*>EPA
United States
Environmental Protection
Agency
Aisdr
AGENCY FOR TOXIC SUBSTANCES
AND DISEASE REGISTRY
EPA/600/R-24/020 2 | April 2024 | www.epa.gov/research
Synthetic Turf Field Recycled Tire Crumb
Rubber Research Under the Federal
Research Action Plan
FINAL REPORT PART 2-
EXPOSURE CHARACTERIZATION APPENDICES VOLUME 2
Centers for Computational Toxicology and Exposure, Environmental Measurement and
Modeling, Environmental Solutions and Emergency Response, and Public Health and
Environmental Assessment, Office of Research and Development
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EPA/600/R-24/020.2
April 2024
Synthetic Turf Field Tire Crumb Rubber
Research Under the Federal Research
Action Plan
Final Report Part 2 -
Exposure Characterization Appendices
Volume 2
April 16, 2024
By
U.S. Environmental Protection Agency / Office of Research and Development (EPA/ORD)
Centers for Disease Control and Prevention / Agency for Toxic Substances and Disease Registry
(CDC/ATSDR)
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Disclaimer
This document has been reviewed by the U.S. Environmental Protection Agency and the Agency for
Toxic Substances and Disease Registry and approved for release. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
Preferred citation: U.S. EPA & CDC/ATSDR. (2024). Synthetic Turf Field Recycled Tire Crumb
Rubber Research Under the Federal Research Action Plan Final Report: Part 2 - Exposure
Characterization (Volumes 1 and2). (EPA/600/R-24/020). U.S. Environmental Protection Agency,
Centers for Disease Control and Prevention/Agency for Toxic Substances and Disease Registry.
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Foreword
The U.S. Environmental Protection Agency (EPA) Office of Research and Development (ORD) and the
Centers for Disease Control and Prevention (CDC) Agency for Toxic Substances and Disease Registry
(ATSDR) have worked collaboratively to complete the research activities on synthetic turf playing fields
under the "Federal Research Action Plan on Recycled Tire Crumb Used on Playing Fields and
Playgrounds" (FRAP). The Agencies have released the research activities' results in two parts. The Part
1 Report (U.S. EPA & CDC/ATSDR, 2019) summarizes the research effort to characterize tire crumb
rubber, which includes characterizing the components of, and emissions from, recycled tire crumb
rubber. The exposure characterization report (Part 2 - this report) summarizes the potential exposures
that may be experienced by users of synthetic turf playing fields with recycled tire crumb rubber infill,
such as how people come in contact with the materials, how often and for how long. It includes the
results from a supplemental biomonitoring study conducted by CDC/ATSDR. This Part 2 exposure
characterization report completes FRAP efforts with respect to playing fields.
The study is not a risk assessment; however, the results of the research described in the FRAP reports
will advance our understanding of exposure to inform the risk assessment process. We anticipate that the
results from this multi-agency research effort will be useful to the public and interested stakeholders to
understand the potential for human exposure to chemicals found in recycled tire crumb rubber used on
synthetic turf fields.
This report has been prepared to communicate to the public the research objectives, methods, results and
findings for the exposure characterization research conducted as part of the Federal Research Action
Plan. The report has undergone independent, external peer review in accordance with EPA and CDC
policies. A response-to-peer review comments document accompanies the release of the Part 2 report.
The mission of the EPA is to protect human health and the environment so that future generations inherit
a cleaner, healthier environment that supports a thriving economy. Science at EPA provides the
foundation for credible decision-making to safeguard human health and ecosystems from environmental
pollutants. ORD is the scientific research arm of EPA, whose leading-edge research helps provide the
solid underpinning of science and technology for the Agency. ORD supports six research programs that
identify the most pressing environmental health research needs with input from EPA offices, partners
and stakeholders.
CDC works 24/7 to protect America from health, safety and security threats, both foreign and in the
United States. ATSDR is a non-regulatory, environmental public health agency that was established by
Congress under the Comprehensive Environmental Response, Compensation, and Liability Act of 1980.
ATSDR protects communities from harmful health effects related to exposure to natural and man-made
hazardous substances by responding to environmental health emergencies; investigating emerging
environmental health threats; conducting research on the health impacts of hazardous waste sites; and
building capabilities of and providing actionable guidance to state and local health partners.
Maureen Gwinn
Principal Deputy Assistant Administrator for
EPA Office of Research and Development
Aaron Bernstein
Director
Agency for Toxic Substances and Disease
Registry
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Authors, Contributors, and Reviewers
Lead Authors:
Kent Thomas
Elizabeth Irvin
Annette Guiseppi-Elie
Angela Ragin-Wilson
Jose Zambrana, Jr.
U.S. EPA, Office of Research and Development, Center for Public Health
and Environmental Assessment (EPA/ORD/CPHEA)
Centers for Disease Control and Prevention, Agency for Toxic Substances
and Disease Registry (CDC/ATSDR)
U.S. EPA, Office of Research and Development, Immediate Office of the
Assistant Adminstrator (EPA/ORD/IOAA)
Centers for Disease Control and Prevention, Agency for Toxic Substances
and Disease Registry (CDC/ATSDR)
U.S. EPA, Office of Research and Development, Center for
Environmental Measurement and Modeling (EPA/ORD/CEMM)
Collaborating Federal Organizations:
U.S. Consumer Product Safety Commission
U.S. Defense Centers for Public Health-Aberdeen (former U.S. Army Medical Command, Army Public
Health Center)
iii
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Contributing Authors:
Authors
Affiliation
Kelsey Brady, Michael Lewin, Zheng Li, Teresa
Wang
CDC/ATSDR
Nichole Brinkman
EPA/ORD/Center for Environmental Solutions
and Emergency Management (CESER)
Matthew Clifton, Carry Croghan, Kasey
Kovalcik, Georges-Marie Momplaisir, Karen
Oliver, Gene Stroup, Mark Strynar, Xiaoyu Liu,
Brian Schumacher
EPA/ORD/CEMM
Peter Egeghy, Monica Linnenbrink
EPA/ORD/C enter for Computational Toxicology
and Exposure (CCTE)
Marsha Morgan
EPA/ORD/CPHEA
Barbara Jane George, Steven Gardner, Edward
Heithmar, Ashley Jackson, Jianping Xue, Donald
Whitaker, Larissa Hassinger (Student Services
Contractor [SSC], Oak Ridge Associated
Universities [ORAU]), Linda Phillips
formerly with the U.S. EPA Office of Research
and Development
Chris Carusiello, Ksenija Janjic
U.S. EPA, Office of Land and Emergency
Management, Office of Resource Conservation
and Recovery (EPA/OLEM/ORCR)
Brandon Law, Aleksandr Stefaniak
CDC, The National Institute for Occupational
Safety and Health (CDC/NIOSH)
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Contributors:
Contributors
Affiliation
Emily Adler, Tyra Barrett, Carol Cusack, Michelle
Dittrich, John Marr, Miranda Mitchell, Christopher
Mugford, Chris Poulet, Nykiconia Preacely, Tara
Serio, Timothy Turner, Aaron Grober, Britnee Bailey,
Julianne Botelho, Antonia Calafat, Joaudimir (Joy)
Castro Georgi, Alfonsina (Sina) De Leon Salazar,
Christopher Hamilton, Rebecca Hunt, Erin (Nikki)
Pittman, Debra Trinidad, Denise Tevis, Hubert
Vesper, Neelam Zahoor, Enada Archibold, Yuesong
Wang, Cynthia D. Ward, Kathleen Caldwell
CDC/ATSDR
Lillian Alston (Senior Environmental Employee
[SEE]), Andrea Clements, Scott Keely, Asja Korajkic,
James McCord, Larry McMillan (SEE), Brian
McMinn, Gary Norris, Margie Vazquez (QA),
Richard Walker (SEE), Alan Williams, Libby Nessley
(QA)
EPA/ORD/CEMM
Elin Ulrich, Ann Richard, Antony Williams
EPA/ORD/CCTE
Christine Alvarez (Quality Assurance [QA]), Maliha
Nash, Holly Ferguson (QA), Emily Snyder
EPA/ORD/CPHEA
Susan Burden, Michelle Henderson (QA), Sania Tong-
Argao (QA)
EPA/ORD/Office of Science Advisor, Policy
& Engagement (OSAPE)
Brittany Stuart (QA), James Noel (QA)
EPA/ORD/Office of Science Information
Management (OSIM)
Marisol Figueroa, Megan Maguire
EPA/ORD/IO A A
Gregory Grissom (ORISE Participant), Jacqueline
McQueen, Fu-Lin Chen, Kathleen Hibbert, Tammy
Jones-Lepp, Myriam Medina-Vera, Sandra Utile-
Okechukwu (ORISE Participant), Kelly Widener, Ron
Williams
Formerly with the U.S. EPA, Office of
Research and Development
Matt Allen, Tamira Cousett, Christopher Fuller,
Denise Popeo-Murphy, Mary Wright, Patrick Lawler,
Guy Fazzio
Jacobs Technology Incorporated (JTI)
Julia Campbell, Justicia Rhodus, Samantha Shattuck
Pegasus Technical Services
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Reviewers:
Reviewers
Affiliation
Eric Hooker
U.S. Consumer Product Safety Commission
Kiran Alapaty, Kevin Oshima
EPA/ORD/CEMM
Geoffrey Braybrooke, Michael R. Bell, Debra C.
Colbeck, Jarod M. Hanson, Sherri L. Hutchens,
Mark S. Johnson, Jeffrey G. Leach, Charles E.
McCannon, Robert L. von Tersch
APHC, now the U.S. Defense Centers for Public
Health-Aberdeen
Bob Thompson
Formerly with the U.S. EPA, Office of Research
and Development
Michael Firestone, Kathleen Schroeder (SEE)
Formerly with the U.S. EPA, Office of the
Administrator, Office of Children's Health
Protection
Nicole Villamizar
EPA/OLEM/ORCR
Marcus Aguilar
U.S. Environmental Protection Agency, Region 9
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Acknowledgments
Contract support to the EPA was provided by Jacobs Technology, Inc under Contract EP-C-15-008, the
Eastern Research Group, Inc. under Contract EP-C-12-029, Oregon State University under Purchase
Order EP-18-Z-000023, and Pegasus Technical Services under Contract EP-C-15-010. Special
acknowledgements are given to Justicia Rhodus of Pegasus Technical Services for technical editing, and
to Attainx, contractor to the EPA for graphics and media support under Contract
68HERH23D0009 G&M. Authors and contributors included student service contractors to EPA Larissa
Hassinger under Contract EP-D-15-003, and Oak Ridge Institute for Science and Education (ORISE)
participants Gregory Grissom, James McCord, and Sandra Utile-Okechukwu under an interagency
agreement with the Department of Energy. Larry McMillan, Lillian Alston and Richard Walker were
supported under the Senior Environmental Employment Program.
Special acknowledgements are given to the external peer reviewers who reviewed the draft report under
contract EP-C-17-017 with the Eastern Research Group, Inc.
• Alesia Ferguson, MPH, Ph.D.: Associate Professor, College of Public Health, University of
Arkansas Medical Sciences
• Panagiotis Georgopoulos, Ph.D.: Professor, School of Public Health, Rutgers University
• Tee L. Guidotti, MD, MPH: Consultant, Occupational and Environmental Health
• Maria Llompart, Ph.D.: Professor, Department of Analytical Chemistry, University of Santiago
de Compostela, Spain
• Martin Reinhard, Ph.D.: Professor Emeritus, Stanford University
• P. Barry Ryan, Ph.D.: Professor, Rollins School of Public Health, Emory University
• Clifford P. Weisel, Ph.D.: Tenured Professor, Environmental and Occupational Health Sciences
Institute (EOHSI), Rutgers University
Special acknowledgements are given to collaborators at the U.S. Consumer Product Safety Commission,
Army Public Health Center (now the Defense Centers for Public Health-Aberdeen), the National
Toxicology Program of the National Institutes of Environmental Health Sciences, and the California
Environmental Protection Agency's Office of Environmental Health Hazard Assessment.
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Table of Contents
Disclaimer i
Foreword ii
Authors, Contributors, and Reviewers iii
Acknowledgments vii
Table of Contents viii
Acronyms and Abbreviations ix
Appendix A Biomonitoring Study 1
Appendix B Quality Assurance and Quality Control 89
Appendix C Standard Operating Procedures (SOPs) for Exposure Characterization Research 130
Appendix D Synthetic Turf Field Facility User Questionnaires - Adult/Adolescent and Youth/Child
Versions 611
Appendix E Exposure Characterization Meta-Data Collection Forms 627
Appendix F Blood Metals and Serum Metals Analysis Protocols 635
Appendix G Video Activity Data 829
Appendix H Feasibility Assessment for Silicone Wristband Passive Samplers at Synthetic Turf Fields
835
viii
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Acronyms and Abbreviations
ACGM
American Conference of Governmental Industrial Hygienists
ACH
Air change per hour
ADI
Acceptable daily intake
ADPA
Acetone-diphenylamine condensation product
AEMD
Air and Energy Management Division
ANOVA
Analysis of variance
ANSI
American National Standards Institute
APHC
U.S. Army Public Health Center
ASTM
American Society for Testing and Materials
ASTSWMO
Association of State and Territorial Solid Waste Management Officials
AT SDR
Agency for Toxic Substances and Disease Registry
BHA
Butylated hydroxyanisole
BTEX
Benzene, toluene, ethylbenzene, xylenes
°C
Degrees Celsius
CAES
Connecticut Agricultural Experiment Station
Cal-OEHHA
California Office of Environmental Health Hazard Assessment
CalEPA
California Environmental Protection Agency
CalOSHA
California Division of Occupational Safety and Health
CAS
Chemical Abstracts Service
CASE
Connecticut Academy of Science and Engineering
CDC
Centers for Disease Control and Prevention
CDEP
Connecticut Department of Environmental Protection
CDPH
Connecticut Department of Public Health
CFU
Colony forming units
CICAD
Concise International Chemical Assessment Documents
cm
Centimeter
coc
Chemicals of concern
COPC
Chemicals of potential concern
CPSC
Consumer Product Safety Commission
CSF
Cancer slope factor
cv
Coefficient of variance
d
day
DAD
Diode array detector
DAS
Data acquisition system
DBA + ICDP
Sum of Dibenz[a,h]anthracene and Indeno(l,2,3-cd)pyrene
DCC
Daily calibration checks
DDC
Direct dermal contact
ddPCR
Droplet digital polymerase chain reaction
DGI
Dust and gas inhalation
DNA
Deoxyribonucleic acid
DQI
Data quality indicators
ECHA
European Chemicals Agency
ECR
Excess cancer risk
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EHHI Environment and Human Health, Inc.
EOHSI Environmental and Occupational Health Sciences Institute
EPA U.S. Environmental Protection Agency
EU European Union
FDEP Florida Department of Environmental Protection
FLM Fence line monitor
FR Federal Register
FRAP Federal Research Action Plan on Recycled Tire Crumb Used on Playing Fields and
Playgrounds
g Gram
GC/MS Gas chromatography/mass spectrometry
GC/TOFMS Gas chromatography/time-of-flight mass spectrometry
GS/MS/MS Gas chromatography/tandem mass spectrometry
h Hour
h"1 Per hour
HEAST Health Effects Assessment Summary Table
HHRA Human health risk assessment
HI Hazard index
HPLC High performance liquid chromatography
HR-ICPMS High resolution magnetic sector inductively coupled plasma mass spectrometer
IAP Internal audit program
IARC International Agency for Research on Cancer
ICP/AES Inductively coupled plasma-atomic emission spectrometry
ICP/MS Inductively coupled plasma/mass spectrometry
ICP-OES Inductively coupled plasma - optical emission spectrometry
IDL Instrument detection limit
10 AA Immediate Office of the Assistant Administrator
IPCS WHO International Programme on Chemical Safety
IRIS U.S. EPA Integrated Risk Information System
ISRI Institute of Scrap Recycling Industries, Inc.
JTI Jacobs Technology, Inc.
KEMI Swedish Chemicals Inspectorate
kg Kilogram
L Liter
LC/MS Liquid chromatography/mass spectrometry
LIMS Laboratory Information Management System
LOD Limit of detection
LOQ Limit of quantitation
LRGA Literature Review and Data Gaps Analysis
m Meter
mg Milligram
MADL Maximum allowable dose levels
Max Maximum
MCL Maximum contaminant limit
MDL Method detection limit
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mecA
Gene for methicillin resistance
mg
Milligram
min
Minute
mL
Milliliter
MOS
Margin of safety
MQL
Method quantifiable limit
MQL
Minimum quantitation level
MRL
Minimum reportable limit
MRL
Minimum risk level
MRM
Multiple reaction monitoring
MRSA
Methicillin-resistant Staphylococcus aureus
N/A
Not applicable/Not available
NAAQS
National Ambient Air Quality Standards
NCCT
U.S. EPA National Center for Computational Toxicology
NCEA
U.S. EPA National Center for Environmental Assessment
NCEH
CDC National Center for Environmental Health
ND
Nondetect
NERL
U.S. EPA National Exposure Research Laboratory
NFL
National Football League
ng
Nanogram
NHEERL
U.S. EPA National Health and Environmental Effects Research Laboratory
NHTSA
National Highway Traffic Safety Administration
NIOSH
National Institute for Occupational Safety and Health
NIPH
Norwegian Institute of Public Health
NIST
National Institute of Standards and Technology
NOAEL
No observed adverse effect level
NOEC
No observable effects concentration
NOEL
No observable effects limit
NR
Not reported
NRMRL
U.S. EPA National Risk Management Research Laboratory
NSRL
No significant risk level
NTP
U.S. National Toxicology Program
NYDEC
New York Department of Environmental Conservation
NYDOH
New York Department of Health
OCHP
U.S. EPA Office of Children's Health Protection
OEHHA
Office of Environmental Health Hazard Assessment
OLEM
U.S. EPA Office of Land and Emergency Management
OMB
U.S. Office of Management and Budget
ORAU
Oak Ridge Associated Universities
ORCR
U.S. EPA Office of Resource Conservation and Recovery
ORD
U.S. EPA Office of Research and Development
ORISE
Oak Ridge Institute for Science and Education
OSHA
Occupational Safety and Health Administration
OSP
U.S. EPA Office of Science Policy
OTOS
N-Oxydiethylenedithiocarbamyl-N -oxydi ethylenesulfenamide
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OTR
Off-the-road
PAH
Polyaromatic hydrocarbon
PCB
Polychlorinated biphenyl
PCR
Polymerase chain reaction
PQL
Practical quantification limit
PEHSU
Pediatric Environmental Health Specialty Unit
PEL
Permissible exposure limit
PM
Particulate matter
PNEC
Predicted no effect concentration
POP
Priority organic pollutants
ppbv
Parts per billion by volume
ppm
Parts per million
PQAM
Program Quality Assurance Manager
PPRTV
Provisional peer-reviewed toxicity value
PRA
Paperwork Reduction Act
PSA
Particle size analysis
PUF
Polyurethane foam
QA
Quality assurance
QAM
Quality assurance manager
QAPP
Quality assurance project plan
QMP
Quality management plan
QC
Quality control
REACH
Registration, Evaluation, Authorisation, and Restriction of Chemicals
REL
Recommended exposure limit/Reference exposure levels
RfC
Reference concentration
RfD
Reference dose
RH
Relative humidity
RIVM
Netherlands National Institute for Public Health and the Environment
RM
Rubber mulch
RMA
Rubber Manufacturers Association
RNA
Ribonucleic acid
RPD
Relative percent difference
rRNA
Ribosomal ribonucleic acid
%RSD
Percent relative standard deviation
RTP
Research Triangle Park (North Carolina)
RWC
Rain water contact
SA/BW
Surface area to body weight ratio
SBR
Styrene-butadiene rubber
SEE
Senior Environmental Employee
SEM
Scanning electron microscopy
SF
Slope factor
SOP
Standard operating procedure
SPME
Solid-phase microextraction
ssc
Student Services Contractor
STC
Synthetic Turf Council
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STEL Short term exposure limit
Suml5PAH Sum of 15 of the 16 EPA 'priority' PAHs
SumBTEX Sum of benzene, toluene, ethylbenzene, m/p-xylene, and o-xylene
SVOC Semivolatile organic compound
TCC Tire Crumb Characterization
TCLP Toxicity characteristic leaching procedure
TCR Tire crumb rubber
TCRS Tire Crumb Research Study
TLV Threshold limit value
TOF Time of flight
TOFMS Time-of-flight mass spectrometry
TPE Thermoplastic elastomers
TSA Technical systems audit
TSP Total suspended solids
TWA Time weighted average
TWP Tire wear particles
UCHC University of Connecticut Health Center
|ig Microgram
jam Micrometer
|iL Microliter
UR Unit risk
URL Uniform resource locator
U.S. United States of America
U.S. EPA United States Environmental Protection Agency
UV Ultraviolet spectrometry
VID Video identification number
VOC Volatile organic compound
WDOH Washington State Department of Health
WHO World Health Organization
WM Wood mulch
XRF X-ray fluorescence spectrometry
yr Year
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Appendix A
Biomonitoring Study
1
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Supplemental Biomonitoring Study of Exposure
During Activities Conducted on Synthetic Turf
Fields with Tire Crumb Rubber Infill
Summary Report
April 16, 2024
Prepared by
United States Department of Health and Human Services
Agency for Toxic Substances and Disease Registry Office of Community Health
Hazard Assessment
Atlanta, Georgia 30341
Disclaimer: This document has been reviewed by the Agency for Toxic Substances and Disease
Registry and approved for release. Use of trade names is for identification only and does not
constitute endorsement by the Public Health Service of the U.S. Department of Health and
Human Services.
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Contents
Acronyms and Abbreviations iii
1. Executive Summary 1
2. Introduction 2
3. Methods 3
3.1. Recruitment 3
3.2. Data Collection 5
3.3. Data Analysis 6
4. Results 8
4.1. Study Population and Urine Sample Properties 8
4.2. Study Population Description 8
4.3. Pre- and Post-Activity PAH Concentration Differences 11
4.4. Univariate Regression Modelling 19
4.5. Full Model Multivariable GLM Regression 21
4.6. Comparison to NHANES PAH Concentrations 24
5. Discussion 30
5.1. Limitations and Recommendations 32
6. Conclusions 33
7. Preparers of the Report 33
8. References 34
Appendices 38
Appendix A: Supplemental Figures 39
Appendix B: Supplemental Tables 43
List of Tables
Table 1. Study Participant Characteristics 9
Table 2. Properties of Differences in Ln-Transformed Pre- and Post-Activity Burden Levels for Specific
Gravity-Adjusted Urinary PAHs, by All Participants 13
Table 3. Properties of Differences in Ln-Transformed Pre- and Post-Activity Burden Levels for Specific
Gravity-Adjusted Urinary PAHs, by Field Type 14
Table 4. Properties of Differences in Ln-Transformed Pre- and Post-Activity Body Burden Levels for
Creatinine-Adjusted Urinary PAHs, by All Participants 16
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Table 5. Properties of Differences in Ln-Transformed Pre- and Post-Activity Body Burden Levels for
Creatinine-Adjusted Urinary PAHs, by Field Type 17
Table 6. Univariate GLM models for Field Type, by Specific Gravity-Adjusted Urinary PAHs 19
Table 7. Univariate GLM models for Field Type, by Creatinine-Adjusted Urinary PAHs 20
Table 8. Multivariable GLM models for Field Type, by Specific Gravity-Adjusted Urinary PAHs 21
Table 9. Multivariable GLM models for Field Type, by Creatinine Gravity-Adjusted Urinary PAHs 22
Table 10. Comparison of Geometric Means (95% CI) by Age and Urinary PAH, Pre-Activity Biomonitoring
Study Concentrations versus NHANES 2015-2016 26
List of Figures
Figure 1. Overview of Three Facilities for Recruitment of Study Participants 4
Figure 2. Difference in post- and pre-activity concentration for 1-hydroxynapthalene measurements, In-
transformed, by participant and field type. Specific gravity-adjusted (left) and creatinine-
adjusted (right) 11
Figure 3. Comparison of Urinary PAH Concentrations Across Biomonitoring Study Participants and
NHANES 2007-2008 and 2016-2017 Participants Overall, by Adjustment Method 25
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Acronyms and Abbreviations
ATSDR Agency for Toxic Substances and Disease Registry
BMI Body Mass Index
CDC Centers for Disease Control and Prevention
CPSC Consumer Product Safety Commission
CRE Creatinine
DLS Division of Laboratory Sciences
EPA U.S. Environmental Protection Agency
FRAP Federal Research Action Plan on Recycled Tire Crumb Used on Playing Fields and
Playgrounds
GLM Generalized Linear Model
Ln Natural log
LOD Limit of detection
NCEH National Center for Environmental Health
NHANES National Health and Nutrition Examination Survey
No. Number
OMB U.S. Office of Management and Budget
PAH Polycyclic Aromatic Hydrocarbon
SG Specific Gravity
STC Synthetic Turf Council
U.S. United States of America
U.S. EPA United States Environmental Protection Agency
U.S. HHS United States Department of Health and Human Services
1-NAP 1-Hydroxynaphthalene
1-PHE 1-Hydroxyphenanthrene
1-PYR 1-Hydroxypyrene
2-FLU 2-Hydroxyfluorene
2-NAP 2-Hydroxynaphthalene
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2 & 3-PHE Sum of 2-Hydroxyphenanthrene and 3-Hydroxyphenanthrene
3-FLU 3-Hydroxyfluorene
iv
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1. Executive Summary
In 2016, the Centers for Disease Control and Prevention/Agency for Toxic Substances and
Disease Registry (CDC/ATSDR) and the U.S. Environmental Protection Agency (EPA), in
collaboration with the Consumer Product Safety Commission (CPSC), launched a multi-agency
research effort known as the Federal Research Action Plan on Recycled Tire Crumb Used on
Playing Fields and Playgrounds (FRAP). To address the public's concerns about the use of
recycled tire crumb rubber on synthetic turf fields, the FRAP focused on assessing potential
human exposure, which includes conducting research activities to characterize the chemicals
associated with recycled tire crumb rubber and to identify the ways in which people may be
exposed to those chemicals based on their activities on synthetic turf fields [EPA and
CDC/ATSDR 2019],
In 2022, CDC/ATSDR conducted a biomonitoring study to supplement the FRAP's pilot-scale
human exposure study conducted in 2017 [EPA and CDC/ATSDR 2024]. This report summarizes
key findings as they relate to the following objectives:
• Objective 1: Expand upon the FRAP's pilot-scale study by including a larger sample size
of synthetic turf with recycled tire crumb rubber infill users and a comparison group of
natural grass field users.
• Objective 2: Examine potential associations in pre- and post-activity urinary polycyclic
aromatic hydrocarbon (PAH) metabolite concentrations with field type (i.e., synthetic
turf fields with recycled tire crumb rubber infill and natural grass fields).
• Objective 3: Compare study participants' urinary concentrations to those found in the
noninstitutionalized general U.S. population using National Health and Nutrition
Examination Survey (NHANES) data.
CDC/ATSDR's biomonitoring study included questionnaire administration to participants and
the collection of pre- and post-activity urine sampling. Results compiled from a total of 161
study participants aged between 7-77 years are included in this report. The 7 urinary PAH
metabolites assessed at the CDC National Center for Environmental Health (NCEH) Division of
Laboratory Sciences (DLS) included: 1-hydroxynaphthalene (1-NAP), 2-hydroxynaphthalene (2-
NAP), 2-hydroxyfluorene (2-FLU), 3-hydroxyfluorene (3-FLU), 1-hydroxyphenanthrene (1-PHE),
1-hydroxypyrene (1-PYR), and the sum of 2-hydroxyphenanthrene and 3-hydroxyphenanthrene
(2 & 3-PHE).
Notably:
• Pre- and post-activity differences in urinary PAH concentrations were not associated
with field type (i.e., synthetic turf with recycled tire crumb rubber infill and natural grass
fields).
• Pre- and post-activity differences in urinary PAH concentrations varied by statistical
method and urinary dilution adjustment (i.e., specific gravity, creatinine) method.
1
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• The best predictor of post-activity urinary PAH concentration was pre-activity
concentration.
• Except for 2-NAP, pre-activity PAH concentrations were lower than those in the general
U.S. population (NHANES 2015-2016).
These results indicate recycled tire crumb rubber infill users and natural grass field users
experienced similar differences in pre-and post-activity PAH concentrations. Importantly,
CDC/ATSDR's biomonitoring study as detailed in this report is not a risk assessment. However,
combined with the initiatives of the FRAP, this study's findings contribute to the extensive
research portfolio regarding the use of tire crumb rubber infill in playing fields.
2. Introduction
There are more than 12,000 synthetic turf fields installed in the United States [STC et al. 2016].
Millions of people use and/or work at these synthetic turf fields across a range of settings,
including municipal and county parks; schools, colleges, and universities; professional sports
stadiums and practice fields; and military installations. Approximately 95% of synthetic turf
fields utilize small pieces of recycled tire ("recycled tire crumb rubber") either as infill
exclusively or in mixture with sand or alternative infills [STC et al. 2016]. Tires are manufactured
with a range of chemicals; additionally, tires may also pick up and absorb chemicals over their
lifetime of use and serve as a sorbent for chemicals in the air and dust [EPA and CDC/ATSDR
2019]. Users of synthetic turf fields with recycled tire crumb rubber infill can potentially be
exposed to chemicals such as polycyclic aromatic hydrocarbons (PAHs) in a variety of ways,
including while breathing (i.e., inhalation exposure), contacting the material with their skin (i.e.,
dermal exposure), and by ingesting the material (i.e., ingestion exposure) [EPA, CDC/ATSDR,
and CPSC 2016; EPA and CDC/ATSDR 2019],
Parents, athletes, schools, and communities have raised concerns about the safety of recycled
tire crumb rubber used as infill for playing fields and playgrounds. To fill important data gaps
and address key environmental and human health questions regarding the use of recycled tire
crumb rubber, the Centers for Disease Control and Prevention/Agency for Toxic Substances and
Disease Registry (CDC/ATSDR), U.S. Environmental Protection Agency (U.S. EPA), and U.S.
