Sampling and Analysis of Environmental Chemical Pollutants: A Complete Guide

Sampling and Analysis of Environmental Chemical Pollutants

A Complete Guide

Second Edition

Emma Popek

Walnut Creek, California, USA

Table of Contents

Cover image

Title page

Copyright

Dedication

Acknowledgments

Acronyms and Abbreviations

Chemical Symbols

Introduction to the Second Edition

Chapter 1. The Sample and the Error

Abstract

1.1 The Concept of Relevant and Valid Data

1.2 Importance of a Stepwise Approach

1.3 Seven Steps of the Sample’s Life

1.4 Total Error and Its Sources

1.5 Total Error and Data Usability

Chapter 2. Environmental Chemical Pollutants

Abstract

2.1 Pollutant Classification

2.2 Physical and Chemical Properties as Fate and Transport Indicators

2.3 Volatile Organic Compounds

2.4 Persistent Organic Pollutants

2.5 Toxic Metals

2.6 Action Levels and Regulatory Overview

Chapter 3. Bird’s Eye View of Project Planning

Abstract

3.1 What Are Data Quality Objectives?

3.2 Sampling Design

3.3 Definitive, Screening, and Effective Data

3.4 Data Quality Indicators

3.5 Field QC/QA Samples

3.6 How to Navigate the Analytical Method Maze

3.7 Analytical Method and Laboratory Selection

3.8 Cost Estimate

3.9 Planning Documents

3.10 Preparedness and Coordination

Chapter 4. Practical Approach to Sampling

Abstract

4.1 Seven Steps of the Sampling Process

4.2 Sample Custody and Tracking

4.3 Sample Preservation Methods

4.4 Sample Packing and Shipment

4.5 Soil Sampling Designs

4.6 Sampling for Volatile Organic Compounds

4.7 Sampling for Semivolatile Organic and Inorganic Compounds

4.8 Water Sampling

4.9 Surface Sampling With Wipes

4.10 Equipment Decontamination

4.11 Field Measurements

4.12 Field Screening Methods

4.13 Field Records

Chapter 5. Understanding the Analytical Laboratory

Abstract

5.1 Requirements for Laboratory Operation

5.2 Laboratory Organization

5.3 The Seven Steps of Laboratory Process

5.4 Compound Quantitation

5.5 Analytical Techniques and Their Applications

5.6 Laboratory Quality Assurance

Chapter 6. Data Quality Assessment

Abstract

6.1 Data Evaluation

6.2 The Seven Steps of Data Evaluation

6.3 The Seven Steps of the DQA

Appendix 1. Priority Toxic Pollutants and Priority Substances

Appendix 2. Maximum Concentrations of Contaminants for the Toxicity Characteristics

Appendix 3. List of California Toxic Substances, Their Soluble Threshold Limit Concentrations, and Total Threshold Limit Concentrations

Appendix 4. PCB Cleanup Levels for Various Matrices

Appendix 5. Definitions of Basic Statistical Terms

Appendix 6. Example of a Sampling and Analysis Plan Table of Contents

Appendix 7. Example of Field Sampling Supplies and Equipment Checklist for Soil Sampling

Appendix 8. Example of a Chain-of-Custody Form

Appendix 9. Examples of a Custody Seal and a Sample Label

Appendix 10. Example of a Sample Tracking Log

Appendix 11. Analytical Method References, Containers, Preservation, and Holding Time for Soil Samples

Appendix 12. Analytical Method Requirements, Sample Containers, Preservation, and Holding Time for Water Samples

Appendix 13. Stockpile Statistics Worksheet

Appendix 14. Example of a Sample Container Tracking Log

Appendix 15. Example of a Groundwater Sampling Form

Appendix 16. Example of a Monitoring Well Sampling Sheet (Micropurge)

Appendix 17. Example of a Laboratory Cooler Receipt Form

Appendix 18. Gas Chromatography/High-Performance Liquid Chromatography Analysis Data Package Content

Appendix 19. Gas Chromatography/Mass Spectrometry Analysis Data Package Content

Appendix 20. Trace Element Analysis Data Package Content

Appendix 21. Inorganic Compound Analysis Data Package Content

Appendix 22. Calculations Used for Compound Quantitation

Appendix 23. Data Evaluation Checklist—Organic Compound Analysis

Appendix 24. Data Evaluation Checklist—Trace Element Analysis

Appendix 25. Data Evaluation Checklist—Inorganic Compound Analysis

References

Index

Copyright

Elsevier

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This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

Notices

Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library

Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress

ISBN: 978-0-12-803202-2

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Dedication

To generations—to Tamara, Ezra, and Auriel.

Acknowledgments

The Guide summarizes the experience of a generation of environmental professionals including chemists, engineers, geologists, risk assessors, and database managers. I wish to express my gratitude to my colleagues and friends Rose Condit, Delia Smith, Terry Fong, and Pamela Jespersen for their steady support and advice and to Greg Qatsha for his help with technical issues. A special acknowledgment goes to John Goyette of Curtis and Tompkins Laboratories, who provided the chromatograms for the graphics in the Guide and kept me abreast with the latest practices in analytical chemistry. I wish to thank the members of my family for their support and interest in the advance of this book.

