that humans must face today, not only
because of the direct effects of plastics but also because of the variety of contami-
nants they can release to the environment. Probably, the most important ones are
phthalic acid esters (PAEs), since they easily migrate from the polymeric matrix to
the surrounding media, acting as endocrine disruptors in human organisms and
resulting in multiple diseases. Their occurrence in water matrices is of especial
importance, since it is essential for life, and the presence of PAEs, even at very low
levels, can cause serious health problems. This book chapter aims at providing a
general and critical overview of the different analytical methodologies that have
been developed for the analysis of PAEs in water samples and which are based on
the application of sorbent-based microextraction techniques, which is one of the
current trends in the Analytical Chemistry field.
*Corresponding author: jhborges@ull.edu.es
Inamuddin, Mohd Imran Ahamed, Rajender Boddula, and Tauseef Ahmad Rangreez (eds.) Applied
Water Science Volume 1: Fundamentals and Applications, (1–62) © 2021 Scrivener Publishing LLC
1
2 Applied Water Science Volume 1
Keywords: Phthalic acid esters, analytical methods, sample preparation,

microextraction techniques, water samples, sorbents
1.1 Introduction
Phthalic acid esters (PAEs) are a group of dialkyl or alkylaryl esters of
phthalic acid (see Figure 1.1), commonly known as phthalates, which
are widely used as additives in the polymer industry but also added to
paints, adhesives, lubricants, and cosmetics, among others [2]. As an
example, low-molecular PAEs such as butyl benzyl phthalate (BBP),
dibutyl phthalate (DBP), and diethyl phthalate (DEP) are widely used
as solvents and emulsifiers to maintain color and fragrance mainly in
beauty products and pharmaceuticals, while high-molecular PAEs such
as di(2-ethylhexyl) phthalate (DEHP) are highly used as plasticizers to
make polymeric materials more workable and flexible. As a result of the
extremely high production of such products, especially plastics, PAEs are
exorbitantly present in the daily life. Among them, DEHP is the most
currently used. In fact, its production as plasticizer is estimated to be
a quarter of the total [3, 4]. Due to these widespread applications and
intensive production, together with the fact that they are only retained
in the polymer structure through weak secondary molecular interactions
and not covalently, PAEs can easily migrate to the environment. As a
result, PAEs have become ubiquitous contaminants in the environment,
in particular, they can be found in natural waters such as lake, river, sea,
and ground waters [5, 6], especially those adjacent or downstream from
industrial locations [5]. In addition, their possible migration to drink-
ing waters that are in contact with plastic materials like mineral and tap
waters must also be taken into account, as well as their final presence in
waste waters [5, 7].
It has already been demonstrated that many PAEs act as endocrine dis-
ruptors and that they can be toxic for reproduction, even at extremely
low concentrations [8–11]. Even more worrying is the fact that certain
PAEs can be easily degraded in the environment by bacteria and fungi
and their degradation products can also have an important toxicity. Such
is the case of DEHP that can be degraded to DBP, DEP, and especially to
mono-2-ethylhexyl phthalate (MEHP), which has shown to be more toxic
than DEHP [12, 13] (see Figure 1.2). As a result of the high human expo-
sure to PAEs and their metabolites, their potential risks for health and
their persistence, several organizations have established an increasingly
broad and restrictive legislation. As examples, the European Union has
Phthalates Microextraction From Water 3
O
R1
O
O
R2
O
Name Abbreviations R1 Group R2 Group
Dimethyl phthalate DMP

Diethyl phthalate DEP
DMEP O O
Di(2-methoxyethyl) phthalate
Dipropyl phthalate DPP
Di(2-ethoxyethyl) phthalate DEEP O O
Benzylbutyl phthalate BBP
Dibutyl phthalate DBP
Diisobutyl phthalate DIBP
Di(2-butoxyethyl) phthalate DBEP O O
Di-n-pentyl phthalate DNPP
Diisopentyl phthalate DIPP
Dicyclohexyl phthalate DCHP
Dihexyl phthalate DHXP
Di(2-ethylhexyl) phthalate DEHP
Di-n-octyl phthalate DNOP
Diisononyl phthalate DINP
Diisodecyl phthalate DIDP
Figure 1.1 The chemical structures of PAEs. Adapted from [1]. PAEs, phthalic acid esters.
listed several PAEs as compounds suspected to produce endocrine abnor-

malities [15] and the International Agency for Research on Cancer has
classified DEHP in the group 2B (possibly carcinogenic to humans) [16].
Moreover, the US Environmental Protection Agency (EPA) has included
several PAEs (BBP, DBP, DEHP, DEP, dimethyl phthalate (DMP), and
di-n-octyl phthalate (DNOP)) in its priority list of pollutants and has
O
O
O
DEHP
β-oxidation
De-esterification
β-oxidation
O
O O
O
O
OH O
MEHP O
DBP
β-oxidation
De-esterification
O
cation
terifi O
D e-es
ion O
ficat
steri
OH De - e O
DEP
O
O Trans-esterification
OH Trans-esterification
PA Trans-esterification Trans-esterification
Figure 1.2 DEHP biodegradation pathways to obtain MEHP, DBP, and DEP. Reprinted
from [14] with permission from Elsevier. DBP, dibutyl phthalate; DEHP, di-2-ethylhexyl
phthalate; DEP, diethyl phthalate; MEHP, mono-2-ethylhexyl phthalate; PA, polyacrylate.
established limits of 6 µg/L and 400 µg/L for DEHP and di(2-ethylhexyl)
adipate (DEHA) in drinking water, respectively [17], while this maximum
allowed concentration has been established in 8 µg/L for DEHP by the
World Health Organization [18] and in 1.3 µg/L in surface waters by the
European Union [19]. Considering all the above mentioned, it is clear that
there is an increasing need to develop highly sensitive and reliable analyt-
ical methods for monitoring trace amounts of PAEs in different samples
and, especially, in water.
PAEs have been analyzed in water samples using gas chromatog-
raphy (GC) coupled to flame ionization detectors (FIDs) [20], mass
spectrometry (MS) [21] and tandem MS (MS/MS) [22], or high-

performance liquid chromatography (HPLC) coupled to diode array
detectors (DADs) [23], ultraviolet (UV) [24], and MS [25]. Among
them, GC is normally the preferred technique since most PAEs are
nonpolar and thermostable. It is important to notice that, in all these
analytical methods, it has been necessary to include previous sample
preparation steps before instrumental analysis to achieve accurate and
sensitive results. These steps consist on the isolation and pre-concen-
tration of PAEs since they can be found in water samples at extremely
low concentrations. However, since PAEs are not ionizable in water,
these samples are normally analyzed directly or after a simple filtration
without pH adjustment regardless of the sample preparation technique
used in each case [26].
In this context, special attention should be paid to the risk of sample
contamination during their analysis, which would result in false positives
and/or over-estimated concentrations. As it has already been said, PAEs
are ubiquitous contaminants and this includes their possible presence in
any laboratory since they can be found in solvents, reagents, filters, etc.
Consequently, previous washing steps using PAE-free solvents, if possible
(since most organic solvents also contain some PAEs), subsequent heating
of non-volumetric glassware at high temperatures (450–550°C) for several
hours (4–5 h), washing volumetric or any glassware material with strong
oxidizing agents, and, in some cases, even wrapping in heat-treated alumi-
num foil to avoid adsorption of PAEs from the air are carried out, among
others [27–29]. Despite all these precautions, residues of PAEs may finally
appear, and the analysis of blanks should be developed on a daily basis in
every batch of samples so that background levels can be suitably subtracted
[21, 25, 30].
Until very recently, the most widely used sample preparation methods,
also for the analysis of PAEs in water samples, have been based on the
use of liquid-liquid extraction (LLE) and solid-phase extraction (SPE) [31,
32]. The need for developing quicker, simpler, and miniaturized extraction
procedures able to maintain or even to improve the required sensitivity
of the analysis has resulted in the development of new sample prepara-
tion techniques. In this sense, microextraction techniques have gained
notoriety since the extraction is carried out using amounts of extracting
phase much smaller than the sample amount (extraction of analytes is not
always exhaustive). Microextraction techniques have inherent advantages
such as exceptionally high enrichment factors, simplicity, time saving, and
the generation of small amounts of organic solvent or reagents wastes,
without affecting reproducibility, and compatibility with most analytical
instrumentation [33–36]. Among these new alternatives, sorbent-based