Consumer Products and Safety Commission (CPSC) launched the Federal Research Action Plan
on Recycled Tire Crumb Used on Playing Fields and Playgrounds (FRAP) in 2016.1 Key activities
since performed as part of the FRAP included: a literature review and data gaps analysis [EPA,
CDC/ATSDR, and CPSC 2016]; a tire crumb rubber characterization study [EPA and CDC/ATSDR
2019]; and a human exposure characterization study [EPA and CDC/ATSDR 2016 Research
Protocol; EPA and CDC/ATSDR 2024],
The primary aims of the human exposure characterization research study were to (1) collect
human activity data for synthetic turf field users that will reduce the reliance of default
exposure factor assumptions in exposure and risk assessment; and (2) conduct an exposure
measurement sub-study for people using synthetic turf fields with tire crumb rubber infill, in
1 Additional information describing the FRAP are available at: https://www.atsdr.cdc.gov/frap/index.html.
2
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what are likely to be among the higher exposure scenarios to improve understanding of
potential exposures, particularly for the dermal and ingestion exposure pathways [EPA and
CDC/ATSDR 2016 Research]. To meet these objectives, CDC/ATSDR and U.S. EPA collaborated
on a pilot-scale human exposure characterization study among field users of synthetic turf with
tire crumb rubber infill (Office of Management and Budget [OMB] Control No. 0923-0058). The
pilot-scale study involved questionnaire administration and several types of sample collection,
including field environment samples, personal samples (air, dermal wipes), and biological
samples (urine and blood pre-activity and post-activity). The sample size for biological
measurements was small: 14 participants provided urine samples and 13 provided blood
samples. Urine samples were analyzed for 7 PAHs and serum samples derived from the blood
samples were analyzed for metals. Results from the pilot-scale study are detailed in the FRAP
Part 2 Report [EPA and CDC/ATSDR 2024],
In spring and summer 2022, CDC/ATSDR conducted participant recruitment for a supplemental
biomonitoring measurements study regarding exposure during activities performed on
synthetic turf fields with tire crumb rubber infill (OMB Control Number: 0923-0062). The design
of this study addressed limitations of the 2017 pilot study, including the small sample size of
participants and a lack of a comparison population. CDC/ATSDR's supplemental biomonitoring
study included questionnaire administration and pre- and post-activity urine sampling among
users of synthetic turf fields with tire crumb rubber infill and users of natural grass fields. Data
collection efforts were consistent with those in the original pilot study's research protocol [EPA
and CDC/ATSDR 2016 Research Protocol] but modified in scope (i.e., questionnaire
administration and urine sampling but no blood sampling) to achieve the following objectives:
Objective 1: Expand upon the pilot-scale study by including a larger sample size of synthetic turf
with recycled tire crumb rubber users and a comparison group of natural grass field users.
Objective 2: Examine potential associations in pre- and post-activity urinary PAH metabolite
concentrations with field type (i.e., synthetic turf fields with recycled tire crumb rubber infill
and natural grass fields).
Objective 3: Compare study participants' urinary PAH concentrations to those found in the
noninstitutionalized general U.S. population using National Health and Nutrition Examination
Survey (NHANES) data.
3. Methods
3.1. Recruitment
Study participants were recruited from 3 athletic facilities (2 outdoor and 1 indoor, as shown in
Figure 1) in two U.S. census regions2 during April-September 2022. The two outdoor facilities
2The U.S. census regions are four geographic groupings of states that subdivide the United States, including:
Midwest (Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South
Dakota, and Wisconsin); Northeast (Connecticut, Maine, Massachusetts, New Hampshire, New Jersey, New York,
3
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consisted of synthetic turf fields with tire crumb rubber infill co-located with natural grass
fields. The single indoor facility consisted of a synthetic turf field with tire crumb rubber infill. At
the time of study recruitment, the indoor field with recycled tire crumb rubber infill was
approximately 4 years old, while the 2 outdoor synthetic turf fields with recycled tire crumb
rubber infill were approximately 8 and 9 years old. Natural grass field users served as a
comparison group for examining the potential association between pre- and post-activity PAH
concentration differences with field type. The synthetic turf fields were previously included in
the tire crumb characterization research activity of the FRAP (OMB Control No. 0923-0054).
Eligible study participants included a convenience sample of field users ages 7 years and older
who engaged in physical activity on the synthetic turf fields with recycled tire crumb rubber or
natural grass fields. Exclusion criteria included those who self-reported smoking or living in a
household with someone who smokes. Additionally, natural grass participants were excluded if
they indicated playing on synthetic turf with tire crumb rubber infill in the past 24 hours. Field
users were asked to complete a study questionnaire and provide both pre- and post-activity
urine samples.
Figure 1. Overview of Three Facilities for Recruitment of Study Participants
Facility 1
jfjU-i
Facility 2
dTc
Iff:
[il^j
Outdoor facility
Natural grass and synthetic turf fields (co-located)
Indoor facility
Synthetic turf field
Facility 3
D <> [
lip' A Jrp;
!
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of informed consent was in place, the only record linking the participants to the research was a
consent document and study ID; no names or other personally identifiable data were
collected.3 A two-year extension for the research study was granted due to delays encountered
with the COVID-19 pandemic.
3.2. Data Collection
3.2.1. Questionnaire Administration
Questionnaires were administered to eligible field users on the date of urine sampling
collection to obtain information on participant activity patterns that could affect the duration
or frequency of their potential exposures. Participants were informed the questionnaire would
take about 30 minutes to complete. Depending on the age of the participant, slightly different
questionnaire versions were used for administration either directly to participants ages 13
years or older, or to a parent or guardian of participants ages 7-12 years. Questionnaire items
also included non-activity-related factors that could affect PAH concentrations, such as
demographics (e.g., age, gender, and race), mode of commute to the field, and consumption of
grilled foods in the past 24 hours, among others.
3.2.2. Urine Sample Collection and Processing
Both pre- and post-activity urine samples were collected to control for baseline body burden
levels and adjust for the effects of metabolic processes to better isolate the effects of activity
and potential exposure related to recycled tire crumb rubber infill. Consistent with the FRAP
pilot study protocol for urine collection, preparation, and storage procedures, participants were
provided with a sealed sterile urine collection cup to provide urine samples on-site using either
facility restrooms or port-a-potties. Samples were shipped on dry ice to the CDC National
Center for Environmental Health (NCEH) Division of Laboratory Sciences (DLS) for measurement
of PAH metabolites, specific gravity, and creatinine concentrations. In alignment with the CDC
NHANES panel [CDC 2020], 7 PAH metabolites were quantified using online solid phase
extraction high performance liquid chromatography/tandem mass spectrometry (SPE-HPLC-
MS/MS) [Wang 2017]. The PAH metabolites included 1-hydroxynaphthalene (1-NAP), 2-
hydroxynaphthalene (2-NAP), 2-hydroxyfluorene (2-FLU), 3-hydroxyfluorene (3-FLU), 1-
hydroxyphenanthrene (1-PHE), 1-hydroxypyrene (1-PYR), and the sum of 2-
hydroxyphenanthrene and 3- hydroxyphenanthrene (2 & 3-PHE).4
3Detailed information describing the consenting process, forms, and protocol including Supplemental Exposure
Measurement Supplemental Study Materials and questionnaires are available at:
https://www.reginfo.gov/public/do/PRAViewlCR7ref nbr=202106-0923-001.
Consistent with NHANES, 2-3-PHE values are comparable to the sum of urinary levels of 2-hydroxyphenanthrene
and 3-hydroxyphenanthrene. Additional information is available at: https://wwwn.cdc.gov/Nchs/Nhanes/2013-
2014/PAH H.htm.
5
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3.3. Data Analysis
3.3.1. Specific Gravity and Creatinine Adjustments
To account for the effect of urinary dilution and facilitate comparisons with data produced from
other studies, all urinary PAH metabolites were adjusted for specific gravity and creatinine. The
outcome variables in this analysis were urinary PAH metabolite concentrations, their specific
gravity and creatinine adjusted values, and In-transformed versions of each.
Urine specific gravity (SG) was measured and used to adjust PAH concentrations for urine
dilution according to the formula,
^sg - ^measured x (1.0194 - l)/(p - 1),
where Cmeasured W3S the individual observed urine PAH concentration, p was the individual
observed SG, and 1.0194 was the average SG of all urine samples in this study [Alhamdow
2017],
Creatinine (CRE) was used to adjust PAH concentrations using the ratio method according to
the formula,
^-Ratio — ^-measured /CRE
where Cmeasured W3S the individual observed urine PAH concentration and CRE was the
corresponding creatinine concentration.
3.3.2. Covariates
Covariate data was collected from a questionnaire administered at the time of sample
collection. Categorical variables used in this analysis were age category (children [7-9 years],
youth [10-12 years], adolescent [13-17 years], adult [18+ years]); sex (male, female); Hispanic
ethnicity (Hispanic, Non-Hispanic); race (Asian, White, Other [Non-Hispanic participants who
indicated Black, Native Hawaiian/Other Pacific Islander, multiple races, or did not report race]),
field type (natural grass or synthetic turf), field environment (indoor or outdoor); consumption
of grilled, barbequed, smoked, or deep fried food in the last 24 hours (yes or no); facility
location by U.S. census region (i.e., South or West); activity (e.g., lacrosse, soccer, other); BMI
categories (underweight, normal, overweight, and obese; with cut points at <18.5, <25, <30,
and >=30, respectively, for adults).5
5CDC growth charts were used to calculate BMI for participants <20 years old with cut points defined at BMI
percentages (0,5), [5,85), [85,95), and 95+. Because age was only collected for whole years and age-in-months is
required to properly use growth charts, BMI calculations for participants under 20 years old were subject to
misclassification due to rounding. See SAS Program for CDC Growth Charts. See:
https://www.cdc.gov/nccdphp/dnpao/growthcharts/resources/sas.htm.
6
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Continuous variables used in the analysis included PAH concentrations, specific gravity
concentrations, creatinine concentrations, age (rounded to whole years), height, weight,
number of months that a participant reported having used a field, and time (minutes) spent
commuting to the field on a typical day.
Various measures were calculated to assess the probability distributions of PAH concentrations;
this included distribution plots, Q-Q plots, a statistical test of normality (Shapiro-Wilk test),
calculated distribution measures such as kurtosis (a measure of the heaviness of a distribution's
tail) and skewness (a measure of the asymmetry of a distribution). Regression of non-
transformed concentrations can result in statistical associations solely attributable to outliers
and generally do not meet the assumptions of common statistical methods, such as normality.
Ln-transformation serves to lessen the influence of large concentrations that are typical of log-
normally distributed biomarker data. Distribution plots and tests of normality (data not shown)
indicated that the PAH concentrations were approximately log-normally distributed. Based on
these assessments, PAH concentrations were In-transformed for regression analyses.
Specifically, the difference of the individual In-transformed pre- and post-activity data were
examined, which is equivalent to the In of the ratio of concentrations on the original scale:
In(post) - ln(pre)= ln(post/pre)
3.3.3. Statistical Analysis
Analyses were conducted in SAS software, version 9.4 LTS Level 1M7 of the SAS System for
Windows. Copyright (c) 2002-2012 by SAS Institute Inc., Cary, NC, USA. Proc SGPLOT and
SGPANEL were used to create plots for data visualization; Procs TTEST and UNIVARIATE were
used to assess pre- and post-activity changes in PAH concentration; and Proc GLM was used to
investigate statistical associations between pre- and post-activity differences in PAH
concentration with covariates that were selected a priori based on their potential association
with PAH concentrations.
Regression modeling focused on three dependent variables: pre-activity, post-activity, and
differences between pre- and post-activity concentrations. The key independent variable was
field type (synthetic turf vs. natural grass), and models were adjusted for covariates. General
linear models were used to test whether variables such as field type were associated with
observed pre- and post-activity differences in concentrations (defined as post concentration
minus pre concentration). In these models, the intercept tested whether there was an overall
difference between pre- and post-activity mean concentrations. Additionally, the beta
coefficient for a covariable measured whether there was a difference in pre- and post-activity
differences between levels of the covariate. The focus of this investigation was the potential
association between field type (synthetic turf or natural grass) and increased PAH
concentration, post-activity.
3.3.4. PAH Metabolite Comparisons to the General U.S. Population
Study participants' urinary PAH metabolite concentrations were compared to those among the
non-institutionalized U.S. population by age group using NHANES data from 2015-2016 and
7
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2007-2008. The 2015-2016 NHANES cycle was the most recent cycle to contain PAH
concentrations. Because specific gravity was not measured in the 2015-2016 cycle, only
unadjusted and creatinine-adjusted concentrations could be compared. Pre-activity
concentrations from this study were used for comparison, as NHANES participants did not
engage in physical activity prior to specimen collection, and post-activity concentrations among
this present study's participants were likely affected by hydration changes. The 2007-2008
cycle was used to compare the present study's specific gravity adjusted PAH metabolite
concentrations; this was the only cycle that measured both creatinine and specific gravity.
4. Results
4.1. Study Population and Urine Sample Properties
A total of 172 participants were recruited for the study, among whom all provided
questionnaires and 171 provided pre- and/or post-activity urine samples. Among the 171
participants, a total of 10 participants were excluded from the analysis due to at least one of
the following factors: missing post-activity urine sampling (n=4), shipping-related delays of
urine samples which might have compromised sample integrity (n=3), or flagged upon sample
processing (n=3). Thus, 10 participants were excluded, leaving a total of 161 participants who
were included in this analysis. Finally, one participant had an interfering substance code for 1-
NAP, but valid measurements for all other analytes, and so the analysis sample size for 1-NAP
specifically was reduced to 160 participants. All participants were recruited in the evening or
afternoon due to activity schedules. Participants spent an average of 1 hour and 39 minutes
(range: 40 minutes to 2 hours and 58 minutes) between pre- and post-urine collections.
In total, 6% of PAH measurements were below the limit of detection (LOD). Specifically, 134 of
2252 PAH measurements (160 participants x 7 analytes x 2 measurements + 1 participant x 6
analytes x 2 measurements) were below the LOD. Four of these PAH measurements had a zero
value and were replaced by the limit of detection (LOD) divided by a/2; four creatinine
measurements that had missing values due to being less than the lowest standard were also
replaced by the LOD divided by a/2. Non-zero values below LOD were unchanged.
4.2. Study Population Description
Table 1 presents the characteristics of the study participants. As shown, among the 161 study
participants, a total of 82% (n=132) played on synthetic turf with tire crumb rubber infill and
the remaining 18% (n=29) on natural grass. Moreover, 25% of study participants used an indoor
field of synthetic turf with tire crumb rubber infill, and all other participants utilized outdoor
fields. Across the three facilities and two U.S. census regions, 68% of the study participants
were recruited from the South and 32% from the West. The study population for this analysis
comprised 27% female and 73% male, with an age range of 7 to 77 years and a median age of
14 years at the time of specimen collection. Ages were distributed as approximately 15%
children (7-9 years), 17% youth (10-12 years), 32% adolescent (13-17 years), and 37% adult (18+
8
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years).6 By race, 63% of participants identified as White persons; 14% as Asian persons; and
23% as Black persons, Native Hawaiian or Pacific Islander persons, persons of multiple races, or
did not report race. By ethnicity, approximately 28% of participants identified as Hispanic or
Latino persons. The most common field activity was soccer (74%), followed by lacrosse (17%),
with various other activities (e.g., football, flag football, field hockey) making up the remaining
9%. By BMI, 60% of participants had a normal BMI, 20% had an overweight BMI, 10% had an
obese BMI, and 5% had an underweight BMI. As noted in the footnote above, because BMI
calculations for those under age 20 years depend on age-in-months, and because age was only
collected to the nearest whole year, these BMI results may be subject to misclassification. All
study participants reported having travelled to the facilities by car, with a median commute
time of 20 minutes. Responses to the question, "how long have you been coming to this
facility?" ranged from 0 to 120 months. Moreover, 33% of study participants reported having
eaten grilled, barbequed, smoked, or deep-fried food within the 24 hours prior to sample
collection.
Table 1. Study Participant Characteristics
Variable
Group
Value
Field Type, n(%)
Synthetic Turf with Tire
Crumb Infill
132 (82)
Field Type, n(%)
Natural Grass
29(18)
Field Environment, n(%)
Outdoor
120 (75)
Field Environment, n(%)
Indoor
41 (25)
Facility's US Census Region, n(%)
South
109 (68)
Facility's US Census Region, n(%)
West
52 (32)
Sex, n(%)
Male
118 (73)
Sex, n(%)
Female
43(27)
Age Category, n(%)
[range: 7-77 years]
Child (7-9 years)
24(15)
Age Category, n(%)
[range: 7-77 years]
Youth (10-12 years)
27(17)
Age Category, n(%)
[range: 7-77 years]
Adolescent (13-17 years)
51 (32)
""Percentages may not total to 100% due to rounding.
9
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Variable
Group
Value
Age Category, n(%)
[range: 7-77 years]
Adult (18+ years)
59 (37)
Race, n(%)
White
102 (63)
Race, n(%)
Asian
22(14)
Mixed/Other: Black,
Native Hawaiian/Other
Race, n(%)
Pacific Islander, multiple
races, or did not report
race
37 (23)
Hispanic Ethnicity, n(%)
No
113 (72)
Hispanic Ethnicity, n(%)
Yes
44(28)
Hispanic Ethnicity, n(%)
Refused
1(1)
Field Activity, n(%)
Soccer
119 (74)
Field Activity, n(%)
Lacrosse
27(17)
Field Activity, n(%)
Other
15 (9)
Past 24-Hour Grilled Food
Consumption, n(%)
No
106 (67)
Past 24-Hour Grilled Food
Consumption, n(%)
Yes
53 (33)
Weight (lbs), mean(med)[range]
N/A
131 (125) [50-131]
Height (inches), mean(med)[range]
N/A
64 (65) [48-76]
BMI, mean(med)[range]
N/A
22 (20) [11-44]
Length of time coming to facility
(months), mean(med)[range]
N/A
30 (14)[0-120]
ength of commute to field (minutes),
mean(med)[range]
N/A
22 (20)[2-120]
Note: N/A = not applicable
Percentages may not total to 100% due to rounding.
Data for race is presented in these categories due to small cell sizes.
10
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Length of time coming to facility was assessed by the question, "How long have you been coming to this facility?" and length of
commute to the field was assessed by the question, "How many minutes did it take you to get to practice today?"
4.3. Pre- and Post-Activity PAH Concentration Differences
As shown in the representative figures for 1-NAP (Figure 2). most study participants' PAH
concentrations increased post-activity after adjustment for specific gravity (left). However, the
equivalent result for creatinine ratio adjustment demonstrated a more even distribution
between those whose concentrations increased compared to those whose concentrations
decreased (right). Moreover, the identification of the participants who had the largest post-
minus pre-activity degree of change in concentrations was dependent upon the adjustment
method. The participants identified as having the biggest increases (when based on specific
gravity adjustment) played on natural grass, whereas those identified based on creatinine
adjustment played on synthetic turf (see Supplemental Figures Sl-1 through Sl-6 for additional
plots). As shown later in this report, these differences in post- and pre-activity PAH
concentrations were not associated with field type.
Figure 2. Difference in post- and pre-activity concentration for 1-hydroxynapthalene
measurements, In-transformed, by participant and field type. Specific gravity-adjusted (left)
and creatinine-adjusted (right).
Study Participant Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf] | Field Type ¦ Natural Grass ¦ Synthetic Turf]
Statistical differences in pre- and post-activity body burden levels for urinary PAHs are
presented for specific gravity-adjusted concentration differences by all participants (Table 2)
and by field type (Table 3). Additionally, statistical differences in pre- and post-activity body
burden levels for urinary PAHs are presented for creatinine-adjusted concentration differences
by all participants (Table 4) and by field type (Table 5). For specific-gravity adjusted and In-
transformed PAH concentrations, there was a statistically significant difference in mean
concentrations when comparing pre- and post-activity differences for all 7 PAHs (p-values
<0.05). However, this was irrespective of whether participants played on synthetic turf with tire
crumb rubber infill or natural grass fields. Fewer differences were observed when examining
creatine-adjusted and In-transformed PAH concentrations; pre-and post-activity concentration
differences were statistically significant for 1-PYR (mean: -1.76 [ig/L, p<0.Q5) and 2-NAP (mean:
11
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0.163 |-ig/L, p<0.05). As with the specific gravity-adjusted results, differences observed with
creatinine-adjusted data were irrespective of whether participants played on synthetic turf with
tire crumb rubber infill or natural grass fields. Statistical analysis of differences by additional
measures are displayed in Supplemental Tables Sl-1 through Sl-7 (specific gravity-adjusted)
and Supplemental Tables S2-1 through S2-7 (creatinine-adjusted).
Generally, pre- and post-activity concentrations were correlated. Specifically, the pre- and post-
activity correlations of the urinary PAH metabolites ranged from 0.81 to 0.85 for specific
gravity-adjusted concentrations, and 0.76 to 0.86 for creatinine-adjusted concentrations. This
was consistent overall and by age group.
12
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Table 2. Properties of Differences in Ln-Transformed Pre- and Post-Activity Burden Levels for Specific Gravity-Adjusted Urinary
PAHs, by All Participants
Urinary PAH
Minimum
Maximum
Median
Mean
P-Value
Standard P-Value of of Signed
Deviation t Statistic Rank Test
1-Hydroxynaphthalene (ng/L)
160
-2.32
2.32
.436
.506
.633
<.0001
<.0001
.-Hydroxyphenanthrene (ng/L)
161
-1.91
3.02
.437
.473
.523
<.0001
<.0001
1-Hydroxypyrene (ng/L)
161
-1.86
2.61
.231
.268
.538
<.0001
<.0001
2 & 3-Hydroxyphenanthrene
(Hg/L)
161
-1.55
2.55
.375
.410
.464
<.0001
<.0001
2-Hydroxyfluorene (ng/L)
161
-2.04
2.20
.395
.439
.489
<.0001
<.0001
2-Hydroxynaphthalene (ng/L)
161
-2.45
3.13
.548
.607
.646
<.0001
<.0001
3-Hydroxyfluorene (ng/L)
161
-1.66
2.52
.417
.451
.519
<.0001
<.0001
Note: PAH = Polycyclic Aromatic Hydrocarbon.
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Table 3. Properties of Differences in Ln-Transformed Pre- and Post-Activity Burden Levels for Specific Gravity-Adjusted Urinary
PAHs, by Field Type
P-Value
of
Signed
Standard
P-Value of
Rank
Field Type
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
t Statistic
Test
Synthetic
Turf
1-
Hydroxynaphthalene
(M-g/L)
132
-2.32
1.91
.446
.497
.609
<.0001
<.0001
Synthetic
Turf
1-
Hydroxyphenanthrene
(M-g/L)
132
-.831
1.69
.437
.471
.428
<.0001
<.0001
Synthetic
Turf
1-Hydroxypyrene
(M-g/L)
132
-1.86
1.45
.232
.260
.490
<.0001
<.0001
Synthetic
Turf
2 & 3-
Hydroxyphenanthrene
(Mg/L)
132
-1.55
1.54
.381
.414
.428
<.0001
<.0001
Synthetic
Turf
2-Hydroxyfluorene
(Mg/L)
132
-2.04
1.81
.414
.442
.481
<.0001
<.0001
Synthetic
Turf
2-
Hydroxynaphthalene
(Mg/L)
132
-2.45
3.13
.558
.605
.621
<.0001
<.0001
Synthetic
Turf
3-Hydroxyfluorene
(Mg/L)
132
-1.66
2.02
.421
.440
.484
<.0001
<.0001
Natural
Grass
1-
Hydroxynaphthalene
(Mg/L)
28
-1.02
2.32
.359
.545
.747
0.0006
<.0001
Natural
Grass
1-
Hydroxyphenanthrene
(Mg/L)
29
-1.91
3.02
.389
.482
.839
0.0044
<.0001
Natural
Grass
1-Hydroxypyrene
(Mg/L)
29
-1.15
2.61
.166
.304
.727
0.0323
0.0131
14
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P-Value
of
Signed
Standard P-Value of Rank
Field Type Urinary PAH n Minimum Maximum Median Mean Deviation t Statistic Test
Natural
Grass
2 & 3-
Hydroxyphenanthrene
(M-g/L)
29
-.433
2.55
.291
.390
.612
0.0019
0.0003
Natural
Grass
2-Hydroxyfluorene
(M-g/L)
29
-.223
2.20
.311
.426
.533
0.0002
<.0001
Natural
Grass
2-
Hydroxynaphthalene
(M-g/L)
29
-.729
2.76
.432
.619
.762
0.0002
<.0001
Natural
Grass
3-Hydroxyfluorene
(Mg/L)
29
-.661
2.52
.374
.502
.663
0.0003
<.0001
Note: PAH = Polycyclic Aromatic Hydrocarbon.
15
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Table 4. Properties of Differences in Ln-Transformed Pre- and Post-Activity Body Burden Levels for Creatinine-Adjusted Urinary
PAHs, by All Participants
Urinary PAH
Minimum Maximum Median Mean
Standard
Deviation
P-Value
of Signed
P-Value of Rank
t Statistic Test
1-
Hydroxynaphthalene
160
-2.11
2.35
-.011
.061
.577
0.1866
0.4666
(Hg/gCRE)
1-
Hydroxyphenanthrene
161
-2.17
2.42
-.028
.029
.490
0.4560
0.9324
(|ag/gCRE)
1-Hydroxypyrene
(Hg/gCRE)
161
-3.47
1.72
-.154
-.176
.619
0.0004
0.0002
2 & 3-
Hydroxyphenanthrene
161
-1.69
1.90
-.073
-.034
.477
0.3622
0.0866
(Hg/gCRE)
2-Hydroxyfluorene
(^g/gCRE)
161
-1.25
2.18
-.020
-.005
.458
0.8950
0.1987
2-
Hydroxynaphthalene
161
-1.43
2.75
.088
.163
.581
0.0005
0.0002
(|ag/gCRE)
3-Hydroxyfluorene
(^g/gCRE)
161
-1.37
2.24
-.019
.007
.482
0.8575
0.5660
Note: PAH = Polycyclic Aromatic Hydrocarbon.
16
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Table 5. Properties of Differences in Ln-Transformed Pre- and Post-Activity Body Burden Levels for Creatinine-Adjusted Urinary
PAHs, by Field Type
P-Value
of
P-Value
Signed
Standard
oft
Rank
Field Type
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Synthetic
Turf
1-Hydroxynaphthalene
(Hg/gCRE)
132
-2.11
2.35
-.012
.049
.585
0.3419
0.6207
Synthetic
Turf
1-Hydroxyphenanthrene
(Hg/gCRE)
132
-1.30
2.42
-.034
.022
.429
0.5539
0.9550
Synthetic
Turf
1-Hydroxypyrene
(Hg/gCRE)
132
-3.47
1.22
-.162
-.189
.591
0.0003
0.0002
Synthetic
Turf
2 & 3-
Hydroxyphenanthrene
132
-1.69
1.90
-.066
-.035
.472
0.3993
0.1857
(Hg/gCRE)
Synthetic
Turf
2-Hydroxyfluorene
(Hg/gCRE)
132
-1.25
2.18
-.028
-.007
.482
0.8762
0.2427
Synthetic
Turf
2-Hydroxynaphthalene
(Hg/gCRE)
132
-1.43
2.75
.095
.156
.592
0.0029
0.0009
Synthetic
Turf
3-Hydroxyfluorene
(iJig/gCRE)
132
-1.37
2.24
-.008
-.009
.484
0.8308
0.4891
Natural
Grass
1-Hydroxynaphthalene
(Hg/gCRE)
28
-1.29
1.37
.003
.117
.547
0.2673
0.5484
Natural
Grass
1-Hydroxyphenanthrene
(Hg/gCRE)
29
-2.17
2.07
-.005
.059
.712
0.6578
0.8911
Natural
Grass
1-Hydroxypyrene
(Hg/gCRE)
29
-1.42
1.72
-.024
-.119
.742
0.3956
0.4025
Natural
Grass
2 & 3-
Hydroxyphenanthrene
(Hg/gCRE)
29
-.802
1.66
-.096
-.033
.509
0.7320
0.2365
17
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
Field Type
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Natural
Grass
2-Hydroxyfluorene
(|ag/gCRE)
29
-.518
1.31
.000
.003
.338
0.9588
0.7562
Natural
Grass
2-Hydroxynaphthalene
(Hg/gCRE)
29
-.545
1.81
.011
.196
.535
0.0582
0.1413
Natural
Grass
3-Hydroxyfluorene
(|ag/gCRE)
29
-.924
1.63
-.065
.079
.473
0.3764
0.9245
Note: PAH = Polycyclic Aromatic Hydrocarbon.
18
-------
4.4. Univariate Regression Modelling
Univariate general linear model (GLM) regression parameter estimates for differences in pre-
and post-activity concentrations by field type were examined using specific gravity-adjusted
(Table 6) and creatinine-adjusted (Table 7) data among participants with non-missing covariate
data (n=156). For all urinary PAHs, differences in pre- and post-activity concentrations could not
be explained by field type. Overall, mean differences between pre- and post-activity
concentration were statistically significant for specific gravity-adjusted results, but not
statistically significant for creatinine adjusted-results. Regardless of adjustment method,
however, these differences were not associated with field type in the univariate analyses.