Acronyms and Abbreviations

2,4,5-T 2,4,5-trichlorophenoxyacetic acid

2,4-D 2,4-dichlorophenoxyacetic acid

AA atomic absorption

ACD airtight coring device

APHA American Public Health Association

API American Petroleum Institute

ARAR applicable or relevant and appropriate requirement

ASTM American Society for Testing and Materials

BaP benzo[a]pyrene

BFB bromofluorobenzene

bgs below ground surface

BTEX benzene, toluene, ethylbenzene, xylene

CAS Chemical Abstract Service

CCC calibration check compounds

CCR California Code of Regulations

CCV continuing calibration verification

CERCLA Comprehensive Environmental Response, Compensation, and Liability Act

CF calibration factor

CFC chlorofluorocarbon

CFR Code of Federal Regulations

CLP Contract Laboratory Program

COC chain-of-custody

CRQL contract required quantitation limit

CSM conceptual site model

CVAA cold vapor atomic absorption

CWA Clean Water Act

DCE dichloroethene

DDD dichlorodiphenyldichloroethane

DDE dichlorodiphenyldichloroethene

DDT dichlorodiphenyltrichloroethane

DF dilution factor

DFTPP decafluorotriphenylphosphine

DHHS US Department of Health and Human Services

DNAPL dense nonaqueous-phase liquid

DO dissolved oxygen

DOD US Department of Defense

DOE US Department of Energy

DOT US Department of Transportation

DQA Data Quality Assessment

DQAR Data Quality Assessment Report

DQIs Data Quality Indicators

DQOs Data Quality Objectives

DRO diesel range organics

DT degradation time

ECD electron capture detector

EDD electronic data deliverable

ELCD electrolytic conductivity detector

EPA US Environmental Protection Agency

EU European Union

FAO Food and Agriculture Organization

FID flame ionization detector

FIFRA Federal Insecticide, Fungicide, and Rodenticide Act

FLAA flame atomic absorption

FPD flame photometric detector

FSP Field Sampling Plan

GAC granular activated carbon

GALP Good Automated Laboratory Practice

GC gas chromatography

GC/MS gas chromatography/mass spectrometry

GFAA graphite furnace atomic absorption

GIS Geographic Information System

GLPS Good Laboratory Practice Standards

GPS Global Positioning System

GRO gasoline range organics

HCH hexachlorocyclohexane

HDPE high-density polyethylene

HP hazardous properties

HPLC high performance liquid chromatography

IARC International Agency for Research on Cancer

IATA International Air Transportation Association

ICP inductively coupled plasma

ICP–AES inductively coupled plasma–atomic emission spectrometry

ICP–MS inductively coupled plasma–mass spectrometry

ICV initial calibration verification

ID identification

IDL instrument detection limit

IDW investigation-derived waste

ISM incremental sampling methodology

ISO International Standardization Organization

IUPAC International Union of Pure and Applied Chemistry

LCL lower control limit

LCS laboratory control sample

LCSD laboratory control sample duplicate

LDPE low-density polyethylene

LDR Land Disposal Restrictions

LIMS laboratory information management system

LLOQ lower limit of quantitation

LNAPL light nonaqueous-phase liquid

LOD limit of detection

LOQ limit of quantitation

MCL maximum contaminant level

MDL method detection limit

MS matrix spike

MSA method of standard additions

MSD matrix spike duplicate

MTBE methyl tertiary butyl ether

ND not detected

NELAC National Environmental Laboratory Accreditation Conference

NELAP National Environmental Laboratory Accreditation Program

NIST National Institute for Standards and Technology

NPD nitrogen-phosphorus detector

NPDES National Pollutant Discharge Elimination System

NTU nephelometric turbidity unit

ORP oxidation-reduction potential

PAHs polycyclic (polynuclear) aromatic hydrocarbons

PARCC precision, accuracy, representativeness, comparability, and completeness

PBDE polybrominated diphenyl ether

PBMS Performance-Based Measurement Systems

PBT persistent, bioaccumulative and toxic

PCB polychlorinated biphenyl

PCDD polychlorinated dibenzo-p-dioxin

PCDF polychlorinated dibenzofuran

PCE perchloroethylene, tetrachloroethene

PDB passive diffusion bag

PE performance evaluation

PEF potency equivalence factor

PID photoionization detector

POP persistent organic pollutant

POTW publicly owned treatment works

PPE personal protective equipment

PT proficiency testing

PTFE polytetrafluoroethene

PVC polyvinyl chloride

QA quality assurance

QAPP Quality Assurance Project Plan

QC quality control

RCRA Resource Conservation and Recovery Act

RF response factor

RL reporting limit

RPD relative percent difference

RRF relative response factor

RRO residual range organics

RSD relative standard deviation

RSL Regional Screening Level

RT retention time

SAP Sampling and Analysis Plan

SDG Sample Delivery Group

SDWA Safe Drinking Water Act

SEDD Staged Electronic Data Deliverable

SHE standard hydrogen electrode

SIM selected ion monitoring

SOP standard operating procedure

SOQ Statement of Qualifications

SOW Statement of Work

SPCC system performance check compound

SPLP Synthetic Precipitation Leaching Procedure

STLC soluble threshold limit concentrations

SVOC semivolatile organic compound

TAL target analyte list

TCDD tetrachlorodibenzo-p-dioxine

TCDF tetrachlorodibenzofuran

TCE trichloroethene

TCLP Toxicity Characteristic Leaching Procedure

TDS total dissolved solids

TEF toxicity equivalence factor

TEQ toxicity equivalency quotient

TNI The NELAC Institute

TNT trinitrotoluene

TPH total petroleum hydrocarbons

TSCA Toxic Substances Control Act