microextraction techniques have been widely used due to the great diver-
sity of commercially available sorbents, as well as new extraction sorbents
(in particular nanomaterials) that are constantly being proposed for their
direct use or after a previous functionalization to enhance their selectivity
[35–37].
As a result of the above-mentioned issues, the aim of this book chap-
ter is to provide a general overview of the sorbent-based microextraction
techniques applied to the analysis of PAEs in water samples, which mainly
include solid-phase microextraction (SPME), dispersive SPE (dSPE), and
magnetic dSPE (m-dSPE), among others. The extraction ability to quanti-
tatively and selectively extract these target analytes will be commented and
discussed.
1.2 Solid-Phase Microextraction

SPME has been the sorbent-based microextraction technique most used
for the analysis of PAEs in water samples (see Table 1.1) probably, among
other reasons, because it allows to reduce the risk of PAEs contamination
during sample extraction with respect to other conventional extraction
techniques. On the one hand, the absence of organic solvents and addi-
tional steps reduces PAEs background levels. On the other, water is in
many occasions a simple and clean matrix that contains few interferences,
so the direct immersion (DI) mode can be used without hardly any impair-
ment of its lifetime (except for waste waters or marine water). Moreover, in
SPME, extraction, pre-concentration and direct desorption into analytical
instruments can be easily integrated in most cases.
The first studies in which SPME was applied for PAEs extraction
from water samples dealt with the direct application of commercial fiber
coatings, including polydimethylsiloxane (PDMS), polyacrylate (PA),
PDMS-divinylbenzene (DVB), carboxen (CAR)-PDMS, and carbowax
(CW)-DVB. As examples, Cao [21] demonstrated the better performance
of PDMS-DVB fibers compared to PDMS and DVB-CAR-PDMS fibers for
the headspace (HS) SPME extraction of nine PAEs (DMP, DEP, DIBP, DBP,
BBP, DHXP, DEHA, DEHP, and DNOP) from bottled water samples, while
Polo et al. [28] found that PDMS-DVB fibers also give higher extraction
efficiency than PDMS, PA, CAR-PDMS, and CW-DVB fibers for DBP, BBP,
and DNOP, but CAR-PDMS and PA fibers show a better extraction perfor-
mance for DMP and DEP, and for DEHP, although the first one provided
better results for simultaneous analysis of the target PAEs from bottled,
Table 1.1 Some examples of the application of SPME and SBSE for the analysis of PAEs in water samples.
Matrix (sample Sample Separation Recovery Residues
PAEs amount) pretreatment technique LOQ study found Comments Reference
SPME
DMP, DEP, Mineral, river, SPME using a GC-MS 0.0067– 87–110% at One sample A multifactor categorical [28]
DBP, BBP, industrial PDMS-DVB 0.34 0.5 and of each design was used
DEHP, port, fiber, stirring µg/L 2.5 µg/L water were for optimization
and sewage, and at 100°C in DI analyzed purposes. PDMS-DVB
DNOP waste waters mode for 20 min, and fiber showed higher
(10 mL) and desorption contained extraction efficiency
at 270°C for all PAEs at than PDMS, PA, CAR-
5 min levels from PDMS and CW-DVB
0.011 to fibers for DBP, BBP,
6.17 µg/L and DNOP, but CAR-
PDMS for DMP and
DEP, and PA for DEHP.
DI-SPME provided
better sensitivity than
HS mode
(Continued)
Phthalates Microextraction From Water
7
8
Table 1.1 Some examples of the application of SPME and SBSE for the analysis of PAEs in water samples. (Continued)
DEHA, DMP, Mineral water SPME using a GC-MS - - Eleven samples PDMS-DVB fiber showed [21]
DEP, BBP, (10 mL plus PDMS-DVB were higher extraction
DIBP, 10 or 30% fiber, stirring at analyzed efficiency than PDMS
DBP, w/v NaCl) 90°C in DI mode and residues and DVB-CAR-PDMS
DHXP, for 60 min, and of DEP, fibers
DEHP, desorption at DIBP, DBP,
and 270–280°C for and DEHP
DNOP 5 min were found
at levels
from 0.052
to 1.72 µg/L
DPP, DBP, Mineral and tap SPME using a GC-FID 0.17–0.33 90–113% at Three mineral - [40]
DIBP, and water (10 MWCNTs- µg/L 5 and 50 water

DNPP mL) PPy fiber, µg/L samples
stirring at room and 1 tap
temperature in water were
DI mode for analyzed
60 min, and and
desorption at contained at
250°C for 25 min least 1 PAE
at levels
from 0.6 to
7.90 µg/L,
except 1 of
the mineral
water
samples
(Continued)
DMP, DEP, Mineral, SPME using a MIP GC-MS 0.0072– 94.54– One sample DBP was used as the [45]
DBP, tap and fiber, stirring at 0.069 105.34% of each template molecule. MIP
DAP, and reservoir 60°C in DI mode µg/L water were fiber showed higher
DNOP waters (12 for 30 min, and analyzed extraction efficiency
mL plus 10% desorption at and than a non-imprinted
w/v NaCl) 250°C for 10 min contained polymer fiber, and
at least 2 PDMS, PA and
PAEs at CW-DVB fibers
levels from
0.07 to 0.53
µg/L
DMP, DEP, Water (5 mL SPME using a PA GC-MS 0.007– - Six samples PA fiber showed higher [95]
DBP, BBP, plus 6% w/v fiber, stirring 0.027 were extraction efficiency
DEHP, NaCl) at room µg/L analyzed than PDMS fiber. Urine
DINP, and temperature in and was also analyzed
DNOP DI mode for contained
50 min, and at least 2
desorption at PAEs at
270°C for 2 min levels from
0.4 to 78.8
µg/L
(Continued)
9
10
DIBP, DBP, River and SPME using GC-MS 0.013– 61.9–87.1% One sample Bamboo charcoal fiber [47]
BMPP, tap waters a bamboo 0.067 at 0.1, of each showed greater
DNPP, (- mL) charcoal fiber, µg/L 0.5, and water were extraction efficiency
DHXP, stirring at room 1 µg/L analyzed than PDMS, PDMS-
BBP, temperature in and no DVB and PA fibers for
DCHP, DI mode for residues DNOP and DINP, but
DEHP, 20 min, and were lower for DIBP, DBP,
DIPP, desorption at detected and DNPP
DNOP, 280°C for 10 min
and DINP
DBP, DIBP, Mineral water SPME using a GC-FID, 0.17–0.40 86–107% at One sample TiO2 NPs fiber showed better [39]
BBP, and (9 mL plus TiO2 NPs fiber, GC-MS µg/L 2 µg/L was extraction efficiency than
DEHP 20% w/v stirring at 30°C analyzed PDMS and poly(3,4-
NaCl) in DI mode for and ethylenedioxythiophene)-
75 min, and residues TiO2 fibers. DI-SPME
desorption at of DIBP provided better sensitivity
285°C for 5 min and DEHP than HS mode
were found
at 1.0 and
2.2 µg/L,
respectively
(Continued)
DMP, DEP, Mineral, river SPME using a GC-FID 0.033– 79.62– One sample SiO2-PDMS-MWCNTs [43]
DBP, and and tap SiO2-PDMS- 0.067 109.3% of each fiber showed better
DEHP waters (15 MWCNTs fiber, µg/L at 10 water were extraction efficiency
mL) stirring at 40°C µg/L analyzed than PDMS, PA and
in DI mode for and DVB-CAR-PDMS fibers
30 min, and residues of
desorption at DBP and
280°C for 2 min DEHP were
found at
5.26 and
8.47 µg/L,
respectively,
in the
mineral
water
sample
(Continued)
11
12
DPP, DIBP, Mineral and tap SPME using a poly- GC-FID 0.10–0.25 91–115% at Three mineral NaCl and dextrose injection [42]
DBP, waters (10 o-aminophenol- µg/L 5 and 50 water solutions were also
DNPP, mL) MWCNTs fiber, µg/L samples analyzed
BBP, and stirring at 35°C and 1
DEHP in DI mode for tap water
60 min, and sample
desorption at were
280°C for 2 min analyzed
and
contained
at least 2
PAEs at
levels from
0.3 ± 0.02
to 8.1 ±
0.19 µg/L,
except for
1 mineral
water
sample
(Continued)
DBP, BBP, Tap, barreled SPME using a GC-MS/MS 0.0038- 73.4- One sample A Box-Behnken design was [41]
DEHA, drinking PS-MWCNTs 0.059 103.8% of each used for optimization
DEHP, and pond fiber, stirring µg/L at 0.05 water were purposes
and waters (10 at room and 0.2 analyzed
DNOP mL plus 15% temperature in µg/L and
w/v NaCl) DI mode for contained
60 min, and at least
desorption at 1 PAE at
280°C for 5 min levels from
0.038 ±
0.004 to
0.060 ±
0.007 µg/L
(Continued)
13
14
DPP, DBP, Mineral, tanked SPME using a GC-FID 0.2–0.3 88–108% at One sample A central composite [20]
DEHA, and tap G-PVC fiber, µg/L 10 and of each design was used for
and waters, and stirring at 70°C 20 µg/L water were optimization purposes.
DEHP boiling in HS mode analyzed Sunflower and olive oils
water for 35 min, and and residues were also analyzed
exposed desorption at of DPP
to a PET 230°C for 4 min and DBP
container were found
(10 mL plus at 2.1 and

