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Applications of Time-of-Flight and Orbitrap Mass Spectrometry in Environmental, Food, Doping, and Forensic Analysis

Advisory Board

Applications of Time-of-Flight and Orbitrap Mass Spectrometry in Environmental, Food, Doping, and Forensic Analysis

Copyright

Contents

Contributors to Volume 71

Series Editor's Preface

Preface

I - Instrumentation

1 - Orbitrap Mass Spectrometry: Evolution and Applicability

1. INTRODUCTION

2. EVOLUTIONARY ROUTE OF THE ORBITRAP TECHNOLOGY

3. ION SOURCE CAPABILITIES ASSOCIATED WITH ORBITRAP TECHNOLOGY

4. WORKING MODES IN QUANTITATIVE ANALYSIS

5. CONCLUSION

REFERENCES

2 - Advances in Time-of-Flight Mass Spectrometry

1. INTRODUCTION

1.1 Basic Concepts of TOF-MS

1.2 LC/MS Instrumentation

1.3 Application Demands

2. CURRENT IMPROVEMENTS IN TOF INSTRUMENTATION

2.1 Ion Production

2.2 Ion Sampling

2.3 Resolving Power

2.3.1 Chromatographic Factor

2.3.2 Nonchromatographic Factors

2.3.3 Off-Axis Energy Spread

2.3.4 Ion Mirror

2.3.5 Flight Path Length

2.4 Mass Accuracy

2.5 Ion Detection

2.6 High-Speed Digitisation

3. GC/MS INSTRUMENTATION

3.1 Via Electron Ionisation

3.1.1 Current Developments

3.2 Via GC-APCI Interface to LC/MS Systems

3.3 The Future of GC-Based TOF MS

4. IM-TOF-MS ADDING ADDITIONAL DIMENSIONALITY

4.1 Historical Background and Basic Principles

5. CONCLUSION

ACKNOWLEDGEMENT

REFERENCES

3 - Ambient Ionisation–High-Resolution Mass Spectrometry: Environmental, Food, Forensic and Doping analysis

1. INTRODUCTION

2. AMBIENT IONISATION METHODS

2.1 Desorption Electrospray Ionisation

Reactive DESI

DESI Imaging

Nano-DESI

2.2 Other Spray-Based Ionisation Techniques

Extractive Electrospray Ionisation

Paper Spray Ionisation (PSI)

Easy ambient Sonic-Spray Ionisation (EASI)

Electrospray-Assisted Laser Desorption Ionisation (ELDI)

2.3 Direct Analysis in Real Time

Dopant-Assisted DART

2.4 Low-Temperature Plasma

3. AMBIENT MASS SPECTROMETRY APPLICATIONS

3.1 Environmental

3.2 Food

3.3 Forensics

3.4 Doping

4. CONCLUDING REMARKS

ACKNOWLEDGEMENTS

REFERENCES

II - Target Analysis,Identification, andSuspect Screening

4 - High-Resolution Mass Spectrometry in Doping Control

1. INTRODUCTION

2. TARGETED ANALYSIS

3. UNTARGETED DETECTION

3.1 General Considerations

3.2 Retrospective Analysis

3.3 Metabolic Studies

3.3.1 New Doping Agents

3.3.2 Long-Term Metabolites of AAS

3.3.3 Metabolite Identification

3.4 Additional Untargeted Applications

3.4.1 Identification of Unknowns

3.4.2 Metabolomic Approaches

4. CONCLUSIONS

ACKNOWLEDGEMENTS

REFERENCES

5 - Application of LC-Time-of-Flight and Orbitrap-MS/MS for Pesticide Residues in Fruits and Vegetables