TSS total suspended solids

TTLC Total Threshold Limit Concentration

U undetected

UCL upper control limit

USACE US Army Corps of Engineers

USDA US Department of Agriculture

UST underground storage tank

UV ultraviolet

VIS visible

VOC volatile organic compound

VSP Visual Sample Plan

WHO World Health Organization

WP Work Plan

XRF X-ray fluorescence

Chemical Symbols

°C degrees Celsius

°F degrees Fahrenheit

µg microgram

µg/kg microgram per kilogram

µg/L microgram per liter

µg/m³ microgram per cubic meter

µL microliter

µm micron

µmho/cm micromho per centimeter

µS/cm microSiemens per centimeter

cm centimeter

cm² square centimeter

eV electronvolt

g gram

g/cm³ gram per cubic centimeter

g/mole gram per mole

gal gallon

gal/min gallon per minute

kg kilogram

m meter

mg milligram

mg/kg milligram per kilogram

mg/L milligram per liter

mho ohm−1

min minute

mL milliliter

mL/min milliliter per minute

mm millimeter

mS/m millisiemens per meter

mV millivolts

M mole

ng/L nanogram per liter

nm nanometer

pg/g picogram per gram

pg/L picogram per liter

ppb part per billion

ppm part per million

S Siemens

Introduction to the Second Edition

Much has been learned about the nature and toxicity of chemical pollutants in the last 50 years. Today we are certain that some of them stay in the environment for a long time and have an ability to move with wind, dust, and rain. Their lifetimes may exceed the span of a human life. They may produce unforeseen long-term consequences in faraway places. The presence of chemical pollutants in the environment is not as noticeable as the effects of climate change—the melting of glaciers, the dying of coral reefs, the turning of arable land into desert. Typically, chemical pollutants stay invisible in the environment unless a dramatic release event takes place, such as a chemical spill in a major river, an overturned train accident, or a chemical explosion and fire. An invisible, unnoticed, and unidentified pollutant may stay in the environment for an indefinite period of time until a reason arises for an investigation to detect its presence and conduct an environmental cleanup. A hidden pollutant may provide a cumulative quantity of poison that has a potential to sicken or kill a living organism, from a miniscule member of zooplankton to the top-of-food-chain mammal.

A chemical pollutant manifests itself through the effects it produces on the living organisms, from extinction of species to human illness. The people of Minamata Bay in Japan had been sick and dying from mercury poisoning over the course of many years until the cause of the sickness became associated with consumption of local seafood contaminated with methylmercury. The source of pollution was the local chemical factory discharging untreated wastewater into the sea. Only after in Flint, MI, children started showing the symptoms of lead poisoning did the lead concentrations in their tap water receive serious attention. But this was too late for many.

In 1949, an American conservationist Aldo Leopold wrote in his book A Sand County Almanac: All ethics so far evolved rest upon a single premise: that the individual is a member of a community of interdependent parts. The land ethic simply enlarges the boundaries of the community to include soils, waters, plants and animals, or collectively the land. The land ethic as defined by Leopold applies to the modern-day issues of local and global environmental pollution with industrial chemicals. In the 21st century a comprehensive concept of the environment comprises the land (soils, waters, plants, and animals) and the air. As individuals, we are responsible for keeping clean the air we breathe, the soil we walk on, and the water we drink. As local communities, we must take care of the land we live on. As a global community, we are capable of resolving global problems in a shared effort. It is our ethical duty as individuals and communities to safeguard the uncontaminated land for future generations.

The fact is that the modern society cannot exist without industrial chemicals many of which become environmental pollutants. The fact also is that environmental pollutants are practically omnipresent. In our work we may sample and analyze for hundreds of pollutants but find only a few. We would not find any if appropriate pollution controls were in place. The pollutants that are not found in the environment are as important as the ones that are found, because they demonstrate that the land continues to be uncontaminated.

Operating under typically limited budgets, we must be focused and highly efficient in our work to produce valid and relevant data without wasting time and money. Achieving this goal requires thoughtful planning, skillful field execution, and competent data quality assessment. This Guide is a resource that will help students and professionals alike understand the issues of environmental chemical pollutants, capitalize on years of existing environmental sampling and analysis practices, and become knowledgeable and efficient in the task at hand.

The Guide’s second edition is not only about the methods of sampling and analysis. It has been updated to include a new discussion (Chapter 2, Environmental Chemical Pollutants) on the physical and chemical properties of environmental pollutants that enable their global reach. Understanding the chemical pollutant behavior in the environment enables us to develop conceptual site models and prepare focused sampling and analysis plans.