30% w/v 1.8 µg/L,
NaCl) respectively,
only in the
boiling
water
exposed
to a PET
container
(Continued)
DMP, DEP, Sea water (10 SPME using a GC-MS 0.00017– 68.0– Eleven sample Sediment was also analyzed [96]
DIBP, mL) PDMS fiber, 0.0011 114.0%, was by conventional SPE
DBP, stirring at 35°C µg/L but analyzed
DMEP, in DI mode for 55.4% and
BMPP, 40 min, and for contained
DEEP, desorption at DMP, at least 9
DNPP, 40°C for 6 min at 100 PAEs at
BBP, and 300 levels from
DHXP, µg/L 0.270 to
DBEP, 1.39 µg/L
DCHP,
DPhP,
DEHP,
DNOP,
and DINP
(Continued)
15
16
DEP, DIBP, River, bottled SPME using a GC-µ-ECD 0.13–0.64 90.3–106% One sample Polyamide6-MnO fiber [44]
DBP, and mineral polyamide6- µg/L at 10 of each showed better extraction
BBP, and waters (4 MnO fiber, and 100 water were efficiency than PDMS
DEHP mL plus 20% stirring at 80°C µg/L analyzed fiber. Soda was also
w/v NaCl) in HS mode and residues analyzed
for 30 min, and of DEP,
desorption at DIBP and
200°C for 5 min DBP were
found at
levels from
9.24 to
29.3 µg/L,
respectively,
in the bottle
and mineral
waters
DMP, DEHP, Tap and sea SPME using a GO-1- GC-MS 0.017–0.10 87.6– One sample GO-1-(3-aminopropyl)- [52]
DBP, water (20 (3-aminopropyl)- µg/L 101.2% of each 3-vinyl imidazolium
DNPP, mL adjusted 3-vinyl at 1 and water were bromide fiber showed
BBP, and at pH 4) imidazolium 5 µg/L analyzed, higher extraction
DNOP bromide/ and no efficiency than GO-1-
tetrafluoroborate residues (3-aminopropyl)-3-
fiber, stirring at were vinyl imidazolium
35°C in DI mode detected tetrafluoroborate, PA
for 30 min, and and CAR-PDMS fibers.
desorption at Coffee was also analyzed
175°C for 5 min
(Continued)
DEP, DPP, Water (- mL SPME using a GC-FID 0.11–1.50 78.6– Three sample OH-TPB-COFs fiber [46]
DAP, plus 20% OH-TPB-COFs µg/L 101.9% were showed better extraction
DBP, w/v NaCl) fiber, stirring at 1 and analyzed efficiency than PDMS
BBP, and at 105°C in HS 5 µg/L and fiber
DEHP mode for 50 min, contained
and desorption at least 4
at 250°C for 7 PAEs at
min levels from
1.39 to 5.78
µg/L
DMP, DBP, Mineral water IT-SPME using CE-DAD, 0.59–9.83 78.8– One sample AC-PS-DVB monolithic [62]
DINP, (9 mL) AC-PS-DVB UHPLC-UV µg/L 104.6% was column showed better
DEP, BBP, monolithic at 50 analyzed, extraction efficiency
DEHP, columns, and µg/L and no than AC-poly(BMA-
DNOP, desorption with residues EDMA) monolithic
and DIDP 1.5 mL ACN were column. ACN showed
detected higher extraction
efficiency than MeOH
as desorption solvent.
(Continued)
17
18
DMP, DEP, Disposable IT-SPME using HPLC-DAD 0.07–0.16 77–120% at One sample PDA-melamine- [23]
DAP, tableware, PDA-melamine- µg/L 10 and of each formaldehyde aerogel-
BBP, DBP, plastic cup formaldehyde 15 µg/L water were carbon-fiber tube
DNPP, and river aerogel-carbon- analyzed showed better extraction
and waters (45 fiber tube, and and efficiency than
DCHP mL plus 2% desorption with residues of melamine-formaldehyde
v/v MeOH) MeOH-water for DAP, BBP aerogel-carbon-fiber and
0.6 mL and DNPP bare carbon-fiber tubes

were found
at levels
from 0.12
to 0.99 µg/L
in the water
in plastic
cup
(Continued)
SBSE
DMP, DEP, Sea and SBSE using a GC-MS 0.0003– 95–124% at One river A Plackett–Burman and [65]
DBP, BBP, esturiane PDMS stir bar, 0.063 0.1 µg/L water 2 central composite
DEHP, waters (20 stirring at room µg/L sample and designs were used
and mL plus 30% temperature for 2 estuarian for optimization
DNOP w/v NaCl 60–200 min, water purposes. 6 polycyclic
and 20% v/v and thermal samples aromatic hydrocarbons,
MeOH) desorption at were 12 polychlorinated
300°C for 10 min analyzed biphenyls and 3
and nonylphenols were also
contained analyzed
all PAEs at
levels from
0.0036 ±
0.0004 to
1.314 ±
0.018 µg/L
(Continued)
19
20
DMP, DEP, Sea water (25 SBSE using a GC-MS 0.00027– - No samples The stir bar coated with 150 [66]
DIBP, mL plus 5% PDMS stir bar, 1.63 were µl PDMS showed higher
DBP, w/v NaCl stirring at room µg/L analyzed extraction efficiency
DMEP, and 10% v/v temperature for than coated with 50
DMPP, MeOH) 120 min, and µL and 75 µL PDMS,
DEEP, desorption with and 150 µL PDMS over
DNPP, 200 μL MeOH carbon film. A mix
DHXP, and 50 μL ACN MeOH-ACN showed
BBP by sonication for higher extraction
DBEP, 50 min efficiency than MeOH
DCHP, and dichloromethane as
DEHP, desorption solvent

