Handbook of environmental analysis

Handbook of environmental analysis : chemical pollutants in air, water, soil, and solid wastes / author, Pradyot Patnaik.. Appendix E: Characteristic Masses of Miscellaneous Organic Pol

Handbook of

Environmental Analysis

Chemical Pollutants in

Air, Water, Soil, and Solid Wastes

Pradyot Patnaik

Second Edition

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Library of Congress Cataloging-in-Publication Data

Patnaik, Pradyot.

Handbook of environmental analysis : chemical pollutants in air, water, soil, and solid

wastes / author, Pradyot Patnaik 2nd ed.

p cm.

Includes bibliographical references and index.

ISBN 978-1-4200-6581-7 (alk paper)

my brother, Dr Pradipta Patnaik,

in loving memory

PART Analytical Techniques

Detectors 25 Calibration 26 Calculations 27

“Nitrogen Rule” 36

Tuning 42

Calibration 45 References 47

Contents vii

8 Analysis of Metals by Atomic Absorption and Emission Spectroscopy 89

10 Application of High-Performance Liquid Chromatography in

I

PART I Specifi c Classes of Substances and

Aggregate Properties

15 Alkalinity 145 Calculation 145

Procedure 148 Reagents 148

Procedure 155 Reagents 156

Procedure 156 Reagents 157

Procedure 157 Calculation 158

Calculation 159 Procedure 160

Procedure 162 Reagents 162

Procedure 163

Reagents 166

Contents ix

SPE–LC/MS Method (Liquid Chromatography Tandem Mass

23 Emerging Pollutants: Pharmaceuticals and Personal Care Products 191

References 204

28 Hardness 233

Calculation 234 Titration 234

Miscellaneous Methods for Analysis of Glyphosate Residues in

References 246

Analysis 248

Procedure 264 Calculation 264

Procedure 272 Reagents 272

Extraction 274 Analysis 275

40 Pesticides: Carbamate, Urea, and Triazine 305

Contents xiii

Quantitation 355

Procedure 373

Radium 374

Precipitation and Emanation Method to Measure

Radon 378 Uranium 379

Tritium 383

Interference 418 Procedure 418 Calculation 418

Procedure 419 Calculation 419 Reagents 419

Procedure 424 Calculation 424 Reagents 425

Procedure 427

Standardization 428 Reagents 429

Interference 432 Procedure 432 Calculation 432 Reagents 433

Contents xv

Procedure 434 Calculation 435 Reagents 435

Reagents 437 Analysis 439

Calculation 439 Interference 440

Interference 441 Procedure 442 Calculation 442

Procedure 443 Reagents 444

Apparatus 446

Correlation Coeffi cient (γ) 630

Method Detection Limits for Organic Pollutants in Aqueous Samples 633

Appendix C: Preparation of Molar and Normal Solutions of Some

Appendix E: Characteristic Masses of Miscellaneous Organic Pollutants

Appendix F: Volatility of Some Additional Organic Substances (Not Listed

Appendix H: A Full List of NIOSH Analytical Methods for Indoor Air

Appendix J: Inorganic Test Procedures for Analysis of Aqueous Samples:

Appendix K: U.S EPA’S Analytical Methods for Organic Pollutants in

Index 771

List of Tables

Table 3.1 Polarity of Stationary Phases 23 Table 3.2 Separation Effi ciency and Sample Capacity of GC

Columns of Varying IDs 25

Table 4.1 BFB Tuning Requirement for Volatile Organic Analysis 42 Table 4.2 DFTPP Tuning Requirement for Semivolatile Organic Analysis 43 Table 5.1 Stationary Phases for Solid Phase Extraction 51 Table 5.2 Cleanup Methods for Organic Extracts 53 Table 6.1 Titrimetric Procedures Applied in Environmental Analysis 58 Table 6.2 Some Common Acid–Base Indicators 59 Table 6.3 Common Oxidizing Agents for Redox Titrations 65 Table 6.4 Set of Potentiometric Titration Data as an Example 84 Table 7.1 Common Pollutants 87 Table 8.1 Acid Combination Suggested for Sample Preparation 91 Table 8.2 Recommended Wavelength, Flame Type, and Technique for

Flame Atomic Absorption Analysis 93

Table 8.3 Substances Added to the Sample for the Removal of Interference

in Graphite Furnace Atomic Absorption Method 94

Table 8.4 Recommended Wavelength and the Instrument Detection

Level in ICP Emission Spectrometry 99

Table 8.5 Recommended Analytical Masses for Element Detection 100 Table 8.6 Mass Ions for Internal Standards 101 Table 8.7 Interference from Isobars and Matrix Molecular Ions 101 Table 8.8 Recommended Elemental Equations for Calculations 102 Table 9.1 Application of Ion-Selective Electrodes in Environmental