The Guide’s goal is to enable practicing professionals to gain a wider view of the complexities of project work and to better understand the needs and priorities of other project participants. Another goal is to offer a comprehensive perspective of project work to students of environment data collection, including step-by-step procedures and practical tips for everyday project tasks.

Chapter 1

The Sample and the Error

Abstract

This chapter introduces the concepts of valid, relevant, and usable data, the total error, and the three phases of data collection (planning, implementation, and assessment). Components of total error are discussed in terms of data quality indicators and their acceptance criteria. It explains how this Guide divides the data collection phases into distinctive tasks, dissects the tasks into manageable steps, and provides instructions and practical advice on their execution, all aimed on the reduction of the total error.

Keywords

Planning; implementation; assessment; data quality objectives; stepwise approach; total error; data quality indicators and acceptance criteria

1.1 The Concept of Relevant and Valid Data

One of the main concerns of any environmental project is the collection of relevant and valid data. These are the data of the type, quantity, and quality that are appropriate and sufficient for the project decisions. The standards for data relevancy and validity stem from the intended use of the data since different uses require different type, quantity, and quality of data. For example, data requirements for a risk assessment project would be different from those of a waste disposal project; the requirements for site investigation data would be different from these for site closure.

Data relevancy and validity are unrelated concepts, a fact that is not always recognized by all project participants. Data can be perfectly valid and yet irrelevant for their intended use. Conversely, the quality of data may be flawed in some way, as is usually the case in the real world, and nevertheless, they can be used for project decisions.

How do the project participants assure that the collected data are of the correct type, quantity, and quality, or in other words are relevant and valid? To address different aspects of data collection, the process can be divided into three distinctive phases: planning, implementation, and assessment [1]. These phases contain a total of seven unique data collection tasks, all designed to assure the relevancy and validity of the data:

Task 1—Data quality objectives (DQOs) development

Task 2—Sampling and analysis plan (SAP) preparation

Task 3—Sampling and field data collection

Task 4—Field quality assurance (QA) and quality control (QC)

Task 5—Laboratory analysis

Task 6—Data evaluation

Task 7—Data quality assessment (DQA).

If all seven tasks are conducted properly, the collected data will be not only valid and relevant to the project objectives, but they will also be robust and solid, like the most durable structures on Earth, the pyramids. That is why the data collection process is best depicted as a pyramid, constructed of three ascending layers, representing the three phases of the data collection process, planning, implementation, and assessment, as shown in Fig. 1.1.

Figure 1.1 Three phases of environmental chemical data collection process.

Each of the three phases contains several major tasks that are conducted consecutively. The data collection pyramid is built from the bottom up through carrying out these seven tasks. Take one pyramid layer or one task out, and the whole structure becomes incomplete and prone to collapse.

1.1.1 Planning

The foundation for the collection of relevant and valid data is laid out in the planning phase through the completion of Task 1—DQOs development and Task 2—SAP preparation. The DQO process enables the project participants to come to the understanding of the intended data uses and to identify the necessary types, quantity, and quality of data for each separate use. In other words, the requirements for the collection of relevant and valid data are defined through the DQO process early in the planning phase of the data collection. The project DQOs, the sampling design, and the type, quantity, and quality of data are stated in the SAP together with the requirements for field and laboratory QA/QC and data evaluation procedures necessary to achieve these objectives. The SAP requirements define the course of the implementation and assessment phases of the data collection process.

1.1.2 Implementation

The implementation phase of the data collection process takes place in the field and at the laboratory where the SAP provisions are implemented. This phase consists of Task 3—Sampling and field data collection, Task 4—Field QA/QC, and Task 5—Laboratory analysis. In theory, if all sampling, analysis, and QA/QC tasks of this phase are conducted to the requirements of the SAP, the collected data will be relevant and valid. In reality, most projects have variances from the requirements specified in the SAP, hence a need for the next phase of data collection, i.e., assessment.

1.1.3 Assessment

The assessment phase offers us the tools to verify that the data are truly relevant and valid. The assessment phase includes Task 6—Data evaluation and Task 7—DQA. Data validity is established through the application of data evaluation procedures; their relevancy for making project decisions is determined in the course of the DQA process.

Like building the pyramids, the three-phase collection process of relevant and valid data is a daunting undertaking that can be best achieved by placing one stone at a time through a stepwise approach to each task.

1.2 Importance of a Stepwise Approach

A stepwise approach to the planning phase (Fig. 1.2) based on the DQO process for determining the type, quality, and quantity of data that would be sufficient for valid decision making has been a proven and useful method in any environmental project work [1]. Each step of the DQO process addresses a specific facet of the future data collection design. The DQO process enables us to define the intended use of the data; the data quality appropriate for the intended use; the sampling rationale and strategy; and many other important aspects of data collection.

Figure 1.2 The seven steps of the DQOs process.

The seven steps of the DQO process detailed in Chapter 3, Bird’s Eye View of Project Planning mold our reasoning into a logical and informed approach by turning project planning into a structured and consistent process. Chapter 3 describes the seven steps of the DQO process and, using examples, explains how to apply them for planning of environmental data collection. Once understood, the DQO process can be used not only for environmental project planning, but also for any planning that we may face in everyday life. It is nothing more than a common-sense planning instrument that promotes gathering of information needed for educated decision making, logical thinking in decision making, and evaluation of risks associated with every decision.