Table 6. Univariate GLM models for Field Type, by Specific Gravity-Adjusted Urinary PAHs
P-Value
Dependent oft
Urinary PAH Variable Parameter Estimate Statistic
1-Hydroxynaphthalene (ng/L) Difference Intercept 0.60 <.001
1-Hydroxynaphthalene (ng/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.11
0.430
1-Hydroxyphenanthrene
(M-g/L)
Difference
Intercept
0.57
<.001
1-Hydroxyphenanthrene
(M-g/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.10
0.356
1-Hydroxypyrene (ng/L)
Difference
Intercept
0.36
<.001
1-Hydroxypyrene (ng/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.10
0.357
2 & 3-Hydroxyphenanthrene
(M-g/L)
Difference
Intercept
0.42
<.001
2 & 3-Hydroxyphenanthrene
(Mg/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.01
0.941
2-Hydroxyfluorene (ng/L)
Difference
Intercept
0.45
<.001
2-Hydroxyfluorene (ng/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.00
0.996
2-Hydroxynaphthalene (ng/L)
Difference
Intercept
0.62
<.001
2-Hydroxynaphthalene (ng/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.00
0.971
3-Hydroxyfluorene (ng/L)
Difference
Intercept
0.54
<.001
3-Hydroxyfluorene (ng/L)
Difference
Field Type (Synthetic Turf
versus Natural Grass)
-0.10
0.357
19
-------
Table 7. Univariate GLM models for Field Type, by Creatinine-Adjusted Urinary PAHs
Urinary PAH
Dependent Variable
Parameter
P-Value oft
Estimate Statistic
1-Hydroxynaphthalene
(Hg/gCRE)
1-Hydroxynaphthalene
(|ag/gCRE)
Hydroxyphenanthrene
(Hg/gCRE)
1-
Hydroxyphenanthrene
(|ag/gCRE)
1-Hydroxypyrene
(iJig/gCRE)
1-Hydroxypyrene
(|ag/gCRE)
2 & 3-
Hydroxyphenanthrene
(Hg/gCRE)
2 & 3-
Hydroxyphenanthrene
(|ag/gCRE)
2-Hydroxyfluorene
(IJig/gCRE)
2-Hydroxyfluorene
(|ag/gCRE)
2-Hydroxynaphthalene
(Hg/gCRE)
2-Hydroxynaphthalene
(|ag/gCRE)
3-Hydroxyfluorene
(IJig/gCRE)
3-Hydroxyfluorene
(Hg/gCRE)
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Difference
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
Field Type
(Synthetic Turf
0.17
-0.12
0.14
-0.12
-0.07
-0.12
-0.01
-0.03
0.02
-0.02
0.19
-0.02
0.11
-0.12
0.127
0.324
0.115
0.235
0.536
0.346
0.922
0.790
0.836
0.836
0.091
0.842
0.210
0.236
20
-------
P-Value oft
Urinary PAH
Dependent Variable
Parameter
Estimate
Statistic
versus Natural
Grass)
Note: PAH = Polycyclic Aromatic Hydrocarbon.
4.5. Full Model Multivariable GLM Regression
The first step taken prior to conducting multivariable regression was to address concerns about
the potential for collinearity and data separation. For this study, all natural grass fields were
located outdoors and co-located with outdoor synthetic fields; thus the field environment
variable (indoor vs. outdoor) was also a measure of field type (synthetic turf vs. natural grass).
All indoor participants were recruited from the same field, and thus the same location (U.S.
Census Region; South or West). All volleyball players were female and recruited from the same
outdoor facility, and thus the same region. For these reasons, a new variable containing
mutually exclusive categories was generated and tested against models with individual
variables; models with individual variables performed best.
As an additional exploratory step, auto-selection algorithms were used to identify variables
associated with pre-activity, post-activity, and differences of concentrations as the dependent
variable in multivariable models for specific gravity-adjusted and creatinine-adjusted data (data
not shown). Field type was not statistically significant in any of the models of pre-and post-
activity differences in concentration. For both specific gravity- and creatinine-adjusted results,
the best predictor of post-activity concentration was the study participant's pre-activity
concentration; this was consistent with the earlier finding that pre- and post-activity
concentrations were highly correlated.
Multivariable GLM regression parameter estimates for differences in pre- and post-activity
concentrations by field type, adjusted for all other previously described variables are described
in Table 8 (specific-gravity adjusted) and Table 9 (creatinine-adjusted). As with the univariate
analysis, the difference in pre- and post- concentrations were not associated with field type.
Table 8. Multivariable GLM models for Field Type, by Specific Gravity-Adjusted Urinary PAHs
Urinary PAH
Dependent
Variable
Parameter
Estimate
P-Value oft
Statistic
1-Hydroxynaphthalene
(Hg/L)
1-Hydroxynaphthalene
(Hg/L)
1-
Hydroxyphenanthrene
(Hg/L)
Difference
Difference
Difference
Intercept
Field Type
(Synthetic Turf
versus Natural
Grass)
Intercept
0.61
-0.03
0.53
0.032
0.867
0.014
21
-------
Dependent
P-Value oft
Urinary PAH
Variable
Parameter
Estimate
Statistic
1 _
Field Type
-L
Hydroxyphenanthrene
(Mg/L)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.23
0.108
1-Hydroxypyrene
(M-g/L)
Difference
Intercept
0.16
0.493
Field Type
1-Hydroxypyrene
(M-g/L)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.2
0.204
2 & 3-
Hydroxyphenanthrene
Difference
Intercept
0.34
0.101
(M-g/L)
2 & 3-
Hydroxyphenanthrene
(Mg/L)
Difference
Field Type
(Synthetic Turf
versus Natural
Grass)
-0.16
0.234
2-Hydroxyfluorene
(Mg/L)
Difference
Intercept
0.44
0.049
Field Type
2-Hydroxyfluorene
(Mg/L)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.13
0.363
2-Hydroxynaphthalene
(Mg/L)
Difference
Intercept
0.51
0.082
Field Type
2-Hydroxynaphthalene
(Mg/L)
Difference
(Synthetic Turf
versus Natural
Grass)
0.2
0.299
3-Hydroxyfluorene
(Mg/L)
Difference
Intercept
0.45
0.055
Field Type
3-Hydroxyfluorene
(Mg/L)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.24
0.107
Note: PAH = Polycyclic Aromatic Hydrocarbon.
Table 9. Multivariable GLM models for Field Type, by Creatinine Gravity-Adjusted Urinary
PAHs
Dependent
P-Value oft
Urinary PAH
Variable
Parameter
Estimate
Statistic
1-Hydroxynaphthalene
(Mg/gCRE)
Difference
Intercept
-0.10
0.696
22
-------
Dependent
P-Value oft
Urinary PAH
Variable
Parameter
Estimate
Statistic
Field Type
1-Hydroxynaphthalene
(|ag/gCRE)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.01
0.939
1-
Hydroxyphenanthrene
Difference
Intercept
-0.17
0.386
(Hg/gCRE)
1 _
Field Type
1
Hydroxyphenanthrene
(|ag/gCRE)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.21
0.108
1-Hydroxypyrene
(^g/gCRE)
Difference
Intercept
-0.54
0.046
Field Type
1-Hydroxypyrene
(|ag/gCRE)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.18
0.311
2 & 3-
Hydroxyphenanthrene
Difference
Intercept
-0.37
0.080
(^g/gCRE)
2 & 3-
Hydroxyphenanthrene
(|ag/gCRE)
Difference
Field Type
(Synthetic Turf
versus Natural
Grass)
-0.14
0.298
2-Hydroxyfluorene
(^g/gCRE)
Difference
Intercept
-0.27
0.198
Field Type
2-Hydroxyfluorene
(|ag/gCRE)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.11
0.401
2-Hydroxynaphthalene
(^g/gCRE)
Difference
Intercept
-0.20
0.444
Field Type
2-Hydroxynaphthalene
(|ag/gCRE)
Difference
(Synthetic Turf
versus Natural
Grass)
0.21
0.206
3-Hydroxyfluorene
(^g/gCRE)
Difference
Intercept
-0.26
0.230
Field Type
3-Hydroxyfluorene
(|ag/gCRE)
Difference
(Synthetic Turf
versus Natural
Grass)
-0.23
0.105
Note: PAH = Polycyclic Aromatic Hydrocarbon.
23
-------
4.6. Comparison to NHANES PAH Concentrations
Pre-activity PAH concentrations among study participants were compared to values in the
general U.S. population using secondary analysis of publicly available NHANES data. To facilitate
these comparisons, PAH concentrations were adjusted for specific gravity or creatinine
concentration. Specific gravity was only collected in the 2007-2008 NHANES cycle, whereas
creatine was collected in all NHANES cycles including the most recent cycle available (2015-
2016) at the time of data analysis. 2-3 PHE was not available in 2007-2008 NHANES.
Comparison of this study's specific gravity-adjusted results to those of the 2007-2008 NHANES
cycle may not be entirely comparable due to the observed trend of decreasing concentrations
over time for most PAHs. In NHANES, PAH concentrations markedly decreased over time,
except for 2-NAP where creatinine-adjusted geometric mean concentrations were 3.88 (5.45-
4.26) |ag/gCRE in 2007-2008 and 5.35 (4.86-5.90) |ag/gCRE in 2015-2016 (Supplemental Table
S3). Additionally, pre-activity PAH geometric mean concentrations of study participants were
lower than corresponding NHANES values except for adjusted 2-NAP concentrations (Figure 3).
Additional stratifications by age category and NHANES 2015-2016 PAH comparison values are
displayed in Table 10. This observation was consistent by age category except youth, where
concentrations were 4.97 (3.49-7.09) |ag/gCRE among youth in the study compared to 5.22
(4.24-6.44) |ag/gCRE among youth in NHANES 2015-2016, indicating no significant difference.
24
-------
Figure 3. Comparison of Urinary PAH Concentrations Across Biomonitoring Study Participants
and NHANES 2007-2008 and 2016-2017 Participants Overall, by Adjustment Method
0
0.15
0.00
0.15
0.00
0.2
0.1
0.0
0.4
0.2
0.0
15
0
0.15
0.00
ni
if ai
m
ai
il
11 nl
-m
¦i
m al
li al
m
~i
IS ii ni
\%
¦¦
ii _¦
ni,
hI
In
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m al
ii -¦
%
z
W
X
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W
X
Oh
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i
-------
Table 10. Comparison of Geometric Means (95% CI) by Age and Urinary PAH, Pre-Activity Biomonitoring Study Concentrations
versus NHANES 2015-2016
NHANES 2015-
Study
Participants
Pre-Activity
NHANES 2015-
2016
2016
Geometric
Geometric
Study Participants
Geometric
Mean,
Mean,
Pre-Activity
Mean,
Creatinine-
Creatinine-
Age
Study
NHANES
Geometric Mean,
Unadjusted
Adjusted
Adjusted
Category
Urinary PAH
n
n
Unadjusted (pg/L)
(pg/L)
(pg/gCRE)
(pg/gCRE)
Children
1-Hydroxynaphthalene
24
111
.997
.557-1.79)
.817 (.625-1.07)
1.47 (.842-2.57)
1.17 (.908-1.50)
Children
1-Hydroxyphenanthrene
24
112
.052
.029-.090)
.083 (.068-.100)
.076 (.049-.119)
.119 (.097-.146)
Children
1-Hydroxypyrene
24
112
.077
.048-.124)
.134 (.104-.172)
.114 (.071-.183)
.193 (.145-.257)
Children
2 & 3-
Hydroxyphenanthrene
24
112
.082
.046-.144)
.098 (.078-.122)
.121 (.075-.194)
.140 (.112-.176)
Children
2-Hydroxyfluorene
24
112
.096
.053-.173)
.132 (.101-.171)
.142 (.089-.225)
.189 (.140-.256)
Children
2-Hydroxynaphthalene
24
112
7.52
4.31-13.1)
3.31 (2.49-4.40)
11.1 (6.41-19.2)
4.76 (3.84-5.89)
Children
3-Hydroxyfluorene
24
112
.055
.030-.099)
.063 (.048-.082)
.081 (.049-.133)
.090 (.067-.122)
Youth
1-Hydroxynaphthalene
27
175
.709
.499-1.01)
.864 (.695-1.07)
.728 (.522-1.02)
1.03 (.847-1.25)
Youth
1-Hydroxyphenanthrene
27
176
.069
.054-.089)
.085 (.074-.097)
.071 (.059-.087)
.101 (.089-.115)
Youth
1-Hydroxypyrene
27
176
.084
.066-.108)
.124 (.111-.140)
.086 (.072-.104)
.148 (.132-.166)
26
-------
.26 (
.54 (
22 (
i72 (
95 (
186 (
.15 (
.05 (
.39 (
72 (
i62 (
90 (
Urinary PAH
Study Participants
Pre-Activity
Study NHANES Geometric Mean,
n n Unadjusted (|ag/L)
NHANES 2015-
2016
Geometric
Mean,
Unadjusted
(Hg/L)
Study
Participants
Pre-Activity
Geometric
Mean,
Creatinine-
Adjusted
(Hg/gCRE)
2 & 3-
Hydroxyphenanthrene
2-Hydroxyfluorene
2-Hydroxynaphthalene
3-Hydroxyfluorene
1-Hydroxynaphthalene
1-Hydroxyphenanthrene
1-Hydroxypyrene
2 & 3-
Hydroxyphenanthrene
2-Hydroxyfluorene
2-Hydroxynaphthalene
3-Hydroxyfluorene
1-Hydroxynaphthalene
27
27
27
27
51
51
51
51
51
51
58
59
175
176
176
272
272
272
272
272
.094 (.073-.121) .106
.100
176 4.84
.047
267 .603
.049
.078
.079
.090
269 4.92
.039
1767 .929
093-.120) .096 (.081-.114)
.075-.135) .129
3.14-7.45) 4.39
.034-.065) .061
.450-.808) .860
.035-.069) .094
.065-.094) .124
.058-.107) .114
.066-.123) .151
3.36-7.19) 5.11
.029-.051) .067
.611-1.41) 1.75
112-.149) .103
3.50-5.51) 4.97
,050-.073) .049
,745-.994) .945
,080-.110) .077
107-.144) .123
,098-.133) .123
130-.175) .142
4.15-6.29) 7.71
057-.080) .060
1.50-2.04) .970
.088-.121)
3.49-7.09)
.039-.060)
,724-1.23)
.066-.091)
,097-.156)
.103-.148)
118-.170)
5.82-10.2)
,050-.074)
,710-1.33)
27
-------
.19 (
.33 (
.37 (
!24(
,45 (¦
199 (
,69 (
.15 (
.33 (
.34 (
111 (
,35 (¦
Urinary PAH
Study Participants
Pre-Activity
Study NHANES Geometric Mean,
n n Unadjusted (|ag/L)
NHANES 2015-
2016
Geometric
Mean,
Unadjusted
(Hg/L)
Study
Participants
Pre-Activity
Geometric
Mean,
Creatinine-
Adjusted
(Hg/gCRE)
1-Hydroxyphenanthrene 59
1-Hydroxypyrene
2 & 3-
Hydroxyphenanthrene
2-Hydroxyfluorene
2-Hydroxynaphthalene
3-Hydroxyfluorene
1-Hydroxypyrene
2 & 3-
Hydroxyphenanthrene
2-Hydroxyfluorene
59
59
59
59
59
1-Hydroxynaphthalene 161
1-Hydroxyphenanthrene 161
161
161
161
1868 .113 (.085-.150)
2-Hydroxynaphthalene 161
1866 .121
1867 .135
1867 .146
1819 7.31
1863 .059
2320 .782
2428 .071
2426 .093
2426 .099
2427 .111
2376 6.04
.109
099-.120) .118 (.097-.143)
.090-.163) .122
.102-.178) .126
.109-.195) .205
5.34-10.0) 4.99
.043-.081) .090
.638-.959) 1.56
.060-.085) .106
.080-.108) .123
.084-.117) .123
.093-.131) .194
4.97-7.35) 4.92
111-.134) .127
113-.141) .141
180-.233) .152
4.36-5.71) 7.64
,077-.106) .062
1.36-1.79) .976
097-.116) .089
112-.134) .116
111-.137) .124
172-.218) .138
4.33-5.59) 7.54
.099-.162)
117-.169)
.126-.184)
6.12-9.54)
.050-.077)
,822-1.16)
.079-.100)
101-.133)
.110-.139)
123-.155)
6.45-8.80)
28
-------
Study
Participants
NHANES 2015-
NHANES 2015-
Pre-Activity
2016
2016
Geometric
Geometric
Study Participants
Geometric
Mean,
Mean,
Pre-Activity
Mean,
Creatinine-
Creatinine-
Age
Study
NHANES
Geometric Mean,
Unadjusted
Adjusted
Adjusted
Category
Urinary PAH
n
n
Unadjusted (ng/L)
(Hg/L)
(Hg/gCRE)
(Hg/gCRE)
All
3-Hydroxyfluorene
161
2423
.049 (.041-.059)
.086 (.074-.099)
.061 (.054-.070)
.093 (.083-.105)
Note: Age Category includes children (ages 7-9 years), youth (ages 10-12 years), adolescents (13-17 years), and adults (18 and older).
PAH = Polycyclic Aromatic Hydrocarbon.
"NHANES n" corresponds to number of NHANES Participants with unadjusted urinary concentrations.
29
-------
5. Discussion
Synthetic turf with recycled tire crumb rubber infill contains many substances, including PAHs
[Armada 2021; Gomes 2021; Marsili 2014; Murphy 2022; US EPA and ATSDR 2019], PAHs are a
large class of widespread chemicals generally produced during the incomplete burning of
organic substances, such as coal, oil and gas, garbage tobacco, and charbroiled meat [ATSDR
1995]. Routes of PAH exposure include ingestion, inhalation, and dermal contact both in
occupational and non-occupational settings [ATSDR 1995]. Once inside the body, PAHs are
metabolized by the liver into monohydroxylated metabolites and excreted rapidly in urine and
feces with half-life in the human body of less than 30 hours (Hudson-Hanley). Therefore,
urinary PAH metabolites represent useful non-invasive biomarkers for assessing recent PAH
uptake from all exposure routes [Ganzleben et al. 2017; Gunnier 2006; Srogi 2007].
Supplementing the pilot-scale human exposure measurements collected under the FRAP [EPA
and ATSDR 2024], this biomonitoring study examined urinary PAHs to assess the exposure
potential for individuals who performed activities on turf fields with recycled tire crumb rubber
infill. The same 7 urinary metabolites assessed in both studies are regularly monitored in the
general U.S. population [CDC 2020], and the four parent PAHs (anthracene, fluorene,
phenanthrene, pyrene) are among EPA's 16 Priority Pollutants [US EPA 2014]. This
supplemental study distinguishes itself in several ways. First, it featured a larger convenience
sample of study participants compared to the pilot study conducted under the FRAP; urine
samples from 161 participants with age ranging from 7-77 years were analyzed, compared to
urine samples from 14 participants in the pilot study with an age range of 11-21 years. This
larger sample size allowed for the examination of potential differences by select demographic
characteristics and behaviors. Additionally, this supplemental study also included a group of
participants whose activities took place on natural grass fields. Although the sample size of
natural grass participants was relatively small, this comparison group provided an important
examination of pre- and post-activity differences by field type.
In this study, pre- and post-activity urinary PAH concentration differences were not associated
with field type, regardless of urine adjustment method or statistical method applied. Consistent
with the pilot-scale study [EPA and CDC/ATSDR 2024], most participants demonstrated an
increase in specific gravity-adjusted PAH concentrations after performing field activities.
However, the increase occurred irrespective of field type, among both natural grass participants
as well as synthetic turf with recycled tire crumb rubber participants. Also consistent with the
pilot-scale study, our findings indicated fewer significant pre- and post-activity differences
when utilizing creatinine-adjusted results, underscoring the influence of urine-dilution
methods. These differences may potentially be attributed to how the degree of correlation of
specific gravity and creatinine with the true hydration status of an individual may vary due to
endogenous and exogenous factors [Kuiper 2021]. In the context of PAHs, for example, children
are generally a vulnerable group with potential for higher exposure to PAHs compared to adults
due in part to their less efficient detoxification system, lower body weight, and higher
inhalation rates [Oliveira et al. 2019]. Though age was not associated with post-activity PAH
concentrations, it was associated with some pre-activity concentrations. Additionally, potential
30
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sex-specific effects or differential responses to PAH exposure continue to be areas of
exploration [Farzan 2016; Xing 2023; Yang 2021], and differences in BMI or body composition
may contribute to differential PAH metabolism [Stallings 2018; Wang 2022]. However, in this
study, neither sex nor BMI were statistically associated with pre- and post-activity differences in
PAH concentrations in univariate or multivariate regression models.
In the absence of other measures of urinary dilution such as osmolality and urine flow rate
[Middleton 2016], the comprehensive approach taken in this present study facilitated
examination of other datasets, including NHANES 2007-2008 and 2015-2016. NHANES 2007-
2008 data, which collected both specific gravity and creatinine, also revealed large differences
between specific gravity- and creatinine-adjusted PAH concentrations. Our comparison of
creatinine-adjusted PAH concentrations available in both NHANES cycles indicated that urinary
PAH concentrations markedly decreased over time, except for 2-NAP. Differences in creatinine-
adjusted urinary 2-NAP were detected in pre- and post-activity samples from this biomonitoring
study as well as the previous pilot-scale study [EPA and CDC/ATSDR 2024]. In both the studies,
the creatinine adjusted 2-NAP concentration (geometric mean) was higher pre- and post-
activity when compared to the general US population based on available NHANES data. In our
biomonitoring study, this observation held for all age groups except for youth (participants
aged 10-12 years). Previous urinary biomarker investigations utilizing NHANES have also
indicated naphthalene, the parent PAH of 2-NAP with widespread presence in ambient and
indoor air, as the dominant PAH in the U.S. population [Li 2008]. Data from the pilot-study,
however, indicated low levels of naphthalene in tire crumb rubber infill, field air, field dust, field
wipe, and drag sled samples [U.S. EPA and CDC/ATSDR 2024].
Overall, measurable amounts of urinary hydroxylated metabolites of PAHs were found in users
of both synthetic turf fields and natural grass fields. However, finding a measurable amount of
urinary hydroxylated metabolites of PAHs does not indicate they cause an adverse health effect
[ATSDR PAH Clinical Assessment 2023]. Previous biomonitoring studies have demonstrated that
nearly 100% of the general U.S. population have detectable levels of urinary PAH metabolites
[Grainger 2006]. Exposure to PAHs in the general population occurs mostly through inhalation
of polluted air and cigarette smoke, and ingestion of food containing PAHs [ATSDR 1995].
Others have demonstrated that an exposure-free period of 24-48 hours is often required for
PAH biomarkers to reach pre-exposure baseline [Zheng 2012; Brzeznicki 1997; Chien 2010; Viau
1995]. More recently, data from Choi et al. 2023 demonstrated that the fractional urinary
excretion of urinary PAHs ranged from 0.07 % to 11.3% and that most were excreted within 24
hours after exposure, though the obtained fractional urinary excretion values only reflected
oral intake [Choi 2023]. Accordingly, this study excluded participants who were smokers,
excluded natural grass participants who had played on synthetic turf within the past 24 hours,
and accounted for the ingestion of grilled foods within the past 24 hours. Outdoor synthetic
turf fields were also co-located with natural grass fields to help account for potential PAHs in
ambient air. Nevertheless, this study could not fully control for potential exposures to
chemicals from other sources and environmental media that could occur off the field. As
described previously [EPA and CDC/ATSDR 2019], while there is concern about chemical
exposures resulting from the use of recycled tire in synthetic turf fields, it is important to
consider that some PAHs and other chemicals are also found in surface soil and may be present
31
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in othertypes of fields, including natural grass fields. For example, metals (including lead) and
PAHs (including benzo[a]pyrene) of potential concern at synthetic turf fields with tire crumb
rubber infill are also often found in surface soil present at natural grass playing fields [EPA and
CDC/ATSDR 2019],
5.1. Limitations and Recommendations
Like the pilot-scale human exposure measurement study conducted as part of the FRAP, this
current study's examination of participant activity on synthetic turf fields was limited in design
to assess exposure to recycled tire crumb rubber (infill alternatives were not included) and did
not investigate exposure to synthetic turf field materials or components such as synthetic grass
blades and backing material. Also consistent with the constraints of the research activities in
the FRAP, there was no way to determine the specific tire sources for tire crumb rubber at the
participating fields. While the facility and indoor or outdoor field environment was considered,
this study did not examine the potential of dust transfer or effects of water-runoff between the
co-located natural grass fields and synthetic turf fields. Future research activities may also
choose to expand the scope of exposure measurement studies to incorporate synthetic turf
fields that use alternative types of infill as another means of comparison further allowing
communities to make more informed choices.
Though some statistical models indicated a difference between pre- and post-activity PAH
concentrations, these differences were dependent on choices such as In-transformation, urine
dilution adjustment method, and model specification. In all cases, observed pre- and post-
activity differences were not explained by field type (exposure to synthetic turf). Observed
differences could be due to unmeasured variables, such as changes in hydration level through
perspiration. However, it is unknown whether a participant drank fluids between the two
specimen collections, nor how much fluid they lost due to intensity of activity. For the urine
collection, participants were directed to not touch the inside of the urine specimen container to
prevent or minimize chances of sample contamination. However, the study recruitment team
cannot confirm that all participants followed the specified procedures.
For future related studies, additional information obtained at the time of specimen collection
might help provide insights on factors affecting PAH concentrations. For example, asking about
fluid consumption during the activity (between pre- and post-specimen collections), and taking
pre- and post-body-weight measurements (to measure potential fluid loss or gain) could help
tease out factors driving pre- and post-activity concentration differences. As previous studies
have indicated the potential effect of vaporization and weathering on organic chemical level
concentrations [Marsili et al. 2014; EPA and CDC/ATSDR 2019], additional efforts could examine
or account for the role of fluctuations in weather or field temperatures over time. Moreover,
although information including the time recorded between samplings and general patterns of
activity were captured in this study, these data may not directly correspond to the level of
activity each participant exerted on the field; additional measures could be included to account
for behaviors specific to the day-of specimen collection.
32
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6. Conclusions
Although this study's findings cannot be generalized to the universe of synthetic field users with
exposures to tire crumb rubber infill in the United States, this study provides valuable
information to better understand and identify the potential chemical exposures. Notably, pre-
and post-activity differences in urinary PAH concentrations were not associated with field type
(i.e., synthetic turf with recycled tire crumb rubber infill compared to natural grass). This was
consistent regardless of the urine dilution adjustment method applied or the statistical
regression technique employed. When examining pre- and post-activity urinary PAH
concentration differences overall, results varied by statistical method; methods that mitigated
the effect of extreme observations were more likely to yield results that were not statistically
significant, indicating that outliers could be driving some of the results. After exploring the role
of different variables associated with pre- and post-activity concentrations, the best predictor
of post-activity urinary PAH concentration was pre-activity concentration. Except for 2-NAP,
pre-activity PAH concentrations were lower than those in the general U.S. population using
2015-2016 NHANES comparison data. It is important to note that this report is not a risk
assessment. However, this study's findings supplement the pilot-scale human exposure
measurements collected under the FRAP and contribute to the overarching portfolio of
research activities needed to understand the potential for human exposure to chemicals found
in recycled tire crumb rubber used on synthetic turf fields.
7. Preparers of the Report
Prepared by:
Agency for Toxic Substances and Disease Registry (ATSDR)
U.S. Department of Health and Human Services
Lead Authors
Teresa Wang, PhD
Epidemiologist, Office of Community Health Hazard Assessment, ATSDR
Twwang@cdc.gov
Michael Lewin, MS
Mathematical Statistician, Office of Community Health Hazard Assessment, ATSDR
Mlewin@cdc.gov
Collaborating Federal Organizations
U.S. EPA
33
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Contributors
Kelsey Brady, MPH
Epidemiologist, Office of Community Health Hazard Assessment, ATSDR
Elizabeth Irvin, PhD
Director, Office of Community Health Hazard Assessment, ATSDR
Angela Ragin-Wilson, PhD
Deputy Director, Office of Associate Director, ATSDR
Reviewers
Alesia Ferguson, MPH, PhD
Professor, North Carolina Agricultural and Technical State University
P. Barry Ryan, PhD
Professor Emeritus, Emory University Rollins School of Public Health
Vasilis Vasilou, PhD
Professor, Yale School of Public Health
Acknowledgements
We sincerely thank those who participated in the study. We appreciate the CDC/ATSDR staff
who facilitated the recruitment and data collection efforts, including Emily Adler, Tyra Barrett,
Carol Cusack, Michelle Dittrich, John Marr, Miranda Mitchell, Christopher Mugford, Chris
Poulet, Nykiconia Preacely, Tara Serio, and Timothy Turner. We also thank the CDC/NCEH/DLS
laboratory staff who performed the high-quality laboratory analyses, including Britnee Bailey,
Julianne Botelho, Antonia Calafat, Joaudimir (Joy) Castro Georgi, Alfonsina (Sina) De Leon
Salazar, Christopher Hamilton, Rebecca Hunt, Erin (Nikki) Pittman, Debra Trinidad, Denise Tevis,
Hubert Vesper, Neelam Zahoor, Enada Archibold, Yuesong Wang, and Cynthia D. Ward.
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Appendices
38
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Appendix A: Supplemental Figures
Figure Sl-1. Difference in post- and pre-activity concentration for 1-hydroxyphenanthrene
measurements, In-transformed, by participant and field type. Specific gravity-
adjusted (left) and creatinine-adjusted (right).
Figure Sl-2. Difference in post- and pre-activity concentration for 1-hydroxypyrene
measurements, In-transformed, by participant and field type. Specific gravity-
adjusted (left) and creatinine-adjusted (right).
