TABLE OF CONTENTS

COVER

TITLE PAGE

LIST OF CONTRIBUTORS

PREFACE

CHAPTER 1: PRINCIPLES AND APPLICATIONS OF ION CHROMATOGRAPHY

1.1 PRINCIPLES OF ION CHROMATOGRAPHY
1.2 ION CHROMATOGRAPHY APPLICATIONS
1.3 SAMPLE PREPARATION FOR ION CHROMATOGRAPHY
1.4 SELECTED METHODOLOGICAL ASPECTS OF ION DETERMINATION WITH ION CHROMATOGRAPHY
1.5 ION CHROMATOGRAPHY DEVELOPMENT PERSPECTIVES
1.6 REFERENCES

CHAPTER 2: MASS SPECTROMETRIC DETECTORS FOR ENVIRONMENTAL STUDIES

2.1 INTRODUCTION
2.2 MASS SPECTROMETRIC DETECTORS
ACKNOWLEDGMENTS
2.3 REFERENCES

CHAPTER 3: HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY COUPLED TO INDUCTIVELY COUPLED PLASMA MS/ELECTROSPRAY IONIZATION MS

3.1 SEPARATION PRINCIPLES
3.2 DETECTION PRINCIPLES
3.3 HYPHENATED TECHNIQUES
3.4 HPLC(IC)–ICP-MS/ESI-MS
3.5 APPLICATIONS AND CONCLUSION
3.6 REFERENCES

CHAPTER 4: APPLICATION OF IC-MS IN ORGANIC ENVIRONMENTAL GEOCHEMISTRY

4.1 INTRODUCTION
4.2 CARBOXYLIC ACIDS
4.3 CARBOHYDRATES
4.4 AMINES AND AMINO ACIDS
4.5 TRENDS AND PERSPECTIVES
4.6 REFERENCES

CHAPTER 5: ANALYSIS OF OXYHALIDES AND HALOACETIC ACIDS IN DRINKING WATER USING IC-MS AND IC-ICP-MS

5.1 INTRODUCTION
5.2 SOURCE OF OXYHALIDES AND HAAS
5.3 ANALYSIS OF OXYHALIDES AND HAAS
5.4 APPLICATION FOR MONITORING OF OXYHALIDES AND HAA IN DRINKING WATER
SUMMARY
5.5 REFERENCES

CHAPTER 6: ANALYSIS OF VARIOUS ANIONIC METABOLITES IN PLANT AND ANIMAL MATERIAL BY IC-MS

6.1 INTRODUCTION
6.2 OPTIMIZATION OF HPIC AND MS SETTINGS
6.3 APPLICATION OF THE METHOD IN ANALYSIS OF METABOLITES IN PLANT AND ANIMAL MATERIAL
CONCLUSIONS
6.4 REFERENCES

CHAPTER 7: ANALYSIS OF PERCHLORATE ION IN VARIOUS MATRICES USING ION CHROMATOGRAPHY HYPHENATED WITH MASS SPECTROMETRY

7.1 INTRODUCTION
7.2 PRECAUTIONS UNIQUE TO ION CHROMATOGRAPHY–MASS SPECTROMETRY
7.3 RESULTS AND DISCUSSION
ACKNOWLEDGMENT
7.4 REFERENCES

CHAPTER 8: SAMPLE PREPARATION TECHNIQUES FOR ION CHROMATOGRAPHY

8.1 INTRODUCTION
8.2 WHEN AND WHY IS SAMPLE PREPARATION REQUIRED IN ION CHROMATOGRAPHY?
8.3 AUTOMATION OF SAMPLE PREPARATION (IN-LINE TECHNIQUES)
8.4 SAMPLE PREPARATION METHODS
8.5 TRACE ANALYSIS AND PRECONCENTRATION FOR ION CHROMATOGRAPHIC ANALYSIS
8.6 IN-LINE PRESEPARATIONS USING TWO-DIMENSIONAL ION CHROMATOGRAPHY (2D-IC)
8.7 SAMPLE PREPARATION OF SOLID SAMPLES
8.8 AIR ANALYSIS USING ION CHROMATOGRAPHY – APPLICATION TO GASES AND PARTICULATE MATTER
8.9 POSTCOLUMN ELUENT TREATMENT PRIOR TO MS DETECTION
8.10 CONCLUDING REMARKS
8.11 REFERENCES