DPhP, and
DNOP
µ-ECD, micro-electron capture detector; AC, activated carbon; ACN, acetonitrile; BBP, benzylbutyl phthalate; BMA, butyl methacrylate; BMPP, bis(4-methyl-2-pentyl)
phthalate; CAR, carboxen; CE, capillary electrophoresis; COFs, covalent organic frameworks; CW, carbowax; DAD, diode-array detector; DAP, diallyl phthalate;
DBEP, di(2-butoxyethyl) phthalate; DBP, dibutyl phthalate; DCHP, dicyclohexyl phthalate; DEEP, di(2-ethoxyethyl) phthalate; DEHA, di(2-ethylhexyl) adipate;
DEHP, di(2-ethylhexyl) phthalate; DEP, diethyl phthalate; DHXP, dihexyl phthalate; DI, direct immersion; DIBP, diisobutyl phthalate; DIDP, diisodecyl phthalate;
DINP, diisononyl phthalate; DIPP, diisopentyl phthalate; DMEP, di(2-methoxyethyl) phthalate; DMP, dimethyl phthalate; DMPP, dimethylethyl phthalate; DNOP,
di-n-octyl phthalate; DNPP, di-n-pentyl phthalate; DPhP, diphenyl phthalate; DPP, dipropyl phthalate; DVB, divinylbenzene; EDMA, ethylene dimethacrylate; FID,
flame ionization detector; G, graphene; GC, gas chromatography; GO, graphene oxide; HPLC, high-performance liquid chromatography; HS, headspace; IT-SPME,
in tube-solid-phase microextraction; LOQ, limit of quantification; MeOH, methanol; MIP, molecularly imprinted polymer; MS/MS, tandem mass spectrometry;
MS, mass spectrometry; MWCNTs, multi-walled carbon nanotubes; NPs, nanoparticles; PA, polyacrylate; PAE, phthalic acid ester; PDA, poly(dopamine); PDMS,
polydimethylsiloxane; PET, polyethylene terephthalate; PPy, polypyrrole; PS, polystyrene; PVC, polyvinylchloride; SBSE, stir bar sorptive extraction; SPE, solid-
phase extraction; SPME, solid-phase microextraction; TPB, 2,4,6-triphenoxy-1,3,5-benzene; UHPLC, ultra-performance liquid chromatography; UV, ultraviolet.
industrial harbor, river, urban collector, and influent and effluent waste
water samples. As expected, the optimal SPME fiber for the extraction of
a particular phthalate depends on both the properties of the coating and
the PAEs since these compounds differ from each other in terms of polar-
ity and volatility and, therefore, on their distribution between the fiber
coating and the matrix. In addition, low-molecular PAEs are more vola-
tile than those of high-molecular weight [38]. As a result, low-molecular
PAEs would be expected to be more efficiently extracted when HS mode
is used [38]. However, they have a certain solubility in water and, as con-
sequence, they volatilize very slowly from this kind of matrices. Contrary,
although high-molecular PAEs are less volatile, they have a lower water
solubility and they volatilize faster at higher temperatures than it could be
expected [38]. Accordingly, it has been observed that DEHP and DNOP
are extracted from different water samples more efficiently than BBP, DEP,
and DMP using HS-SPME [28, 39]. Nevertheless, most of the works pub-
lished on this topic are based on DI-SPME instead of HS-SPME.
As it has already been said, the fiber coating plays a key role in the SPME
of PAEs from water samples. However, the types of commercial fibers are
still limited, which reduces their application field. In addition, under cer-
tain conditions they have low thermal and chemical stability. Furthermore,
they are fragile since they are based on fused silica supports. Consequently,
most of the subsequent studies have been focused on developing new
highly selective, efficient, inexpensive, and robust SPME fibers with con-
trollable thickness through different coating techniques. For this purpose,
a wide variety of new fibers based on the use of carbon-based nanomateri-
als [40–43], metal oxide nanoparticles (NPs) [39, 44], molecular imprinted
polymers (MIPs) [45], covalent organic frameworks (COFs) [46], and
bamboo charcoal [47] have been reported, among others.
The development of carbon-based coatings for stainless-steel fibers has
been an important research field as a result of the exceptional properties
these materials have, such as great chemical and thermal stability, high sur-
face area and great capacity to establish π-π interactions with the aromatic
groups of the PAEs [37, 48, 49]. Moreover, they can be easily dispersed in a
polymer matrix to obtain coatings that provide considerably better charac-
teristics than those of virgin polymers. Among them, multi-walled carbon
nanotubes (MWCNTs) have been the most used, which are large molecules
composed by numerous electronically aromatic delocalized carbon atom
layers and rolled up into a cylinder. As examples of the use of this kind of
coatings for the extraction of PAEs from water samples, Asadollahzadeh et
al. [40] made a fiber coated with an oxidized MWCNTs-polypyrrole (PPy)
composite while Behzadi et al. [42] used MWCNTs-poly-o-aminophenol,
both obtained through electrochemical polymerization, for the extraction

of mineral water samples. Song et al. [41] also prepared a MWCNTs-
polystyrene (PS) material via electrostatic interactions as SPME coating,
and Zhang et al. [43] developed a SiO2-PDMS-MWCNTs fiber by a sol-gel
method. In both cases, drinking and environmental water samples were
analyzed. All these fiber coatings presented a porous structure with very
large surface areas where both phases (the MWCNTs and polymer) took
part in the extraction procedure, enhancing the final adsorption capacity
of the fiber. Moreover, in the last work, the organic-inorganic bilayer struc-
ture was designed to increase the stability and durability of the coating. In
particular, a stainless-steel fiber was coated with a SiO2 layer, which was
used as support for the chemical bonding of the second layer of PDMS-
MWCNTs (see Figure 1.3). The first coating with a SiO2 layer is a general
procedure widely used for coating different surfaces or particles [50, 51].
Compared with commercial PDMS, PA, and DVB-CAR-PDMS fibers, this
new coating showed better extraction efficiency and longer lifetimes (150
vs. 50–100 times) for the extraction of DMP, DEP, DBP, and DEHP. It is also
noteworthy to mention the extensive study that was conducted by these
authors to evaluate the influence of salt addition on the extraction effi-
ciency. It was observed that the addition of different kinds of salts such as
OC2H5 CF3COOH OH
C2H5O Si OC2H5 + H2O HO Si OH
OC2H5 OH
TEOS
Si O Si O Si OH OH OC2H5
n HO Si O Si OH + + C2H5O Si OC2H5
O O O +
Si O Si O Si OH n OC2H5
n
O O O MWNTs
TSO-OH TEOS
O O Si O Si O
Si O Si O Si O Si O Si O O O n
CF3COOH n n Si
O O O O
Si O Si O Si O Si O Si O O O
n O Si O Si O
O O O nO
n
needle SiO2 film stationary phase
Figure 1.3 Schematic representation of the SiO2-PDMS-MWNTs fiber preparation. Reprinted

from [43] with permission from The Royal Society of Chemistry. MWNTs, multi-walled
carbon nanotubes; TEOS, tetraethoxysilane; TSO-OH, hydroxyl terminated silicone oil.
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CHAPTER XIX.
OTHERWISE THAN INTENDED
Scarcely had the housekeeper given this answer to her master’s