The concept of a seven-step process is the underlying theme of this Guide. Any task, insurmountable as it may seem at a first glance, becomes feasible once broken into small, consecutive, and achievable steps. Each step has its own objectives that we can meet without difficulty if we rely on clear and well-written instructions to guide us through each detail of the step. The Guide divides the data collection phases into distinctive tasks as shown in Fig. 1.1, dissects the tasks into manageable steps, and provides instructions and practical advice on their execution.

1.3 Seven Steps of the Sample’s Life

Environmental projects revolve around environmental data collection, such as analytical chemistry data for environmental chemical pollutants. Chemical data enable us to conclude, whether hazardous conditions exist at a site and whether such conditions create a risk to human health and the environment. We gather environmental chemical data by collecting samples of soil, water, and other environmental media at the right time and at the right place and by analyzing them for chemical pollutants. In other words, in the core of every environmental project lies an environmental sample.

Like a living organism, an environmental sample has a finite life span and is as sensitive as living matter. It contains chemicals that undergo changes when exposed to light, air, or to variations in temperature and pressure, it houses live bacterial colonies, and contains bubbling gases or radionuclides. Physical and chemical processes constantly take place in the sample, and in this chapter we shall respectfully call it the Sample, for it lives and dies like a living organism.

The life of the Sample consists of seven consecutive periods or steps illustrated by a diagram in Fig. 1.3. These steps are irreversible, and mistakes made by the Sample’s handlers at any of them may prove fatal for the Sample’s life.

Figure 1.3 The seven steps of the Sample’s life.

Once conceived during the planning phase of the project (Step 1), the Sample gestates within the environment for an indefinite period of time until we identify the sampling point in the field (Step 2) and collect the Sample (Step 3). Identifying a correct sampling point is a critical issue because using an inappropriate sampling design or collecting samples from wrong locations may cause the whole project to go astray. The Sample is born at the moment it has been collected and placed in a container (Step 3). An improper sampling technique or a wrong sample container can make the Sample unsuitable for analysis. In fact, incorrect sample containers, packaging, and shipping during transfer from the field to the laboratory are among the leading causes of data invalidation. The Sample is then transferred to the laboratory (Step 4). Mistakes made by any of the Sample’s handlers at Steps 3 and 4 have a potential to invalidate the Sample and cause its premature demise.

The Sample is analyzed at the laboratory (Step 5), and in the course of analysis it often ceases to exist (Step 6), being completely used up in the analytical procedure. Step 5 conceals many dangers for the Sample’s well-being because laboratory mistakes in preparation or analysis may jeopardize data validity and render the Sample useless. If not completely used up during analysis, the Sample nevertheless expires (Step 6) when it reaches the limit of its holding time as prescribed by the analytical method. The Sample thus reaches the end of its life and is discarded. However, its legacy is the chemical data (Step 7). In the afterlife of the Sample, chemical data become the Sample’s alter ego and acquire a life of their own. Whether they are valid or invalid, the chemical data are the Sample’s immortal legacy and a testimony to our ability to plan and execute environmental projects.

1.4 Total Error and Its Sources

As we already know, an environmental sample is a fragile living matter that can be severely damaged at every step of its existence. Due to the inherent heterogeneity of environmental media and a host of potential errors associated with sampling, analysis, and data management, the collection of environmental chemical data is not an exact science. In fact, all environmental chemical data are only the estimates of the true condition that these data represent. In order to make these estimates more accurate, we must examine the sources of errors and take measures to control them.

Total error is a combination of various errors that may occur during sampling, analysis, and in data management. It is important to understand that total error cannot be completely eliminated; it can only be controlled and minimized. Total error cannot be expressed in a convenient numeric manner. It is a concept that encompasses quantifiable, statistical parameters and the factors that can be described only in qualitative terms. The components of total error can be grouped into two general categories: sampling errors and non-sampling errors (Fig. 1.4). Some sampling errors originate in the planning phase of the data collection process, whereas others are made during the implementation phase. Non-sampling errors may take place in the implementation and assessment phases.

Figure 1.4 Sampling error is the greatest contributor to total error.

Certain types of errors that may take place during data collection are obvious and manageable; however, the most damaging errors are hidden from plain view. For example, we usually closely scrutinize analytical measurement errors because they are easy to understand, quantify, and control. At the same time, we need to recognize the fact that errors made during sampling may be far more consequential for the data relevancy and validity than analytical measurement errors. Such errors originate from poor planning, negligence, lack of knowledge or simple mistakes, and because they cannot be expressed numerically, they are described in qualitative terms. These qualitatively described errors constitute a major proportion of the total error of sampling and analysis and they easily overpower the effect of quantifiable measurement errors.

Take, for example, errors originating in the planning phase. They cannot be quantified, but their effects on data relevancy and validity could be devastating. As a result of poor planning, the purpose of data collection is often not clearly understood, and wrong types of data are collected. Incomplete or erroneous planning always negatively affects the project field implementation and produces data of inadequate quality or insufficient quantity that cannot be used for project decisions. Another source of errors that cannot be quantified is the haphazard, unfocused, or poorly conducted field and laboratory implementation. It may lead to data gaps or to the production of unnecessary or unusable data. The cumulative effect of various unquantifiable errors made in the planning and implementation phases erodes data validity and reduces their relevancy.