INDEX

END USER LICENSE AGREEMENT

List of Illustrations

CHAPTER 1: PRINCIPLES AND APPLICATIONS OF ION CHROMATOGRAPHY

Figure 1.1 Block diagram of an ion chromatograph with a conductometric detector.
Figure 1.2 Classification of detection methods in ion chromatography.
Figure 1.3 Chromatogram of anions in drinking water.
Figure 1.4 Chromatogram of cations in industrial wastewater.
Figure 1.5 Chromatogram of inorganic anions in rain water.
Figure 1.6 Chromatogram of simultaneous separation of As(III), As(V), Sb(III), Sb(V), Tl(I), and Tl(III) ions in the Kłodnica river water sample.

CHAPTER 3: HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY COUPLED TO INDUCTIVELY COUPLED PLASMA MS/ELECTROSPRAY IONIZATION MS

Figure 3.1 Overview about combinations of chromatographic principles with mass spectrometric detection.
Figure 3.2 Anion and cation exchange chromatograms of arsenic species [9].
Figure 3.3 Example for mixed-mode ion chromatography for the speciation of arsenic with IC-ICP-MS. All arsenic species are commercially available for their identification. Analytical column: IonPacAS7+AG 7, Eluent: pH-Wert <5 (HNO₃ – gradient) [12].
Figure 3.4 Separation principles and properties of stationary, mobile phase and analyte.
Figure 3.5 ICP-MS with a triple quadrupole arrangement. NG: nebulizer gas (Ar), OG: optional gas (Mix Ar/O₂), PG: plasma gas (Ar), AG: auxiliary gas (Ar), QMA 1: first quadrupole mass analyser, CRC: collision/reaction cell (octopole, hexapole), QMA 2: second quadrupole mass analyser, EM: electron multiplier.
Figure 3.6 RP-HPLC chromatograms with ICP-MS detection of a fish extract with simultaneous detection of As, P, and S after reaction with O₂ in the CRC.
Figure 3.7 Ion chromatogram with ICP-MS detection of Gd complexes used as MRI contrast agents. Detection: m/z 157 (Gd); separation: anion-exchange column, ammonium acetate gradient, flow rate 1 ml min⁻¹ [28].
Figure 3.8 Example for mixed-mode ion chromatography for the speciation of arsenic with IC–ICP-MS. All arsenic species are commercially available for their identification. Analytical Column: IonPacAS7+AG 7, Eluent: pH-Wert < 5 (HNO₃ – gradient) [12].
Figure 3.9 HPLC–HR-ICP-MS/HR-ESI-MS analysis of a brown alga (Saccharina latissima) [36].
Figure 3.10 HPLC–ICPMS/ESIQTOFMS of arsenolipids detected in canned cod liver extract and indicated by the extracted ion chromatograms (EIC) in the ESI-MS Chromatogram. As⁺ signal (m/z 75) was compared simultaneously with the extracted ion chromatogram (EIC) recorded by ESI-MS [39].