inquiry, when a loud knocking at the front door, and the long tinkling
of the electric bell, announced that some one was there, some one,
as they all guessed, who was acquainted with what had happened.
There was something so startling in this thundering at the door at
the very moment when they were on their way upstairs towards the
room which they imagined to be the scene of a tragedy, that both Sir
Robert and Mrs. Hawkes stopped and turned upon the staircase.
“Who’s that?” hissed the housekeeper.
A man-servant had run to the door, but Sir Robert turned once
more and pointed imperiously upwards.
“Go on, go on, or let me pass,” he said.
And then, as if the knocking at the door had been only the result of
their own imaginations, excited by their fears, they both hurried on
up the stairs.
Swiftly there passed through the minds of both a succession of
terrible thoughts, born of the events of the past month. The
housekeeper was as well aware as her master and mistress
themselves that there was acute tension between them, and in all
the anxiety and suspense which the whole household had endured
since the thefts from the gallery had become known and whispered
about, the chief hope of everybody that some sort of satisfactory way
out of the family difficulties might be found, centred on Rhoda
Pembury.
With her quiet manners, her attachment to the invalid boy, her
evident efforts to preserve the peace between husband and wife, the
girl had endeared herself to the lower members of the household as
well as to Caryl, and Mrs. Hawkes in particular had persisted in
believing that she would end by finding means to bring the ill-
assorted couple together.
But now the housekeeper was filled with fear that the peace-maker
had been the victim of a fresh tragedy.
She was even vaguely suspicious as to the hand by which such a
tragedy as she feared might have been brought about. It was
inevitable that some inkling of the truth about the death of poor
Langton should have trickled through to the servants’ hall during
those ten years which had elapsed since the death of the butler, that
gossip should have fixed upon Jack Rotherfield as the possible
holder of the clue to that old mystery.
Now, therefore, it was not surprising that Mrs. Hawkes should ask
herself whether Jack Rotherfield, who had already the guilt of one
outrage at his door, might not have committed another. If Rhoda
Pembury had been murdered because she stood between Lady
Sarah and her husband’s rival, who but that rival could have been
guilty of the act?
So thought Mrs. Hawkes as she hurried along the corridor to the
door of Rhoda’s room.
Bursting it open without knocking, so sure was she that the sounds
she had heard proceeded from this room, the housekeeper found
herself in darkness. The electric light had not been turned on. The
window was open, the curtains were drawn back, and a little light
came from the moon, not long risen.
For a moment Mrs. Hawkes saw nothing. Then, her eyes
becoming accustomed to the gloom, she perceived that there was
something on the floor close by the window, something that did not
move, did not utter a sound.
She moved forward quickly, and knelt down on the floor. Then a
shudder went through her, and she sat back with a low cry.
Once more bending down, she raised the inert mass from the
floor, turned the limp head, stared down into the ghastly face.
For a moment sight and sense seemed to fail her, and then she
was roused by sounds of voices and footsteps outside the door.
Scrambling quickly to her feet, the housekeeper hurried across the
floor, just as a loud knock sounded on the door of the room.
She heard the rattling of the handle and quickly turned the key in
the lock at the sound of master’s voice.
“Mrs. Hawkes, can I speak to you? Can you come out?”
She tried to recover her natural voice, as she answered quickly:
“In one moment, Sir Robert. Will you send for a doctor at once?”
“A doctor!” The voice was that of Jack Rotherfield.
“What has happened?” This was in Sir Robert’s voice.
There was a pause, during which Mrs. Hawkes heard other voices
in a confused buzz.
“There has been an accident. A bad accident, I’m afraid.”
“Yes, yes. An accident. But I was the cause of it. I did it. Oh, God,
let me come in, let me in.”
These words were uttered in the strong voice of Jack Rotherfield,
and at the same moment there came a terrific lunge against the
door, which he was trying to break open.
The stern voice of Sir Robert, remonstrating, had the desired
effect of making the young man desist, and then the housekeeper
heard her master giving orders to one of the men-servants to go at
once for a doctor.
In the meantime Mrs. Hawkes had hurriedly recrossed the floor to
the window, and made one more examination of the body of the
woman lying in a heap on the rug under the window.
Then the voice of Jack Rotherfield sounded loud and clear above
all the others outside.
“She’s dead, I know she’s dead.”
“Hush!”
It was Minnie who was trying to silence him, but the young man
still ejaculated, in a tone of passionate remorse and horror,
“I know she’s dead. I know it. It was I killed her.”
“What!”
Sir Robert hissed out the word, in horror and dismay.
Jack Rotherfield went on, in a deathlike silence which made every
word ring out:
“I meant only to frighten her. It was an accident. I fired a revolver
into the air, as I thought, but the bullet struck her as she leaned out
of the window.”
There were sounds of sobbing and suppressed screaming, and in
the midst of it Sir Robert knocked again at the door.
“You had better let me come in.”
The housekeeper turned the key in the lock, and opened the door.
At the same moment a figure came flying along the corridor from
Caryl’s room, and Rhoda Pembury, pale and alarmed, joined the little
group of three persons: Sir Robert, Jack Rotherfield, and Mrs.
Hawkes.
“What is it? What has happened?” cried the girl. “What is all the
noise?”
Sir Robert fell back, reeling.
“Thank God!” he said hoarsely, under his breath, as he looked at
her.
She stared at him, trembling, then at Jack Rotherfield, who was
striving to get past Mrs. Hawkes; and at the housekeeper, who held
him fast by the arm.
The housekeeper suddenly relaxed her hold of Jack and beckoned
to Rhoda.
“Come in with me,” she said.
Rhoda staggered back.
“What is it? In my room?” stammered she.
The housekeeper nodded.
“Lady Sarah,” she whispered. “She is—” And with her lips she
formed the word “dead.”
Both Sir Robert and Rhoda understood, and in silence they both
entered the room, where Mrs. Hawkes turned up the light.
There, under the window, in her light satin dress, with the jewels
round her neck and on her hands, the flowers still pinned to her
bodice, her beautiful dark hair disordered by her fall, lay Lady Sarah,
inert, lifeless.
A little dark stain on her satin bodice showed where the blood had
oozed through from the wound in her breast.
Jack Rotherfield burst into the group and threw himself on the
ground beside the dead woman. Unprincipled as he was, guilty as he
was, not one of the three persons present could fail to be moved by
the anguish in his face. Solemn as the moment was, and deeply as
they were all impressed by the swiftness of the unexpected and as
yet imperfectly understood tragedy, not one of those three, Sir
Robert, Rhoda, or Mrs. Hawkes, showed half the despair which
convulsed the features of the young man.
He was mad with grief. He babbled out words to which they would
all fain have shut their ears; he took the lifeless hands and pressed
them within his own, staring down at the dead face, calling to her,
now loudly, now softly, in a way which wrung all their hearts.
The group broke up on the arrival of the doctor, and only Mrs.
Hawkes and Sir Robert remained in the room while he made his brief
examination.
There had never been the least doubt about the result of it. Lady
Sarah had been shot through the heart, and must have died
instantaneously.
Jack Rotherfield made no secret of the fact that he had been the
cause of her death, but it soon leaked out that, while he declared
that he had accidentally shot the lady, while intending only to attract
her attention and to frighten her, he had believed, as he did so, that
the woman he was frightening was Rhoda Pembury.
It was Lady Sarah’s scream which had acquainted him with the
fact that the bullet had struck the wrong woman.
His explanations, rambling and confused, deceived no one. All his
hearers knew that he must have been on the watch for Rhoda’s
appearance at the window of her room, where it was often her habit
to sit looking out at the water that ran through the grounds. The room
being unlighted, the moment he saw a woman’s figure at the window,
Jack had jumped to the conclusion that it was that of Rhoda
Pembury, and he had shot her, by his own account accidentally, but
none the less effectually.
He was suffered to leave the house without molestation, and
indeed it was necessary to suggest his withdrawal, so anxious was
he to remain in the vicinity of the dead woman to whom, it could not
be doubted, he had been deeply attached.
It was the doctor who got rid of him, and who then turned his
attention to Rhoda, upon whom the tragic event, which she
understood better than any one, had had an overwhelming effect.
For a short time she lay prostrate, absolutely overcome by the
knowledge that it was in mistake for herself that Jack Rotherfield had
shot Lady Sarah. Rhoda remembered the glances which the
unfortunate lady had thrown repeatedly in her direction during dinner,
and did not doubt that Lady Sarah had gone to the room of her boy’s
companion in order to speak to her privately. There seated or
standing at the window, in the half darkness, she had been mistaken
by Jack Rotherfield for Rhoda, and, although his statement was to
the effect that his intention had only been to attract her attention or to
frighten her—for he had given both explanations—Rhoda was quite
sure that he had intended to shoot her, in revenge for what she had
done in keeping him apart from Lady Sarah, or to prevent any
indiscretions on her part in the shape of revelations concerning the
death of Langton.
Suddenly Rhoda raised herself from the couch in Lady Sarah’s
boudoir where she had been placed.
“Caryl!” she whispered.
Mrs. Hawkes, having superintended the carrying of the body of
poor Lady Sarah into her own bedroom, had left Sir Robert alone
with the dead lady and had given her attention to Rhoda.
Rhoda had caught the faint sound of the boy’s voice, through the
open doors. He was calling for her.
“I must go to him.” She struggled to her feet, and turning
unsteadily, said: “Mrs. Hawkes, will you send word to the Priory of
what has happened? And ask whether Lady Eridge will come? She
will have to take Caryl away.”
“Yes. Quite right. I hadn’t thought of it.”
Rhoda went slowly to the boy’s room and found him crying in his
little bed. His nurse was with him, doing her best to soothe him, but
rumours of the tragedy which had killed his mother had already
reached his ears, and he would not be comforted without his friend.
“Rhoda, Rhoda,” cried he, as she came in, looking very white, “Is it
true? Is mama dead?”
“Oh, they shouldn’t have told you!”
“But I guessed.” She was beside him by this time, and his arm was
round her neck. “You remember that evening when she was kind,
and kissed me, and cried? I knew that meant something was going
to happen, and I’ve wondered and wondered what it was. Now I
know.”
Rhoda wiped away her own tears. He drew her head down to his
level.
“Poor mama. I’m sorry. She was so pretty!” There was a pause,
while Rhoda acquiesced, sobbing. Then he said quickly: “But you will
stay with me, won’t you?”
Rhoda did not know what to say.
“Your grandmama will want to take care of you, Caryl, I think,” she
said. “She will be very, very kind, and so will your aunts, I’m sure.”
“Yes, they’re all kind, but I want you. Will you promise to stay with
me?”
“I can’t promise anything yet. You must wait, and be sure we will
take good care of you, Caryl,” said the girl, who could scarcely
speak.
The wrench of the tragedy had been great: that of parting with
Caryl would, she felt, be greater still. Yet how was it to be avoided?
Within half an hour the marchioness arrived with Lady Aileen; and
both, after a long and distressing interview with Sir Robert, came
with him into Caryl’s room.
At once Rhoda noticed, with deep distress, that there was a
difference in his manner to herself.
Instead of being merely sad and grave, Sir Robert, when he turned
towards her, was distant, formal, stern and cold. She was cut to the
heart, and understood that he looked upon her as in part the cause
of the death of his wife.
True though this was, in a sense, yet as Rhoda was wholly
innocent in the matter, she felt that it was an injustice that she should
be treated in this manner.
In the circumstances, it was, of course, impossible either to
explain or to accuse. She could only submit, and suffer.
Before many minutes were over, however, she had something to
think about which distracted her thoughts, for the time, from Sir
Robert and his unkindness.
Lady Eridge, deeply distressed as she was at her daughter’s
sudden and tragic death, seemed to feel something not unlike a
sense of relief that her troubles on behalf of the erratic and self-
willed Lady Sarah were at an end.
“What are you going to do, Miss Pembury?” she asked in a low
voice, as she bent over the boy.
“She is going to stay with me,” cried Caryl, as he joined his hands
together round Rhoda’s neck, and clinging to her, refused to relax his
hold.
Lady Eridge looked at her.
“You can’t stay here, of course?”
“Of course not. I am going away at once,” said Rhoda.
The boy burst into loud sobs.
The marchioness bent down to whisper in her ear.
“I’m going to take him to the Priory, to-night, out of the way of
everything. His father will not mind, I’m sure.”
“No. That will be the best thing possible.”
“Will you come with him?”
“Oh, to the Priory? I think I’d rather not. You see I feel so
miserable, and as if I were guilty of—of——”
“Hush! That is absurd. If you come with us, there will be no
question that it will be best for you as well as for Caryl. And it will
show that her people understand. Now will you come?”
Still feeling as if she were held guilty by the boy’s father, Rhoda
glanced towards him.
“If Sir Robert agrees, I’ll go,” said she.
The marchioness went over to him and they exchanged a few
words. Then Lady Eridge came back.
“He agrees with me that nothing could be better. And he thinks
that you had better both come at once. Of course you had better be
near at hand, for there will be questions to answer, since the terrible
affair happened in your room. And you will be near enough at the
Priory.”
It was settled at once. Within an hour little Caryl had been
removed to his couch on wheels, and wrapped up carefully, was on
his way to the Priory, in the company of Rhoda, his grandmother,
and one of his aunts.
Rhoda took care not to meet Sir Robert before leaving the house.
She could not face those cold looks of his again. And it was with a
very heavy heart, and a sense that, in spite of her utmost efforts, she
had lost a dear friend, that she left the Mill-house for a second time.
CHAPTER XX AND LAST.
SIR ROBERT’S SECRET
Safely housed at the Priory, Rhoda escaped much of the terrible