Figure Sl-3. Difference in post- and pre-activity concentration for 2 & 3-hydroxyphenanthrene
measurements, In-transformed, by participant and field type. Specific gravity-
adjusted (left) and creatinine-adjusted (right).
Figure Sl-4. Difference in post- and pre-activity concentration for 2-hydroxyfluorene
measurements, In-transformed, by participant and field type. Specific gravity-
adjusted (left) and creatinine-adjusted (right).
Figure Sl-5. Difference in post- and pre-activity concentration for 2-hydroxynapthalene
measurements, In-transformed, by participant and field type. Specific gravity-
adjusted (left) and creatinine-adjusted (right).
Figure Sl-6. Difference in post- and pre-activity concentration for 3-hydroxyfluorene
measurements, In-transformed, by participant and field type. Specific gravity-
adjusted (left) and creatinine-adjusted (right).
39
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Figure Sl-1. Difference in post- and pre-activity concentration for 1-hydroxyphenanthrene
measurements, In-transformed, by participant and field type. Specific gravity-adjusted (left)
and creatinine-adjusted (right).
Study Participant
Study Participant
Field Type ¦ Natural Grass ¦ Synthetic Turf
Field Type ¦ Natural Grass ¦ Synthetic Turf
Figure Sl-2. Difference in post- and pre-activity concentration for 1-hydroxypyrene
measurements, In-transformed, by participant and field type. Specific gravity-adjusted (left)
and creatinine-adjusted (right).
Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf |
Study Participant
Field Type ¦ Natural Grass ¦ Synthetic Turf
40
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Figure Sl-3. Difference in post- and pre-activity concentration for 2 & 3-
hydroxyphenanthrene measurements, In-transformed, by participant and field type. Specific
gravity-adjusted (left) and creatinine-adjusted (right).
Study Participant
Field Type ¦ Natural Grass ¦ Synthetic Turf
Figure Sl-4. Difference in post- and pre-activity concentration for 2-hydroxyfluorene
measurements, In-transformed, by participant and field type. Specific gravity-adjusted (left)
and creatinine-adjusted (right).
Study Participant Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf | | Field Type ¦ Natural Grass ¦ Synthetic Turf |
Study Participant
Field Type ¦ Natural Grass 1 Synthetic Turf |
41
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Figure Sl-5. Difference in post- and pre-activity concentration for 2-hydroxynapthalene
measurements, In-transformed, by participant and field type. Specific gravity-adjusted (left)
and creatinine-adjusted (right).
Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf]
Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf |
Figure Sl-6. Difference in post- and pre-activity concentration for 3-hydroxyfluorene
measurements, In-transformed, by participant and field type. Specific gravity-adjusted (left)
and creatinine-adjusted (right).
Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf]
Study Participant
| Field Type ¦ Natural Grass ¦ Synthetic Turf |
42
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Appendix B: Supplemental Tables
Table Sl-1. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by field environment
Table Sl-2. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by age category
Table Sl-3. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by sex
Table Sl-4. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by race
Table Sl-5. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by field location
Table Sl-6. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by facility
Table Sl-7. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by BMI category
Table Sl-8. Properties of differences in In-transformed pre- and post-activity body burden
levels for Specific Gravity-adjusted urinary PAHs, by activity
Table S2-1. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by field environment
Table S2-2. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by age category
Table S2-3. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by sex
Table S2-4. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by race
Table S2-5. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by field location
Table S2-6. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by facility
Table S2-7. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by BMI category
Table S2-8. Properties of differences in In-transformed pre- and post-activity body burden
levels for Creatinine-adjusted urinary PAHs, by activity
43
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Table S3. Comparison of creatinine-adjusted urinary PAH concentrations, NHANES 2015—2016
and 2007-2008
44
-------
Table Sl-1. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by field environment
P-Value
of
Signed
Field
Standard
P-Value of
Rank
Environment
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
t Statistic
Test
Outdoor
1-
Hydroxynaphthalene
(Hg/L)
119
-1.09
2.32
.434
.514
.638
<.0001
<.0001
Outdoor
1-
Hydroxyphenanthrene
(Hg/L)
120
-1.91
3.02
.433
.476
.545
<.0001
<.0001
Outdoor
1-Hydroxypyrene
(Hg/L)
120
-1.20
2.61
.230
.284
.534
<.0001
<.0001
2 & 3-
Outdoor
Hydroxyphenanthrene
(Hg/L)
120
-.822
2.55
.359
.414
.466
<.0001
<.0001
Outdoor
2-Hydroxyfluorene
(Hg/L)
120
-.780
2.20
.384
.440
.464
<.0001
<.0001
Outdoor
2-
Hydroxynaphthalene
(Hg/L)
120
-.732
3.13
.539
.637
.646
<.0001
<.0001
Outdoor
3-Hydroxyfluorene
(Hg/L)
120
-.716
2.52
.390
.441
.511
<.0001
<.0001
Indoor
1-
Hydroxynaphthalene
(Hg/L)
41
-2.32
1.50
.453
.482
.624
<.0001
<.0001
Indoor
1-
Hydroxyphenanthrene
(Hg/L)
41
-.796
1.69
.437
.464
.459
<.0001
<.0001
Indoor
1-Hydroxypyrene
(Hg/L)
41
-1.86
1.14
.233
.221
.551
0.0139
0.0004
45
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P-Value
of
Signed
Field Standard P-Value of Rank
Environment Urinary PAH n Minimum Maximum Median Mean Deviation t Statistic Test
2 & 3-
Indoor
Hydroxyphenanthrene
(M-g/L)
41
-1.55
1.42
.395
.396
.465
<.0001
<.0001
Indoor
2-Hydroxyfluorene
(M-g/L)
41
-2.04
1.72
.452
.437
.563
<.0001
<.0001
Indoor
2-
Hydroxynaphthalene
(M-g/L)
41
-2.45
1.51
.586
.522
.646
<.0001
<.0001
Indoor
3-Hydroxyfluorene
(Mg/L)
41
-1.66
2.02
.475
.481
.547
<.0001
<.0001
Note: PAH = Polycyclic Aromatic Hydrocarbon.
46
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Table Sl-2. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by age category
P-Value
of
P-Value
Signed
Age
Standard
oft
Rank
Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Adolescent
1-Hydroxynaphthalene
(M-g/L)
51
-.385
1.91
.510
.671
.549
<.0001
<.0001
Adolescent
1-Hydroxyphenanthrene
(M-g/L)
51
-.171
2.45
.539
.647
.491
<.0001
<.0001
Adolescent
1-Hydroxypyrene(ng/L)
51
-1.86
2.61
.219
.270
.670
0.0059
0.0011
2 & 3-
Adolescent
Hydroxyphenanthrene
(M-g/L)
51
-.160
2.55
.424
.535
.475
<.0001
<.0001
Adolescent
2-Hydroxyfluorene (ng/L)
51
-.518
2.20
.476
.535
.488
<.0001
<.0001
Adolescent
2-Hydroxynaphthalene
(Mg/L)
51
-.239
2.58
.700
.793
.632
<.0001
<.0001
Adolescent
3-Hydroxyfluorene (ng/L)
51
-.698
2.52
.519
.547
.531
<.0001
<.0001
Adult
1-Hydroxynaphthalene
(Mg/L)
58
-2.32
2.32
.378
.419
.713
<.0001
<.0001
Adult
1-Hydroxyphenanthrene
(Mg/L)
59
-1.91
3.02
.344
.319
.601
0.0001
<.0001
Adult
1-Hydroxypyrene (ng/L)
59
-1.20
2.05
.207
.187
.519
0.0074
0.0005
2 & 3-
Adult
Hydroxyphenanthrene
(Mg/L)
59
-1.55
1.57
.306
.272
.454
<.0001
<.0001
47
-------
Age
Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Standard
Deviation
P-Value
oft
Statistic
P-Value
of
Signed
Rank
Test
Adult
2-Hydroxyfluorene (ng/L)
59
-2.04
1.72
.351
.335
.523
<.0001
<.0001
Adult
2-Hydroxynaphthalene
(M-g/L)
59
-2.45
3.13
.435
.517
.792
<.0001
<.0001
Adult
3-Hydroxyfluorene (ng/L)
59
-1.66
2.02
.374
.376
.568
<.0001
<.0001
Child
1-Hydroxynaphthalene
(M-g/L)
24
-1.09
1.35
.358
.271
.583
0.0322
0.0338
Child
1-Hydroxyphenanthrene
(M-g/L)
24
-.223
1.39
.460
.474
.397
<.0001
<.0001
Child
1-Hydroxypyrene(ng/L)
24
-.720
1.45
.299
.372
.450
0.0005
0.0002
Child
2 & 3-
Hydroxyphenanthrene
(Mg/L)
24
-.539
1.54
.398
.438
.472
0.0001
<.0001
Child
2-Hydroxyfluorene (ng/L)
24
-.517
1.81
.355
.399
.466
0.0004
<.0001
Child
2-Hydroxynaphthalene
(Mg/L)
24
-.044
1.15
.525
.500
.306
<.0001
<.0001
Child
3-Hydroxyfluorene (ng/L)
24
-.433
1.16
.287
.346
.421
0.0005
0.0002
Youth
1-Hydroxynaphthalene
(Mg/L)
27
-.596
1.48
.636
.587
.569
<.0001
<.0001
Youth
1-Hydroxyphenanthrene
(Mg/L)
27
-.236
1.31
.401
.479
.400
<.0001
<.0001
Youth
1-Hydroxypyrene(ng/L)
27
-.144
1.00
.284
.348
.324
<.0001
<.0001
48
-------
Age
Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Standard
Deviation
P-Value
oft
Statistic
P-Value
of
Signed
Rank
Test
Youth
2 & 3-
Hydroxyphenanthrene
(M-g/L)
27
-.330
1.20
.382
.449
.398
<.0001
<.0001
Youth
2-Hydroxyfluorene (ng/L)
27
-.400
1.44
.511
.523
.401
<.0001
<.0001
Youth
2-Hydroxynaphthalene
(M-g/L)
27
-.260
1.52
.484
.549
.466
<.0001
<.0001
Youth
3-Hydroxyfluorene (ng/L)
27
-.214
1.38
.498
.527
.439
<.0001
<.0001
Note: PAH = Polycyclic Aromatic Hydrocarbon.
49
-------
Table Sl-3. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by sex
P-Value
of
Signed
Standard
P-Value of
Rank
Sex
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
t Statistic
Test
Male
1-Hydroxynaphthalene
(M-g/L)
117
-2.32
2.32
.394
.479
.605
<.0001
<.0001
Male
1-Hydroxyphenanthrene
(M-g/L)
118
-.796
3.02
.437
.509
.503
<.0001
<.0001
Male
1-Hydroxypyrene (ng/L)
118
-1.86
2.61
.228
.288
.546
<.0001
<.0001
2 & 3-
Male
Hydroxyphenanthrene
(M-g/L)
118
-1.55
2.55
.376
.422
.470
<.0001
<.0001
Male
2-Hydroxyfluorene (ng/L)
118
-2.04
2.20
.394
.446
.502
<.0001
<.0001
Male
2-Hydroxynaphthalene
(Mg/L)
118
-2.45
3.13
.525
.569
.608
<.0001
<.0001
Male
3-Hydroxyfluorene (ng/L)
118
-1.66
2.52
.408
.451
.514
<.0001
<.0001
Female
1-Hydroxynaphthalene
(Mg/L)
43
-1.08
1.97
.648
.578
.706
<.0001
<.0001
Female
1-Hydroxyphenanthrene
(Mg/L)
43
-1.91
1.38
.401
.374
.568
<.0001
<.0001
Female
1-Hydroxypyrene (ng/L)
43
-1.20
1.37
.256
.212
.517
0.0103
0.0016
2 & 3-
Female
Hydroxyphenanthrene
(Mg/L)
43
-.822
1.28
.368
.377
.451
<.0001
<.0001
50
-------
P-Value
of
Signed
Standard P-Value of Rank
Sex Urinary PAH n Minimum Maximum Median Mean Deviation t Statistic Test
Female 2-Hydroxyfluorene (ng/L) 43 -.780 1.27 .395 .422 .456 <.0001 <.0001
Female 2-Hydroxynaphthalene 43 ^25g ?3g <0M1 <0(m
(Mg/L)
Female 3-Hydroxyfluorene (ng/L) 43 -.716 1.38 .515 .451 .538 <.0001 <.0001
Note: PAH = Polycyclic Aromatic Hydrocarbon.
51
-------
Table Sl-4. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by race
p-
Value
of
P-Value
Signed
Standard
oft
Rank
Race
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
White
1-Hydroxynaphthalene
(M-g/L)
101
-1.09
1.97
.429
.505
.603
<.0001
<.0001
White
1-Hydroxyphenanthrene
(M-g/L)
102
-.236
2.45
.399
.489
.446
<.0001
<.0001
White
1-Hydroxypyrene(ng/L)
102
-1.86
2.61
.227
.248
.502
<.0001
<.0001
2 & 3-
White
Hydroxyphenanthrene
(M-g/L)
102
-.539
2.55
.359
.424
.443
<.0001
<.0001
White
2-Hydroxyfluorene (ng/L)
102
-.518
2.20
.369
.452
.445
<.0001
<.0001
White
2-Hydroxynaphthalene
(Mg/L)
102
-.729
3.13
.539
.638
.629
<.0001
<.0001
White
3-Hydroxyfluorene (ng/L)
102
-.698
2.52
.365
.455
.474
<.0001
<.0001
Mixed,Other, Unknown
1-Hydroxynaphthalene
(Mg/L)
37
-.596
2.32
.510
.573
.597
<.0001
<.0001
Mixed,Other, Unknown
1-Hydroxyphenanthrene
(Mg/L)
37
-.351
3.02
.426
.463
.578
<.0001
<.0001
Mixed,Other, Unknown
1-Hydroxypyrene(ng/L)
37
-.948
2.05
.293
.360
.543
0.0003
<.0001
2 & 3-
Mixed,Other, Unknown
Hydroxyphenanthrene
(Mg/L)
37
-.330
1.57
.407
.412
.395
<.0001
<.0001
52
-------
P-
Value
of
P-Value
Signed
Standard
oft
Rank
Race
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Mixed,Other, Unknown
2-Hydroxyfluorene (ng/L)
37
-.400
1.72
.370
.425
.448
<.0001
<.0001
Mixed,Other, Unknown
2-Hydroxynaphthalene
(M-g/L)
37
-.509
2.76
.435
.525
.589
<.0001
<.0001
Mixed,Other, Unknown
3-Hydroxyfluorene (ng/L)
37
-.419
2.02
.405
.456
.540
<.0001
<.0001
Asian
1-Hydroxynaphthalene
(M-g/L)
22
-2.32
1.16
.628
.395
.819
0.0344
0.0083
Asian
1-Hydroxyphenanthrene
(M-g/L)
22
-1.91
1.28
.596
.414
.742
0.0160
0.0147
Asian
1-Hydroxypyrene(ng/L)
22
-1.20
1.45
.219
.207
.681
0.1683
0.0950
2 & 3-
Asian
Hydroxyphenanthrene
(Mg/L)
22
-1.55
1.14
.469
.341
.651
0.0228
0.0118
Asian
2-Hydroxyfluorene (ng/L)
22
-2.04
1.18
.648
.404
.725
0.0163
0.0034
Asian
2-Hydroxynaphthalene
(Mg/L)
22
-2.45
1.49
.800
.604
.813
0.0022
0.0006
Asian
3-Hydroxyfluorene (ng/L)
22
-1.66
1.29
.551
.422
.687
0.0089
0.0057
Note: PAH = Polycyclic Aromatic Hydrocarbon.
53
-------
Table Sl-5. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by field location
P-Value
of
P-Value
Signed
Standard
oft
Rank
U.S. Census Region
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
South
1-Hydroxynaphthalene
(Hg/L)
109
-2.32
1.91
.432
.484
.609
<.0001
<.0001
South
1-
Hydroxyphenanthrene
(Hg/L)
109
-.831
2.45
.442
.492
.479
<.0001
<.0001
South
1-Hydroxypyrene (ng/L)
109
-1.86
2.61
.232
.257
.550
<.0001
<.0001
2 & 3-
South
Hydroxyphenanthrene
(Hg/L)
109
-1.55
2.55
.378
.418
.472
<.0001
<.0001
South
2-Hydroxyfluorene
(Hg/L)
109
-2.04
2.20
.408
.446
.503
<.0001
<.0001
South
2-Hydroxynaphthalene
(Hg/L)
109
-2.45
3.13
.536
.561
.615
<.0001
<.0001
South
3-Hydroxyfluorene
(Hg/L)
109
-1.66
2.52
.472
.466
.516
<.0001
<.0001
West
1-Hydroxynaphthalene
(Hg/L)
51
-1.08
2.32
.448
.553
.685
<.0001
<.0001
West
1-
Hydroxyphenanthrene
(Hg/L)
52
-1.91
3.02
.399
.433
.608
<.0001
<.0001
West
1-Hydroxypyrene(ng/L)
52
-1.15
2.05
.230
.291
.515
0.0002
<.0001
54
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
U.S. Census Region
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
2 & 3-
West
Hydroxyphenanthrene
(Hg/L)
52
-.539
1.57
.365
.393
.452
<.0001
<.0001
West
2-Hydroxyfluorene
(Hg/L)
52
-.518
1.81
.368
.425
.463
<.0001
<.0001
West
2-Hydroxynaphthalene
(Hg/L)
52
-.729
2.76
.573
.704
.702
<.0001
<.0001
West
3-Hydroxyfluorene
(Hg/L)
52
-.698
1.92
.360
.419
.529
<.0001
<.0001
Note: PAH = Polycyclic Aromatic Hydrocarbon.
The U.S. census regions are four geographic groupings of states that subdivide the United States, including: Midwest (Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota,
Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin); Northeast (Connecticut, Maine, Massachusetts, New Hampshire, New Jersey, New York, Pennsylvania,
Rhode Island, and Vermont); South (Alabama, Arkansas, Delaware, District of Columbia, Florida, Georgia, Kentucky, Louisiana, Maryland, Mississippi, North Carolina, Oklahoma,
South Carolina, Tennessee, Texas, Virginia, and West Virginia); and West (Alaska, Arizona, California, Colorado, Hawaii, Idaho, Montana, Nevada, New Mexico, Oregon, Utah,
Washington, and Wyoming).
55
-------
Table Sl-6. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by facility
Facility
Urinary PAH
Minimum Maximum Median Mean
Standard
Deviation
P-Value
of
Signed
P-Value of Rank
t Statistic Test
Facility 1
1-Hydroxynaphthalene
(Hg/L)
68
-1.09
1.91
.431
.485
.604
<.0001
<.0001
Facility 1
1-Hydroxyphenanthrene
(Hg/L)
68
-.831
2.45
.455
.509
.493
<.0001
<.0001
Facility 1
1-Hydroxypyrene (ng/L)
68
-1.20
2.61
.228
.279
.553
<.0001
<.0001
Facility 1
2 & 3-
Hydroxyphenanthrene
(Hg/L)
68
-.822
2.55
.353
.431
.479
<.0001
<.0001
Facility 1
2-Hydroxyfluorene (ng/L)
68
-.780
2.20
.389
.452
.467
<.0001
<.0001
Facility 1
2-Hydroxynaphthalene
(Hg/L)
68
-.732
3.13
.487
.585
.599
<.0001
<.0001
Facility 1
3-Hydroxyfluorene (ng/L)
68
-.716
2.52
.430
.457
.500
<.0001
<.0001
Facility 2
1-Hydroxynaphthalene
(Hg/L)
41
-2.32
1.50
.453
.482
.624
<.0001
<.0001
Facility 2
1-Hydroxyphenanthrene
(Hg/L)
41
-.796
1.69
.437
.464
.459
<.0001
<.0001
Facility 2
1-Hydroxypyrene(ng/L)
41
-1.86
1.14
.233
.221
.551
0.0139
0.0004
Facility 2
2 & 3-
Hydroxyphenanthrene
(Hg/L)
41
-1.55
1.42
.395
.396
.465
<.0001
<.0001
56
-------
Facility
Urinary PAH
n Minimum Maximum Median Mean
Standard
Deviation
P-Value
of
Signed
P-Value of Rank
t Statistic Test
Facility 2
2-Hydroxyfluorene (ng/L)
41
-2.04
1.72
.452
.437
.563
<.0001
<.0001
Facility 2
2-Hydroxynaphthalene
(Hg/L)
41
-2.45
1.51
.586
.522
.646
<.0001
<.0001
Facility 2
3-Hydroxyfluorene (ng/L)
41
-1.66
2.02
.475
.481
.547
<.0001
<.0001
Facility 3
1-Hydroxynaphthalene
(Hg/L)
51
-1.08
2.32
.448
.553
.685
<.0001
<.0001
Facility 3
1-Hydroxyphenanthrene
(Hg/L)
52
-1.91
3.02
.399
.433
.608
<.0001
<.0001
Facility 3
1-Hydroxypyrene (ng/L)
52
-1.15
2.05
.230
.291
.515
0.0002
<.0001
2 & 3-
Facility 3
Hydroxyphenanthrene
(Hg/L)
52
-.539
1.57
.365
.393
.452
<.0001
<.0001
Facility 3
2-Hydroxyfluorene (ng/L)
52
-.518
1.81
.368
.425
.463
<.0001
<.0001
Facility 3
2-Hydroxynaphthalene
(Hg/L)
52
-.729
2.76
.573
.704
.702
<.0001
<.0001
Facility 3
3-Hydroxyfluorene (ng/L)
52
-.698
1.92
.360
.419
.529
<.0001
<.0001
Note: Facility 1 and Facility 3 consisted of outdoor, co-located fields (natural grass, synthetic turf with tire crumb rubber infill). Facility 2 consisted of an indoor, synthetic turf
field with tire crumb rubber infill.
PAH = Polycyclic Aromatic Hydrocarbon.
57
-------
Table Sl-7. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by BMI category
P-Value
of
Signed
BMI
Standard
P-Value of
Rank
Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
t Statistic
Test
Normal
1-Hydroxynaphthalene
(Hg/L)
101
-2.32
1.97
.453
.519
.687
<.0001
<.0001
Normal
1-Hydroxyphenanthrene
(Hg/L)
102
-1.91
2.45
.440
.462
.542
<.0001
<.0001
Normal
1-Hydroxypyrene(ng/L)
102
-1.86
2.61
.225
.227
.575
0.0001
<.0001
2 & 3-
Normal
Hydroxyphenanthrene
(Hg/L)
102
-1.55
2.55
.371
.394
.497
<.0001
<.0001
Normal
2-Hydroxyfluorene (ng/L)
102
-2.04
2.20
.402
.421
.514
<.0001
<.0001
Normal
2-Hydroxynaphthalene
(Hg/L)
102
-2.45
3.13
.582
.645
.696
<.0001
<.0001
Normal
3-Hydroxyfluorene (ng/L)
102
-1.66
2.52
.421
.427
.544
<.0001
<.0001
Obese
1-Hydroxynaphthalene
(Hg/L)
17
-.519
1.09
.346
.302
.465
0.0164
0.0305
Obese
1-Hydroxyphenanthrene
(Hg/L)
17
.020
1.29
.365
.440
.371
0.0002
<.0001
Obese
1-Hydroxypyrene(ng/L)
17
-.192
.952
.241
.272
.324
0.0032
0.0021
2 & 3-
Obese
Hydroxyphenanthrene
(Hg/L)
17
-.049
1.42
.362
.404
.365
0.0003
<.0001
58
-------
P-Value
of
Signed
BMI
Standard
P-Value of
Rank
Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
t Statistic
Test
Obese
2-Hydroxyfluorene (ng/L)
17
-.089
1.34
.370
.437
.381
0.0002
<.0001
Obese
2-Hydroxynaphthalene
(Hg/L)
17
-.729
1.40
.473
.510
.507
0.0008
0.0011
Obese
3-Hydroxyfluorene (ng/L)
17
-.162
1.28
.405
.436
.426
0.0006
0.0007
Overweight
1-Hydroxynaphthalene
(Hg/L)
33
-.634
2.32
.574
.560
.573
<.0001
<.0001
Overweight
1-Hydroxyphenanthrene
(kig/L)
33
-.351
3.02
.491
.547
.585
<.0001
<.0001
Overweight
1-Hydroxypyrene(ng/L)
33
-.571
2.05
.234
.405
.524
0.0001
<.0001
2 & 3-
Overweight
Hydroxyphenanthrene
(kig/L)
33
-.351
1.57
.407
.459
.404
<.0001
<.0001
Overweight
2-Hydroxyfluorene (ng/L)
33
-.157
1.72
.406
.495
.440
<.0001
<.0001
Overweight
2-Hydroxynaphthalene
(Hg/L)
33
-.509
2.76
.477
.590
.614
<.0001
<.0001
Overweight
3-Hydroxyfluorene (ng/L)
33
-.419
2.02
.472
.527
.521
<.0001
<.0001
Underweight
1-Hydroxynaphthalene
(Hg/L)
8
-.026
1.48
.501
.573
.468
0.0105
0.0156
Underweight
1-Hydroxyphenanthrene
(kig/L)
8
.054
.862
.328
.410
.301
0.0063
0.0078
Underweight
1-Hydroxypyrene(ng/L)
8
-.593
.944
.173
.207
.472
0.2548
0.1953
59
-------
P-Value
of
Signed
BMI Standard P-Value of Rank
Category Urinary PAH n Minimum Maximum Median Mean Deviation t Statistic Test
2 & 3-
Underweight Hydroxyphenanthrene 8 -.090 1.54 .273 .461 .533 0.0443 0.0234
(Hg/L)
Underweight 2-Hydroxyfluorene (ng/L) 8 -.103 1.81 .347 .522 .608 0.0455 0.0156
Underweight ^"V*oxynaphthalene g 07Q lu ^ 468 354 o.0073 0.0078
Underweight 3-Hydroxyfluorene (ng/L) 8 .048 1.16 .434 .503 .428 0.0127 0.0078
Unknown
1-Hydroxynaphthalene
(Hg/L)
.266
.266
.266
.266
N/A
N/A
1.0000
Unknown
1-Hydroxyphenanthrene
(Hg/L)
.210
.210
.210
.210
N/A
N/A
1.0000
Unknown
1-Hydroxypyrene (ng/L) 1
.330
.330
.330
.330
N/A
N/A
1.0000
Unknown
2 & 3-
Hydroxyphenanthrene 1
(Hg/L)
.057
.057
.057
.057
N/A
N/A
1.0000
Unknown
2-Hydroxyfluorene (ng/L) 1
-.139
-.139
-.139
-.139
N/A
N/A
1.0000
Unknown
2-Hydroxynaphthalene
(Hg/L)
.160
.160
.160
.160
N/A
N/A
1.0000
Unknown
3-Hydroxyfluorene (ng/L) 1
.226
.226
.226
.226
N/A
N/A
1.0000
Note: N/A = not applicable.
PAH = Polycyclic Aromatic Hydrocarbon.
BMI categories (underweight, normal, overweight, and obese) corresponded to cut points at <18.5, <25, <30, and >=30, respectively, for adults 20 years and older. CDC growth
charts were used to calculate BMI for participants <20 years old with cut points defined at BMI percentages (0,5), [5,85), [85,95), and 95+. Because age was only collected for
60
-------
whole years and age-in-months is required to properly use growth charts, BMI calculations for participants under 20 years old were subject to misclassification due to rounding.
See SAS Program for CDC Growth Charts. See: https://www.cdc.gov/nccdphp/dnpao/growthcharts/resources/sas.htm.
61
-------
Table Sl-8. Properties of differences in In-transformed pre- and post-activity body burden levels for Specific Gravity-adjusted
urinary PAHs, by activity
P-Value
of
P-Value
Signed
Standard
oft
Rank
Main Activity
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Soccer
1-Hydroxynaphthalene
(Hg/L)
118
-2.32
1.85
.494
.517
.599
<.0001
<.0001
Soccer
1-Hydroxyphenanthrene
(Hg/L)
119
-.831
2.45
.442
.449
.445
<.0001
<.0001
Soccer
1-Hydroxypyrene (ng/L)
119
-1.20
2.61
.234
.292
.494
<.0001
<.0001
2 & 3-
Soccer
Hydroxyphenanthrene
(Hg/L)
119
-1.55
2.55
.395
.412
.469
<.0001
<.0001
Soccer
2-Hydroxyfluorene (ng/L)
119
-2.04
2.20
.441
.454
.513
<.0001
<.0001
Soccer
2-Hydroxynaphthalene
(kig/L)
119
-2.45
3.13
.569
.624
.654
<.0001
<.0001
Soccer
3-Hydroxyfluorene (ng/L)
119
-1.66
2.52
.411
.453
.520
<.0001
<.0001
Lacrosse
1-Hydroxynaphthalene
(kig/L)
27
-1.09
1.91
.385
.503
.636
0.0004
0.0001
Lacrosse
1-Hydroxyphenanthrene
(kig/L)
27
-.072
1.69
.468
.588
.455
<.0001
<.0001
Lacrosse
1-Hydroxypyrene (ng/L)
27
-1.86
1.14
.137
.119
.565
0.2819
0.0929
2 & 3-
Lacrosse
Hydroxyphenanthrene
(kig/L)
27
-.030
1.42
.350
.423
.393
<.0001
<.0001
62
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
Main Activity
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Lacrosse
2-Hydroxyfluorene (ng/L)
27
-.134
1.37
.310
.423
.400
<.0001
<.0001
Lacrosse
2-Hydroxynaphthalene
(Hg/L)
27
-.239
1.51
.483
.555
.435
<.0001
<.0001
Lacrosse
3-Hydroxyfluorene (ng/L)
27
-.276
1.29
.377
.436
.455
<.0001
<.0001
Other
1-Hydroxynaphthalene
(M-g/L)
15
-1.02
2.32
.182
.422
.887
0.0864
0.0946
Other
1-Hydroxyphenanthrene
(M-g/L)
15
-1.91
3.02
.365
.454
1.02
0.1060
0.0181
Other
1-Hydroxypyrene (ng/L)
15
-1.15
2.05
.251
.346
.776
0.1060
0.0833
2 & 3-
Other
Hydroxyphenanthrene
(M-g/L)
15
-.433
1.57
.291
.364
.567
0.0261
0.0302
Other
2-Hydroxyfluorene (ng/L)
15
-.223
1.34
.385
.352
.457
0.0098
0.0151
Other
2-Hydroxynaphthalene
(Mg/L)
15
-.729
2.76
.470
.568
.894
0.0275
0.0215
Other
3-Hydroxyfluorene (ng/L)
15
-.661
1.92
.455
.462
.642
0.0146
0.0181
Note: PAH = Polycyclic Aromatic Hydrocarbon.