CHAPTER 4: APPLICATION OF IC-MS IN ORGANIC ENVIRONMENTAL GEOCHEMISTRY

Figure 4.1 ICE-ESI-TOF-MS chromatograms of major (a and c) and minor (b and d) carboxylates found in sugar beet leaves and tomato xylem sap. Chromatogram traces correspond to the [M−H]⁻ ± 0.03 m/z of each organic acid. For details of the analytical method, refer to Table 4.3.
Figure 4.2 General scheme of experiments including secondary organic aerosol formation in the smog chamber, particles sampling on filters and subsequent extraction in pure water, aqueous-phase processing, and nebulization, together with the applied analytical instruments. AMS: aerosol mass spectrometer, H-TDMA: humidified tandem differential mobility analyzer, SMPS: scanning mobility particle sizer, TD: thermodesorption. For details of the IC-MS method, refer to Table 4.5.
Figure 4.3 SIM-MS traces of organic acids solved in aqueous extracts of organic aerosol particles, sampled during a biomass burning event at Mt Bei Tungyen, Taiwan (Fischer, K., Höffler, S. and Meyer, A. Unpublished Results). SIM signals (acids): 1: gluconic, 2: threonic, 3: lactic, 4: shikimic, 5: formic, 6: saccharic (glucaric), 7: malic, 8: tartaric, 9: tartronic, 10: citric. Analytical details are provided in Table 4.5.
Figure 4.4 SIM-MS traces of (poly)hydroxy carboxylic acids in a soil leachate (B4, Table 4.6). Analytical conditions as in Figure 4.3. SIM signals (acids): 1: isosaccharinic, 2: d-xylonic, 3: d-gluconic, 4: 4-hydroxybutyric, 5: d-glyceric, 6: lactic, 7: shikimic, 8: glycolic, 11: d-galacturonic, 12: d-glucuronic, 14: d-glucaric, 15: malic, 16: tartaric, I.S. (internal standard): terephthalic acid-d₄, 17: citric, 18: isocitric.
Figure 4.5 Conductivity and SIM-MS chromatograms of low-molecular-weight organic acids in microalgae biomass. The peak sizes of the MS chromatogram are not uniformly scaled. Analytical conditions listed in Table 4.5.
Figure 4.6 Schematic representation of the sampling line and the online coupled PILS-HPAEC-MS apparatus. Arrows represent the flow of the aerosol sample and the liquids within the system. STD: standard solution containing internal standard and standard addition of levoglucosan, SUP: suppressor, CC: conductivity cell. The Figure is not to scale. For details of the HPAEC-MS method, refer to Table 4.7.

CHAPTER 5: ANALYSIS OF OXYHALIDES AND HALOACETIC ACIDS IN DRINKING WATER USING IC-MS AND IC-ICP-MS

Figure 5.1 Generation of chlorate and perchlorate during electrolysis of sodium chloride solution using six types of anodes (ruthenium dioxide, RuO₂; titanium dioxide, TiO₂; iridium dioxide, IrO₂; tin dioxide, SnO₂; platinum, Pt; lead dioxide, PbO₂) (sodium chloride, 30 g l⁻¹; current, 2 A; immersed surface area of electrode plate, about 20 cm²; reaction time, 120 min; cathode, Ti).
Figure 5.2 High-yield HAA precursors during chlorination (Echigo et al., 2007). Source: Reprint from Ref. [48] with permission of Jpn. soc. Civil Eng.
Figure 5.3 Selective Reaction Monitoring (SRM) chromatograms of four oxyhalides, HAA9, and bromide in ultrapure water using suppressed IC-MS/MS (target compounds, 1 µg l⁻¹; analytical column, IonPac AS20; mobile phase, aqueous solution of potassium hydroxide; postcolumn solution, mixture of acetonitrile and water [90:10 v/v]).
Figure 5.4 Recovery of (a) oxyhalide and bromide and (b) HAA9 in river and tap waters with and without pretreatment cartridge (*recovery of chlorite and bromide with pretreatment cartridge was excluded; error bar, maximum and minimum values [n = 3]) (target compound in river and tap waters, 5 and 4 µg l⁻¹, respectively; pretreatment cartridge, barium/silver/hydrogen cartridge; dose of ammonium chloride in tap water, 10 mg l⁻¹).
Figure 5.5 SRM chromatograms of three oxyhalides and HAA9 in ultrapure water using suppressed IC-MS/MS (target compounds, 2 µg l⁻¹; analytical column, IonPac AS24; mobile phase, aqueous solution of potassium hydroxide; postcolumn solution, acetonitrile).
Figure 5.6 SRM chromatograms of bromate and common anions in drinking water using LC-MS/MS (analytical column, Acclaim Trinity P1; mobile phase, [A] aqueous solution [pH 5] containing 20 mM ammonium acetate and 0.05% v/v acetic acid and [B] mixture of aqueous solution [pH 5] containing 200 mM ammonium acetate and 0.5% v/v acetic acid and acetonitrile).
Figure 5.7 Concentrations of chlorate and perchlorate in groundwater in Tokyo.
Figure 5.8 Relationships between measured available free chlorine and concentrations of chlorate and perchlorate in hypochlorite solutions.
Figure 5.9 Mean concentration of HAA9 at two to four sampling events in 20 final drinking water samples in England and Wales. Drawn by the author using data in Ref. [79].