anxiety and distress which reigned at the Mill-house during the next
few days.
There was an inquest, but Rhoda happily escaped once more the
trial of being called as a witness. Her health had broken down under
the strain of the past few weeks, and although she was allowed to
see Caryl for a little while every day, she was kept very quiet and
received no visits, even from her own people.
The ladies at the Priory were, however, very kind to her, and did
their best to make her forget what she had gone through.
Nobody knew better than they what she must have suffered at the
hands of the exacting and capricious Lady Sarah, who, with all her
charm, had been a difficult person to live with.
At the inquest Jack Rotherfield was called as a witness, and he
was either lucky enough or clever enough to disarm every one by the
depth of his distress at what he had done.
He declared that, having had a little quarrel with Sir Robert
recently, he had been shy of coming to the house, but that, having
met Miss Pembury one day out of doors, he had been anxious for
her to come out and speak to him again, as he wished her to make
his peace with Sir Robert.
Not being able to attract her attention in any other way, he had on
seeing Miss Pembury, as he supposed, at her window, fired a
revolver which he always carried about with him; and to his horror, a
scream had told him that the bullet had struck the lady whom he had
until that moment believed to be Miss Pembury, but who he then
discovered by the voice to be Lady Sarah.
The story was not at all a probable one, but Jack was in such a
state of acute distress that he produced a favourable impression,
and he was let off lightly in examination and re-examination by the
coroner and jury.
Sir Robert was able to testify to the truth of the statement that
there had been a little quarrel between him and Rotherfield, and to
the certainty he felt that Jack would not willingly have injured Lady
Sarah.
The verdict brought in by the jury was one of death by
misadventure, and the threatened scandal was happily averted.
There was a good deal of gossip, there were rumours, there were
whispers, but no arrest was made, and the affair was hushed up,
though not without some trembling on the part of the families
involved.
Autumn being now well advanced, there was a discussion as to
what should become of the usual holiday at the Riviera, and in the
end it was abandoned by Lady Eridge, who decided to remain at the
Priory. There Caryl was to stay also, and Lady Eridge told Rhoda
that she had questioned Sir Robert about his plans, and that he had
decided to shut up the Mill-house and to go abroad.
“I then suggested,” went on the marchioness, “that we should ask
you to stay with Caryl, and Sir Robert agreed. But really he seems to
take no interest in anything since the death of his wife.”
Rhoda was quite ready to fall in with this arrangement, and she
hoped that, before going away, the baronet would, on saying good-
bye, show her once more a little of his old kindness. For the
remembrance of his cold looks and harsh voice when he spoke to
her on the night of Lady Sarah’s death had made a wound which did
not heal.
To her bitter disappointment, she was told one evening, when she
returned to the Priory after a walk into the town by herself, that Sir
Robert had called in her absence, had said good-bye to his boy, and
that he would start for Egypt that very evening.
Rhoda shed hot tears at the thought that he had gone away
without one word to her. She had revered him so long, had
sympathised with him, done her best to keep the difficult household
going during the lifetime of his wife, that she felt deeply hurt at this
lack of ordinary kindness which she had had a right to expect.
It prepared her for a future in which she would find herself cut off
altogether from the Mill-house and its inmates; for she did not doubt
that, when he returned in the spring, Sir Robert would send for his
son, and she would then get her dismissal.
Rhoda felt that Lady Eridge understood something of her feelings,
for the marchioness was very kind to her, and did her best to prove
that her services were appreciated.
Perhaps Caryl, young as he was, understood too that Rhoda had
not been treated quite well, for he said nothing to her about the
farewell interview with his father.
The winter passed quickly for all that. Rhoda and Caryl became so
devoted to each other that the thought of a possible parting, which
was ever present to the woman and which often occurred to the
child, grew more and more painful.
But at Christmas time there occurred one incident which afforded
Rhoda for the time a little consolation.
It was a visit from Jack Rotherfield.
He arrived at the Priory one afternoon just after luncheon, and had
a long interview with Lady Eridge in the drawing-room, at the end of
which the marchioness sent for Rhoda. The marchioness rose from
her chair, and, advancing towards the girl, who uttered an
exclamation of horror on seeing who the visitor was, said in her ear,
“He has behaved well to us, and he wishes to make some sort of
apology to you.”
And with these words the marchioness left them together.
Jack, who was looking thin and ill, came frankly towards Rhoda.
He did not attempt to shake hands:
“I suppose you are surprised to see me, Miss Pembury,” he said.
“But as Lady Eridge sent for me to explain certain stories about poor
Lady Sarah and me, which had come to her ears, I thought I should
like to see you and to ask your forgiveness for my share in making
you lose your home at the Mill-house.”
Rhoda was not ready with an answer, and she murmured some
indistinct and rather cold words of acknowledgment.
“I know you did your best for her,” he said frankly; “and that you
were perfectly right in doing what I so much resented. All the same,
she would never have been happy with Sir Robert. And you know it.
She irritated him, and she got on his nerves. They were an ill-
matched pair from the first.”
“Why have you come?” asked Rhoda abruptly.
“Lady Eridge sent for me, as I told you. She had heard about those
interviews poor Lady Sarah and I had before she was married. I told
her everything. And I wanted to thank you for holding your tongue.
You might have done for me altogether if you had appeared at the
inquest, or if you had talked afterwards. I beg your pardon with all my
heart for any harm I have ever done you, or for any I, in my mad
rage, may have wished to do you.”
Rhoda could not but think that this frankness in a man of his
character came perilously near to effrontery. But she was not inclined
to stir up the ashes of dead resentments, and she told him that, if Sir
Robert could forgive him, she would not hold back.
“I am writing to him to-night,” said Jack.
The interview was not very long, but when it was over and Jack
Rotherfield had gone away, she fell to wondering what he would say
about her in his letter to Sir Robert.
Her heart was still very sore about the departure of the baronet
without a word of farewell to her, and she felt that he still associated
her unfairly in his mind with all his misfortunes.
It was true, indeed, that she had always been at the Mill-house
when they happened.
As the winter went on, Caryl, who received frequent letters from
his father, without one word in them of Rhoda, became more and
more disturbed as to his future.
He dictated his letters to Rhoda, who transcribed them for him;
but, although they both knew that the baronet must recognise her
handwriting, there was never any message in Sir Robert’s letters to
his son, to any one except the ladies of the marquis’s family, and the
head servants at the Mill-house.
These two, Rhoda and Caryl, began to talk about what they should
do when the spring came, and the boy told her he intended to ask
his father to let him go abroad with her, if she would not come back
to the Mill-house with him.
And so the weeks rolled by until winter was over, and the early
days of April found Caryl still at the Priory in the care of Rhoda.
There had been a long pause since Sir Robert’s last letter, and all
at the Priory were rather anxious as to his movements. He had said