Of course, some errors are more critical than others. Some errors may be fatal, whereas other, while undermining the data quality to some extent, do not completely invalidate the data. Fatal errors are errors of judgment in the planning and implementation phases, such as the selection of inappropriate sampling designs, unrepresentative sampling locations, or the unjustified field deviations from planned sampling designs. Errors of negligence or oversight such as a wrong analysis applied to a sample or a wrong sample selected for analysis can also be fatal. On the other hand, errors in calculations during data reduction or reporting errors, if identified in the assessment phase, can be corrected without consequences for data usability.

1.4.1 Sampling Error

As shown in Fig. 1.4 the sources of sampling error, which is a combination of quantifiable components and qualitative factors, can be divided into two groups, inherent errors and decision errors, and further subdivided into four categories:

1. Errors originating from inherent sample heterogeneity

2. Errors originating from inherent population variability

3. Sampling design errors

4. Field procedure errors.

The quantifiable components of sampling error are the natural heterogeneity within a sample itself and the variability between sample populations that may be randomly selected from the same sampled area. Both of these errors can be evaluated quantitatively in the form of statistical variance and controlled to some extent through the application of appropriate sampling designs.

The qualitative components of the sampling error that may take place in the planning process and in the implementation of field procedures are as follows:

• Sampling design error—collection of excessive or insufficient amount of data; unrepresentative selection of sampling points; wrong time of sampling that may affect data relevancy; choice of improper analysis.

• Field procedure error—misidentified or missed sampling points in the field; failure to use consistent sampling procedures; gaps in field documentation; use of incorrect sampling equipment and sample containers; incorrect sample preservation techniques or storage conditions.

The key factor in minimizing the overall sampling error is the elimination or reduction of these qualitative human errors in sampling design and field procedures. In extreme cases they may have a more powerful effect on data relevancy and validity than errors originating from sample or population heterogeneity. In fact, a thoughtfully conducted planning process takes into account the sample and population variability at the site. Nevertheless, even with the best sampling design, the sampling error, a combination of inherent sample properties and human error, is usually the greatest contributor to the total error.

1.4.2 Non-sampling Error

As shown in Fig. 1.4, non-sampling errors can be categorized into laboratory error and data management error, with laboratory error further subdivided into sample management, measurement, laboratory procedure, analytical methodology, and data interpretation errors.

We can easily quantify measurement error due to existence of a well-developed approach to analytical methods and laboratory QC protocols. Statistically expressed accuracy and precision of an analytical method are the primary indicators of the measurement error. However, no matter how accurate and precise the analysis may be, qualitative factors, such as errors in data interpretation, sample management, and analytical methodology, are likely to increase the overall analytical error or even render results unusable. These qualitative laboratory errors that are usually made due to negligence or lack of information may arise from any of the following activities:

• Sample management error—improper sample storage; analysis of samples that are beyond their holding time; misplaced or mislabeled samples; sample cross-contamination.

• Laboratory procedure error—failure to use proper preparation or analysis procedure; gaps in laboratory documentation.

• Methodology error—failure to use proper methods of sample preparation and analysis; use of nonstandard, unproven analytical methods.

• Data interpretation error—incorrect analytical data interpretation producing false-positive or false-negative results.

Data management errors may occur at the laboratory and at the consulting office. They include incorrect computer program algorithms; transcription and calculation errors; bad laboratory record-keeping practices resulting in data gaps; and other mistakes made due to a general lack of attention to the task at hand.

1.5 Total Error and Data Usability

As shown above, total error consists for the most part of qualitative errors; the quantifiable components constitute only its minor proportion. Qualitative errors have a much greater potential to destroy the whole sampling effort than quantifiable errors, and they are usually the leading cause of resampling and reanalysis.

Clearly, every project team should be concerned with the effect of total error on data relevancy and validity and should make every effort to minimize it. Nevertheless, the cumulative effect of various sampling and non-sampling errors may erode the data validity or relevancy to a point that the data become unusable for project decisions. To evaluate the magnitude of this eroding effect on the collected data, in the third and final phase of data collection process we critically assess the data in order to answer these four questions:

1. Do the data conform to applicable standards and specifications?

2. Are the data technically and legally defensible?

3. Are the data representative of the sampled matrix?

4. Can a decision be made with the desired level of certainty?

The total error can undoubtedly affect the outcome of all four questions. Only after we have established that the collected data are appropriate for the intended use, representative of the sampled matrix, conform to appropriate standards, and are technically and legally defensible, the data can be described as data of known quality. Only the data of known quality may be used for project decisions.

We find the answers to the four questions in the course of the data quality assessment, which is the scientific and statistical evaluation of environmental data to determine if they meet the planning objectives of the project, and thus are of the right type, quality, and quantity to support their intended use [2]. Part of DQA is data evaluation that enables us to find out whether the collected data are valid. Another part of the DQA, the reconciliation of the collected data with the DQOs, allows us to establish data relevancy. Thus, the application of the entire DQA process to the collected data enables us to determine the effect of total error on data usability.