CHAPTER 7: ANALYSIS OF PERCHLORATE ION IN VARIOUS MATRICES USING ION CHROMATOGRAPHY HYPHENATED WITH MASS SPECTROMETRY

Figure 7.1 Typical ICMS setup using single-quad MSD.
Figure 7.2 Trace of 500 ng l⁻¹ perchlorate in reagent water.
Figure 7.3 Trace of 1 ppb perchlorate (m/z 99 and 101) in 3000 ppm TDS.
Figure 7.4 Calibration m/z 99.
Figure 7.5 Calibration m/z 101.
Figure 7.6 Perchlorate fortified at 1 µg l⁻¹ in various matrix concentrations (150–3000 ppm TDS).
Figure 7.7 Extracts of lettuce fortified with 1 µg l⁻¹ perchlorate.

CHAPTER 8: SAMPLE PREPARATION TECHNIQUES FOR ION CHROMATOGRAPHY

Figure 8.1 Schematic representation of (a) planar sandwich and (b) tubular hollow-fiber membrane separation units. In (c) is shown the hyphenation of the flow-through units with an IC system. The injection valve can be regarded as a kind of interface between the two flow systems.
Figure 8.2 Schematic representation of the patented flow-dialysis system used for in-line sample preparation prior to ion chromatography. The two insets show the large surface-to-volume ratio spiral dialysis cell and the principle of dialysis excluding microparticles and high-molecular-weight compounds from membrane transfer (Metrohm AG, Switzerland).
Figure 8.3 Configuration of dialysis probes suitable for selective sampling by direct immersion into the sample solution. (a) Flat-membrane probe with channel length in the range of a few millimeter; (b) Cannula-type microdialysis probe (scheme, photograph and principle of operation).
Figure 8.4 Coupling of gas-diffusion separation with ion chromatography for the determination of ammonium and short-chain ammines. KOH is used to convert the analytes to ammonia and volatile ammines, which diffuse across the membrane and are trapped in a slightly acidic nitric acid solution. Separation of the N-containing cationic species is eventually done by cation-exchange chromatography.
Figure 8.5 Manifold configuration for membrane separation coupled to trace enrichment using sorbent extraction.
Figure 8.6 Scheme of a static diffusion denuder for artifact-free separation of gases and particulate matter. The tiny black dots and the open circles symbolize gas molecules and aerosol particles, respectively.
Figure 8.7 Fully automated system for simultaneous measurement of gaseous ionogenic compounds and particle-bound ions (MARGA). Analytical cycle permits separate gas and particle phase measurements with a time resolution of less than 1 h (redrawn with courtesy of Metrohm AG).