1. INTRODUCTION

2. MASS RESOLUTION

3. MASS ACCURACY

4. WORKFLOWS IN ACCURATE MASS SPECTROMETRY

5. COMPARISON OF ACCURATE MASS SPECTROMETRY AND TRIPLE QUADRUPOLE MASS SPECTROMETRY

6. QUANTITATIVE ANALYSIS IN ACCURATE MASS SPECTROMETRY

7. DATA PROCESSING IN NONTARGETED ANALYSIS

8. CONCLUSIONS

REFERENCES

6 - Identification of Sildenafil Designer Analogues Found in Dietary Supplements

1. INTRODUCTION

2. MATERIALS AND METHODS

2.1 Chemicals and Reagents

2.2 Standard Preparation

2.3 High-Resolution Mass Spectrometer and MSn Analysis (n=1–3)

3. RESULTS AND DISCUSSION

3.1 Sildenafil Analogues with Pyrazolo Pyrimidine-7-one, Ethoxyphenyl and Sulphonamide Moieties (Group A)

3.2 Sildenafil Analogues with Pyrazolo Pyrimidine-7-thione, Ethoxyphenyl and Sulphonamide Moieties (Group B)

3.3 Sildenafil Analogues with Pyrazolo Pyrimidine-7-one/Pyrimidine-7-thione, Propoxyphenyl and Sulphonamide Moieties (Group C)

3.4 Sildenafil Analogues with Pyrazolo Pyrimidine-7-one, Ethoxyphenyl and Acetyl Moieties (Group D)

3.5 Sildenafil Analogues with Pyrazolo Pyrimidine-7-one/Pyrimidine-7-thione and Ethoxyphenyl and Benzamide/Benzothioamide Moiet ...

4. CONCLUSION

REFERENCES

7 - High-Resolution Mass Spectrometry in Metabolite Identification

1. INTRODUCTION

2. ADVANCEMENTS IN HRMS SYSTEMS

2.1 Time-of-Flight Series of Mass Instrumentation

2.1.1 Quadrupole-Time-of-Flight

2.1.2 Quadrupole-Ion Mobility Separation-Time-of-Flight

2.1.3 Ion Trap-Time-of-Flight

2.2 Orbitrap

2.3 Fourier Transform–Ion Cyclotron Resonance Mass Spectrometry

3. HYPHENATION WITH HRMS SYSTEMS

3.1 Liquid Chromatography–Mass Spectrometry

3.2 Gas Chromatography–Mass Spectrometry

3.3 Capillary Electrophoresis–Mass Spectrometry

3.4 Supercritical Fluid Chromatography–Mass Spectrometry

4. DATA ACQUISITION AND DATA MINING TOOLS

4.1 Data-Dependent Acquisition or Information-Dependent Acquisition

4.1.1 Intensity-Dependent

4.1.2 Pseudo-Neutral Loss-Dependent

4.1.3 List-Dependent

4.1.4 Isotope Pattern Dependent

4.1.5 Mass Defect Dependent

4.2 Data-Independent Acquisition

4.2.1 Mass Spectrometry With Ramping of Collision Energies in the Same Run

4.2.2 Sequential Precursor Ion Fragmentation (MS/MSALL)

4.2.3 MS/MSALL With SWATH

4.2.4 All-Ion Fragmentation

4.3 Multiple Mass Spectrometry (MSM)

4.4 Data Mining Tools

4.4.1 Extracted Ion Chromatogram

4.4.2 Background Subtraction

4.4.3 Precursor Ion Filter and Constant Neutral Loss Filter

4.4.4 Data Mining Using Combined Processing Tools

5. ADVANTAGES OF HRMS

5.1 Assessing the Elemental Composition of an Unknown Metabolite

5.2 Appraisal of Metabolic Change From Accurate Mass Shifts

5.3 Differentiation Between Isobaric Molecular Ions

5.4 Structure Elucidation of Metabolites

6. APPLICATIONS OF HRMS IN METABOLITE IDENTIFICATION

6.1 In Vitro Metabolite Identification

6.2 Comprehensive Profiling of Circulating Metabolites

6.3 Metabolite Profiling in Excreta

6.4 Metabolic Soft Spot Determination

6.5 Screening of Reactive Metabolites

6.6 Quantitation of Metabolites

7. CONCLUSION

REFERENCES

8 - LC-TOF-MS for the Identification of Environmental Metabolites and Degradation Products