63
-------
Table S2-1. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by field environment
P-Value
of
P-Value
Signed
Field
Standard
oft
Rank
Environment
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Outdoor
1-Hydroxynaphthalene
(Hg/gCRE)
119
-2.11
2.35
-.006
.061
.593
0.2626
0.4553
Outdoor
1-Hydroxyphenanthrene
(|ag/gCRE)
120
-2.17
2.42
-.029
.025
.521
0.6038
0.8473
Outdoor
1-Hydroxypyrene
(Hg/gCRE)
120
-1.91
1.72
-.122
-.168
.596
0.0026
0.0020
2 & 3-
Outdoor
Hydroxyphenanthrene
(Hg/gCRE)
120
-1.69
1.90
-.087
-.037
.481
0.4029
0.1202
Outdoor
2-Hydroxyfluorene
(^g/gCRE)
120
-1.25
2.18
-.025
-.011
.427
0.7764
0.2220
Outdoor
2-Hydroxynaphthalene
(|ag/gCRE)
120
-1.21
2.75
.064
.185
.596
0.0009
0.0015
Outdoor
3-Hydroxyfluorene
(Hg/gCRE)
120
-1.37
2.24
-.043
-.011
.467
0.8014
0.3588
Indoor
1-Hydroxynaphthalene
(|ag/gCRE)
41
-1.30
1.38
-.066
.059
.538
0.4879
0.8040
Indoor
1-Hydroxyphenanthrene
(^g/gCRE)
41
-1.02
1.37
-.017
.041
.390
0.5062
0.9949
Indoor
1-Hydroxypyrene
(|ag/gCRE)
41
-3.47
1.22
-.169
-.202
.689
0.0681
0.0335
2 & 3-
Indoor
Hydroxyphenanthrene
(^g/gCRE)
41
-1.51
1.23
-.031
-.027
.473
0.7149
0.4868
64
-------
P-Value
of
P-Value
Signed
Field
Standard
oft
Rank
Environment
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Indoor
2-Hydroxyfluorene
(|ag/gCRE)
41
-1.13
1.64
-.020
.014
.545
0.8727
0.6329
Indoor
2-Hydroxynaphthalene
(Hg/gCRE)
41
-1.43
1.51
.114
.098
.533
0.2440
0.0722
Indoor
3-Hydroxyfluorene
(|ag/gCRE)
41
-.889
1.93
.031
.058
.527
0.4831
0.7455
Note: N/A = not applicable
65
-------
Table S2-2. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by age category
P-Value
of
P-Value
Signed
Standard
oft
Rank
Age Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Adolescent
1-Hydroxynaphthalene
(Hg/gCRE)
51
-1.06
2.35
.033
.177
.582
0.0348
0.1076
Adolescent
1-Hydroxyphenanthrene
(|ag/gCRE)
51
-1.09
2.42
.029
.152
.541
0.0502
0.1590
Adolescent
1-Hydroxypyrene
(Hg/gCRE)
51
-3.47
1.72
-.154
-.225
.802
0.0506
0.0379
2 & 3-
Adolescent
Hydroxyphenanthrene
(|ag/gCRE)
51
-1.69
1.90
-.061
.040
.601
0.6330
0.8898
Adolescent
2-Hydroxyfluorene
(^g/gCRE)
51
-1.13
2.18
-.020
.040
.543
0.5996
0.8607
Adolescent
2-Hydroxynaphthalene
(|ag/gCRE)
51
-.897
2.75
.091
.299
.697
0.0035
0.0012
Adolescent
3-Hydroxyfluorene
(Hg/gCRE)
51
-1.01
2.24
.023
.052
.575
0.5183
0.7959
Adult
1-Hydroxynaphthalene
(|ag/gCRE)
58
-1.30
1.38
-.067
.041
.589
0.6013
0.9178
Adult
1-Hydroxyphenanthrene
(^g/gCRE)
59
-2.17
2.07
-.045
-.058
.531
0.4083
0.1599
Adult
1-Hydroxypyrene
(|ag/gCRE)
59
-1.68
1.22
-.168
-.189
.549
0.0104
0.0126
2 & 3-
Adult
Hydroxyphenanthrene
(^g/gCRE)
59
-1.30
1.21
-.100
-.105
.387
0.0411
0.0180
66
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
Age Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Adult
2-Hydroxyfluorene
(|ag/gCRE)
59
-1.25
1.64
-.025
-.042
.438
0.4640
0.1395
Adult
2-Hydroxynaphthalene
(Hg/gCRE)
59
-1.43
2.59
.114
.140
.634
0.0953
0.0420
Adult
3-Hydroxyfluorene
(|ag/gCRE)
59
-1.19
1.93
-.014
-.001
.478
0.9854
0.7149
Child
1-Hydroxynaphthalene
(Hg/gCRE)
24
-2.11
.919
.006
-.156
.653
0.2525
0.6573
Child
1-Hydroxyphenanthrene
(|ag/gCRE)
24
-1.25
.956
-.058
.047
.428
0.5986
0.6573
Child
1-Hydroxypyrene
(^g/gCRE)
24
-1.75
1.08
-.074
-.056
.583
0.6420
0.5597
2 & 3-
Child
Hydroxyphenanthrene
(|ag/gCRE)
24
-1.57
1.28
-.050
.010
.543
0.9270
0.8464
Child
2-Hydroxyfluorene
(^g/gCRE)
24
-1.14
1.55
-.031
-.029
.494
0.7756
0.5597
Child
2-Hydroxynaphthalene
(|ag/gCRE)
24
-.900
.596
.053
.073
.330
0.2922
0.2156
Child
3-Hydroxyfluorene
(^g/gCRE)
24
-1.37
.906
-.106
-.082
.432
0.3636
0.2050
Youth
1-Hydroxynaphthalene
(|ag/gCRE)
27
-.500
1.05
-.030
.077
.426
0.3572
0.5581
Youth
1-Hydroxyphenanthrene
(^g/gCRE)
27
-.605
.452
-.041
-.031
.268
0.5567
0.5268
Youth
1-Hydroxypyrene
(|ag/gCRE)
27
-.964
.484
-.154
-.162
.357
0.0260
0.0276
67
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
Age Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
2 & 3-
Youth
Hydroxyphenanthrene
(Hg/gCRE)
27
-.730
.525
-.068
-.061
.295
0.2939
0.3841
Youth
2-Hydroxyfluorene
(|ag/gCRE)
27
-.518
.765
-.020
.013
.274
0.8023
0.7613
Youth
2-Hydroxynaphthalene
(Hg/gCRE)
27
-.464
.925
-.033
.039
.292
0.4939
0.7792
Youth
3-Hydroxyfluorene
(|ag/gCRE)
27
-.476
.788
-.022
.017
.329
0.7902
0.9070
68
-------
Table S2-3. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by sex
P-Value
of
P-Value
Signed
Standard
oft
Rank
Sex
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Male
1-Hydroxynaphthalene
(Hg/gCRE)
117
-1.98
1.38
-.040
.031
.515
0.5163
0.9860
Male
1-Hydroxyphenanthrene
(Hg/gCRE)
118
-1.09
2.07
-.004
.062
.418
0.1073
0.4189
Male
1-Hydroxypyrene
(Hg/gCRE)
118
-3.47
1.72
-.123
-.158
.622
0.0066
0.0023
2 & 3-
Male
Hydroxyphenanthrene
(Hg/gCRE)
118
-1.69
1.66
-.068
-.025
.449
0.5516
0.1982
Male
2-Hydroxyfluorene
(iJig/gCRE)
118
-1.13
1.64
-.020
-.001
.444
0.9819
0.3271
Male
2-Hydroxynaphthalene
(Hg/gCRE)
118
-1.43
2.59
.064
.123
.493
0.0078
0.0028
Male
3-Hydroxyfluorene
(IJig/gCRE)
118
-1.01
1.93
-.027
.004
.452
0.9190
0.3670
Female
1-Hydroxynaphthalene
(Hg/gCRE)
43
-2.11
2.35
.068
.141
.721
0.2071
0.1873
Female
1-Hydroxyphenanthrene
(IJig/gCRE)
43
-2.17
2.42
-.070
-.063
.644
0.5219
0.1360
Female
1-Hydroxypyrene
(Hg/gCRE)
43
-1.75
1.37
-.192
-.226
.616
0.0206
0.0270
2 & 3-
Female
Hydroxyphenanthrene
(IJig/gCRE)
43
-1.57
1.90
-.090
-.061
.551
0.4729
0.2460
69
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
Sex
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Female
2-Hydroxyfluorene
(Hg/gCRE)
43
-1.25
2.18
-.025
-.015
.502
0.8422
0.3913
Female
2-Hydroxynaphthalene
(Hg/gCRE)
43
-1.21
2.75
.207
.274
.768
0.0240
0.0262
Female
3-Hydroxyfluorene
(Hg/gCRE)
43
-1.37
2.24
.070
.014
.563
0.8716
0.7576
Note: PAH = Polycyclic Aromatic Hydrocarbon.
70
-------
Table S2-4. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by race
P-Value
of
P-Value
Signed
Standard
oft
Rank
Race
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
White
1-Hydroxynaphthalene
(Hg/L)
101
-2.11
2.35
-.011
.056
.580
0.3384
0.5391
White
1-Hydroxyphenanthrene
(Hg/L)
102
-1.25
2.42
-.026
.041
.432
0.3354
0.9775
White
1-Hydroxypyrene (ng/L)
102
-3.47
1.72
-.157
-.200
.601
0.0011
0.0004
2 & 3-
White
Hydroxyphenanthrene
(Hg/L)
102
-1.57
1.90
-.080
-.024
.480
0.6134
0.1316
White
2-Hydroxyfluorene (ng/L)
102
-1.14
2.18
-.016
.004
.448
0.9247
0.3533
White
2-Hydroxynaphthalene
(kig/L)
102
-1.04
2.75
.089
.190
.611
0.0022
0.0020
White
3-Hydroxyfluorene (ng/L)
102
-1.37
2.24
-.024
.007
.459
0.8734
0.6295
Mixed,Other, Unknown
1-Hydroxynaphthalene
(Hg/L)
37
-.445
1.38
.130
.249
.540
0.0080
0.0407
Mixed,Other, Unknown
1-Hydroxyphenanthrene
(kig/L)
37
-.840
2.07
-.008
.139
.521
0.1142
0.3528
Mixed,Other, Unknown
1-Hydroxypyrene (ng/L)
37
-1.91
1.37
-.010
.036
.597
0.7154
0.7844
2 & 3-
Mixed,Other, Unknown
Hydroxyphenanthrene
(kig/L)
37
-.747
1.21
.003
.088
.376
0.1642
0.4184
71
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
Race
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Mixed,Other, Unknown
2-Hydroxyfluorene (ng/L)
37
-.618
1.64
-.008
.101
.458
0.1868
0.7700
Mixed,Other, Unknown
2-Hydroxynaphthalene
(Hg/L)
37
-.594
1.81
.104
.201
.511
0.0222
0.0361
Mixed,Other, Unknown
3-Hydroxyfluorene (ng/L)
37
-.958
1.93
.047
.132
.542
0.1457
0.2539
Asian
1-Hydroxynaphthalene
(M-g/L)
22
-1.30
.686
-.102
-.234
.519
0.0471
0.0359
Asian
1-Hydroxyphenanthrene
(M-g/L)
22
-2.17
.559
-.077
-.214
.617
0.1182
0.1951
Asian
1-Hydroxypyrene (ng/L)
22
-1.78
.852
-.293
-.421
.653
0.0064
0.0034
2 & 3-
Asian
Hydroxyphenanthrene
(M-g/L)
22
-1.69
.541
-.202
-.287
.538
0.0205
0.0164
Asian
2-Hydroxyfluorene (ng/L)
22
-1.25
.489
-.082
-.225
.452
0.0295
0.0703
Asian
2-Hydroxynaphthalene
(Mg/L)
22
-1.43
1.05
-.010
-.024
.534
0.8338
0.7897
Asian
3-Hydroxyfluorene (ng/L)
22
-1.19
.496
-.106
-.206
.422
0.0322
0.0428
Note: PAH = Polycyclic Aromatic Hydrocarbon.
72
-------
Table S2-5. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by field location
P-Value
of
P-Value
Signed
Standard
oft
Rank
U.S. Census Region
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
South
1-Hydroxynaphthalene
(Hg/gCRE)
109
-1.98
2.35
-.041
.041
.571
0.4507
0.9749
South
1-
Hydroxyphenanthrene
(|ag/gCRE)
109
-1.30
2.42
-.005
.050
.471
0.2720
0.8160
South
1-Hydroxypyrene
(Hg/gCRE)
109
-3.47
1.72
-.167
-.185
.627
0.0026
0.0009
2 & 3-
South
Hydroxyphenanthrene
(Hg/gCRE)
109
-1.69
1.90
-.072
-.025
.497
0.6062
0.1429
South
2-Hydroxyfluorene
(Hg/gCRE)
109
-1.25
2.18
-.031
.004
.501
0.9315
0.2432
South
2-Hydroxynaphthalene
(|ag/gCRE)
109
-1.43
2.75
.056
.119
.576
0.0333
0.0289
South
3-Hydroxyfluorene
(Hg/gCRE)
109
-1.19
2.24
-.003
.024
.515
0.6259
0.9509
West
1-Hydroxynaphthalene
(|ag/gCRE)
51
-2.11
1.70
.053
.101
.594
0.2283
0.1706
West
1-
Hydroxyphenanthrene
(Hg/gCRE)
52
-2.17
2.07
-.041
-.015
.529
0.8380
0.5651
West
1-Hydroxypyrene
(|ag/gCRE)
52
-1.75
1.37
-.112
-.157
.607
0.0672
0.0586
73
-------
P-Value
of
P-Value
Signed
Standard
oft
Rank
U.S. Census Region
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
2 & 3-
West
Hydroxyphenanthrene
(Hg/gCRE)
52
-1.57
1.28
-.092
-.055
.437
0.3696
0.3212
West
2-Hydroxyfluorene
(|ag/gCRE)
52
-1.14
1.55
-.005
-.023
.356
0.6367
0.5292
West
2-Hydroxynaphthalene
(iJig/gCRE)
52
-.900
2.63
.139
.256
.585
0.0027
0.0008
West
3-Hydroxyfluorene
(|ag/gCRE)
52
-1.37
.971
-.066
-.029
.408
0.6057
0.3439
Note: PAH = Polycyclic Aromatic Hydrocarbon.
74
-------
Table S2-6. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by facility
Facility
Urinary PAH
Minimum Maximum Median Mean
Standard
Deviation
P-Value
of
Signed
P-Value of Rank
t Statistic Test
Facility 1
1-Hydroxynaphthalene
(Hg/gCRE)
68
-1.98
2.35
-.041
.031
.594
0.6692
0.8895
Facility 1
1-Hydroxyphenanthrene
(|ag/gCRE)
68
-1.30
2.42
.000
.055
.516
0.3811
0.8514
Facility 1
1-Hydroxypyrene (ng/gCRE)
68
-1.91
1.72
-.154
-.175
.592
0.0172
0.0132
2 & 3-
Facility 1
Hydroxyphenanthrene
(|ag/gCRE)
68
-1.69
1.90
-.083
-.023
.515
0.7126
0.1869
Facility 1
2-Hydroxyfluorene
(Hg/gCRE)
68
-1.25
2.18
-.038
-.002
.477
0.9774
0.2511
Facility 1
2-Hydroxynaphthalene
(|ag/gCRE)
68
-1.21
2.75
.020
.131
.604
0.0774
0.2150
Facility 1
3-Hydroxyfluorene
(Hg/gCRE)
68
-1.19
2.24
-.024
.003
.510
0.9551
0.6943
Facility 2
1-Hydroxynaphthalene
(|ag/gCRE)
41
-1.30
1.38
-.066
.059
.538
0.4879
0.8040
Facility 2
1-Hydroxyphenanthrene
(Hg/gCRE)
41
-1.02
1.37
-.017
.041
.390
0.5062
0.9949
Facility 2
1-Hydroxypyrene (ng/gCRE)
41
-3.47
1.22
-.169
-.202
.689
0.0681
0.0335
2 & 3-
Facility 2
Hydroxyphenanthrene
(Hg/gCRE)
41
-1.51
1.23
-.031
-.027
.473
0.7149
0.4868
75
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P-Value
of
Signed
Standard
P-Value of
Rank
Facility
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
t Statistic
Test
Facility 2
2-Hydroxyfluorene
(|ag/gCRE)
41
-1.13
1.64
-.020
.014
.545
0.8727
0.6329
Facility 2
2-Hydroxynaphthalene
(Hg/gCRE)
41
-1.43
1.51
.114
.098
.533
0.2440
0.0722
Facility 2
3-Hydroxyfluorene
(|ag/gCRE)
41
-.889
1.93
.031
.058
.527
0.4831
0.7455
Facility 3
1-Hydroxynaphthalene
(Hg/gCRE)
51
-2.11
1.70
.053
.101
.594
0.2283
0.1706
Facility 3
1-Hydroxyphenanthrene
(Hg/gCRE)
52
-2.17
2.07
-.041
-.015
.529
0.8380
0.5651
Facility 3
1-Hydroxypyrene (ng/gCRE)
52
-1.75
1.37
-.112
-.157
.607
0.0672
0.0586
2 & 3-
Facility 3
Hydroxyphenanthrene
(|ag/gCRE)
52
-1.57
1.28
-.092
-.055
.437
0.3696
0.3212
Facility 3
2-Hydroxyfluorene
(Hg/gCRE)
52
-1.14
1.55
-.005
-.023
.356
0.6367
0.5292
Facility 3
2-Hydroxynaphthalene
(|ag/gCRE)
52
-.900
2.63
.139
.256
.585
0.0027
0.0008
Facility 3
3-Hydroxyfluorene
(Hg/gCRE)
52
-1.37
.971
-.066
-.029
.408
0.6057
0.3439
Note: Facility 1 and Facility 3 consisted of outdoor, co-located fields (natural grass, synthetic turf with tire crumb rubber infill). Facility 2 consisted of an indoor, synthetic turf
field with tire crumb rubber infill.
PAH = Polycyclic Aromatic Hydrocarbon.
76
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Table S2-7. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by BMI category
P-Value
of
P-Value
Signed
Standard
oft
Rank
BMI Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Normal
1-Hydroxynaphthalene
(Hg/gCRE)
101
-2.11
2.35
.017
.067
.628
0.2847
0.3111
Normal
1-Hydroxyphenanthrene
(Hg/gCRE)
102
-2.17
2.42
-.020
.012
.508
0.8159
0.8489
Normal
1-Hydroxypyrene
(Hg/gCRE)
102
-3.47
1.72
-.138
-.223
.665
0.0010
0.0010
2 & 3-
Normal
Hydroxyphenanthrene
(Hg/gCRE)
102
-1.69
1.90
-.072
-.056
.503
0.2648
0.1248
Normal
2-Hydroxyfluorene
(iJig/gCRE)
102
-1.25
2.18
-.017
-.029
.451
0.5140
0.3309
Normal
2-Hydroxynaphthalene
(Hg/gCRE)
102
-1.43
2.75
.120
.195
.643
0.0029
0.0001
Normal
3-Hydroxyfluorene
(Hg/gCRE)
102
-1.37
2.24
.007
-.023
.479
0.6247
0.5831
Obese
1-Hydroxynaphthalene
(Hg/gCRE)
17
-1.06
1.15
-.205
-.074
.502
0.5509
0.3289
Obese
1-Hydroxyphenanthrene
(IJig/gCRE)
17
-.453
1.09
-.003
.063
.360
0.4800
1.0000
Obese
1-Hydroxypyrene
(Hg/gCRE)
17
-1.16
.756
-.168
-.104
.527
0.4266
0.6112
2 & 3-
Obese
Hydroxyphenanthrene
(IJig/gCRE)
17
-.802
1.23
-.115
.027
.435
0.8018
0.8900
77
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P-Value
of
P-Value
Signed
Standard
oft
Rank
BMI Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Obese
2-Hydroxyfluorene
(Hg/gCRE)
17
-.354
1.15
-.020
.060
.393
0.5358
0.8176
Obese
2-Hydroxynaphthalene
(Hg/gCRE)
17
-.545
1.20
.022
.133
.434
0.2237
0.4874
Obese
3-Hydroxyfluorene
(Hg/gCRE)
17
-.461
1.08
-.026
.060
.393
0.5409
0.7819
Overweight
1-Hydroxynaphthalene
(Hg/gCRE)
33
-.921
1.38
-.028
.101
.507
0.2618
0.7202
Overweight
1-Hydroxyphenanthrene
(Hg/gCRE)
33
-.840
2.07
-.030
.088
.542
0.3596
0.9930
Overweight
1-Hydroxypyrene
(iJig/gCRE)
33
-1.11
1.37
-.119
-.055
.552
0.5724
0.1873
2 & 3-
Overweight
Hydroxyphenanthrene
(Hg/gCRE)
33
-.747
1.21
-.031
-.001
.416
0.9904
0.7202
Overweight
2-Hydroxyfluorene
(IJig/gCRE)
33
-.696
1.64
-.031
.035
.480
0.6770
0.5936
Overweight
2-Hydroxynaphthalene
(Hg/gCRE)
33
-.594
1.81
.030
.130
.511
0.1529
0.4144
Overweight
3-Hydroxyfluorene
(IJig/gCRE)
33
-.958
1.93
-.067
.067
.552
0.4882
0.9791
Underweight
1-Hydroxynaphthalene
(Hg/gCRE)
8
-.413
.656
.165
.128
.348
0.3335
0.4609
Underweight
1-Hydroxyphenanthrene
(IJig/gCRE)
8
-.239
.604
-.147
-.035
.286
0.7399
0.3828
Underweight
1-Hydroxypyrene
(Hg/gCRE)
8
-.974
.686
-.357
-.238
.476
0.2004
0.1953
78
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BMI Category
Urinary PAH
n
Minimum
Maximum
Median
Mean
Standard
Deviation
P-Value
oft
Statistic
P-Value
of
Signed
Rank
Test
Underweight
2 & 3-
Hydroxyphenanthrene
(Hg/gCRE)
8
-.373
1.28
-.182
.016
.543
0.9359
0.5469
Underweight
2-Hydroxyfluorene
(|ag/gCRE)
8
-.386
1.55
-.100
.077
.621
0.7348
0.5469
Underweight
2-Hydroxynaphthalene
(Hg/gCRE)
8
-.214
.314
-.046
.023
.200
0.7596
0.8438
Underweight
3-Hydroxyfluorene
(|ag/gCRE)
8
-.445
.906
.068
.058
.447
0.7245
1.0000
Unknown
1-Hydroxynaphthalene
(^g/gCRE)
1
-.188
-.188
-.188
.188
N/A
N/A
1.0000
Unknown
1-Hydroxyphenanthrene
(|ag/gCRE)
1
-.244
-.244
-.244
.244
N/A
N/A
1.0000
Unknown
1-Hydroxypyrene
(Hg/gCRE)
1
-.124
-.124
-.124
.124
N/A
N/A
1.0000
Unknown
2 & 3-
Hydroxyphenanthrene
(|ag/gCRE)
1
-.398
-.398
-.398
.398
N/A
N/A
1.0000
Unknown
2-Hydroxyfluorene
(Hg/gCRE)
1
-.594
-.594
-.594
.594
N/A
N/A
1.0000
Unknown
2-Hydroxynaphthalene
(|ag/gCRE)
1
-.295
-.295
-.295
.295
N/A
N/A
1.0000
Unknown
3-Hydroxyfluorene
(^g/gCRE)
1
-.229
-.229
-.229
.229
N/A
N/A
1.0000
Note: N/A = not applicable.
PAH = Polycyclic Aromatic Hydrocarbon.
79
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Table S2-8. Properties of differences in In-transformed pre- and post-activity body burden levels for Creatinine-adjusted urinary
PAHs, by activity
P-Value of
Standard
P-Value oft
Signed Rank
Main Activity
Urinary PAH
n
Minimum
Maximum
Median
Mean
Deviation
Statistic
Test
Soccer
1-
Hydroxynaphthalene
(Hg/gCRE)
118
-2.11
2.35
.006
.076
.567
0.1465
0.2606
Soccer
1-
Hydroxyphenanthrene
(Hg/gCRE)
119
-1.30
2.42
-.029
.010
.449
0.8081
0.6655
Soccer
1-Hydroxypyrene
(Hg/gCRE)
119
-1.91
1.72
-.121
-.148
.551
0.0042
0.0027
2 & 3-
Soccer
Hydroxyphenanthrene
(Hg/gCRE)
119
-1.69
1.90
-.068
-.027
.484
0.5462
0.2660
Soccer
2-Hydroxyfluorene
(iJig/gCRE)
119
-1.25
2.18
-.019
.015
.480
0.7373
0.4569
Soccer
2-
Hydroxynaphthalene
(Hg/gCRE)
119
-1.43
2.75
.104
.185
.604
0.0011
0.0002
Soccer
3-Hydroxyfluorene
(IJig/gCRE)
119
-1.37
2.24
-.026
.014
.489
0.7635
0.5372
Lacrosse
1-
Hydroxynaphthalene
(Hg/gCRE)
27
-1.98
1.18
-.107
-.024
.572
0.8267
0.7613
Lacrosse
1-
Hydroxyphenanthrene
(IJig/gCRE)
27
-.464
1.09
-.005
.060
.355
0.3872
0.7972
Lacrosse
1-Hydroxypyrene
(Hg/gCRE)
27
-3.47
.756
-.345
-.408
.763
0.0100
0.0016
80
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Main Activity
Urinary PAH
n
Standard
Minimum Maximum Median Mean Deviation
P-Value oft
Statistic
P-Value of
Signed Rank
Test
2&3-
Lacrosse Hydroxyphenanthrene 27 -1.51 1.23 -.062 -.104 .469 0.2588 0.0630
(Hg/gCRE)
Lacrosse
2-Hydroxyfluorene
(|ag/gCRE)
27
-1.13
1.15
-.088
-.105
.440
0.2269
0.1087
Lacrosse
2-
Hydroxynaphthalene
(Hg/gCRE)
27
-.897
1.20
.056
.028
.401
0.7209
0.7972
Lacrosse
3-Hydroxyfluorene
(Hg/gCRE)
27
-.895
1.08
-.066
-.091
.438
0.2905
0.3340
Other
1-
Hydroxynaphthalene
(Hg/gCRE)
15
-1.29
1.37
-.068
.090
.692
0.6223
0.9341
Other
1-
Hydroxyphenanthrene
(|ag/gCRE)
15
-2.17
2.07
.005
.122
.893
0.6048
0.7197
Other
1-Hydroxypyrene
(Hg/gCRE)
15
-1.42
1.37
-.024
.014
.766
0.9450
0.9780
2 & 3-
Other
Hydroxyphenanthrene
(|ag/gCRE)
15
-.697
.892
-.117
.032
.453
0.7911
0.9780
Other
2-Hydroxyfluorene
(Hg/gCRE)
15
-.413
.541
.009
.020
.279
0.7864
0.9341
Other
2-
Hydroxynaphthalene
(|ag/gCRE)
15
-.545
1.81
.011
.236
.661
0.1891
0.4543
Other
3-Hydroxyfluorene
(Hg/gCRE)
15
-.924
.971
.099
.130
.497
0.3288
0.3591
Note: PAH = Polycyclic Aromatic Hydrocarbon.
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Table S3. Comparison of creatinine-adjusted urinary PAH concentrations, NHANES 2015—2016 and 2007—2008
Urinary PAH
NHANES 2007-2008
n
NHANES 2007-2008
geometric mean
(95% CI)
NHANES 2015-2016
n
NHANES 2015-2016
geometric mean
(95% CI)
1-Hydroxynaphthalene
(Hg/gCRE)
2395
2.61 (2.20-3.08)
2318
1.69 (1.50-1.91)
1-Hydroxyphenanthrene
(|ag/gCRE)
2503
.140 (.130-151)
2426
.115 (.106-.125)
1-Hydroxypyrene
(Hg/gCRE)
2476
.118 (.108-.128)
2424
.133 (.125-.141)
2 & 3-Hydroxyphenanthrene
(Hg/gCRE)
N/A
N/A
2424
.134 (.123-.146)
2-Hydroxyfluorene (ng/gCRE)
2477
.304 (.272-.341)
2425
.211 (.191-.232)
2-Hydroxynaphthalene
(|ag/gCRE)
2431
3.88(3.45-4.36)
2374
5.350 (4.86-5.90)
3-Hydroxyfluorene (ng/gCRE)
2479
.118 (.104-.133)
2421
.093 (.083-.105)
Note: N/A = not applicable.
PAH = Polycyclic Aromatic Hydrocarbon.
2&3-Hydroxyphenanthrene was not assessed in NHANES 2007-2008.
82
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Appendix B
Quality Assurance and Quality Control
89
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B.1 Quality Overview and Planning
Appendix B does not describe quality assurance/quality control (QA/QC) activities and results for the
biomonitoring portions of the exposure characterization pilot study. Appendix B describes only those
QA/QC documentation, procedures, and results for EPA-led activities. Biomonitoring QA/QC
procedures and results are described in Appendix A.