List of Tables

CHAPTER 1: PRINCIPLES AND APPLICATIONS OF ION CHROMATOGRAPHY

Table 1.1 Key Events Preceding the Ion Chromatography Invention and Stages of Ion Chromatography Development and Popularization
Table 1.2 ISO Standards Based on Ion Chromatography
Table 1.3 Parameters of Selected Suppressors Used in Ion Chromatography
Table 1.4 Detection Methods and Their Applications in Ion Chromatography
Table 1.5 Selected Parameters of Detectors Applied in Ion Chromatography
Table 1.6 Examples of Metal and Metalloids Species Analyzed Using Hyphenated Methods IC-ICP-MS and IC-MS

CHAPTER 3: HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY COUPLED TO INDUCTIVELY COUPLED PLASMA MS/ELECTROSPRAY IONIZATION MS

Table 3.1 Advantages and Disadvantages of Mass Spectrometer and Their Mass Resolutions and Mass Ranges
Table 3.2 Reviews and Applications

CHAPTER 4: APPLICATION OF IC-MS IN ORGANIC ENVIRONMENTAL GEOCHEMISTRY

Table 4.1 Main Environmental Compartments and Related Matrices (Except Organisms) Relevant as Sources and Reaction Media for Natural Organic Compounds
Table 4.2 Main Topics of Environmental Geochemical Research on Carboxylic Acids (CA)
Table 4.3 Environmental Analysis of Carboxylic Acids by Ion Exclusion Chromatography–ESI-Mass Spectrometry
Table 4.4 Sample Matrix, Sampling, and Sample Preparation Techniques for the Analysis of Carboxylic Acids
Table 4.5 Environmental Analysis of Carboxylic Acids by Ion-Exchange Chromatography–ESI-Mass Spectrometry
Table 4.6 (Poly)hydroxy Carboxylic Acids in Drinking Water and Soil Leachates (B1–B4): Concentrations and Recovery Rates with MS and Conductivity (CD) Detection
Table 4.7 Environmental Analysis of Carbohydrates by IC-ESI-MS
Table 4.8 Sample Matrix, Sampling, and Sample Preparation Techniques for the Environmental Analysis of Carbohydrates (CH)

CHAPTER 5: ANALYSIS OF OXYHALIDES AND HALOACETIC ACIDS IN DRINKING WATER USING IC-MS AND IC-ICP-MS

Table 5.1 Values of Guidelines and Standards for Oxyhalides and HAAs
Table 5.2 Detection Limit of Oxyhalides and HAAs in EPA Methods
Table 5.3 Concentrations of Chlorate and Perchlorate in Source and Finished Water at Water Purification Plants in Japan [71]

CHAPTER 7: ANALYSIS OF PERCHLORATE ION IN VARIOUS MATRICES USING ION CHROMATOGRAPHY HYPHENATED WITH MASS SPECTROMETRY

Table 7.1 Ion Chromatography Parameters
Table 7.2 Mass Spectrometer Parameters
Table 7.3 Average Recovery of 1 µg l⁻¹ Perchlorate Fortified in Various Concentrations of Matrix

CHAPTER 8: SAMPLE PREPARATION TECHNIQUES FOR ION CHROMATOGRAPHY

Table 8.1 Compilation and Nomenclature of Membrane-Based Separation Techniques
Table 8.2 Typical Applications of Dialysis Sample Preparation and Needs for Pretreatment Prior to Sample Admission to In-Line Dialysis IC

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Title: Application of IC-MS and IC-ICP-MS in environmental research / edited by Rajmund Michalski.

Description: Hoboken, New Jersey : John Wiley & Sons, 2016. | Includes bibliographical references and index.

Identifiers: LCCN 2016001708| ISBN 9781118862001 (cloth) | ISBN 9781119085478 (epub)

Subjects: LCSH: Ion exchange chromatography. | Inductively coupled plasma mass spectrometry.