1. INTRODUCTION

2. ACCURATE MASS TOOLS FOR THE IDENTIFICATION OF METABOLITES AND DEGRADATION PRODUCTS

3. PHARMACEUTICALS AND THEIR METABOLITES IN WASTEWATER AND SURFACE WATERS

4. ADVANCED TREATMENT OF LAMOTRIGINE USING UV PHOTOLYSIS, ADVANCED OXIDATION AND OZONE

5. HYDROXYL RADICAL PRODUCTS OF UV/H2O2 OXIDATION OF PHARMACEUTICALS: THE ROLE OF HYDROXYL SUBSTITUTION

6. IDENTIFICATION OF PESTICIDE TRANSFORMATION PRODUCTS IN AGRICULTURAL SOILS

7. IDENTIFICATION OF PESTICIDE TRANSFORMATION PRODUCTS IN GROUNDWATER

8. IDENTIFICATION OF PESTICIDE METABOLITES IN PLANTS

9. CONCLUSIONS

REFERENCES

9 - Application of Orbitrap Mass Spectrometry for the Identification of Transformation Products of Trace Organic Co ...

1. SHORT HISTORY OF ORBITRAP MASS SPECTROMETRY

2. APPLICATION OF ORBITRAP MS FOR NONTARGET, SUSPECT AND TARGET ANALYSIS

2.1 Nontarget and Suspect Analysis

2.2 Target Analysis

3. ORBITRAP MS FOR THE IDENTIFICATION OF TRANSFORMATION PRODUCTS OF TRACE ORGANIC CONTAMINANTS

3.1 Example 1: Biodegradation of Penciclovir in Activated Sludge

3.2 Example 2: Ozonation of Carboxy-Acyclovir

4. CHALLENGES ASSOCIATED WITH IDENTIFICATION OF TPS USING ORBITRAP MS AND POTENTIAL FUTURE SOLUTIONS

REFERENCES

10 - High-Resolution Mass Spectrometry Identification of Micropollutants Transformation Products Produced During Wa ...

1. INTRODUCTION

2. ROLE AND EVOLUTION OF HRMS IN TRANSFORMATION PRODUCTS ELUCIDATION

3. IDENTIFICATION OF TPS OF DIFFERENT CHEMICALS

3.1 Pesticides

3.2 Pharmaceuticals

3.2.1 Antacids

3.2.2 Lipid and Glucose Regulators

3.2.3 Anti-inflammatories and Analgesics

3.2.4 β-Blockers and β-Agonists

3.2.5 Antibiotics

3.2.6 Anticancer Drugs

3.2.7 Contrast Agents

3.2.8 Antiepileptics

3.3 Emerging Pollutants

3.3.1 Personal Care Products

3.3.2 Drugs of Abuse

3.3.3 Cyanotoxins

3.3.4 Steroids

3.3.5 Other Endocrine Disrupting Contaminants: Nonylphenol Derivatives and Bisphenol A

4. OCCURRENCE AND TOXICITY OF TPS

5. CONCLUSIONS AND OUTLOOK

ACKNOWLEDGEMENTS

REFERENCES

11 - Discovery of New Emerging DBPs by High-Resolution Mass Spectrometry

1. INTRODUCTION

2. COMPREHENSIVE DBP IDENTIFICATION IN DRINKING WATER

2.1 Magnetic Sector Instruments

2.2 Orbitraps, Q-TOFs and FT-ICR Mass Spectrometers

3. DBPS IN SWIMMING POOLS

4. DBPS IN BALLAST WATER

5. DBPS FROM EMERGING WASTEWATER CONTAMINANTS

5.1 Pharmaceuticals

5.2 Hormones

5.3 Pesticides

5.4 Algal Toxins

5.5 Benzotriazoles

5.6 Newly Identified Industrial Contaminant that Forms NDMA

6. DBPS IN BIOLOGICAL SAMPLES

7. CONCLUSIONS

ACKNOWLEDGEMENTS

REFERENCES

12 - Suspect Screening of Pharmaceuticals and Related Bioactive Compounds, Their Metabolites and Their Transformati ...

