Beryllium environmental analysis and monitoring

Berylliu m

Environmental Analysis and Monitoring

Edited by

Michael J. Brisson and Amy A. Ekechukwu

Savannah River Nuclear Solutions, Savannah River Site, Aiken, se, USA

RSCPublishin g

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

ISBN: 978-1-84755-903-6

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

© Royal Society of Chemistry 2009

AU rights reserved

Apart /rom fair dealing for the purposes of research for non-commerciaỉ purposes or

for private síudy, criticism or review, as permiiíed under the Copyrìght, Designs

anđ Patenís Ác í 1988 and the Copyright and Reỉated Rights Reguỉations 2003. this

pubỉication may nót be reproduced, stored or Ịransmitted, in any form ÓT by any means,

without the prior permỉssion in writing of The Royaỉ Society of Chemistry or the

copyright oxvner, ÓT in the case of reproduction ìn accordance with the terms of ỉicences

issued hy the Copyright Licensing Ảgencỵ in the VK, or in accordance with the terms

of the ỉicences issued hy the appropriate Reproduction Righls Organization outside the

UK. Enquirìes concerning reproduction outside the terms stated here shouỉd be sém to

The Royal Socỉety of Chemistry át the address prỉnted ôn this page.

Publisheđ by The Royal Society of Chemistry,

Thomas Graham House. Science Park, Milton Road.

Cambridge CB4 0WF, UK

Registered Charity Number 207890

For íiirther iníbrmation see our web site át www.rsc.org Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Pre/ac e

Beryllium is a metal with unique properties thát make Ít useful for a number

of applications, from consumer products such as cell phones, to nuclear

weapons components. These unique properties make Ít difficult to find alter￾natives to beryllium and ensure thát Ít will continue to be used for the fore￾seeable future. However, for some individuals, exposure to beryllium

particulates in the workplace can lead to a sensitization reaction. Sensitized

individuals with beryllium particulates in the lungs are át risk for chronic

beryllium disease (CBD), which can have a long latency period before symp￾toms appear. Sensitization and/or disease can result tròm exposure át very

low levels. As a result, control of exposures to beryllium in the vvorkplace is

essential. Although engineering controls are normally the first line of defense,

exposure monitoring, including sampling and analysis, is also important and

is typically mandated by regulation.

While most metals and metalloids have occupational exposure limits in the

range of milligrams per cubic metre, limits for beryllium are in the microgram

or sub-microgram per cubic metre range. Additionally, some forms of ber￾yllium in the vvorkplace are highly reíractory, making thèm difficult to dissolve

for analytical purposes. These considerations pose unique challenges for

monitoring of beryllium exposure in the workplace. Some of the challenges

include: sampling a sufficient air volume to evaluate short-term exposures;

sampling settled dust (in some cases accumulated over decades) ôn a wide

variety of surfaces; preparing samples to ensure thát all of the workplace

beryllium forms are detected; anđ obtaining sutĩìcient analytical sensitivity.

Since datasets often have a large percentage of results below the laboratory's

reporting limit, data reporting itselí is often a challenge.

Although there is now considerable information ôn beryllium sampling and

analysisin the literature, much of Ít within the last decade, there has úp to now

been no single compendium to survey the literature and provide guidance ôn

best practice. Providing such a resource is our goal for this book. We do nót

Beryllium: Environmental Analysis and Monitoring

Edited by Mỉchael J. Brisson and Amy A. Ekechukvvu

© Royal Society of Chemislry 2009

Published by the Royal Society of chemistry, www.rsc.org

V

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

vi Pre/ace

promote a one-size-fits-all approach; instead, our goal is to provide iníbrma￾tion thát vvill enable users to ensure thát their sampling and analysis techniques

arefit-for-purpose.Hopeíully, we will promote more consistency along the

way.

There are likely more challenges to come. Since there is no known exposure￾response relationship for beryllium sensitization or disease, the trend tovvard

lower occupational exposure limits may continue indeíinitely. There remains

some diAerence of opinion ôn the need for particle size-selective sampling, and

what fractions should be sampled. We also do nót know vvhether some

anthropogenic forms of beryllium are more toxic than others. Future infor￾mation may pointto a need to ditĩerentiate, say, beryllium oxide from ber￾yllium metal or alloy. While major research laboratories can do thát today, the