Analysis 105

Table 10.1 Determination of Organic Analytes by HPLC 111 Table 11.1 Application of Ion Chromatography in Environmental Analysis 116 Table 11.2 Some Common Eluants Used in Ion Chromatography 117 Table 14.1 Some Commercially Used Aldehydes and Ketones 138 Table 21.1 Characteristic LC-MS/MS Parameters for Analysis of Endocrine

Disrupting Metabolites of Nonionic Surfactants and Related

Compounds 180

Table 22.1 Names, Formulas, CAS Numbers, Kow and Vapor Pressure Values

of Some Organophosphate Compounds 185

Table 22.2 Characteristic Mass Ions of Selected Organophosphates for

GC/MS Analysis 186

Table 23.1 Names and CAS Registry Numbers for PPCPs Determined

by Isotope Dilution and Internal Standard HPLC/MS/MS 192

Table 23.2 Group 1 Compounds: LC Gradient and MS Conditions (Acidic

Extractions and ESI+) 195

Table 23.3 Group 1 Acidic Extraction, ESI+ Compound RTs,

Parent–Daughter Transitions, Quantitation References, Method Detection Limits, and Minimum Levels of Quantitations 196

Table 23.4 Group 2 Compounds: LC Gradients and MS Conditions (Acidic

Extraction and ESI+) 198

Table 23.5 Group 2 Compounds: RTs and Parent–Daughter Transitions (ESI+

and Acidic Extraction) 198

Table 23.6 Group 3 Compound: LC Gradient and MS Conditions (Acidic

Extraction and ESI–) 199

Table 23.7 Group 3 Compounds: RTs and Parent–Daughter Transitions

(Acidic Extraction and ESI−) 199

Table 23.8 Group 4 Compound: LC Gradient and MS Conditions (Basic

Extraction and ESI+) 200

Table 23.9 Group 4 Compounds: RTs and Parent–Daughter Transitions

(Basic Extraction and ESI+) 200

Table 24.1 Names and CAS Registry Numbers of Steroids and Hormones 208

Table 24.2 RTs, Exact m/z, and Theoretical m/z Ratios for the TMS

Derivatives of Steroids and Hormones 212

Table 27.1 Purgeable Volatile Halogenated Hydrocarbons and Their

Characteristic Masses 226

Table 27.2 Some Solvent Extractable Halogenated Hydrocarbon Pollutants

and Their Characteristic Masses 228

the Resource Conservation and Recovery Act 274

Table 35.2 Characteristic Masses for Some Common Nitrosamine

Pollutants 276

Table 40.1 Some Common Carbamate Pesticides 307 Table 40.2 Some Common Pesticides Containing Urea Functional Group 309 Table 40.3 DFTPPO Tuning Criteria for LC/MS System Performance Check 311 Table 40.4 Some Common Triazine Pesticides 312 Table 41.1 Some Common Chlorinated Pesticides and Their

Degradation Products 316

Table 41.2 Elution Patterns for Pesticides in Florisil Column Cleanup 318 Table 41.3 Characteristic Masses for Chlorinated Pesticides 321 Table 42.1 Common Organophosphorus Pesticides 325 Table 42.2 Organophosphorus Pesticides Containing Halogen Atoms 327 Table 42.3 Characteristic Ions for Identifi cation of Some Common

Common Phenol Pollutants 341

Table 46.1 Characteristic Ions for Phthalate Esters 351 Table 46.2 EPA and NIOSH Methods for the Analysis of Phthalate Esters 352 Table 47.1 PCBs and Their Chlorine Contents 354 Table 47.2 Common Analytical Columns and Conditions for GC

Analysis of PCBs 354

Table 50.1 Methods of Analysis of Semivolatile Organics 394

Table 50.2 Semivolatile Organic Compounds and Their Retention

Times and Characteristic Mass Ions (U.S EPA Method 8270) 395

Table 50.3 Ion Abundance Criteria for DFTPP (Bis(perfl uorophenyl)phenyl

Phosphine) 403

Table 50.4 Characteristic Masses for Extractable Base/Neutrals and

Acids under the Chemical Ionization (Methane) Conditions

(SM Method 6410) 409

Table 54.1 Sulfi te Standards 435 Table 55.1 Series of Calibration Standard Solutions 438 Table 57.1 Purgeable Organic Compounds 450 Table 57.2 Sample Preparation/Extraction Methods for VOCs 452 Table 57.3 Volatile Organic Compounds by U.S EPA Method TO-14A 456 Table 57.4 NIOSH Method 2549 for Screening VOCs in Air 460 Table 57.5 Miscellaneous and Alternative NIOSH Methods for Some