1.5.1 Data Quality Indicators and Acceptance Criteria

When discussing data quality as a concept, we need to understand that it has a meaning only in relation to the intended use of the data and when defined by a standard that is appropriate for this use. Data can be judged adequate or inadequate only in the context of their intended use and only within the limits of an appropriate standard. For example, a set of data, which is of inadequate quality to be used for site characterization, may be perfectly adequate for another purpose, such as waste disposal profiling. This is possible because two different standards exist for assessing the adequacy of site characterization data and waste profiling data.

How do we access the qualitative and quantitative components of total error for data sets that consist of analytical results and an assortment of field and laboratory records? And how do we define a standard appropriate for the intended data use?

To encompass the seemingly incompatible qualitative and quantitative components of total error, we evaluate them under the umbrella of data quality indicators (DQIs). DQIs are a group of quantitative and qualitative descriptors, namely, precision, bias, accuracy, representativeness, comparability, completeness, and sensitivity [3], used in interpreting the degree of acceptability or usability of data. As indicators of the overall environmental measurement system, which includes field and laboratory measurements and processes, the DQIs enable us to determine the validity of the collected data.

We will revisit the application of DQIs and discuss them in detail in Chapter 3, Bird’s Eye View of Project Planning, Chapter 5, Understanding the Analytical Laboratory, and Chapter 6, Data Quality Assessment. The following brief definitions will help us understand their relation to the concepts of total error and data quality [3, 4]:

• Precision—a measure of agreement among repeated measurements of the same property under identical or similar conditions; calculated as the standard deviation.

• Bias—a systematic or persistent distortion of a measurement process that causes errors in one direction.

• Accuracy—a measure of the overall agreement of a measurement to a known value.

• Representativeness—a qualitative term that describes the degree to which data accurately and precisely represent a characteristic of a population, a parameter variation at sampling point, a process condition, or an environmental condition.

• Comparability—a qualitative term that describes the measure of confidence with which one data point can be compared to another.

• Completeness—a measure of the amount of valid data needed to be obtained from a measurement system.

• Sensitivity—a capability of a method or an instrument to discriminate between measurement responses representing different concentrations of the analyte.

The DQIs are meaningful only if compared to certain standards as a means to determine their acceptability. These qualitative and quantitative standards called acceptance criteria are specified limits placed on characteristic of an item, process, or service defined in requirements document [3].

Similar to DQIs, acceptance criteria are expressed in qualitative and quantitative terms. Some of them are statistically derived values, while others are purely qualitative and represent industry standards and accepted practices. Experimentally derived quantitative parameters (precision, bias, accuracy, completeness, and sensitivity) are evaluated mathematically and compared to numerical acceptance criteria. Representativeness, which is a qualitative parameter, is established by comparing documented field and laboratory procedures to applicable standards and specifications. Comparability, estimated as the closeness of analytical results obtained at two different laboratories, is usually expressed qualitatively. In environmental project work, the DQI acceptance criteria are documented in the SAP.

A comparison of the DQIs to the corresponding acceptance criteria enables us to evaluate all of the quantitative and qualitative aspects of total error. Because every component of total error has an effect on at least one of the DQIs as shown in Table 1.1, we should make every effort to minimize their cumulative degrading influence on the DQIs and consequently, on data quality.

Table 1.1

Components of total error and their influence on DQIs

The DQI acceptance criteria are derived from an extensive system of practices and regulations that define the accepted standard for environmental data collection. Included in this comprehensive standard are environmental laws; guidance documents from government agencies and local authorities, overseeing environmental work; specifications developed by professional organizations and associations; analytical methods and QA guidance manuals; standard test procedures; and industry practices. We rely on this system of rules at every step of environmental data collection. We also use it as a standard during data evaluation, while answering the question Do the data conform to applicable standards and specifications?

The intricate rules for sampling, laboratory analysis, and data quality evaluation, all designed to minimize total error components, apply to every environmental data collection project. The quality of collected data is defined by this system of multidisciplinary rules, and a practical interpretation of these rules lies at the core of this Guide.

Chapter 2

Environmental Chemical Pollutants

Abstract

This chapter provides an overview of common organic and toxic metal pollutants and explains how the physical and chemical properties define the pollutant environmental fate and transport. International conventions on human toxicity classification of carcinogenicity and other health effects are described and illustrated with examples for common chemicals. Production and use history summaries for common volatile organic compounds (solvents and industrial chemicals) and persistent organic pollutants (pesticides, polychlorinated biphenyls, dioxins/furans) highlight their long-term effects and the spread around the world. The chapter explains how international treaties and specific regulations control and limit pollution emissions and protect human health and the environment.

Keywords

Pollutant classification; volatile organic compounds; persistent organic pollutants; toxic metals; action levels; regulatory overview

2.1 Pollutant Classification

The rise of industrialized society produced an unforeseen consequence: contamination of the environment with synthetic chemicals formulated and manufactured as new and advanced products or generated as by-products of industrial processes. The number of man-made industrial chemicals used over the years is countless, and many of them are found in soil, water, and air around the globe.