typical industrial hygiene laboratory cannot. New iníormation ôn these topics

will hopeíully spawn improvements in the areas covered in this book. In the

meantime, we presentthe state of the art as Ítistoday and trust Ít will be of

benefit throughoutthe scientilìc community. MichaelJ. Brisson

Amy A. Ekechukwu

Co-editors

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Contents

Chapter Ì Overview oi Beryllium Sampling and Analysis: Occupational

Hygiene and Environmental Applications Ì

Michael J. Brisson

1.1 Introduction 2

1.2 Goals of this Book 3

1.3 Background 3

1.3.1 Beryllium Sources 3

1.3.2 Beryllium Uses 4

1.3.3 Health Risks 5

1.3.4 Occupational Exposure Limits 6

1.3.5 Impact of us Department of Energy

Regulation 6

1.3.6 Environmental Beryllium and Soil

Remediation 8

1.3.7 Beryllium in Water 8

1.4 Sampling Overview 8

1.4.1 Air Sampling 8

1.4.2 Surface Sampling 9

1.4.3 Dermal and Soil Sampling 10

1.5 Analysis Overvievv 10

1.5.1 Summary of Current Techniques 10

1.5.2 Sample Preparation lo

1.5.3 Data Evaluation and Reporting li

1.5.4 Future Analytical Challenges li

Acknowledgements 12

References 13

Beryllium: Environmental Analysis and Monitoring

Edited by Michael J. Brisson and Amy A. Ekechukvvu

© Royal Society of Chemistry 2009

Published hy the Royal Society of Chemistry, www.rsc.org Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn vii

viii Contenls

Chapter 2 Air Sampling 17

Marlin Harper

2. Ì Introduction 18

2.2 Sampling Strategies 19

2.2. Ì Sampling for Compliance vvith a Limit Value 19

2.2.2 Sampling to Identify a Group Range of

Exposures 21

2.2.3 Real-Time Monitoring 22

2.2.4 Area Versus Personal Sampling 24

2.2.5 Choice of Sampling Time 25

2.3 Aerosols 26

2.3. Ì Sources and Types of Beryllium Aerosols 27

2.3.2 Aerosol Sampling 28

2.3.3 Size-selective Sampling 29

2.3.4 The Inhalable Convention 29

2.3.5 Thoracic Convention 31

2.3.6 Respirable Conventions 32

2.3.7 High Volume Sampling 32

2.3.8 Ukraine Particle Sampling 33

2.3.9 Calibration and Quality Control 34

2.4 Filters 36

2.4. Ì Glass and Quartz Fiber Filters 37

2.4.2 PVC Filters 37

2.4.3 MCE Filters 37

2.4.4 Polycarbonate Filters 38

2.4.5 PTFE Filters 38

2.4.6 Filter Support 38

2.4.7 Filter "Handedness" 38

2.5 Samplers for Inhalable Sampling 38

2.5.1 IOM Sampler 38

2.5.2 Button Sampler 40

2.5.3 GSP Sampler 40

2.5.4 CFC Sampler 41

2.5.5 Evaluating Internal Wall Deposits 41

2.5.6 The CFC and the Inhalable Convention 44

2.5.7 CIP-10 Sampler 44

2.5.8 An Inhalable Convention for Slowly Moving Air 45

2.5.9 Very Large Particles 45

2.6 Samplers for Respirable Sampling 46

2.6.1 Comments ôn Cyclone Design 46

2.6.2 The Dorr-Oliver (DO) or "Nylon" Cyclone 47 2.6.5364 Aluminiu ThHiggens-Dewel IOSeH GS- Cyclon 3m Cyclon Cyclon e 4 l Cyclon e 4 e e 8 9