LIST OF CONTRIBUTORS

Maria Balcerzak; Department of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
Klaus Fischer; Faculty VI – Regional and Environmental Sciences, Department of Analytical and Ecological Chemistry, University of Trier, Behringstr. 21, 54296 Trier, Germany
Wolfgang Frenzel; Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany
Jay Gandhi; Metrohm USA, 4738 Ten Sleep Lane, Friendswood, TX 77546, USA
Adam Konrad Jagielski; Department of Metabolic Regulation, Faculty of Biology, Institute of Biochemistry, University of Warsaw, Miecznikowa 1, 02-096 Warsaw, Poland
Koji Kosaka; Department of Environmental Health, National Institute of Public Health, 2-3-6 Minami, Wako, Saitama 351-0197, Japan
Jürgen Mattusch; Department of Analytical Chemistry, Helmholtz Centre for Environmental Research, Permoserstr. 15, 04318 Leipzig, Germany
Rajmund Michalski; Institute of Environmental Engineering, Polish Academy of Sciences, M. Skłodowskiej-Curie 34, 41-819 Zabrze, Poland
Michal Usarek; Department of Metabolic Regulation, Faculty of Biology, Institute of Biochemistry, University of Warsaw, Miecznikowa 1, 02-096 Warsaw, Poland

PREFACE

Environmental analytical chemistry can be regarded as the study of a series of factors that affect the distribution and interaction of elements and substances present in the environment, the ways they are transported and transferred, as well as their effects on biological systems. In recent years, the importance of monitoring and controlling environmental pollutants has become apparent in all parts of the world. As a result, analysts have intensified their efforts to identify and determine toxic substances in air, water, wastewaters, food, and other sectors of our environment. The toxicological data analyses involve constant lowering of analyte detection limits to extremely low concentration levels.

Speciation analysis, understood as research into various element forms, is gaining importance in environmental protection, biochemistry, geology, medicine, pharmacy, and food quality control. It is popular because what frequently determines the toxicological properties of a compound or element is not its total content, but in many cases, it is the presence of its various forms. Elements occurring in ionic forms are generally believed to be biologically and toxicologically interactive with living organisms. Studying low analytes concentrations, particularly in complex matrix samples, requires meticulous and sophisticated analytical methods and techniques. The latest trends embrace the hyphenated methods combining different separation and detection methods. In the range of ionic compounds, the most important separation technique is ion chromatography. Since its introduction in 1975, ion chromatography has been used in most areas of analytical chemistry and has become a versatile and powerful technique for the analysis of a vast number of inorganic and organic ions present in samples with different matrices. The main advantages of ion chromatography include the short time needed for analyses, possibility of analysis of small volume samples, high sensitivity and selectivity, and a possibility of simultaneous separation and determination of a few ions or ions of the same element at different degrees of oxidation. Mass spectrometry is the most popular detection method in speciation analysis, because it offers information on the quantitative and qualitative sample composition and helps to determine analytes structure and molar masses. The access to the structural data (necessary for the identification of the already known or newly found compounds) poses a challenge for speciation analysis as higher sensitivity of detection methods contributes to the increased number of detected element forms.

Couplings of ion chromatography with MS or ICP-MS detectors belong to the most popular and useful hyphenated methods to determine different ion forms of metals and metalloids ions (e.g., Cr(III)/Cr(VI), As(III)/As(V)), as well as others ions (e.g., bromate, perchlorate). IC-MS and IC-ICP-MS create unprecedented opportunities, and their main advantages include extremely low limits of detection and quantification, high precision, and repeatability of determinations.

The intent of this book is to introduce anyone interested in the field of ion chromatography, species analysis and hyphenated methods (IC-MS and IC-ICP-MS) the theory and practice. This book should be interesting and useful for analytical chemists engaged in environmental protection and research, with backgrounds in chemistry, biology, toxicology, and analytical chemistry in general. Moreover, employees of laboratories analyzing environmental samples and carrying out species analysis might find general procedures for sample preparation, chromatographic separation, and mass spectrometric analysis.

Rajmund Michalski
Zabrze, Poland

6 February 2016