Chemical pollutants are divided into two general categories: inorganic (mostly metals) and organic (carbon-based compounds). Although metals are natural constituents of the earth’s crust, their elevated concentrations produced by industrial activity can be toxic to human and ecological receptors. The majority of elemental metals and their compounds and complexes are extremely stable in the environment. Metal-containing particulate matter can be transported over long distances by wind and aquatic sediment. Metals constitute a distinct class of toxic pollutants that we place in the base of the chemical pollutant pyramid to emphasize their stability (Fig. 2.1). This pyramid is built upward with organic compounds in the order of increasing volatility and decreasing stability in the environment.

Figure 2.1 Three major classes of environmental chemical pollutants.

Organic pollutants are divided into two classes based on the boiling point: volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs). This division reflects the differences in the chemical properties of the two classes that define their environmental fate and transport. These differences also define the analytical techniques appropriate for their detection and quantitation.

In qualitative terms, organic compounds that evaporate under normal temperature and pressure belong to the VOC class. Because volatility is related to the boiling point, organic compounds can be quantitatively classified based on their boiling points. The World Health Organization (WHO) defines VOCs [5] as organic compounds with the boiling point range of 240 to 260 degrees Celsius (°C). The European Environment Agency provides a qualitative definition of VOCs [6]: Organic chemical compounds that under normal conditions are gaseous or can vaporize and enter the atmosphere. VOCs include such compounds as methane, benzene, xylene, propane, and butane. Methane is primarily emitted from agriculture (from ruminants and cultivation), whereas non-methane VOCs are mainly emitted from transportation, industrial processes and use of organic solvents. In routine environmental project work the VOC class does not include the gases methane, ethane, butane, or propane because they require special methods of sampling and analysis. However, man-made halogenated derivatives of these gases fall within the VOC class together with aromatic and other halogenated hydrocarbons and solvents, volatile petroleum fuels (gasolines, jet fuels) and petroleum-based solvents (naphtha, mineral spirits), ketones, acetates, nitriles, acrylates, ethers, sulfides, and organic lead compounds. Fig. 2.1 shows VOCs on the top of the pollutant pyramid. Their main transport mode is volatilization from soil and surface water into the atmosphere where they are destroyed by sunlight, ozone, oxygen, and moisture. VOCs have varying degrees of water solubility and under certain conditions can travel significant distances with the groundwater in the aquifer.

The middle part of the pyramid between highly stable metals and highly unstable VOCs is occupied by SVOCs, a class of organic compounds with the boiling point ranging from 250°C to 400°C [5]. This class includes a large number of industrial chemicals, pesticides, phenols, ketones, ethers, phthalate esters, anilines, pyridines, and many others. The line between VOCs and SVOCs is somewhat blurred, and there is a number of compounds that fall into both classes. Important to understand is that SVOCs do have a certain degree of volatility and water solubility. They are much more resistant to environmental degradation than VOCs and are mobile in the environment being transported with particulate matter by wind, with aquatic sediment, and through food chains. Many of them have a global presence at trace concentrations. A group of SVOCs with a particularly persistent behavior in the environment, with a capacity to bioaccumulate through food chains, and with human and ecological toxicity was recognized internationally as persistent organic pollutants (POPs). POPs are persistent, bioaccumulative, and toxic (PBT) and have an ability to spread around the globe. For this reason, they were addressed internationally through a world treaty, the Stockholm Convention on Persistent Organic Pollutants, discussed in Section 2.4.1.

Toxicity of environmental chemical pollutants is evaluated based on their effects on human and animal health, the most significant of which is human carcinogenicity, the ability to induce cancer in humans. Different agencies in different countries classify chemicals in relation to carcinogenicity based on the data obtained from human epidemiological statistics and laboratory animal studies. Classification definitions may be worded differently but in essence they are very close. The WHO International Agency for Research on Cancer (IARC) classifies chemicals (referred to as agents) into several categories based on their carcinogenicity [7] as follows:

• Group 1—The agent is carcinogenic to humans when there is sufficient evidence of carcinogenicity to humans.

• Group 2A—The agent is probably carcinogenic to humans when there is limited evidence of human carcinogenicity and sufficient evidence of laboratory animal carcinogenicity.

• Group 2B—The agent is possibly carcinogenic to humans when there is limited evidence of human carcinogenicity and less than sufficient evidence of laboratory animal carcinogenicity.

• Group 3—The agent is not classifiable as to its carcinogenicity to humans when there is inadequate evidence of human and laboratory animal carcinogenicity.

• Group 4—The agent is probably not carcinogenic to humans when there is evidence suggesting the lack of carcinogenicity in humans and laboratory animals.

The US Environmental Protection Agency (EPA) and the US Department of Health and Human Services (DHHS) have equivalent classifications. Classifications may change as new data analysis is obtained.

Aside from carcinogenicity, chemicals may have a range of other long-term and short-term toxic effects on human health such as neurological, hematological, immunological, reproductive, developmental, congenital, respiratory, cardiovascular, hepatic, renal, endocrine, dermal, ocular, and skeletomuscular. The toxic and carcinogenic properties of chemical pollutants that present a risk to human health are the cause of remediation of contaminated media. Toxicity to ecological receptors and the resulting disruption of populations and contamination of food chains