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Coníents ix

2.6.7 GK2.69 Cyclone 49

2.6.8 FSP-10 Cyclone 49

2.7 Sampling for Diíĩerent Fractions 49

2.8 Sampling in Beryllium Facilities 50

2.9 Sampling Emissions Sources for Beryllium 53

2.10 Analytical Considerations for Selecting a Sampling

Method 53

ĩ. 11 Air Sampling in Retrospective Exposure Assessments 55

2.12 Conclusion 55

Bibliography 56

References 57

Chapter 3 Surĩace Sampling: Successhil Suríace Sampling for

Bervllium 68

Gỉenn L. Rondeau

3.1 Surface Sampling 68

3.1.1 Wipe Sampling 69

3.1.2 Buik Sampling 70

3.1.3 Vacuum Sampling 71

3.2 Locations of Sample Points and Number

ofSamples 71

3.2.1 Randomly Selected Sample Points 71

3.2.2 Biased or Judgmental Sample Points 72

3.3 Sampling Techniques 72

3.3.1 Speed and Pressure 72

3.3.2 Selection of Sampling Medium 72

3.3.3 Determining Surface Area 73

3.3.4 Field Analysis 74

3.3.5 Protecting Sample Process and Samples from

Contamination 74

3.3.6 Inappropriate Sampling or Techniques 75

3.4 Sample Planning 75

3.4. Ì Determine Needs 75

3.4.2 Contaminated Surfaces 76

3.4.3 Planning Tools 76

3.4.4 Standard Operating Procedure 76

3.4.5 Overall Sampling Plan 76

3.4.6 Site History 78

3.5 Sampling Safety 78

3.5.1 Personal Protection Equipment 78

3.5.2 Personal Factors and Needs 78

3.5.3 Sample Protection 80

3.6 Recordkeeping 81 3.6.21 Oversigh Chain-of-custod t of Samplin y 8 g 1

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Contenís

3.6.3 Photography Requirements and Permits 82

3.7 Selecting and Pre-qualifying the Laboratory 82

3.7. Ì Quality Control Measures 83

3.8 Sampling Supplies 83

3.8.1 Consumable Supplies 83

3.8.2 Non-consumable Supplies 84

3.9 Summary 85

Acknovvledgements 86

Reíerences 86

Chapter 4 Sample Dissolution Reagents for Beryllium: Applications

in Occupational and Environmental Hỵgiene 89

Kevin Ashley and Thomas J. Oatts

4. Ì Introduction 90

4.2 Background 90

4.3 Beryllium in Geological Media 90

4.3.1 Beryllium Ores 91

4.3.2 Soils and Silicates 91

4.4 Occupational Hygiene Samples 92

4.4. Ì Workplace Air Samples 93

4.4.2 Surface Samples 95

4.4.3 Bulk Samples 96

4.5 Summary 97

Acknovvledgements 97

References 98

Chapter 5 Heating Sources for Berỵllium Sample Preparation:

Applications in Occupational and Environmental Hỵgiene 102

T. Mark McCleskey

5.1 Introduction 103

5.2 Background 103

5.3 Beryllium in Geological Media and Soils 105

5.4 Occupational Hygiene Samples 107

5.4.1 Workplace Air Samples 107

5.4.2 Surface Samples 109

5.5 Summary no

References 111

Chapter 6 BeryUium Analỵsis by Inductively Coupled Plasma Atomic

Emission Spectrometry and Inductivelỵ Coupled Plasma

Mass Spectromeưy 113

Melecita M. Archuỉeta and Brandy Duran

6.1 Introduction 114

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Contents

6.2 Preparation of Samples 114

6.2.1 Methods Available for Sample Analysis by

ICP-AESor ICP-MS 115

6.2.2 Analytical Considerations for Selecting a

Sample Preparation Method 115

6.2.3 Challenges with Beryllium Samples for

Analysis hy ICP-AESor ICP-MS 116

6.3 Quality Control and Quality Assurance 118

6.4 ICPOverview 119

6.5 Analysis by ICP-AES 121

6.5.1 Interferences 121

6.5.2 Considerations when Working With

Beryllium 123

6.6 Analysis by ICP-MS 124

6.6.1 Selectivity and Interferences 125

6.6.2 Considerations when XVorking with Beryllium 129

References 129

Chapter 7 Beryllium Analysis by Non-Plasma Based Methods 131

Anoop Agrawal and Amy Ekechukwu

7.1 Introduction 131

7.2 Fluorescence 132

7.2.1 Background 132

7.2.2 Applications 132

7.3 Atomic Absorption 136

7.3.1 Background 136

7.3.2 Applications 137

7.4 UV-Visible Spectroscopy 138

7.5 Electrochemistry 140

7.5.1 Adsorptive Stripping Voltammetric

Measurements of Trace Beryllium átthe

Mercury Filra Electrode 140

7.5.2 Beryllium-Selective Membrane Electrode

Based ôn Benzo-9-crown-3 141

7.5.3 New DiaminoCompound as Neutral

Ionophore for Highly Selective and

Sensitive PVC Membrane Electrode for

Be(ĩi) lon 142

7.5.4 Beryllium-Selective Membrane Sensor Based

ôn 3,4-Di[2-(2-Tetrahydro-2H-Pyranoxy)]

Ethoxy Styrene-Styrene Copolymer 142

7.5.5 New Diamino Compound as Neutral

7.6 Other Method PVIonophor C Membran s e for Highl e Electrod y Selectiv e foer Be(II and Sensitiv ) lon e 141432

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

xii Conlenís

7.6.1 Utilization of Solid Phase Spectrophotometry

for Determination of Trace Amounts of

Beryllium in Natural Water 143

7.6.2 Selective Determination oi Beryllium(II) lon

át Picomole per Decimeter Cubed Levels by

Kinetic Diíĩerentiation Mode Reversed-Phase

High-Performance Liquid Chromatography

with Fluorometric Detection Using

2-(2'-Hydroxyphenyl)-10-hydroxybenzo[h]qui￾noline as Precolumn Chelating Reagent 143