Volatile Organic Compounds in Air 461

Table 65.1 Asbestos Types and Their Compositions 482 Table D.1 Equivalent Conductance, λ° for Common Ions in Water at 25°C 644

Table I.1 Description of U.S EPA Methods for Air Analysis 691 Table I.2 Individual Organic Pollutants in Air: U.S EPA Methods 692

in detail in many chapters Because of the new approach and the novelty

in their analyses, references from recent literature are cited only in the new chapters for the benefi t of the readers pursuing research in those

fi elds

Although many new analytical techniques are discussed in this tion with chemical structures and reactions, the format of this book essen-tially remains that of a reference handbook, similar to the fi rst edition

edi-Any comments, thoughts, and suggestions from readers would be greatly appreciated for the improvement of this book in its future editions I hope this book serves its purpose.

Pradyot Patnaik

Burlington, New Jersey

Preface to the First Edition

Th e subject of environmental analysis has expanded in recent years into a fully grown scientifi c fi eld on its own merit Th ere is, however, a dearth of

a single volume on the subject which adequately covers all aspects of ronmental analysis Th is book attempts to combine the features of both a reference handbook as well as a textbook

envi-Th is book presents a brief discussion on the analytical techniques and the methods of determination of chemical pollutants in aqueous, solid, and air samples at trace concentrations

Th e topics in this book are presented under three broad parts Part I lights diff erent analytical techniques including instrumentation, sample preparations, wet methods, air analysis, and immunoassay Instrumental methods include primarily gas chromatography, mass spectrometry, high performance liquid chromatography, and spectrophotometric methods Part II presents analytical methodologies for diff erent classes of organic and inorganic pollutants in aqueous, solid, and air matrices Substances of similar structures, or functional groups, or similar properties have been grouped together Th is should guide users of this book to select analytical procedures to analyze compounds not listed in this book In Part III, ana-lytical methodologies and physical properties are presented individually for some selected compounds

high-Most of the analytical methods in Parts II and III of this book are abstracted from the methodologies of the U.S Environmental Protection Agency, National Institute for Occupational Safety and Health, Standard Methods for the Examination of Water and Wastewater, and the American Society for Testing and Materials Some methods are abstracted from other reliable publications or journal articles Th e few suggested methods

of analysis as found in this handbook are based either on the structural features of the compounds or the author’s own experimental work and personal communications

Appendices at the end of this book provide instant information on a wide array of topics ranging from sample preservation to statistical cal-culation Chemical equations, structures, problems, and examples of their solutions are presented wherever necessary.

Th e author would greatly appreciate any comments and suggestions that would serve to improve this book in its future editions

Acknowledgments

I wish you to thank Joseph Clements, acquisition editor; Amber Donley, project coordinator; Joette Lynch, project editor; and the staff at CRC Press/Taylor & Francis for the production of this book I would also like to thank Manisha Patnaik and Chirag Patnaik for their help in the prepara-tion of the manuscript I am especially thankful to my wife Sanjukta for her patience and constant support

Pradyot Patnaik, PhD, is currently the laboratory director of the

Environmental and Analytical Laboratory of the Interstate Environmental Commission at Staten Island, New York, and is a researcher at the Center for Environmental Science at City University of New York at Staten Island

He is an adjunct professor at the New Jersey Institute of Technology in Newark, New Jersey, and also teaches at the Community College of Philadelphia, Philadelphia, Pennsylvania He was formerly the director of the special research project at Environmental Testing and Technologies

in Westmont, New Jersey, and later became the director of Rancocas Environmental Laboratory in Delanco, New Jersey

Prior to this, Dr Patnaik was a postdoctoral research scientist at Cornell University, Ithaca, New York He received his BS and MS in chemistry from Utkal University in India and his PhD from the Indian Institute of Technology, Bombay

Dr Patnaik is the author of three other books: A Comprehensive Guide

to the Hazardous Properties of Chemical Substances (John Wiley, New York), the Handbook of Inorganic Chemicals (McGraw-Hill, New York), and Dean’s Analytical Chemistry Handbook (McGraw-Hill, New York) He

has also authored several research papers

Concentration of a solution as volume percent (v/v)

R = 0.082 L · atm/mol · K (when pressure and volume are expressed in

atm and L, respectively)

Glossary of Terms: Units, Conversions, and Abbreviations xxxvii

Vapor pressure is the pressure of a vapor in equilibrium with its liquid

•

or solid form It is temperature dependent, and expressed in mm Hg or torr It is a characteristic of the volatility of a substance Th e higher the vapor pressure of a substance, the more volatile it is Vapor pressure data

in this book are presented at the temperature 20°C

gram molecular weight (mol)Density of a gas at STP

AA Atomic absorption (spectrophotometry)