1. INTRODUCTION

2. LC-HRMS TECHNOLOGIES

3. WHAT IS SUSPECT SCREENING?

4. SUSPECT SCREENING IN ENVIRONMENTAL MATRICES

4.1 Suspect Screening in Wastewaters

4.2 Suspect Screening in Surface Waters

5. SUSPECT SCREENING IN BIOTA AND HUMANS

6. CONCLUSIONS AND FUTURE ADVANCES

ACKNOWLEDGEMENTS

REFERENCES

III - Nontarget Analysis

13 - Nontarget Analysis of Environmental Samples Based on Liquid Chromatography Coupled to High Resolution Mass Spe ...

1. INTRODUCTION

2. ANALYTICAL METHODOLOGIES

2.1 Sample Pretreatment and Extraction

2.2 High Resolution Mass Spectrometry Coupled to Liquid Chromatography Performance

2.3 Confidence Level of the Identifications

3. STRATEGIES TO CHARACTERISE ORGANIC POLLUTANTS IN ENVIRONMENTAL SAMPLES

3.1 Prioritisation Approaches

3.2 Software Strategies for Nontarget Analysis

3.3 Retention Time Prediction Applied to the Analysis of Unknown Compounds

3.4 Workflows and Strategies

4. EXPECTED FUTURE DEVELOPMENTS AND RESEARCH NEEDS

ACKNOWLEDGEMENTS

REFERENCES

14 - Nontargeted Analysis of Persistent Organic Pollutants by Mass Spectrometry and GC×GC

1. INTRODUCTION

1.1 The Challenge Posed to Environmental Chemists

1.2 The Classical Approach to Identifying Environmental Contaminants

1.3 New Types of Mass Spectrometers Offer Enhanced Capabilities for Environmental Analysis

2. COMPREHENSIVE TWO-DIMENSIONAL CHROMATOGRAPHY TECHNIQUES FOR THE IDENTIFICATION OF HALOGENATED COMPOUNDS

3. (ULTRA)HIGH-RESOLUTION MASS SPECTROMETRY

3.1 What Is (Ultra)high-Resolution Mass Spectrometry?

3.2 The Kendrick Mass Defect Plot

3.3 Using Mass Defect Plots to Identify (Unknown) Halogenated Contaminants

3.4 Automated Mass Defect Filtering and Combining Mass Defect Plots With GC×GC

4. COMPLEMENTARY CHEMICAL IONISATION TECHNIQUES

4.1 Negative Chemical Ionisation

4.2 Atmospheric Pressure Chemical Ionization (APCI) and Photoionization (APPI)

5. SUMMARY

REFERENCES

15 - High-Resolution Mass Spectrometry in the Effect-Directed Analysis of Water Resources

1. INTRODUCTION

2. GENERAL OVERVIEW OF THE EDA APPROACH

3. CHEMICAL ANALYSIS IN EDA

4. GENERIC SCREENING AND TARGET METHODS IN EDA

5. IDENTIFICATION STRATEGIES

5.1 Spectral Library Search

5.2 Suspect Screening

5.3 Unknown Identification

5.4 Candidate Structure Search and Selection

6. CONCLUSIONS AND FUTURE PERSPECTIVES

ACKNOWLEDGEMENT

REFERENCES

IV - Conclusions

16 - Conclusions and Future Directions

1. INTRODUCTION

2. INSTRUMENTATION

2.1 (Quadrupole) Time-of-Flight Mass Spectrometry

2.2 Orbitrap-Mass Spectrometry

2.3 Ambient Ionisation Mass Spectrometry

3. APPLICATIONS IN TARGET AND SUSPECT ANALYSIS

3.1 Pesticide Residues in Food

3.2 Doping Control

4. STRATEGIES AND CHALLENGES IN THE IDENTIFICATION OF METABOLITES AND TRANSFORMATION PRODUCTS

4.1 Identification of Metabolites of Pharmaceuticals

4.2 Characterisation of Disinfection By-products

4.3 Environmental Degradates and Metabolites

5. NONTARGET ANALYSIS

5.1 Persistent Organic Pollutants

5.2 LC-MS-based Nontarget Analysis

6. OPPORTUNITIES AND FUTURE DIRECTIONS

REFERENCES

Index

A

B

C

D

E

F

G

H

I

K

L

M

N

O

P

Q

R

S

T

U

V

W

X

Z

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