References 144

Chapter 8 Data Use, Quality, Reporting, and Communication 147

Nancy E. Grams and Charles B. Davis

8.1 Introduction and Overview 148

8.1.1 Laboratory Reports 148

8.1.2 "Reporting Limits" and "Detection Limits" 149

8.1.3 Uses of Beryllium Data 151

8.2 "Detection Limits" and Related Concepts 152

8.2.1 Currie's Detection and Quantitation Concepts 152

8.2.2 Implementations of Currie's Concepts: the us

EPA MDL 162

8.2.3 Recent Advances: ASTM Contributions 165

8.2.4 "Reporting Limits" 166

8.3 Data and Measurement Quality Objectives 167

8.3.1 Evaluation of Data Quality Objectives 167

8.3.2 Alternativesto "Detection Limits" 173

8.3.3 Total Measurement Uncertainty 174

8.4 Using Uncensored Data 175

8.4.1 Using Uncensored Data: Technical Issues 176

8.4.2 Using Uncensored Data: Non-technical Issues 177

8.5 Summary 178

Reíerences 179

Chapter 9 Applicatỉons, Future Trends, and Opportunities 182

Geoffrey Braybrooke and Paul F. Wambaclì

9.1 Introduction 183

9.2 Monitoring 183

9.2.1 Baseline Monitoring 183

9.2.2 Compliance Monitoring 184

9.2.3 Diagnostic Monitoring 185

9.2.4 Exposure Monitoring 185

9.2.5 Future Trends 185

9.3 Air Samplins 186

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Coments xui

9.4 Analytical Methods 187

9.5 Speciation 187

9.6 Making Use of Censored Data 188

9.7 Dermal Sampling 188

9.8 Surface Dust Sampling 189

9.9 Real-Time/Near Real-Time Measurement 189

9.9.1 Research History 189

9.9.2 Future Research Directions 191

References 192 Subject Index 194

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

CHAPTER Ì

Overview o f Berylliu m Sampling

and Analysis*^

Occupational Hygiene and Envỉronmental

Appỉỉcatỉon s

MICHAEL J. BRISSON

Senior Technical Advisor, Savannah River Nuclear Solutions, Analytical

Laboratories, Savannah River Site, Aiken, se 29808, USA

Abstract

Because of its unique properties as a lightvveight metal with high tensile

strength, beryllium is widely used in applications including cell phones, golf

clubs, aerospace, and nuclear weapons. Beryllium is also encountered in

industries such as aluminium manufacturing, and in environmental remedia￾tion projects. Workplace exposure to beryllium particulates is a growing con￾cern, as exposure to minute quantities of anthropogenic forms of beryllium

may lead to sensitization and to chronic beryllium disease, which can be fatal

and for which no cure is currently known. Furtherraore, there is no known

* This article was prepaređ by a us Government contractor employee as part of his oíĩìcial đuties.

The ưs Government retains a nonexclusive, paid-up, irrevocable lỉcense to publish or reproduce

this work, ÓT allow others to do so for us Government purposes.

i

Disclaimer. Mention of company names or products does nót constitute endorsement by Savannah

Rỉver Nuclear Solutions (SRNS) or the us Department of Energy (DOE). The findings and

conclusions presented in this chapter are those of the author and do nót necessarily represent the

views of SRNS or DOE.

Beryllium: Environmental Analysis and Monitoring

Edited by Michael J. Brisson and Amy A. Ekechukvvu

© Royal Society of Chemistry 2009

Publỉshed by the Royal Society of Chemistry, www.rsc.org Ì Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

2 Chapler Ì

exposure-response relationshíp vvith which to establish a "safe" maximum Ievel

of beryllium exposure. As a result, the current trend is toward ever lovver

occupational exposure limits. which in tùm make exposure assessment. both in

terms ofsampling and analysis, more challenging. The problems are exacer￾bated by diíĩìculties in sample preparation forreíractory forms of beryllium.

such as beryllium oxide, and by indicationsthát some beryllium forms may be

more toxic than others. This chapter provides an overvíew of sources and uses

of beryllium, healthrisks.and occupational exposure limits. ít also provides a

general overview of sampling, analysis, and data evaluation issues thát will be

explored in greater depth in the remaining chapters. The goal of this book is to

provide a comprehensive resource to aid personnel in a wide variety of dis￾ciplines in selecting sampling and analysis methods thát will facilitate informed

decision-making in workplace and environmental settings.