ASTM American Society for Testing and Materials

CAS Chemical Abstract Service

ECD Electron capture detector

EPA (U.S EPA) United States Environmental Protection AgencyFID Flame ionization detector

FPD Flame photometric detector

GC/MS Gas chromatography/mass spectrometry

HECD Hall electrolytic conductivity detector

HPLC High-performance liquid chromatography

HRMS High-resolution mass spectrometry

ICP Inductively coupled plasma (emission spectrometry)ICP-MS Inductively coupled plasma (mass spectrometry)

IR Infrared (spectrophotometry)

LC/MS Liquid chromatography/mass spectrometry

NIOSH National Institute for Occupational Safety and Health

NTP Normal temperature and pressure

OSHA Occupational Safety and Health Administration

SFE Supercritical fl uid extraction

SM Standard methods (for the examination of water and

wastewater)SPE Solid phase extraction

TCD Th ermal conductivity detector

UV Ultraviolet (spectrophotometry)

Part

Analytical Techniques

in the environment are continually increasing Th erefore, the analysis of chemical pollutants in the environmental matrices has entered into a new phase in the last decade Modifi cations in instrumentation, sampling, and sample preparation techniques have become essential to keep up with the requirements of achieving parts per trillion (ppt) to low parts per billion (ppb) detection levels, as well as to achieve a faster speed of analysis In addition, more stringent quality-control (QC) requirements in analytical methods have become necessary to obtain high data quality Th is has led

to the many new methodologies that are diff erent from the conventional macro and semimicro analytical approach

Environmental analysis today—like any other scientifi c fi eld—relies heavily on instrumentation Organic pollutants are primarily determined

by gas chromatography (GC), gas chromatography/mass spectrometry (GC/MS), and high-performance liquid chromatography (HPLC), meth-ods Th ese techniques too are not adequate to measure several classes of the so-called emerging pollutants Th e fi eld of mass spectrometry, there-fore, has broadened from the low-resolution to high-resolution stage and from the electron-impact to electrospray ionization mode in order to detect and quantify pollutants at much lower concentrations New meth-ods involving liquid chromatography/mass spectrometry (LC/MS) are being developed to measure pollutants of larger molecular masses that cannot be determined by GC/MS However, there is also a growing inter-est in alternative techniques, such as Fourier transform infrared spectros-copy (FTIR) Specially designed capillary columns have come up for GC analysis to achieve high resolution and better separation of many closely eluting isomers Another major development in organic analysis is HPLC

determination using post-column derivatization Many classes of stances such as aldehydes, ketones, and carboxylic acids may be accurately determined by using such techniques.

sub-Most organic compounds may be best analyzed by GC/MS Such GC/

MS or GC analysis, however, is preceded by either a “purge and trap” centration step or a liquid or solid phase extraction step using a suitable organic solvent Th e purge and trap method for aqueous samples is appli-cable for volatile substances that have lower solubility in water A mass spectrometer should be used wherever possible to identify the compounds more correctly Although it has a lower sensitivity than other GC detec-tors, mass spectrometry is, by far, the most confi rmatory test for com-pound identifi cation

con-Methodologies for inorganic anions and metals have undergone rapid growth similar to chromatographic techniques Notable among these technologies are the atomic absorption and emission spectroscopy and ion chromatography (IC) Th e latter is a rapid method to determine sev-eral anions, simultaneously Th e IC approach may be modifi ed further to measure such weak anions as carboxylates and cyanide

Sample preparation is a key step in all environmental analyses Two major areas of development in this area are solid phase extraction and supercritical fl uid extraction Both techniques have made the extraction

of pollutants from the aqueous and nonaqueous matrices relatively simple, fast, and less expensive Th ese processes, along with gel permeable chro-matography, provide effi cient methods of removing interferences

Th e analytical methods of measuring pollutants in ambient air have developed tremendously in recent years Although these methods employ the same analytical instrumentation (i.e., GC, GC/MS, HPLC, IR, atomic absorption, IC, and the electrode methods), the air sampling technique is probably the most important component of such analysis Th e use of cryo-genic traps and high-pressure pumps has supplemented the impinger and sorbent tube sampling techniques

Th e nature and the number of pollutants that are currently regulated constitute only a fraction of those found in the environment In addition, their chemical characteristics and concentrations may vary widely New and alternative methodologies that are simple, rapid, and reliable need to

be developed Enzyme immunoassay and portable GC and IR techniques need greater attention Another area of interest, with future applications,

is the application of functionalized carbon nanotubes for specifi c ses In the separation fi eld, micromembrane techniques appear promising for the future