The U.S. Environmental Protection Agency (EPA) requires that all data collected for the
characterization of environmental processes and conditions are of the appropriate type and quality for
their intended use. This is accomplished through an EPA-wide quality system for environmental data.
Components of the EPA quality system can be found at http://www.epa.gov/quality/. EPA policy is
based on ANSI/ASQ E4-2004 (an American National Standard). This standard recommends a tiered
approach that includes the development and use of Quality Management Plans (QMPs). The
organizational units in EPA that generate and/or use environmental data are required to have EPA-
approved QMPs. Programmatic QMPs may also be written when program managers and their QA staff
decide a program is of sufficient complexity to benefit from a QMP.
A programmatic QMP was developed for the research conducted under the Federal Research Action
Plan on Recycled Tire Crumb Used on Playing Fields and Playgrounds, described here as the Tire
Crumb Research Study (TCRS). The TCRS QMP describes the program's organizational structure,
defines and assigns QA and QC responsibilities, and describes the processes and procedures used to
plan, implement and assess the effectiveness of the quality system. The TCRS QMP is supported by
project-specific QA project plans (QAPPs).
The TCRS QAPPs provide the technical details and associated QA/QC procedures for the research
activities that address TCRS objectives as described in the TCRS Research Protocol, "Collections
Related to Synthetic Turf Fields with Crumb Rubber Infill." Written sample collection and analysis
research-level standard operating procedures (SOPs) were also prepared to support the QAPPs, when
appropriate.
The following elements were critical for producing high-quality research results:
• Research projects comply with Agency requirements and guidance for QAPPs, including the
use of systematic planning;
• Technical system audits (TSAs) and data quality reviews, as described in the QMP or project-
specific QAPPs;
• QA review of all products that include environmental data; and
• Inclusion of a QA/QC section in the final study report.
This research was supported by a Program QA Manager (PQAM) who was independent of the technical
work and who assisted the QA staff in the implementation of the TCRS quality program and QMP
requirements. Requirements specified in the TCRS QMP and QAPPs were intended to ensure
consistency in the QA approach for all participating organizations.
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B.2 Quality Assurance Activities and Results
B.2.1 Quality Assurance Project Plans
As part of the QA processes implemented in this research study, QAPPs were prepared by research staff
for several components of the TCRS, including the Literature Review/Gaps Analysis and the tire crumb
rubber characterization, and the exposure characterization. QAPPs were reviewed and approved by the
respective research staff supervisors and QAMs. QAPPs (or QAPP addendums) prepared for the tire
crumb characterization portion of the study were described in the Part 1 Report (EPA/600/R-19/051).
One QAPP and two QAPP addendums were prepared for the TCRS exposure characterization pilot
study (Table B-l) and related activity assessment research.
Table B-l. Quality Assurance Project Plans (QAPPs) and Addendums for Exposure Characterization
#
QAPP Title
Approval Date
1
Activity Characterization for the Tire Crumb Research Study
June 2016
2
QAPP Addendum for the Tire Crumb Research Study -Exposure
Characterization Pilot Study
August 2017
3
QAPP Addendum for the Tire Crumb Research Study Exposure
Characterization Pilot Study Procedures for Exposure Pathway Modeling
March 2018
B.2.2 Standard Operating Procedures
Research-level SOPs were developed for all sample collection, data collection and sample analysis
activities. Prior to undertaking the activities covered by a SOP, the SOP was reviewed and approved by
the respective research staff supervisors and QAMs. Research-level SOPs developed or applied in the
exposure characterization pilot study are provided in Appendix C.
B.2.3 Technical Systems Audits
The EPA Office of Research and Development (ORD) quality program requires at least one audit be
conducted per project, at a minimum. However, due to the high visibility and multi-component nature of
the TCRS, a robust quality review process (including technical system audits and data quality reviews)
was implemented to identify and correct issues immediately. Several audits for tire crumb sample
collection and sample analysis activities were previously described in the Part 1 Report (U.S. EPA &
CDC/ATSDR, 2019). Additional technical system audits (TSAs) were conducted on exposure pilot
study field sampling and for the publicly-available videography data compilation. The purpose of each
audit was to ensure that the research tasks prescribed within the QAPPs or SOPs were verified and
documented. These audits are summarized in Table B-2. No significant findings were identified
during the audits, and minor findings that were identified did not directly affect the integrity or
quality of the data.
B.2.4 Deviations from the QAPPs or SOPs
There were no significant deviations from the QAPP addendums listed in Table B-l. Deviations from
SOPs identified during field or laboratory activities were documented and confirmed, if applicable,
during field or laboratory audits. All SOPs unique to this project that deviated from the original
procedure were amended and, if needed, reviewed by the QAM and approved by the analyst's
supervisor. Minor changes such as mislabeled sampling containers, contaminated sampling tools or
issues identified in the field related to specific samples or information collection were documented on
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the TCRS field forms and chain of custody.
93
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Table B-2. Tire Crumb Research Study Exposure Characterization Technical System Auditsa'b
Date
Target
Description
Interviewed
Auditor
09/25 -
27/2017
Exposure
Characterization Field
Sampling and
Monitoring
TSA of field data collection activities and adherence to planned activities was
conducted at a one exposure pilot study location. In addition, data extraction
activities taken from videos recorded during the field collection at this location was
conducted upon return to the RTP EPA NERL laboratory by JTI. This TSA was
extended to assess if JTI followed the approved SOP for Videography of Activity
Characterization Study Participants. No corrective actions were deemed necessary
and no findings were identified.
Kent Thomas, Matt
Allen, team lead for
JTI and team
members which
included Denise
Popeo-Murphy,
Patrick Lawler, and
Guy Fazzio
Christine Alvarez
12/06/2016
Videography and
Surveys
Onsite TSA was conducted at the NERL laboratory, RTP office to assess QA/QC
procedures specified in the SOP for Collecting and Using Extant Publicly Available
Video. Coding of the extant videography data had not been performed prior or
during the audit, therefore, only those activities involving collection and handling
of videography files could be assessed. Findings included lack of research
notebooks to document daily activities. Corrective action was issued to the group
coding the collected data and to the task lead.
Marsha Morgan
Brittany Stuart,
Christine Alvarez
reviewed the
research notebook
after completion
of audit
a All documentation associated with these audits including audit reports, corrective actions and email correspondence is documented and saved in the TCRS QA
SharePoint, https://usepa.sharepoint.com/sites/ORD Work/TCRS%20OA/SitePages/Home.aspx
b TSA = technical system audit; TCRS = Tire Crumb Research Study; QAPP = quality assurance project plan; SOP = standard operating procedure; RTP = Research
Triangle Park; EPA = U.S. Enviromnental Protection Agency; NERL = National Exposure Research Laboratory; JTI = Jacobs Technology, Incorporated; QA = quality
assurance; QC = quality control
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B.2.5 Data Quality Reviews
Reviews of data quality were performed at several stages throughout the course of the research study
(Table B-3). Data produced through field sample collection, data collection and sample analysis
received data quality reviews by QAMs and/or secondary technical expert reviewers. Reviews were
performed after data were produced and before they were submitted for data processing or included in
data analysis.
Much of the analytical chemistry measurement data for the exposure characterization pilot study was
compiled, standardized and processed by data managers to prepare data analysis files. Data quality
reviews were performed to verify that the data in the data analysis files were correct and complete and
that all processing calculations were performed correctly.
Using the data analysis files, data were organized to prepare outputs for reporting, such as tables and
figures. Statistical summaries of the data were prepared and in some cases, statistical testing was
performed. Data quality reviews were performed to ensure that the data analysis outputs were complete
and correct and that data calculations and analyses were performed correctly.
Finally, multiple data quality reviews were performed to verify that the outputs from the data analyses
were correctly and completely compiled in report tables and figures. This set of data quality reviews is
depicted in the Table B-3, but does not quantify the number of reviews completed for data compilation
and analysis.
Table B-3. Data Quality Reviews of Tire Crumb Exposure Characterizationa b
Data/Information Type
Technical Lead
Reviewer
Completion Date
Field Data
Kent Thomas
Margie Vazquez
02/09/2018
Metals ICP/MS Digests
Kasey Kovalcik
Clay Nelson
02/26/2018
SVOC GC/MS/MS
Scott Clifton/Dawn Mills
Elin Ulrich
01/25/2018, 02/13/2018
SVOC LC/MS
Larry McMillan, Elin Ulrich
Jim Starr
02/14/2018, 02/27/2018
VOC TOFMS
Don Whitaker
Christine Alvarez and Rachel
Porter
Final date: 03/08/2018
Filter Weighing
Chen Fu-Lin
Kent Thomas, Rachel Porter,
Christine Alvarez check
01/24/2018
Characterization and
Videography Summary
Jacobs Technology
Incorporated
Marsha Morgan/Christine
Alvarez
10/2017 and 12/2017
a ICP/MS = inductively coupled plasma/mass spectrometry; SVOC = semivolatile organic compound; GC/MS/MS = gas
chromatography/tandem mass spectrometry; GC/MS = gas chromatography/mass spectrometry; LC/MS = liquid
chromatography/mass spectrometry; VOC = volatile organic compound; TOFMS = time of flight mass spectrometry
b Errors or issues identified during data quality reviews (e.g., transcription errors) are documented on the TCRS QA
SharePoint, https://usepa.sharepoint.com/sites/ORD Work/TCRS%20QA/SitePages/Home.aspx
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B.3 Quality Control Overview
Numerous quality control activities and analyses were performed over the course of the study and
included, but were not limited to the following:
• Sample collection media and sample containers were pre-cleaned or purchased as certifiably
clean, when appropriate;
• Whenever possible, media were evaluated prior to field deployment to ensure minimal
background or interferences, and blank media were analyzed to assess potential background
contamination;
• Chain of custody procedures were implemented for all samples;
• Field quality control samples, consisting of blank, spike, and duplicate samples, were taken
when applicable; location-specific field blanks were taken to and handled in the field in the
same manner as samples, including opening and closing of containers, where appropriate;
• Laboratory quality control samples were applied, as appropriate, for each analysis method and
included one or more of the following: procedure or method blanks and spikes, matrix blanks
and spikes where feasible, and replicate sample analysis;
• Reference standards were obtained from reputable and traceable sources, where available;
• Solvents used for device cleaning, media preparation, or sample extraction were HPLC-grade or
better in purity;
• Appropriate methods were used to determine analytical detection or quantifiable limits and to
quantify target chemical amounts in samples;
• Blank and recovery correction were applied, as appropriate;
• Research notebooks were maintained.
Key quality control measures and their results are reported in this Appendix, including:
• Completeness: a measure of the amount of verified data obtained from a measurement system
compared to the amount of data that was expected to be obtained under normal conditions.
• Quantification Limits: the lowest concentration or amount of analyte that can be measured in an
analytical method to a known and acceptable degree of confidence and precision. This is
determined in a manner that is appropriate and applicable for each type of measurement.
• Background: the amount of analyte or signal present that was not associated with the sample
and can interfere with or inflate measurement results. Background is assessed by using unspiked
field and/or laboratory media and analyses.
• Precision: a measure of mutual agreement among individual measurements of the same
property, usually under prescribed similar conditions. Precision is best expressed in terms of the
standard deviation.
• Accuracy: the degree of agreement of measurements (or an average of measurements) with an
accepted reference or true value. Accuracy is a measure of the bias or systematic error in a
system and was assessed by measuring recovery of target analytes through laboratory analysis
and where applicable, through combined field and laboratory conditions and procedures.
Each of these general quality criteria and the process by which they were addressed were not universal
throughout the study. Each analyst's task and characterization process could differ substantially;
therefore, it was impossible to have a single standard operating procedure or consistent approach for
addressing or validating all methods used in tire crumb rubber characterization and exposure
96
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measurement analysis. This Appendix describes how each method addressed the general quality control
measures described above.
Each analytical method had its own set of quality control measures appropriate for that method. In
addition to the assessments listed above, the SOPs for the sample collection and sample analysis
methods described quality control elements that were implemented for each method. Not all quality
control procedures and results are reported here. For example, calibration procedures and acceptance
criteria, mass spectrometer tuning check procedures, and other quality-related activities related to
quantitative analysis were described in the quantitative analysis SOPs. Quality control procedures for
field sample collection and analysis were also described in their respective SOPs.
£3.3.7 Exposure Characterization Pilot Study
The exposure characterization pilot study included several types of quality control samples for each field
and lab medium that was sampled (Tables B-4 and B-5, respectively). Field blanks were used to assess
potential contamination or background. Where applicable, the field blanks (e.g., dermal wipes and field
wipes) were handled at the field site in the same way the samples were handled to account for any
potential contamination during handling (e.g., chemical transfer from gloves). Spiked field controls were
deployed where possible to assess overall analyte recovery through the field condition, transport,
storage, and analysis activities. Duplicate samples were collected when possible to assess overall
measurement precision. Laboratory blanks and laboratory spiked controls were prepared to assess
background and recovery for media not deployed to the field sites.
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Table B-4. Number and Types of Field Quality Control Samples for Exposure Field Study8
Sample Type
Analytes
First Field
Sampled -
Field Blanks
(# per field)
First Field
Sampled - Spiked
Field Control
(# per field)
First Field
Sampled -
Co-located
Duplicate Sample
(# per field)
Remaining
Fields -
Field Blanks
(# per field)
Remaining
Fields - Spiked
Field Control
(# per field)
Remaining
Fields -
Co-located
Duplicate Sample
(# per field)
Personal Samples
Airb VOCs
0
0
0
0
0
0
Personal Samples
Dermal SVOCs
2
2
0
1
1
0
Personal Samples
Dermal Metals
2
2
0
1
1
0
Field Air
VOCs (passive)
2
2
1
1
1
1
Field Air
VOCs (active)
2
2
1
1
1
1
Field Air
SVOCs
2
2
1
1
1
1
Field Air
Particulates/Metals
2
0
1
1
1
Field Drag Sled
SVOCs
2
2
1
1
1
1
Field Surface Wipe
SVOCs
2
2
1
1
1
1
Field Surface Wipe
Metals
2
2
1
1
1
1
Field Dust
SVOCs
2
0
0
1
0
1
Field Dust
Metals
2
0
0
1
0
1
a VOC = volatile organic compound; SVOC = semivolatile organic compound
b QC samples for personal air VOCs are covered in the passive facility air VOC collection since they use the same sampler
98
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Table B-5. Number and Types of Laboratory Quality Control Samples8
Sample Type
Analytes
First Field
Sampled -
Lab Blank
(# per field)
First Field
Sampled - Spiked
Lab Control
(# per field)
First Field
Sampled
1 ah Replicateb
(# per field)
Remaining
Fields -
Lab Blank
(# per field)
Remaining
Fields - Spiked
Lab Control
(# per field)
Remaining
Fields - Lab
Replicateb
(# per field)
Personal Samples
Air0 VOCs
0
0
0
0
0
0
Personal Samples
Dermal SVOCs
2
2
2
1
1
1
Personal Samples
Dermal Metals
2
2
2
1
1
1
Field Air
VOCs (passive)
2
2
0
1
1
0
Field Air
VOCs (active)
2
2
0
1
1
0
Field Air
SVOCs
2
2
2
1
1
1
Field Air
Particulates/Metals
2
0
2
1
1
1
Field Drag Sled
SVOCs
2
2
2
1
1
1
Field Surface Wipe
SVOCs
2
2
2
1
1
1
Field Surface Wipe
Metals
2
2
2
1
1
1
Field Dust
SVOCs
2
2
1
1
1
1
Field Dust
Metals
2
2
1
1
1
1
a VOC = volatile organic compound; SVOC = semivolatile organic compound
b Replicate analysis of sample extract
0 QC samples for personal air VOCs are covered in the passive facility air VOC collection since they use the same sampler
99
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Overall project-level DQI are listed in Table B-6. Because there are no standard methods for sample
collection and analysis procedures for measuring environmental and personal exposures at synthetic turf
fields, the DQI target values developed for exposure characterization were considered to be objectives
and were assessed as the work proceeded and following work completion. Additional data quality
indicators were described, where applicable, in the technical SOPs for each experimental or analytical
method.
Table B-6. Target Exposure Characterization Pilot Study Quantitative Data Quality Indicator Objectivesab
Metric
Precision
(%)
Accuracy (%)
% Completeness -
Collection
% Completeness -
Analysis
Metals ICP/MS
±25
75 - 125
90
95
VOC TD/GC/TOFMS
±25
70-130
90
95
SVOC GC/MS/MS
±25
70-130
90
95
SVOC LC/MS
±25
70-130
90
95
a Collection completeness is based on the number of samples attempted for collection. It is not based on the overall design
goals for numbers of fields and participants
b VOC = volatile organic compound; TD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass
spectrometry; SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry;
LC/MS = liquid chromatography/mass spectrometry; ICP/MS = inductively coupled plasma/mass spectrometry
B.4 Exposure Characterization Pilot Study Quality Control Results
Exposure characterization pilot study quality control information, measurements, and results are
reported in the following subsections for:
• Measurement of total suspended particulate in field air samples (Section B.4.1),
• Measurement of metals by ICP/MS in field air, field dust, field wipe, and dermal wipe samples
(Section B.4.2),
• Measurement of VOCs by TD/GC/TOFMS in field air samples (Section B.4.3),
• Measurement of SVOCs by GC/MS/MS in field air, field dust, field wipe, drag sled, and dermal
wipe samples (Section B.4.4),
• Attempted measurement of SVOCs by LC/MS in field air, field dust, field wipe, drag sled, and
dermal wipe samples (Section B.4.5),
• Field user questionnaires (Section B.4.6), and,
• Video activity data analysis (Section B.4.7).
B.4.1 Total Suspended Particulate in Field Air QC Samples
Total suspended particulate was measured in field air during four sample collection events. All
scheduled samples were successfully collected and analyzed. Five field blanks carried to the field sites
and returned with the samples had average weight increases on the filters of 5.8 ± 4.4 |ag/fiIter. Five lab
blanks that remained in the laboratory had average weight increases on the filters of 1.6 ± 3.4 |ig/filter.
The average field blank result was subtracted from the total suspended particulate measurement prior to
calculating concentrations in air. The average percent relative standard deviation for four duplicate
sample collection and analysis measurements was 11 ± 5.0%.
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B.4.2 Metals in Field Air, Field Dust, Field Wipe, and Dermal Wipe QC Samples
Completeness - All (100%) of the scheduled exposure characterization pilot study samples were
successfully analyzed for metals by ICP/MS.
Quantification Limits - Table B-7 reports the minimum reportable limits for metal analytes for field
wipe, dermal wipe, field dust, and field air samples.
Table B-7. Minimum Reportable Limits for Metals in Field and Dermal Wipe, Field Dust, and Field Air
Filter Samples Analyzed by ICP/MS8
Chemical
Field Wipes
Minimum
Reportable Limit
(ng/cm2)
Dermal Wipes
Minimum
Reportable Limit
(ng/cm2)
Field Dust Samples
Minimum
Reportable Limit
(mg/kg)
Field Air Filters
Minimum
Reportable Limit
(ng/m3)b
Aluminum
0.00686
0.05692
0.783
2.93
Antimony
0.00019
0.00155
0.035
0.03
Arsenic
0.00319
0.02646
0.039
0.50
Barium
0.00192
0.01594
1.460
1.29
Beryllium
0.00041
0.00343
0.031
0.79
Cadmium
0.00007
0.00057
0.023
0.16
Chromium
0.00090
0.00749
0.147
0.20
Cobalt
0.00008
0.00069
0.012
0.46
Copper
0.00060
0.00501
0.144
1.06
Iron
0.01037
0.08602
1.743
11.22
Lead
0.00070
0.00583
0.549
0.30
Magnesium
0.00579
0.04805
1.855
13.85
Manganese
0.00023
0.00190
0.084
0.33
Molybdenum
0.00014
0.00116
0.028
0.05
Nickel
0.00009
0.00078
0.015
0.57
Rubidium
0.00760
0.06302
0.045
1.82
Selenium
0.01153
0.09565
3.344
2.92
Strontium
0.00094
0.00783
0.295
0.22
Tin
0.00005
0.00045
0.017
0.05
Vanadium
0.00101
0.00834
0.113
0.19
Zinc
0.00677
0.05614
0.425
2.84
a ICP/MS = inductively coupled plasma/mass spectrometry
b Based on a nominal air sampling volume of 3.43 m3
Blanks - Table B-8 reports average concentrations of metals across field and laboratory blanks for field
and dermal wipes and field air filters. Relatively high background levels were observed in the wipe
materials for aluminum, iron, magnesium and zinc. These were also elements with relatively high
measurement results in the tire crumb rubber samples. Metals concentrations were adjusted for each
sample by subtracting the field blank result obtained for each field site from the analysis result for each
metal in samples collected at that field site.
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Table B-8. Field and Laboratory Blank Quality Control Results for Metals in Field and Dermal
Wipes and Field Air Filters Analyzed by ICP/MSa'b
Chemical
Field and Dermal
Wipe Blanks
Mean (ng/wipe)
Field and Dermal
Wipe Blanks
Standard Deviation
(ng/wipe)
Field Air Filter
Blanks Mean
(ng/filter)
Field Air Filter
Blanks Standard
Deviation
(ng/filter)
Aluminum
4120
3370
137
44
Antimony
38.5
3.8
3.87
7.13
Arsenic
74.2
11.5
< MRL
N/A
Barium
147
36
< MRL
N/A
Beryllium
6.72
1.47
< MRL
N/A
Cadmium
10.4
1.6
< MRL
N/A
Chromium
72.9
11.1
49.1
2.7
Cobalt
2.78
0.95
< MRL
N/A
Copper
728
79
25.9
20.8
Iron
3610
637
72.9
55.4
Lead
19.6
6.3
1.61
1.08
Magnesium
18,800
619
21.9
13.8
Molybdenum
39.6
3.5
0.320
0.099
Nickel
53.5
12.8
4.44
3.24
Rubidium
< MRL
N/A
< MRL
N/A
Selenium
< MRL
N/A
< MRL
N/A
Strontium
140
21
1.05
0.53
Tin
7.29
11.53
1.53
1.02
Vanadium
11.9
1.8
0.872
0.084
Zinc
81,700
6760
122
87.9
a ICP/MS = inductively coupled plasma/mass spectrometry; MRL = minimum reportable limit; N/A = not applicable
b Wipe Blanks (n=18), Field Air Sample Blanks (n=8)
Recovery - Table B-9 reports recovery results for metal analytes from the method spike solution and
field and dermal wipe spiked controls across field and laboratory sampling. Average recoveries from the
spiked controls ranged from 83% to 120%.
No standard synthetic turf field dust sample is available, and there are no methods for spiking an
equivalent dust with metals. The National Institute of Standards and Technology (NIST) standard
reference material (SRM) 1648a (urban particulate matter) was used to prepare field and laboratory
controls. Recovery of metals from this material were uneven, and not all metals had certified values.
Results are shown in Table B-10. Recoveries for cadmium, cobalt, lead and zinc ranged from 74% to
110%. However, the average recovery for chromium was only 20%. It is not known how well this urban
particulate matter SRM represents dust collected from synthetic turf fields. No recovery adjustments
were performed for the exposure characterization pilot study samples.
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Table B-9. Spike Recovery Quality Control Results for Metals in Field and Dermal Wipes After Microwave
Digestion by ICP/MSa'b
Chemical
Method Spike
Mean % Recovery
Method Spike
% Recovery
Standard Deviation
Wipe Spiked Controls
Mean % Recovery
Wipe Spiked Controls
% Recovery
Standard Deviation
Aluminum
97
7
85
25
Antimony
92
3
94
5
Arsenic
78
8
87
3
Barium
99
4
98
5
Beryllium
89
5
91
3
Cadmium
89
4
91
5
Chromium
96
5
98
8
Cobalt
97
5
95
4
Copper
94
4
95
5
Iron
96
5
93
7
Lead
97
4
96
5
Magnesium
94
4
93
5
Molybdenum
94
5
95
4
Nickel
94
4
95
6
Rubidium
96
4
96
5
Selenium
70
7
83
5
Strontium
98
5
94
5
Tin
98
5
91
6
Vanadium
96
5
95
4
Zinc
92
6
120
48
a ICP/MS = inductively coupled plasma/mass spectrometry
b Method Spikes (n=8). Wipe Spiked Controls (n=18); Spike = 250 microliters (|iL): Spike solution from SCP Science
(Champlain, NY)
Table B-10. Recovery Quality Control Results for Metals in Dust Surrogate (NIST SRM 1648a
Urban Particulate Matter) Analyzed by ICP/MSa'b
Chemical
NIST 1648a
Mean % Recovery
NIST1648a
% Recovery Standard Deviation
Aluminum
34
6
Antimony
68
13
Arsenic
116
21
Barium
*
N/A
Beryllium
*
N/A
Cadmium
94
15
Chromium
20
3
Cobalt
74
14
Copper
106
19
Iron
55
10
Lead
97
15
Magnesium
95
17
103
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Table B-10 Continued
Chemical
NIST 1648a
Mean % Recovery
NIST1648a
% Recovery Standard Deviation
Molybdenum
*
N/A
Nickel
78
13
Rubidium
30
5
Selenium
88
13
Strontium
88
15
Tin
*
N/A
Vanadium
86
15
Zinc
110
20
aNIST = National Institute of Standards and Technology; SRM = standard reference material;
ICP/MS = inductively coupled plasma/mass spectrometry; N/A = not applicable
b NIST SRM 1648a (n=8); approximately 20-30 mg of sample used
* Several elements do not have certified reference values
Precision -Duplicate samples were collected for field air and for field wipe samples. Measurement
precision results for metals in these duplicate samples are reported in Table B-l 1. Average % relative
standard deviation (%RSD) values for metals in field air duplicates ranged from 3.7% to 98%. The
average %RSDs for cobalt, lead, and zinc in field air duplicates were 6%, 11%, and 39%, respectively;
the average %RSD for chromium was 56%. Average %RSD values for metals in field wipes ranged
from 7% to 24% for all metals except cobalt, which had an average %RSD of 53%. Duplicate
measurement results for field wipes may include components of both measurement precision as well as
spatial heterogeneity in loading levels across sampled surfaces.
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Table B-ll. Measurement Precision Quality Control Results for Metals in Duplicate
Field Air and Field Wipe Samples Analyzed by ICP/MS
Chemical
Field Air Duplicate Samples
Average % Relative Standard
Deviation
Field Wipe Duplicate Samples
Average % Relative Standard
Deviation
Aluminum
6.8
12
Arsenic
12
10
Barium
9.1
24
Beryllium
31
11
Cadmium
98
16
Cobalt
6.0
53
Chromium
56
13
Copper
46
11
Iron
7.0
15
Magnesium
3.7
7
Manganese
9.1
11
Molybdenum
21
9
Nickel
75
14
Lead
11
19
Rubidium
7.0
15
Antimony
12
12
Selenium
32
ND°
Tin
66
23
Strontium
8.1
14
Vanadium
8.5
11
Zinc
39
21
a ICP/MS = inductively coupled plasma/mass spectrometry
b Field Air Duplicate Samples (n=4 sample pairs). Field Wipe Duplicate Samples (n=3 sample pairs)
0 Selenium was not detected in field wipe samples
DOI- Based on the quality control measurement results, DQI objectives were met for lead in all media.
All metals met recovery objectives in the field air and the field and dermal wipe media; however,
recoveries were uneven in the dust surrogate (NIST SRM 1648a) media. Precision was uneven in the
field air media, but all metals except cobalt met the precision objective in the wipe media.
B.4.3 VOCs in Field Air QC Samples
Completeness - All (100%) of the scheduled exposure characterization pilot study active fence line
monitor (FLM) field air samples were successfully collected and analyzed. None of the sample
measurement results from the Radiello passive field air samples or personal air samples were reported in
Volume 1 of this report due to inconsistent sample collection rates determined between laboratory and
field trials and because of unacceptably low recoveries for benzothiazole and methyl isobutyl ketone.
However, results for the Radiello quality control samples are reported in this Appendix.
Quantification Limits - Table B-12 reports the method detection limits for VOC analytes in FLM field
air samples.
105
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Table B-12. Minimum Detection Limits for VOCs Measured in
Fence Line Monitor Air Samples Analyzed by TD/GC/TOFMS8
Chemical
FLM Air Samples
Minimum Detection Limits
(ng/m3)b
Freon 12
2.94
1,3 -Butadiene
8.24
trans-2-Butene
6.47
cis-2-Butene
8.24
Freon 11
5.29
1,1 -Dichloroethene
14.7
Freon 113
4.12
1,1 -Dichloroethane
21.2
cis-1,2-Dichloroethene
43.5
1,2-Dichoroethane
21.2
1,1,1-Trichloroethane
45.3
Benzene
49.4
Carbon tetrachloride
35.3
1,2 -Dichloropropane
29.4
Trichloroethene
81.2
Methyl isobutyl ketone
64.1
Toluene
14.7
T etrachloroethene
2.35
Chlorobenzene
1.76
Ethylbenzene
4.71
m,p-Xylene
9.41
Styrene
14.1
o-Xylene
5.29
4-Ethyltoluene
30.6
1,3,5 -Trimethy lbenzene
20.0
m-Dichlorobenzene
5.88
p-Dichlorobenzene
9.41
o-Dichlorobenzene
5.29
Benzothiazole
282
aTD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass spectrometry; VOC = volatile organic
compound; FLM = fence line monitor
b Based on a nominal air sample volume of 0.017 m3
Blanks - Table B-13 reports average amounts of VOC analytes measured in FLM run blanks (blank
tubes prepared in the analysis laboratory), laboratory blanks, and field blanks. All average VOC results
for the FLM blanks were < 1.02 ng/tube. Table B-14 reports average amounts of VOC analytes
measured in Radiello passive field air and personal air laboratory and field blanks. All average VOC
results for the Radiello blanks were < 1.62 ng/tube. Air sample concentrations were adjusted by
subtracting the field blank result obtained for each field site from the analysis result for each VOC in
samples collected at that field site.