nothing about coming home, had not answered a question put on the
subject by his son, and there was much perplexity as to the cause of
his silence.
It was now six months since the death of Lady Sarah, and the first
horror of the event had passed away.
Rhoda had been pushing Caryl’s wheeled couch about the
grounds for him to admire the early spring flowers in the borders,
and the daffodils among the grass on the slopes opposite to the
house, and she had just taken him indoors, when the fancy seized
him that he would like a bunch of daffodils to put in the big flower-
vase in the old nursery which had been given up to him as a sitting-
room.
Rhoda went out to get the flowers, carrying on her arm a wooden
trug containing a knife to cut them with.
She had got into the winding walk that led to the grass slopes
when she suddenly became aware that there was a gentleman
coming towards her from the little gate that led through the
plantation.
She stopped, her heart beating very fast. For it was Sir Robert
Hadlow.
He stopped too, and then he came towards her.
The joy she felt on seeing that he did not mean to avoid her got
into her head and rendered her so confused and excited that she
was without words when he came up.
Raising his hat rather formally, as she thought, but without the cold
sternness which had characterised his manner on the fatal night of
Lady Sarah’s death, he said:
“How do you do, Miss Pembury. I hope my unannounced arrival
has not caused you any alarm. All is well, I hope, with the ladies, and
with Caryl?”
“Oh, yes, they are all quite well. And Caryl, I think, is getting a little
stronger. The doctor spoke very promisingly indeed only two days
ago about him.”
“That’s excellent news. And you? Have you been well? I think,
Miss Pembury, you are looking thinner.”
Rhoda reddened. She was beginning to recover some of her lost
self-possession.
“I am glad to be able to say that you look better, much better. I
think your change must have done you a great deal of good.”
“Not the least doubt about it. Next winter, if all goes well, I think I
shall take Caryl with me if I go away.”
“You are longing to see him. Will you go in without preparing him?
or shall I tell him first?”
“Well, first I should like a little talk with you. Can you spare me five
minutes?”
“Oh, yes.”
She turned, and they walked in silence along the winding path,
bordered on one side by a well kept hedge which was as yet only
faintly green. He looked better and happier too, Rhoda thought, than
he had done in the old days at the Mill-house. Certainly he had then
led such a life of anxiety on account of his wife’s caprices and Jack
Rotherfield’s escapades that domestic tranquillity was out of the
question.
As the silence continued, Rhoda presently stole a glance at Sir
Robert, and found that he was looking at her intently.
“You have been very unfairly treated,” he said abruptly.
The blood rushed into her face.
“I have been very happy—with Caryl,” she answered in a whisper.
“Yes. But while you were at the Mill-house you had to suffer a
great deal, both from my wife and from me. Between the two of us
the situation, for a girl, must have been almost unendurable. But for
your feeling for Caryl you could not have borne it.”
“That’s all over now,” she said in a stifled voice. “I can remember
only the best part of it, your kindness, and Lady Sarah’s brilliant
charm.”
A shadow passed over his face.
“Yes,” he said solemnly. “That’s what I like to recollect. The best,
the brightest side.” He paused and then said abruptly:
“I’m afraid I was rather brutal to you on that last night, the terrible
night.”
Rhoda drew a long breath.
“Brutal! Oh, no. You couldn’t be that. You were cold, you even
seemed hard, but it was because you were not yourself, you were—
overwhelmed.”
He listened in silence, and there was a pause. They still walked
along the winding path, where there was just room for two, side by
side.
“It wasn’t exactly that,” he said. “I have a confession to make, a
terrible confession.”
Rhoda’s cheeks blanched. What was he going to say?
“You were wounded, I suppose, that I went away without saying
good-bye to you, when you had been so good to my boy, so patient
with my wife, so conscientious for me?”
“Oh, pray don’t think about it. Of course, at such a time, after such
a tragedy——”
He cut her short.
“Tragedy! Yes, it was a tragedy. Can you guess, I wonder, what a
tragedy it was to me?”
“I think I can. Worshipping this lovely woman, in all her beauty and
charm, the effect upon you must have been stupendous,
unimaginable.”
Sir Robert turned upon her suddenly, with a fire she had never
before seen shining in his eyes.
“That was not the worst part of it,” he said in a sonorous voice.
“What I was suffering from when that awful sight was suddenly
presented to my eyes was—self-reproach. Self-reproach so terrible,
so keen, that I could have cut off my right hand, drowned myself,
shot myself, in the depths of my own self-abasement.”
Rhoda almost thought he had lost his reason, so amazing, so
preposterous did such an attitude seem in the husband who had
done so much for a wife who neglected and despised him.
With a pained frown he went on:
“I have felt the need of confession for a long time, ever since, in
fact, and now I must make it and have done with it, once for all. The
sight of her dead white face struck me dumb with anguish, with self
remorse, not because I loved her, but—because I hated her.”
“Oh, no, no. It’s not possible. When you were so patient, so tender,
so indulgent!”
He turned to her quickly:
“And that was the reason why. I was not indulgent, but over-
indulgent. It was to salve my conscience, to stifle it. Heaven knows,”
he went on earnestly, “that I loved her passionately, desperately
once. For years she was my ideal; to the last in appearance she
remained my model of loveliness in a woman. But she had lost my
heart long before she died. She could have kept it easily enough had
she wished. But she did not wish. My affection bored her, and she
killed it, killed it deliberately. Knowing that the link between us was
so slender that it might at any moment snap, and wishing for Caryl’s
sake to keep it intact, I put up with everything, I yielded to her in
everything. I made sacrifices, I gave up my own wishes to hers. But,”
and he turned upon her again with fire in his quiet eyes, “I should not
have been so indulgent, so yielding, if I had loved her. It was the
tragedy of it that I had grown to hate her. When she lay dead I felt
remorse, excitement, horror. But of tenderness scarcely a trace.
And,” he lowered his voice as if in shame, “it was because I felt as I
did feel that I had to go away without seeing you, or speaking to you.
I was afraid that you would find me out. It would have shocked you.
You might have found out more too. So it was better that I should go
as I did go.”
Half-stunned, Rhoda turned and led the way back to the house.
“You must see Caryl,” she said hoarsely.
She could scarcely realise the secret with which she had been
entrusted. It was so hard, remembering his indulgence to his wilful
wife, to understand the motive which had prompted his excess of
kindness.
They went upstairs to Caryl’s room, after Sir Robert had met and
spoken to the ladies of the house.
The boy had seen him from his window, and was clapping his
hands with glee.
“Papa, papa,” cried he, “Oh, how glad, how glad I am!”
He seized his father’s hand, and received his kiss, and then he
held out his other hand to Rhoda.
“Come here, Rhoda, come here,” cried he.
Timidly, and as it were reluctantly, she came. Caryl put her hand
into that of his father, and held them together.
“Papa, you won’t let her go now, will you?” he whispered.
Rhoda was crying. Sir Robert looked at her very tenderly over the
little wheel-couch, and said in a low voice as he pressed her hand in
his:
“No, Caryl, I won’t let her go away again.”
THE END
TRANSCRIBER’S NOTES
Florence Warden was the pseudonym of Florence Alice (Price)
James.
Minor spelling inconsistencies (e.g. dinner-gong/dinner gong,
newcomer/new-comer, etc.) have been preserved.
Alterations to the text:

Punctuation: quotation mark pairings and a missing comma.
[Chapter XII]
“though Lady Sarah appared to be chattering idly to Jack” to
appeared.
[End of text]
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Applied Water Science Volume 1:

Fundamentals and Applications

Applied Water Science, Volume 2: Remediation

Applied Soil Chemistry Inamuddin

Biodiesel Technology and Applications Inamuddin

Biodegradable Materials and Their Applications

Mathematics and Computer Science, Volume 1 Sharmistha

Polymer Science and Nanotechnology: Fundamentals and

Self-Healing Smart Materials and Allied Applications

Polymers Coatings: Technology and Applications 1st

Fundamentals and Applications

Wiley Global Headquarters

Limit of Liability/Disclaimer of Warranty

Library of Congress Cataloging-in-Publication Data

Cover image: Pixabay.com

Printed in the USA

2.3.4.1 Conventional Removal Methods 83

4.2 Key Scientific Issues Concerning Water and

6.3.1 Fenton and Photo-Fenton Process 182

8.5 Biological Processes For Swine Wastewater Treatment 236

9.3 Conclusions 267

12 Radionuclides: Availability, Effect, and Removal Techniques 331

13 Applications of Membrane Contactors for Water Treatment 361

14.2 Effect of Sulfate Contamination on Human Health 384

16 Water Quality Monitoring and Management: Importance,

18 Qualitative and Quantitative Analysis of Water 469

18.7.5 Total Dissolved Solids 494

19.2.5.7 Informatics and AI Nanofluid-Enhanced

Applied Water Science

problem from wastewater. Both conventional methods and modern-day

Departamento de Ciencias Básicas, Facultad de Ingeniería, Universidad EAN,

Bogotá D.C., Colombia

*Corresponding author: jhborges@ull.edu.es

Keywords: Phthalic acid esters, analytical methods, sample preparation,

Name Abbreviations R1 Group R2 Group

Dimethyl phthalate DMP

Di(2-ethoxyethyl) phthalate DEEP O O

Benzylbutyl phthalate BBP

Dibutyl phthalate DBP

Diisobutyl phthalate DIBP

Di(2-butoxyethyl) phthalate DBEP O O

Di-n-pentyl phthalate DNPP

Diisopentyl phthalate DIPP

Dicyclohexyl phthalate DCHP

Dihexyl phthalate DHXP

Di(2-ethylhexyl) phthalate DEHP

Di-n-octyl phthalate DNOP

Diisononyl phthalate DINP

Diisodecyl phthalate DIDP

listed several PAEs as compounds suspected to produce endocrine abnor-

spectrometry (MS) [21] and tandem MS (MS/MS) [22], or high-

instrumentation [33–36]. Among these new alternatives, sorbent-based

1.2 Solid-Phase Microextraction

DIBP, and water (10 MWCNTs- µg/L 5 and 50 water

(10 mL plus at 2.1 and

0.6 mL and DNPP bare carbon-fiber tubes

DEHP, desorption solvent

both obtained through electrochemical polymerization, for the extraction