1.1 Introduction

Control of occupational exposure in the workplace, characterization of envir￾onments or legacy areas, and management of environmental or workplace

remediation projects. all require careful planning and execution, includins

development of appropriate sampling plans, up-front understanding of

laboratory capabilities, and proper evaluation of analytical data. This involves

a number of disciplines, including industrial hygienists. laboratory personnel,

statisticians, and line management. Even beíore a sampling plan is developed,

additional disciplines such as medicine, immunology, toxicology, and epide￾miology, are involved to tell us the healthrisksof the material we are trying to

control. Additional disciplines. such as engineering, assist us with implementing

the full hierarchy of controls,1

of which sampling and analysis are a part, to

minimize exposure to toxic substancesin vvorkplace and environmental set￾tings. AU ofthese disciplines must work closely together, beginning with the

design phases of a project or facility, through the end of a project'slifecycle, to

ensure an outcome thát protects workers bút also avoids unnecessary costs to

the project.

Perhaps nowhere is this more true than with beryllium. Because beryllium

exposure must be managed át ultra-trace levels (with the trend being toward

even lower levels), the sampling and analytical challenges associated with

measuring beryllium are greaterthan for most other metal or metalloid parti￾culates. This includes vvorkplaces actively using beryllium, legacy areas vvhere

beryllium was used in the past, and environmental remediation prọịects. New

facilities where beryllium vvill be used need to be designed nót only with

appropriate engineering controls, bút also with consideration of beryllium

sampling and analytical requirements.

This book provides information ôn sampling and analysis techniques thát

have been developed to ensure thát beryllium particulate (vvhether in natural or

environmenta anthropogeni resulting datacl

forms properl settings)y.

caThi evaluate ns

bbooe deíĩectivel kfoísr nósount yintende dsample decision-makin ddtoanprovid d analyzed geindetaile vvorkplac , danmedica d thanedl

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn

Overview of Beryíỉium Sampỉing and Anaỉysis 3

or toxicological iníormation, nor does Ít discuss engineering controls. ít is

íbcused primarily ôn the sampling and analytical state-of-the-art.

This chapter provides background information ôn beryllium sources, uses,

health risks, and exposure limits. ít then provides an overview of sampling and

analysis issues to sét the stage for the detailed discussion of these issues and

techniques in the chapters to follow.

1.2 Goals of this Book

The primary goal of this book is to be a resource thát can be used by all oi the

disciplines involved in beryllium health and safety management, to enable the

best possible sampling and analytical decision-making so thát vvorkers are

better protected from the risks of beryllium in the vvorkplace. Its primary users

would include industrial hygiene practitioners, analytical laboratory personnel,

statisticians, and managers of projects or processes thát either utilize beryllium

or characterize beryllium in legacy or environmental settings. This book should

help such users understand current capabilities and limitations in beryllium

sampling and analysis, both in their own disciplines and in the others, and the

need for good communication with other disciplines to assure success. ít is also

hoped thát this book will be useíul in academic, research and development

settings to encourage additional research to address the many limitations in our

current understanding and capabilities.

ít is nót the intention of this book to tell users to sample or analyze by some

prescribed method(s). There is no "one size íits ai]" approach to beryllium

sampling and analysis, bút Ít is important thát selected methods be fit for

purpose and be defensible (as applicable) to customers, regulators, accrediting

agencies, managers, and perhaps most importantly, to workers whose ber￾yllium exposures are being characterized and managed.

1.3 Background

Beryllium (atomic number 4) is a lightweight metal (density 1.85) with a high

melting point (1287°C), stiíĩness (Young's modulus 287 GPa) and thermal

conductivity (190 Wm~' K~').2

'

3 These properties make beryllium a highly

desirable component for a wide variety of applications.

1.3.1 Beryllium Sources

Beryllium occurs naturally in some 30 dilTerent mineral species.3

In the Earth's

crust, beryllium content is estimated át 2-5 parts per million (ppm) overall, with

speciíìc rocks having úp to 15ppm.4

For the extraction of elemental beryllium,

the species of importance are the beryllium alumino-silicate mineral beryl

(Be3Al2Si6Oig) and the beryllium silicate hydroxide mineral bertrandite

[Be4Si207(OH)2], vvith bertrandite as the principal mineral mined in the United

States, and beryl the principal mineral in other countries.4 Beryl is roasted with

Số hóa bởi Trung tâm Học liệu – ĐHTN http://www.lrc-tnu.edu.vn