106
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Table B-13. Run, Laboratory, and Field Blank Quality Control Results for VOCs in Fence Line Monitor
Air Samples Analyzed by TD/GC/TOFMS8
Chemical
FLM Run
Blank
Mean
(ng/tube)
FLM Run
Blank
Standard
Deviation
(ng/tube)
FLM Lab
Blank
Mean
(ng/tube)
FLM Lab
Blank
Standard
Deviation
(ng/tube)
FLM Field
Blank
Mean
(ng/tube)
FLM Field
Blank
Standard
Deviation
(ng/tube)
Freon 12
0.15
0.06
0.19
0.07
0.17
0.04
1.3 -Butadiene
0.47
0.27
0.33
0.06
0.58
0.40
trans-2-Butene
0.14
0.07
0.11
0.03
0.16
0.07
cis-2-Butene
0.13
0.06
0.11
0.02
0.12
0.09
Freon 11
0.25
0.17
0.33
0.01
0.34
0.01
1,1 -Dichloroethene
0.01
0.05
0.04
0.09
0.04
0.08
Freon 113
0.19
0.22
0.24
0.19
0.24
0.19
1,1 -Dichloroethane
0.00
0.00
0.00
0.00
0.00
0.00
cis- 1,2-Dichloroethene
-0.01
0.03
0.00
0.00
0.00
0.00
1,2-Dichoroethane
0.00
0.00
0.00
0.00
0.00
0.00
1.1.1 -Tricliloroethane
0.06
0.18
0.12
0.23
0.00
0.00
Benzene
0.60
0.16
0.50
0.07
0.57
0.19
Carbon tetrachloride
0.00
0.00
0.00
0.00
0.00
0.00
1.2 -Dicliloropropane
0.00
0.00
0.00
0.00
0.00
0.00
Tricliloroethene
0.31
0.21
0.32
0.16
0.32
0.16
Methyl isobutyl ketone
0.00
0.00
0.00
0.00
0.00
0.00
Toluene
0.56
0.16
0.61
0.07
0.74
0.17
T etrachloroethene
0.31
0.21
0.32
0.16
0.32
0.16
Clilorobenzene
0.08
0.15
0.14
0.17
0.08
0.16
Ethylbenzene
0.38
0.13
0.30
0.15
0.31
0.15
m.p-Xylene
0.94
0.21
0.88
0.03
0.73
0.36
Styrene
0.41
0.39
0.26
0.32
0.40
0.33
o-Xylene
0.41
0.14
0.33
0.16
0.33
0.17
4-Ethyltoluene
0.12
0.20
0.00
0.00
0.07
0.14
1,3,5 -Trimethy lbenzene
0.11
0.13
0.00
0.00
0.04
0.09
m-Diclilorobenzene
0.17
0.22
0.07
0.15
0.07
0.15
p-Dichlorobenzene
0.16
0.22
0.07
0.14
0.07
0.14
o-Diclilorobenzene
0.34
0.20
0.33
0.16
0.24
0.20
Benzotliiazole
0.90
0.45
1.02
0.04
1.00
0.11
a VOC = volatile organic compound; TD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass
spectrometry; FLM = fence line monitor
b FLM Run Blanks (n=18), FLM Laboratory Blanks (n=5), FLM Field Blanks (n=5)
107
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Table B-14. Laboratory and Field Blank Quality Control Results for VOCs in Radiello Passive Air Samples
Analyzed by TD/GC/TOFMS3 b
Chemical
Radiello Lab
Blank Mean
(ng/tube)
Radiello Lab Blank
Standard Deviation
(ng/tube)
Radiello Field
Blank Mean
(ng/tube)
Radiello Field Blank
Standard Deviation
(ng/tube)
Freon 12
0.09
0.08
0.20
0.05
1,3 -Butadiene
0.00
0.00
0.00
0.00
trans-2-Butene
0.00
0.00
0.01
0.01
cis-2-Butene
0.00
0.00
0.01
0.02
Freon 11
0.13
0.15
0.20
0.16
1,1 -Dichloroethene
0.00
0.00
0.04
0.08
Freon 113
0.15
0.18
0.29
0.15
1,1 -Dichloroethane
0.00
0.00
0.07
0.14
cis-1,2-Dichloroethene
0.00
0.00
-0.03
0.05
1,2-Dichoroethane
0.00
0.00
0.09
0.18
1,1,1 -T richloroethane
0.00
0.00
0.11
0.22
Benzene
1.62
0.95
1.14
0.36
Carbon tetrachloride
0.00
0.00
0.12
0.24
1,2 -Dichloropropane
0.00
0.00
0.12
0.23
Trichloroethene
0.31
0.16
0.24
0.19
Methyl isobutyl ketone
0.02
0.05
0.03
0.03
Toluene
0.40
0.03
0.48
0.14
Tetrachloroethene
0.31
0.16
0.24
0.19
Chlorobenzene
0.22
0.18
0.30
0.15
Ethylbenzene
0.22
0.18
0.22
0.18
m,p-Xylene
0.51
0.42
0.68
0.34
Styrene
0.13
0.26
0.13
0.26
o-Xylene
0.24
0.19
0.24
0.19
4-Ethyltoluene
0.07
0.13
0.07
0.13
1,3,5 -T rimethy lbenzene
0.05
0.09
0.04
0.08
m-Dichlorobenzene
0.00
0.00
0.14
0.18
p-Diclilorobenzene
0.00
0.00
0.07
0.14
o-Diclilorobenzene
0.25
0.20
0.41
0.01
Benzotliiazole
0.20
0.40
0.40
0.50
a VOC = volatile organic compound; TD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass
spectrometry
b Laboratory Blanks (n=5), Field Blanks (n=5)
Recovery - Table B-15 reports average recoveries of VOC analytes measured in FLM calibration
checks, spiked laboratory controls, and spiked field controls. Average recoveries ranged from 60% to
139% in the calibration checks, 75% to 176% in the spiked lab controls, and 66% to 170% in the spiked
field controls. Most analytes had recoveries in the range of 70% to 130%. No recovery adjustments were
performed for the exposure characterization pilot study samples.
Table B-16 reports average recoveries of VOC analytes measured in Radiello passive field air and personal
108
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air spiked laboratory controls and spiked field controls. Average recoveries ranged from 4% to 370% in the
spiked field controls. Mean recovery values of 12% or less were observed for methyl isobutyl ketone and
benzothiazole. Mean recovery values of 370% to 373% were observed for cis-l,2-dichloroethene.
Table B-15. Calibration Check and Spike Recovery Quality Control Results for VOCs in Fence Line
Monitor Air Samples Analyzed by TD/GC/TOFMSa'b'c
Chemical
FLM Run
Calibration
Check
Mean %
Recovery
FLM Run
Calibration
Check
% Recovery
Standard
Deviation
FLM Spiked
Lab Controld
Mean %
Recovery
FLM Spiked
Lab Controld
% Recovery
Standard
Deviation
FLM Spiked
Field Control
Mean %
Recovery
FLM Spiked
Field Control
% Recovery
Standard
Deviation
Freon 12
105
5
101
4
100
2
1.3 -Butadiene
86
11
110
3
104
9
trans-2-Butene
96
4
103
3
97
5
cis-2-Butene
95
4
102
4
98
6
Freon 11
98
8
105
3
99
4
1,1 -Dichloroethene
97
8
106
4
104
3
Freon 113
99
5
104
3
102
2
1,1 -Dichloroethane
99
12
125
12
115
8
cis-1,2-Dichloroethene
133
27
150
27
134
8
1,2-Dichoroethane
123
30
132
25
115
8
1,1,1 -T richloroethane
98
12
111
10
102
4
Benzene
93
6
100
3
99
4
Carbon tetrachloride
139
42
109
19
99
6
1.2 -Dichloropropane
109
27
128
22
117
7
Trichloroethene
95
5
103
2
101
1
Methyl isobutyl ketone
60
32
176
79
170
28
Toluene
91
9
101
3
101
4
Tetrachloroethene
95
5
103
2
101
1
Chlorobenzene
99
1
101
2
104
8
Ethylbenzene
86
6
92
3
95
9
m,p-Xylene
86
7
98
2
101
10
Styrene
83
6
95
5
100
13
o-Xylene
88
7
97
2
98
8
4-Ethyltoluene
99
17
99
11
105
21
1,3,5 -T rimethy lbenzene
97
19
93
14
97
24
m-Dichlorobenzene
101
5
94
2
94
8
p-Dichlorobenzene
101
5
93
2
94
9
o-Dichlorobenzene
101
4
89
3
90
8
Benzotliiazole
120
29
75
22
66
6
a VOC = volatile organic compound; TD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass
spectrometry; FLM = fence line monitor
b FLM Run Calibration Check (n=14), FLM Lab Control (n=5), FLM Field Control (n=6); Spike=2.2-14.8 ng/tube
0 Recoveries are calculated using the blank corrected tube results and the theoretical mass (ng) loaded.
d All Lab Spikes were prepared on Carbopack™ X tubes at nominal concentrations of either 1 or 2 ppbv
109
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Table B-16. Field and Laboratory Spike Recovery Quality Control Results for VOCs in Radiello Passive
Samples Analyzed by TD/GC/TOFMS a'b
Chemical
Radiello Spiked
Lab Control
Mean %
Recovery
Radiello Spiked
Lab Control
% Recovery
Standard
Deviation
Radiello Spiked
Field Control
Mean %
Recovery
Radiello Spiked
Field Control
% Recovery
Standard
Deviation
Freon 12
83
5
84
6
1.3 -Butadiene
38
9
56
10
trans-2-Butene
86
3
90
7
cis-2-Butene
83
4
88
6
Freon 11
88
3
91
6
1,1 -Dichloroethene
93
7
96
11
Freon 113
95
3
94
5
1,1 -Dichloroethane
25
15
33
11
cis-1,2-Dichloroethene
373
12
370
15
1,2-Dichoroethane
130
29
155
21
1,1,1 -T ricliloroethane
24
12
26
3
Benzene
90
12
113
28
Carbon tetracliloride
81
36
57
29
1.2 -Dichloropropane
36
28
38
6
Tricliloroethene
96
3
94
5
Methyl isobutyl ketone
3
3
4
3
Toluene
79
3
80
5
Tetrachloroethene
96
3
94
5
Clilorobenzene
95
2
94
2
Ethylbenzene
78
10
74
10
m,p-Xylene
77
12
73
11
Styrene
56
16
55
13
o-Xylene
79
11
75
9
4-Ethyltoluene
69
12
65
14
1,3,5 -T rimethy lbenzene
63
13
60
15
m-Dichlorobenzene
83
2
85
2
p-Diclilorobenzene
83
2
84
1
o-Diclilorobenzene
80
1
81
2
Benzotliiazole
10
6
12
2
a VOC = volatile organic compound TD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass
spectrometry
b Radiello Laboratory Control (n=5), Radiello Field Control (n=4); Spike=2.2-14.8 ng/tube
0 Recoveries are calculated using the blank corrected tube results and the theoretical mass (ng) loaded.
110
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Precision - Duplicate FLM field air measurement precision results are reported in Table B-17. Average
%RSD values for VOCs in field air duplicates ranged from 2% to 43%, with most %RSD values < 25%.
DOI- Most DQI objectives were met for most field air VOC analytes collected using FLM tubes.
Benzothiazole had an average recovery of 66% in spiked field controls. Methyl isobutyl ketone had an
average 170% recovery in the spiked field controls. Trichloroethylene and o-dichlorobenzene had
average relative percent standard deviations greater than 25% in duplicate samples.
Table B-17. Measurement Precision Quality Control Results for Duplicate
Field Air VOC Fence Line Monitor Samples Analyzed by TD/GC/TOFMSa b
Chemical
Field Air FLM Duplicate Samples
Average % Relative Standard Deviation
Methyl isobutyl ketone
20
Benzothiazole
15
1.3 -Butadiene
24
Styrene
20
Benzene
17
Toluene
17
Ethylbenzene
16
m/p-Xylene
17
o-Xylene
17
trans-2-Butene
18
cis-2-Butene
21
4-Ethyltoluene
11
1,3,5 -Trimethy lbenzene
16
1,1 -Dichloroethene
2
1,1 -Dichloroethane
3
cis-1,2-Dichloroethene
NM
1,2-Dichloroethane
19
1,1,1-Trichloroethane
7
Carbon Tetrachloride
33
1,2-Dichloropropane
NM
T richloroethy lene
43
T etrachloroethy lene
16
Chlorobenzene
3
m-Dichlorobenzene
5
p-Dichlorobenzene
9
o-Dichlorobenzene
35
Trichlorofluoromethane (Freon 11)
14
Dichlorodifluoromethane (Freon 12)
4
Trichlorotrifluoroethane (Freon 113)
13
a VOC = volatile organic compound; TD/GC/TOFMS = thermal desorption/liquid chromatography/time-of-flight mass
spectrometry; FLM = fence line monitor; NM = not measured in samples
b Field Air Duplicate Samples (n=4 sample pairs)
111
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6.4.4 SVOCs in Field Air, Field Dust, Field Wipe, Field Drag Sled and Dermal Wipe QC
Samples
Completeness - All (100%) of the scheduled exposure characterization pilot study field air, field dust,
field wipe, field drag sled, and dermal wipe samples were successfully collected and analyzed for
SVOCs by GC/MS/MS.
Quantification Limits - Minimum quantifiable limits (MQLs) for SVOC analytes were determined for
field air, field dust, drag sled, field wipe, and dermal wipe samples. Results are shown in Table B-18.
Table B-18. Minimum Quantifiable Limits for SVOCs in Field Air, Field Dust, Drag Sled, Field Wipe, and
Dermal Wipe Sample Extracts Analyzed by GC/MS/MS8
Chemical
Field Air
MQL
(ng/m3)b
Field Dust
MQL
(mg/kg)
Drag Sled
MQL
(ng/cm2)
Field Wipe
MQL
(ng/cm2)
Dermal Wipe
MQL
(ng/cm2)
Aniline
0.148
0.01
0.000010
0.00108
0.0006-0.0089
n-Butylbenzene
0.074
0.0025
0.000005
0.00027
0.0012-0.0089
Naphthalene
0.148
0.025
0.000005
0.00269
0.0060 - 0.0222
Benzothiazole
0.148
0.005
0.000010
0.00054
0.0024 - 0.0222
Cyclohexylisothiocyanate
0.148
0.005
0.000020
0.00054
0.0012-0.0089
2-Methylnaphthalene
0.740
0.025
0.000050
0.00269
0.0060-0.0089
1 -Methy lnaphthalene
0.296
0.005
0.000020
0.00054
0.0024-0.0089
Dimethyl Phthalate
0.148
0.005
0.000010
0.00054
0.0002 - 0.0044
Acenaphthalene
0.148
0.005
0.000020
0.00054
0.0012-0.0089
2,6-Di-tert-butyl-p-cresol
0.148
0.01
0.000020
0.00108
0.0024 - 0.0222
Diethyl phthalate
0.074
0.25
0.000005
0.02691
0.0024-0.0089
n-Hexadecane
0.740
0.01
0.000050
0.00108
0.0060 - 0.0222
Fluorene
0.030
0.005
0.000005
0.00054
0.0012-0.0044
4-tert-Octylphenol
0.740
0.05
0.000100
0.00538
0.0120-0.0044
2-Bromomethy lnaphthalene
0.740
0.01
0.000050
0.00108
0.0060 - 0.0222
2-Hydroxybenzothiazole
NA
0.005
0.000020
0.00054
0.0602 - 0.222
Dibenzothiophene
0.074
0.005
0.000020
0.00054
0.00060 - 0.0044
Phenanthrene
0.740
0.025
0.000050
0.00269
0.0024 - 0.0444
Anthracene
0.740
0.01
0.000020
0.00108
0.0060 - 0.0444
Diisobutyl phthalate
0.740
0.025
0.000020
0.00269
0.0120-0.222
3 -Methy lphenanthrene
0.740
0.025
0.000050
0.00269
0.0120-0.222
2-Methylphenanthrene
1.479
0.05
0.000050
0.00538
0.0120-0.0889
1 -Methy lphenanthrene
0.148
0.01
0.000010
0.00108
0.0012-0.0089
Dibutyl phthalate
1.479
0.1
0.000100
0.01076
0.0060 - 0.0444
Fluoranthene
0.148
0.01
0.000020
0.00108
0.0012-0.0044
Pyrene
2.959
0.025
0.000050
0.00269
0.0120-0.0444
Benzyl butyl phthalate
0.074
0.025
0.000100
0.00269
0.0006 - 0.0222
bis(2-ethylhexyl) adipate
0.740
0.01
0.000020
0.00108
0.0060 - 0.0222
Benz(a)anthracene
0.296
0.01
0.000020
0.00108
0.0024 - 0.0222
Chrysene
0.074
0.005
0.000010
0.00054
0.0024-0.0089
Bis(2 -ethy lhexy l)phthalate
0.740
0.01
0.000050
0.00108
0.0060 - 0.0222
Di-n-octyl phthalate
0.740
0.005
0.000050
0.00054
0.0006 - 0.0044
112
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Table B-18 Continued
Chemical
Field Air
Field Dust
Drag Sled
Field Wipe
Dermal Wipe
MQL
MQL
MQL
MQL
MQL
(ng/m3)
(mg/kg)
(ng/cm2)
(ng/cm2)
(ng/cm2)
Benzo(b)fluoranthene
1.479
0.01
0.000050
0.00108
0.0012-0.0222
Benzo(k)fluoranthene
0.074
0.01
0.000002
0.00108
0.0024-0.0089
Benzo(e)pyrene
0.296
0.001
0.000005
0.00011
0.0012-0.0089
Benzo(a)pyrene
0.740
0.025
0.000050
0.00269
0.0012-0.0222
Bis(2,2,6,6-tetramethyl-
0.148
0.25
0.000050
0.02691
0.0024 - 0.0222
4piperidyl) sebacate
DBA + ICDP0
0.740
0.01
0.000010
0.00108
0.0024 - 0.0222
Benzo(g,h,i)perylene
0.030
0.01
0.000010
0.00108
0.0060 - 0.0222
Coronene
2.959
0.005
0.000020
0.00054
0.0012-0.0222
a MQL = minimum quantifiable limit; SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem
mass spectrometry
b Based on a nominal air sample volume of 3.38 m3
°DBA + ICDP = Dibenz(a,h)anthracene + Indeno( 1,2,3-cd)pyrene
Blanks - Table B-19 reports average concentrations of SVOC analytes in air filter field and laboratory
blanks. High background levels were observed for diisobutyl phthalate, with other analytes much lower.
Field dust quality control samples were prepared using solvent-cleaned and heat-baked diatomaceous
earth. Table B-20 reports average concentrations of SVOC analytes in dust field and laboratory blanks.
Cyclohexylisothiocyanate was found at 50 ng/sample, with other analytes much lower.
Field air and field dust sample concentrations were adjusted by subtracting the field blank result
obtained for each field site from the analysis result for each SVOC in samples collected at that field site.
Table B-19. Field and Laboratory Blank Quality Control Results for SVOCs in Field Air Samples
Analyzed by GC/MS/MSa'b
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Aniline
0
0
0
0
n-Butylbenzene
1.8
0.6
2
0.4
Naphthalene
4.9
1.1
4
2
Benzothiazole
60.8
16.5
44.1
17.1
Cyclohexylisothiocyanate
0
0
0
0
2-Methylnaphthalene
7
1.4
5.5
2.6
1 -Methy lnaphthalene
3.6
0.8
2.8
1.2
Dimethyl Phthalate
1.1
0.3
1
0.5
Acenaphthalene
0.4
0.1
0.5
0.1
2,6-Di-tert-butyl-p-cresol
6.5
5
1.7
3.3
Diethyl phthalate
142
53.5
69.8
61.4
n-Hexadecane
80.1
45.4
38.5
10.5
113
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Table B-19 Continued
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Fluorene
1.1
0.3
0.6
0.2
4-tert-octylphenol
3.6
2.6
3.6
1.4
2-Bromomethylnaphthalene
0
0
0
0
Dibenzotliiophene
0.1
0.1
0
0.1
Phenantlirene
5.7
2.4
4.6
4.1
Antliracene
0.4
0.1
0.5
0.1
Diisobutyl phthalate
799.5
306.3
573
137.8
3 -Methy lphenantlirene
1.8
0.1
1.7
0.2
2-Methylphenantlirene
2.7
0.1
2.7
0.2
1 -Methy lphenantlirene
0.3
0.1
0.3
0.1
Dibutyl phthalate
47.6
23.7
33.4
17.4
Fluoranthene
0.3
0
0.3
0.1
Pyrene
2.9
0.1
2.9
0.1
Benzyl butyl phthalate
48.8
34.2
30.4
35.8
bis(2-ethylhexyl) adipate
15.8
10.5
16.3
10.3
Benz(a)anthracene
0.2
0.1
0.3
0
Clirysene
0
0
0
0
Bis(2 -ethy lhexy l)phthalate
89.9
57.8
37.8
11.9
Di-n-octyl phthalate
6.9
8.9
1
0.5
Benzo(b)fluoranthene
0
0
0
0
Benzo(k)fluoranthene
0
0
0
0
Benzo(e)pyrene
0.4
0.2
0.5
0.1
Benzo [a] pyrene
1.1
0
1.2
0.1
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
0
0
0
0
DBA + ICDP0
0
0
0
0
Benzo [glii] pery lene
0
0
0
0
Coronene
0
0
0
0
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Blanks (n=5), Lab Blanks (n=4),
0 DBA + ICDP = Sum of Dibenz[a,h]anthracene and Indeno( 1,2,3-cd)pyrene
-------
Table B-20. Field and Laboratory Blank Quality Control Results for SVOCs in Field Dust Samples
Analyzed by GC/MS/MSa'b
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Aniline
0
0
0
0
n-Butylbenzene
0
0
0.3
0.6
Naphthalene
0
0
0
0
Benzothiazole
5.5
3.2
3.3
0.3
Cyclohexylisotliiocyanate
49.6
4.8
40.8
6.4
2-Methylnaphthalene
0.3
0.2
0.2
0
1 -Methy lnaphthalene
0.4
0.1
0.4
0
Dimethyl Phthalate
0.2
0
0.3
0
Acenaphthalene
0
0
0
0
2,6-Di-tert-butyl-p-cresol
4.3
5
0
0
Diethyl phthalate
0
0
0
0
n-Hexadecane
20.2
4.2
16.9
3.9
Fluorene
0.5
0.1
0.5
0
4-tert-octylphenol
0
0
0
0
2-Bromomethy lnaphthalene
0
0
0
0
2-Hydroxybenzotliiazole
3.1
1.9
1.6
0.1
Dibenzotliiophene
0.3
0
0.4
0
Phenantlirene
1
0.1
1
0.1
Anthracene
0
0
0
0
Diisobutyl phthalate
5.5
0.5
5.3
0.9
3 -Methy lphenanthrene
0
0
0
0
2-Methylphenantlirene
0
0
0
0
1 -Methy lphenantlirene
0
0
0
0
Dibutyl phthalate
4.5
0.1
4.3
0.1
Fluoranthene
0.4
0
0.4
0
Pyrene
0
0
0
0
Benzyl butyl phthalate
3.5
0.7
3.5
1.6
bis(2-Ethylhexyl) adipate
0
0
0
0
Benz(a)antliracene
0
0
0
0
Clirysene
0
0
0
0
Bis(2-ethylhexyl)phthalate
13.9
2.7
12
2.1
Di-n-octyl phtlialate
0
0
0
0
B enzo (b )fluoranthene
0.2
0.5
0
0
B enzo (k)fluoranthene
0
0
0
0
Benzo(e)pyrene
0
0
0
0
Benzo(a)pyrene
0
0
0
0
Benzo(glii)perylene
0
0
0
0
Coronene
0.6
0.1
0.7
0.2
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Blanks (n=4). Lab Blanks (n=4)
-------
Table B-21 reports average concentrations of SVOC analytes in field wipe field and laboratory blanks.
Bis(2-ethylhexyl) phthalate had the highest measured background levels (79 ng/wipe). Table B-22
reports average concentrations of SVOC analytes in drag sled field and laboratory blanks. Bis(2-
ethylhexyl) phthalate had the highest measured background levels (930 ng/wipe) followed by
benzothiazole (216 ng/wipe).
Table B-23 reports average concentrations of SVOC analytes in dermal wipe field and laboratory
blanks. Diisobutyl phthalate had the highest measured background levels (2100 ng/wipe) followed by
benzyl butyl phthalate (151 ng/wipe). The field wipe and dermal wipe field blank wipe material was
handled in the field using gloved hands to mimic handling for the samples. Sample concentrations were
adjusted by subtracting the field blank result obtained for each field site from the analysis result for each
SVOC in samples collected at that field site.
Table B-21. Field and Laboratory Blank Quality Control Results for SVOCs in Field Wipes Analyzed by
GC/MS/MSa'b
Chemical
Field Blank Mean
(ng/wipe)
Field Blank
Standard Deviation
(ng/wipe)
Lab Blank Result
(ng/wipe)
Aniline
0
0
0
n-Butylbenzene
2.5
1.5
1.9
Naphthalene
0
0
0.2
Benzothiazole
11.5
3.7
10.7
Cyclohexylisothiocyanate
15.3
19.8
0
2-Methylnaphthalene
0.4
0.3
1.4
1 -Methy lnaphthalene
0.7
0.3
1.6
Dimethyl Phthalate
0.3
0.1
0.3
Acenaphthalene
0.4
0.2
0.6
2,6-Di-tert-butyl-p-cresol
9.3
2
10.7
Diethyl phthalate
21.7
6.1
18
n-Hexadecane
42.6
11
24.8
Fluorene
0.6
0.2
0.7
4-tert-octylphenol
6.9
0.9
4.8
2-Bromomethy lnaphthalene
0
0
0
2-Hydroxybenzothiazole
26.1
15.3
10.9
Dibenzothiophene
0.6
0.3
0.3
Phenanthrene
1.3
0.4
0.9
Anthracene
1
0.3
0.6
Diisobutyl phthalate
44.9
8.1
60.2
3 -Methy lphenanthrene
2.2
0.4
1.7
2-Methylphenanthrene
2.5
0.3
2
1 -Methy lphenanthrene
1.3
0.5
0.6
Dibutyl phthalate
39.8
18.6
35.2
Fluoranthene
0.9
0.2
0.5
Pyrene
2.2
0.2
1.8
Benzyl butyl phthalate
71.4
37.2
199.5
bis(2-ethylhexyl) adipate
43
20.5
6.6
Benz(a)anthracene
0.6
0.2
0.5
116
-------
Table B-21 Continued
Chemical
Field Blank Mean
(ng/wipe)
Field Blank
Standard Deviation
(ng/wipe)
Lab Blank Result
(ng/wipe)
Chrysene
0.6
0.2
0.3
Bis(2-ethylhexyl)phthalate
78.6
38.7
69.8
Di-n-octyl phthalate
3.4
3.9
1
B enzo (b )fluoranthene
0.9
0.1
0.6
B enzo (k)fluoranthene
0.7
0.1
0.5
Benzo(e)pyrene
0.5
0.2
0.1
Benzo(a)pyrene
0.9
0.1
0.7
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
0
0
0
DBA + ICDP0
0.5
0.1
0.6
Benzo(ghi)perylene
0.7
0.1
0.4
Coronene
0.4
0
0.2
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Blanks (n=4), Lab Blanks (n=l)
0 DBA + ICDP = Sum of Dibenz[a,h]anthracene and Indeno( 1,2,3-cd)pyrene
Table B-22. Field and Laboratory Blank Quality Control Results for SVOCs in Drag Sled Wipes Analyzed
by GC/MS/MS
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Aniline
0
0
0
0
n-Butylbenzene
5.2
3.3
11.1
1.4
Naphthalene
3.5
1.8
3.8
1.5
Benzothiazole
215.7
217.5
333.3
437.5
Cyclohexylisothiocyanate
0
0
0
0
2-Methylnaphthalene
3.5
1.6
3.7
1.5
1 -Methy lnaphthalene
2.1
1
2.2
0.9
Dimethyl Phthalate
1.5
0.7
2.3
2.4
Acenaphthalene
0.6
0.2
0.7
0.2
2,6-Di-tert-butyl-p-cresol
9.3
5.2
9.2
7.4
Diethyl phthalate
61.4
10.8
82.7
62.8
n-Hexadecane
95.5
18.2
86.7
67.5
Fluorene
1.1
0.8
1.3
1.5
4-tert-octylphenol
8
2.3
6
1.1
2-Bromomethy lnaphthalene
0
0
0
0
2-Hydroxybenzothiazole
23.1
15.6
41
36.4
Dibenzothiophene
0.5
0.1
0.5
0.2
Phenanthrene
2.7
1.7
4.6
5.3
Anthracene
0.2
0.1
0.3
0.2
117
-------
Table B-22 Continued
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Diisobutyl phthalate
87.2
29.5
78
14.9
3 -Methy lphenantlirene
1.6
0.2
1.8
0.5
2-Methylphenantlirene
1.4
0.2
1.7
0.5
1 -Methy lphenantlirene
0.6
0.3
1.4
1.1
Dibutyl phthalate
135.6
31.5
78.1
25.2
Fluoranthene
0.6
0.3
1.4
1.9
Pyrene
2.4
1
4.4
5.2
Benzyl butyl phthalate
148.7
141.7
136.9
100.3
bis(2-ethylhexyl) adipate
61.5
30.8
22.7
14
Benz(a)anthracene
0.2
0
0.4
0.2
Clirysene
0.2
0.1
0.8
1
Bis(2-ethylhexyl)phthalate
930.4
1004.9
1109.7
1840.4
Di-n-octyl phthalate
1.9
0.5
2.1
0.8
B enzo (b )fluoranthene
0.2
0.3
0.5
0.4
B enzo (k)fluoranthene
0.1
0.2
0.2
0.1
Benzo(e)pyrene
0.2
0.2
0.8
1.7
Benzo(a)pyrene
0.5
0.6
0.9
1.4
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
5.1
4
13.5
3.4
DBA + ICDP°
0
0
0
0
Benzo(glii)perylene
0.2
0.1
0.6
0.9
Coronene
0.3
0
0.3
0.1
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Blanks (n=4). Lab Blanks (n=4)
0 DBA + ICDP= Sum of Dibenz[a,h]anthracene and Indeno(l,2,3-cd)pyrene
Table B-23. Field and Laboratory Blank Quality Control Results for SVOCs in Dermal Wipes Analyzed by
GC/MS/MSa'b
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Aniline
0
0
0
0
n-Butylbenzene
4.6
1.9
5.5
2.2
Naphthalene
2.2
0.4
1.9
0.2
Benzothiazole
5.4
1.4
10.2
2.2
Cyclohexylisothiocyanate
9.8
20.3
12.9
22.1
2-Methylnaphthalene
1.6
0.2
3.6
1.6
1 -Methy lnaphthalene
0
0
0.9
0.8
Dimethyl Phthalate
0.5
0.4
0.1
0.2
118
-------
Table B-23 Continued
Chemical
Field Blank
Mean
(ng/sample)
Field Blank
Standard
Deviation
(ng/sample)
Lab Blank
Mean
(ng/sample)
Lab Blank
Standard
Deviation
(ng/sample)
Acenaphthalene
0.4
0.1
0.2
0.2
2,6-Di-tert-butyl-p-cresol
8.6
5.4
15.5
11.7
Diethyl phthalate
38.2
16.7
41.2
8.9
n-Hexadecane
86.1
26.2
169.4
111.3
Fluorene
0.4
0.1
0.2
0.2
4-tert-octylphenol
30.5
34.9
16.8
8.7
2-Bromomethylnaphthalene
0
0
11.3
11.8
Dibenzotliiophene
0.4
0.1
0.3
0.3
Phenanthrene
0.5
0.4
1.6
1.4
Antliracene
2.1
0.3
0.8
1.2
Diisobutyl phthalate
2102.3
581.9
2146.5
643.8
3 -Methy lphenantlirene
3.2
0.2
3
1.7
2-Methylphenanthrene
3.5
0.3
3.7
0.2
1 -Methy lphenantlirene
0.7
0.2
0.9
0.3
Dibutyl phthalate
85.6
43.7
122.8
39.4
Fluoranthene
0.6
0.2
0.6
0.3
Pyrene
3.2
0.1
2.7
0.7
Benzyl butyl phthalate
151.1
115.1
224.1
160
bis(2-ethylhexyl) adipate
25.3
20.8
374.6
777.2
Benz(a)antliracene
0.3
0.2
0.3
0.4
Clirysene
0.4
0.1
0.3
0.3
Bis(2-ethylhexyl)phthalate
79.9
13.1
108.1
61.2
Di-n-octyl phtlialate
8.5
7.4
2.5
2.2
B enzo (b )fluoranthene
0
0
0
0.1
B enzo (k)fluoranthene
0.3
0.2
0.2
0.4
Benzo(e)pyrene
0.1
0.1
0.2
0.3
Benzo(a)pyrene
0.2
0.3
0.3
0.5
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
3.7
1.3
1.6
0.9
DBA + ICDP0
0
0
0.4
0.4
Benzo(ghi)perylene
0
0
0.9
0.2
Coronene
0
0
0
0
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Blanks (n=5), Lab Blanks (n=5)
0 DBA + ICDP = Dibenz(a,h)anthracene + Indeno(l,2,3-cd)pyrene
-------
Recovery - Table B-24 reports recovery results for SVOC analytes measured in air filter spiked field
controls and spiked laboratory controls. Average recoveries ranged from 0% to 232% for controls not
corrected for blank levels. Most SVOCs had average spiked field control recoveries in a range from 70%
to 120%. Aniline had an average recovery of 18% in spiked field controls, while n-butylbenzene and
napthalene had recoveries of 54% each. These were the three most volatile analytes and there may have
been losses during the extraction solvent volume reduction step. Diisobutyl phthalate and bis(2-
ethylhexyl) adipate had recoveries of 232% and 190%, respectively, in spiked field controls. The
diisobutyl phthalate recovery was inflated by the relatively high background levels (reported in Table B-
23).
Table B-24. Field and Laboratory Spike Quality Control Results for SVOCs in Field Air Samples Analyzed
by GC/MS/MSa'b
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean%
Recovery
Lab Spike
% Recovery
Standard
Deviation
Aniline
18.2
9.1
20.2
3.8
n-Butylbenzene
53.6
2.3
62.4
3.1
Naphthalene
53.5
14.9
64.7
7.2
Benzothiazole
112
8.2
117.3
10.6
Cyclohexylisothiocyanate
119.6
10
127.3
18.8
2-Methylnaphthalene
75
5.1
84.6
7
1 -Methy lnaphthalene
78.1
4.7
87.8
8
Dimethyl Phthalate
74.8
5.2
73.4
4.1
Acenaphthalene
73.6
5
77.2
9.5
2,6-Di-tert-butyl-p-cresol
72.4
5.9
73.4
9.7
Diethyl phthalate
103.6
8.3
97.7
5.7
n-Hexadecane
76.4
5.3
92
11.9
Fluorene
91.2
3.6
96.4
2.5
4-tert-octylphenol
72
9.2
109.7
79.8
2-Bromomethy lnaphthalene
1.7
0.9
6.8
2.4
Dibenzothiophene
104.3
4.6
103.1
6.1
Phenanthrene
90.2
4.8
87.3
4.9
Anthracene
97.6
4.5
94.1
4.7
Diisobutyl phthalate
232.5
63.1
220.9
11.1
3 -Methy lphenanthrene
107.3
3.9
104.5
4.3
2-Methylphenanthrene
101.5
6.5
100.8
6.4
1 -Methy lphenanthrene
110
6.5
109.2
4.7
Dibutyl phthalate
114.1
16.4
123.2
3.9
Fluoranthene
85
4.7
81.9
2.3
Pyrene
82.5
3.8
81.9
2.6
Benzyl butyl phthalate
108.3
27
92
8.8
bis(2-ethylhexyl) adipate
189.6
81.3
211.9
72.5
Benz(a)anthracene
81.8
4.1
82.4
7.3
Chrysene
111.2
6.4
106.8
4.3
Bis(2-ethylhexyl)phthalate
96.5
8.7
94
5.4
Di-n-octyl phthalate
82.9
2.8
82.6
4.9
120
-------
Table B-24 Continued
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean%
Recovery
Lab Spike
% Recovery
Standard
Deviation
B enzo (b )fluoranthene
113.8
14.5
105.5
8.9
B enzo (k)fluoranthene
108.6
4.1
108.4
10.6
Benzo(e)pyrene
69.4
7.7
76.1
6.7
Benzo(a)pyrene
72.9
7.9
75.8
11.5
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
0.3
0.6
0
0.1
DBA + ICDP0
120.8
29.7
115.4
3.5
Benzo(ghi)perylene
95.3
1.4
100.9
11.1
Coronene
100.7
18.2
71.5
11.8
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Spikes (n=5), Lab Spikes (n=5); Spike=500 ng
0 DBA + ICDP = Dibenz(a,h)anthracene + Indeno(l,2,3-cd)pyrene
Table B-25 reports recovery results for SVOC analytes in field dust surrogate spiked field controls and
spiked laboratory controls. Average recovery levels were low and ranged from 36% to 70% for most
analytes. Aniline had an average recovery of 10% in spiked field controls, while n-butylbenzene and
napthalene had recoveries of 19% and 29%, respectively. 2-bromomethylnaphthalene had an average
recovery of 17% in the spiked field controls. The reason for the relatively low recoveries is not clear.
Uniform spiking of dust surrogate material is difficult, and some portion of the spiking solution may not
have been applied directly to the material. It is possible that recoveries from the diatomaceous earth are
not complete using the solvent and extraction method used. It is also not clear whether the surrogate
material provides a quality control measure that can accurately represent recoveries obtained from actual
field dust.
Table B-25. Field and Laboratory Spike Quality Control Results for SVOCs in Field Dust Surrogate
Analyzed by GC/MS/MSab
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean %
Recovery
Lab Spike
% Recovery
Standard
Deviation
Aniline
9.8
1.7
10.5
1.4
n-Butylbenzene
18.7
9.8
22.8
1.9
Naphthalene
28.9
19.3
38.2
1.8
Benzothiazole
50.1
11.5
47.6
2.3
Cyclohexylisothiocyanate
58.1
14.5
65.2
4.6
2-Methylnaphthalene
44.8
17.4
51
2.5
1 -Methy lnaphthalene
40.5
15.9
47.9
2.2
Dimethyl Phthalate
65.9
2
67.9
3.3
Acenaphthalene
37.2
4.6
35.2
2.2
2,6-Di-tert-butyl-p-cresol
25.6
2.5
22
4
Diethyl phthalate
46.8
1.8
47.6
1.9
n-Hexadecane
44.1
3.2
45.2
3.3
121
-------
Table B-25 Continued
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean %
Recovery
Lab Spike
% Recovery
Standard
Deviation
Fluorene
52.4
3.1
55.1
1.9
4-tert-octylphenol
40.5
0.9
40
1.6
2-Bromomethylnaphthalene
17.2
3
14.9
1.7
2-Hydroxybenzothiazole
36.1
4.5
34.5
3.4
Dibenzothiophene
52.4
1.3
53.7
2.5
Phenanthrene
47.4
2.1
48.2
1.6
Anthracene
36.4
3.3
32.1
0.8
Diisobutyl phthalate
39.6
2.4
42.2
2.2
3 -Methy lphenanthrene
42.8
2.6
41.2
2.2
2-Methylphenanthrene
41.7
3.3
40
2.7
1 -Methy lphenanthrene
42.3
3
40.8
2.6
Dibutyl phthalate
37.3
3.2
39.5
3
Fluoranthene
43.3
1.5
44.1
1.8
Pyrene
43.4
2.2
44.6
1.2
Benzyl butyl phthalate
38.4
0.9
40.9
1.3
bis(2-ethylhexyl) adipate
56.5
21.3
87.3
25.9
Benz(a)anthracene
35.6
1
35.6
1.6
Chrysene
57.8
2.5
59.5
2.6
Bis(2-ethylhexyl)phthalate
43.3
0.9
45.6
0.5
Di-n-octyl phtlialate
47
6.2
46.6
2.4
B enzo (b )fluoranthene
50.3
2.2
54.7
1.4
B enzo (k)fluoranthene
54
1.8
61.5
2.4
Benzo(e)pyrene
53.3
3
55.3
5.8
Benzo(a)pyrene
38.1
4.3
36.4
3.8
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
32.1
7.8
0
0
DBA + ICDP0
48
3.4
50.2
4.1
Benzo(g,h,i)perylene
47
1.9
47.7
2.0
Coronene
70.1
4.7
83.1
3.3
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Spikes (n=4). Lab Spikes (n=4); Spike=1667 ng/g (0.1 g sample)
0 DBA + ICDP = Dibenz(a,h)anthracene + Indeno(l,2,3-cd)pyrene
Table B-26 reports recovery results for SVOC analytes in field wipe spiked field controls and spiked
laboratory controls. Average recovery levels above 150% were measured for 2,6-di-tert-butyl-p-cresol,
4-tert-octylphenol, 2-hydroxybenzothiazole, benzyl butyl phthalate, and bis(2,2,6,6-tetramethyl-
4piperidyl) sebacate in spiked field controls. Aniline had an average recovery level of 32% in spiked
field controls, likely due to losses during the solvent extraction volume reduction step. Average
recoveries ranged from 62% to 144% for the remainder of the SVOC analytes.
122
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Table B-26. Field and Laboratory Spike Quality Control Results for SVOCs in Field Wipes Analyzed by
GC/MS/MSa'b
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean %
Recovery
Lab Spike
% Recovery
Standard
Deviation
Aniline
31.7
14.9
29.8
4.9
n-Butylbenzene
79.8
8.4
91.7
7.8
Naphthalene
97.2
6.3
107.9
3
Benzothiazole
97.7
17.7
104.5
24.2
Cyclohexylisothiocyanate
97.7
13.8
106.6
4.6
2-Methylnaphthalene
107.5
5.5
118.1
3.7
1 -Methy lnaphthalene
107.1
5.8
117.3
3.2
Dimethyl Phthalate
71.9
8.9
76.6
4.5
Acenaphthalene
72.2
26.9
77.8
19.1
2,6-Di-tert-butyl-p-cresol
229.1
129.1
201.4
60
Diethyl phthalate
89
1.1
89.9
2.4
n-Hexadecane
106.3
16.9
132.2
30.3
Fluorene
102.5
4.8
105.8
5.5
4-tert-octylphenol
200.8
26.1
219.2
69.6
2-Bromomethy lnaphthalene
18.3
1.4
21.4
3.4
2-Hydroxybenzotliiazole
179.2
51.4
180.4
37.9
Dibenzotliiophene
100.1
1.8
102.5
2.8
Phenantlirene
95.9
3.4
99.1
3.1
Anthracene
95.9
3.4
99.1
3.1
Diisobutyl phthalate
115
12.7
111.4
12.2
3 -Methy lphenanthrene
103.7
8.4
109.4
5.2
2-Methylphenantlirene
94.5
16.2
92.6
3.3
1 -Methy lphenantlirene
100
16.3
101
4.7
Dibutyl phthalate
144.6
15.4
132.9
10.5
Fluoranthene
75.9
1.4
74.9
2.1
Pyrene
78.8
4.1
80
6.3
Benzyl butyl phthalate
167.7
115.8
69.9
4.6
bis(2-ethylhexyl) adipate
181.1
54
147.7
16.5
Benz(a)antliracene
61.7
5.9
63.3
2.7
Clirysene
102.4
1.9
104.2
4.1
Bis(2-ethylhexyl)phthalate
101.8
22.1
83.6
13.3
Di-n-octyl phtlialate
93.9
21
80.1
2
B enzo (b )fluoranthene
81.8
5.6
88
9.5
B enzo (k)fluoranthene
95.1
2.3
95.9
3.3
Benzo(e)pyrene
82.2
5.8
83.2
9.2
Benzo(a)pyrene
80.5
13.5
85.6
6.3
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
298.4
97
300
39.3
123
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Table B-26 Continued
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean %
Recovery
Lab Spike
% Recovery
Standard
Deviation
DBA + ICDP0
82.1
0.8
87.3
6.5
Benzo(ghi)perylene
77.4
1.9
82.9
3.6
Coronene
86.3
17.7
79.5
8.1
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Spikes (n=4). Lab Spikes (n=4); Spike=500 ng
0 DBA + ICDP = Dibenz(a,h)anthracene + Indeno(l,2,3-cd)pyrene
Table B-27 reports recovery results for SVOC analytes in drag sled spiked field controls and spiked
laboratory controls. Average recovery levels above 140% were measured for cyclohexylisothiocyanate,
4-tert-octylphenol, diisobutyl phthalate, dibutyl phthalate, benzo(e)pyrene, and benzo[a]pyrene in field
spike controls. Aniline had average recovery levels of 7% in spiked field controls, likely as a result of
losses during the solvent extraction volume reduction step. 2-bromomethylnaphthalene had an average
recovery of 2% in the spiked field controls. Average recoveries ranged from 46% to 123% for the
remainder of the SVOC analytes.
Table B-27. Field and Laboratory Spike Quality Control Results for SVOCs in Drag Sled Wipes Analyzed
by GC/MS/MSa'b
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean %
Recovery
Lab Spike
% Recovery
Standard
Deviation
Aniline
7
7.3
10.5
8.2
n-Butylbenzene
107.7
10.2
111.6
1.4
Naphthalene
110.8
2.8
107
3.3
Benzothiazole
122.2
3.9
118.5
3.9
Cyclohexylisothiocyanate
172.8
24.7
151.3
58.7
2-Methylnaphthalene
106
1.8
100
1.7
1 -Methy lnaphthalene
104.8
2
98.4
2
Dimethyl Phthalate
88.4
4.8
85.1
5.1
Acenaphthalene
83.2
7.5
78.6
2
2,6-Di-tert-butyl-p-cresol
109.5
20.6
85.2
16.1
Diethyl phthalate
104.9
4
103.5
3.1
n-Hexadecane
99.4
8.7
93.2
2.7
Fluorene
95.1
5
91.9
1.6
4-tert-octylphenol
147.7
10
150
22.4
2-Bromomethy lnaphthalene
1.9
0.2
3.8
0.7
2-Hydroxybenzothiazole
108.1
21.1
96.3
7.2
Dibenzothiophene
61.9
7.1
57.2
4
Phenanthrene
103.9
4.1
105.8
4.8
Anthracene
101.7
3.3
104.1
8.9
Diisobutyl phthalate
142.3
3.8
141
16.4
124
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Table B-27 Continued
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean %
Recovery
Lab Spike
% Recovery
Standard
Deviation
3 -Methy lphenanthrene
120.1
5.6
119.8
5.7
2-Methylphenanthrene
114.7
7.2
119.5
10.9
1 -Methy lphenanthrene
122.5
5.5
124.1
10.8
Dibutyl phthalate
174.4
7.5
163.3
16.2
Fluoranthene
77.1
4.5
73.9
2.2
Pyrene
79.7
4.2
77.1
2.5
Benzyl butyl phthalate
117.6
28.6
101.2
8.2
bis(2-ethylhexyl) adipate
88.7
31.5
65.7
1.4
Benz(a)anthracene
87
2.4
83.8
4.5
Chrysene
96.4
5
95.5
2.7
Bis(2-ethylhexyl)phthalate
105.1
10.5
104.4
9
Di-n-octyl phthalate
114.1
7.3
116.4
3.7
B enzo (b )fluoranthene
47.3
6.4
41.2
2.2
B enzo (k)fluoranthene
70.1
5.9
66.2
2.4
Benzo(e)pyrene
154.3
13
161.1
13.9
Benzo(a)pyrene
147.1
7.5
147.5
7.8
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
91.7
53.3
194.1
82.2
DBA + ICDP0
55.5
7.6
49.1
2.7
Benzo(ghi)perylene
78.4
5
74.9
2.8
Coronene
45.6
11.2
38.1
6.4
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Spikes (n=4), Lab Spikes (n=4); Spike=500 ng
°DBA + ICDP = Dibenz(a,h)anthracene + Indeno( 1,2,3-cd)pyrene
Table B-28 reports recovery results for SVOC analytes in dermal wipe spiked field controls and spiked
laboratory controls. Average recovery levels above 150% were measured for 2,6-di-tert-butyl-p-cresol,
4-tert-octylphenol, diisobutyl phthalate, dibutyl phthalate, and bis(2,2,6,6-tetramethyl-4piperidyl)
sebacate in spiked field controls. The average recovery of 2-bromomethylnaphthalene was 6% in spiked
field controls. Average recoveries ranged from 60% to 144% for the remainder of the SVOC analytes.
No recovery adjustments were performed for the exposure characterization pilot study samples.
125
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Table B-28. Field and Laboratory Spike Quality Control Results for SVOCs in Dermal Wipes
Analyzed by GC/MS/MSab
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean%
Recovery
Lab Spike
% Recovery
Standard
Deviation
Aniline
72.9
30.7
46.5
18.8
n-Butylbenzene
77.4
27.2
96.5
17.8
Naphthalene
95.5
2.9
109.2
10.3
Benzothiazole
86.1
31.3
81.4
16.3
Cyclohexylisothiocyanate
74.3
27.9
93.5
27.4
2-Methylnaphthalene
97.1
8.5
82.9
28.6
1 -Methy lnaphthalene
102.5
8.6
109.1
24.8
Dimethyl Phthalate
70.6
8.7
91.1
13.9
Acenaphthalene
60.4
14.9
70.4
19.3
2,6-Di-tert-butyl-p-cresol
169.4
35.5
166.1
31.1
Diethyl phthalate
95.4
2.3
103.6
14.2
n-Hexadecane
144.1
24.9
126.9
61.4
Fluorene
99.7
20.3
114
23.6
4-tert-octylphenol
188.8
42.1
135.5
61.9
2-Bromomethy lnaphthalene
5.7
4.1
10.3
2.5
Dibenzotliiophene
89.5
9.6
92.3
13
Phenantlirene
96.1
10.5
103.4
3.5
Antliracene
96.5
3.1
94.7
9.1
Diisobutyl phthalate
644.3
28.1
852.7
168.8
3 -Methy lphenantlirene
126.7
7.5
124.2
8.5
2-Methylphenantlirene
104.1
9
105.5
15.3
1 -Methy lphenantlirene
115.6
4.9
111.3
14.8
Dibutyl phthalate
237.5
14.5
310.2
70
Fluoranthene
78.8
3.7
81.4
3.2
Pyrene
76.4
3.1
78.9
2.3
Benzyl butyl phthalate
95.1
5.5
98.7
3.7
bis(2-ethylhexyl) adipate
144
22.1
145.1
17.3
Benz(a)anthracene
69.1
1.5
85.2
31.6
Clirysene
98
5.2
102.6
2.8
Bis(2-ethylhexyl)phthalate
100.9
4.7
104.2
3
Di-n-octyl phthalate
92.8
2.8
101.9
2.7
B enzo (b )fluoranthene
60.7
11.2
63.9
4
B enzo (k)fluoranthene
96.2
7.1
95.9
4.9
Benzo(e)pyrene
95.5
8.7
93.3
7.5
Benzo(a)pyrene
100.6
8.7
96.5
9.8
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
241
46.6
248.8
22.8
-------
Table B-28 Continued
Chemical
Field Spike
Mean %
Recovery
Field Spike
% Recovery
Standard
Deviation
Lab Spike
Mean%
Recovery
Lab Spike
% Recovery
Standard
Deviation
DBA + ICDP0
71.7
15.8
74.2
8
Benzo(ghi)perylene
86.6
4.8
90
3.1
Coronene
51.1
24.4
50.3
6.7
a SVOC = semivolatile organic compound; GC/MS/MS = gas chromatography /tandem mass spectrometry
b Field Spikes (n=5), Lab Spikes (n=5); Spike=500 ng
°DBA + ICDP = Dibenz(a,h)anthracene + Indeno( 1,2,3-cd)pyrene
Precision - Table B-29 shows precision results for SVOC analytes in field air, field wipe and drag sled
duplicate samples when both of the measurement results in a pair were > 0. Average %RSD values for
SVOCs in field air duplicates ranged from 1% to 101%. In many cases, the higher %RSDs were the
result of measurements near or below the minimum quantifiable limits. Average %RSD values for
SVOCs in field wipe duplicates ranged from 2% to 119%, with results for most analytes < 50 %RSD.
Field wipe duplicates may reflect spatial heterogeneity in analytes on the field surface in addition to
measurement precision. In many cases, the higher %RSDs were the result of measurements near or
below the minimum quantifiable limits. Average %RSD values for SVOCs in drag sled duplicates
ranged from 10% to 71%, with results for most analytes < 35%. Drag sled duplicates may reflect spatial
heterogeneity in analytes on the field surface in addition to measurement precision. In many cases, the
higher %RSDs were the result of measurements near or below the minimum quantifiable limits.
Table B-29. Measurement Precision Quality Control Results for Duplicate SVOC Field Air, Field Wipe,
and Drag Sled Samples Analyzed by GC/MS/MSa b
Chemical
Field
Air -
nb
Field Air -
Average
% Relative
Standard
Deviation
Field
Wipe -
nb
Field Wipe -
Average
% Relative
Standard
Deviation
Drag
Sled -
nb
Drag Sled -
Average
% Relative
Standard
Deviation
Phenanthrene
4
42
3
15
3
10
Fluoranthene
4
11
3
12
3
11
Pyrene
4
18
3
14
3
13
Benzo(a)pyrene
1
1
3
4
3
16
Benzo(ghi)perylene
1
40
3
10
3
12
Suml5PAH°
0
NR
3
13
3
10
Benzothiazole
2
49
3
21
3
43
2-Hydroxybenzothiazole
0
NR
3
18
3
25
Dibutyl phthalate
4
89
1
8
3
60
Bis(2-ethylhexyl) phthalate
2
30
3
34
2
35
Aniline
1
20
3
17
0
NR
4-tert-octylphenol
4
31
3
14
3
17
n-Hexadecane
1
48
0
NR
2
40
Naphthalene
2
32
0
NR
1
14
1 -Methy lnaphthalene
1
101
3
44
2
30
127
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Chemical
Field
Air -
nb
Field Air -
Average
% Relative
Standard
Deviation
Field
Wipe -
nb
Field Wipe -
Average
% Relative
Standard
Deviation
Drag
Sled -
nb
Drag Sled -
Average
% Relative
Standard
Deviation
2-Methylnaphthalene
0
NR
3
49
2
33
Acenaphthylene
3
21
2
119
3
14
Fluorene
4
7
2
73
3
33
Anthracene
3
56
2
72
3
15
1 -Methy lphenanthrene
4
34
3
35
3
14
2-Methylphenanthrene
4
28
3
23
3
13
3 -Methy lphenanthrene
4
30
3
21
3
13
Benz(a)anthracene
2
14
3
4
3
18
Clirysene
3
15
3
5
3
10
B enzo (b )fluoranthene
0
NR
3
12
3
18
B enzo (k)fluoranthene
0
NR
3
27
2
33
Benzo(e)pyrene
1
9
3
2
3
13
DBA + ICDPd
0
NR
3
22
3
12
Coronene
1
75
3
24
3
11
Dibenzothiophene
3
18
2
25
3
17
2-Bromomethylnaphthalene
0
NR
0
NR
0
NR
n-Butylbenzene
0
NR
0
NR
0
NR
Dimethyl phthalate
4
29
2
60
3
69
Diethyl phthalate
2
46
1
77
3
71
Diisobutyl phthalate
2
19
1
10
3
51
Benzyl butyl phthalate
2
60
1
60
3
43
Di-n-octyl phthalate
2
96
1
88
3
38
2,6-Di-tert-butyl-p-cresol
1
9
2
47
3
25
Bis(2,2,6,6-tetramethyl-4piperidyl) sebecate
0
NR
3
45
2
44
Cyclohexylisothiocyanate
0
NR
1
34
0
NR
bis(2-Ethylhexyl) adipate
4
65
2
60
3
56
a SVOC = semivolatile organic compound; GC/MS/MS = gas cliromatography/tandem mass spectrometry; NR = not
reported
b Number of duplicate sample pairs in which both measurements are >0.
0 Suml5PAH = Sum of 15 of the 16 EPA 'priority' PAHs, including Acenaphthylene, Anthracene, Benz[a]anthracene,
Benzo[a]pyrene, Benzo(b)fluoranthene, Benzo[ghi]perylene, Benzo(k)fluoranthene, Clirysene, Dibenz[a,h]anthracene,
Fluoranthene, Fluorene, Indeno( 1,2,3-cd)pyrene, Naphthalene, Phenantlirene, Pyrene
dDBA + ICDP= Sum of Dibenz[a,h]anthracene and Indeno( 1,2,3-cd)pyrene
DOI - Recovery and precision DQI objective values were not met for a portion of the SVOC analytes
across the exposure characterization pilot study field air, field dust, field wipe, drag sled and dermal
wipe samples. For each sample type, the quality control results were examined as a whole, and decisions
were made to not report measurement results for some chemicals in Volume 1 of this report. Exclusion
decisions were primarily made because of high background, high recovery or very low recovery.
Analytes that were retained in the report may have not met all DQI objectives in all media.
128
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Analyte measurement results that were not reported in Volume 1 of this report are shown below for each
sample type:
• Field air samples - aniline, napthalene, n-butlybenzene, 2-bromomethylnaphthalene, diisobutyl
phthalate, bis(2-ethylhexyl) adipate, and bis(2,2,6,6-tetramethyl-4piperidyl) sebacate
measurement results were not reported.
• Field dust samples - aniline, napthalene, n-butylbenzene, cyclohexylisothiocyanate, 2-
bromomethylnaphthalene, bis(2-ethylhexyl) adipate, and bis(2,2,6,6-tetramethyl-4piperidyl)
sebacate measurement results were not reported.
• Field wipe samples - aniline, n-butylbenzene, diethyl phthalate, n-hexadecane, 2-
bromomethylnaphthalene, 2-hydroxybenzothiazole, diisobutyl phthalate, dibutyl phthalate,
benzyl butyl were not reported.
• Field drag sled samples - aniline, n-butylbenzene, cyclohexylisothiocyanate, 2-
bromomethylnaphthalene, bis(2-ethylhexyl) phthalate, and bis(2,2,6,6-tetramethyl-4piperidyl)
sebacate measurement results were not reported.
• Dermal wipe samples - cyclohexylisothiocyanate, dimethyl phthalate, diethyl phthalate, 2-
bromomethylnaphthalene, 2-hydroxybenzothiazole, anthracene, diisobutyl phthalate, dibutyl
phthalate, and bis(2,2,6,6-tetramethyl-4piperidyl) sebacate were not reported.
Overall, the methods for SVOC collection and analysis by GC/MS/MS performed adequately, but not
perfectly, for most target analytes. It is likely that better performance in field air sampling would be
obtained through the use of higher flow rates or collection volumes. For this study, it was decided that
portability and battery operation were necessary due to the nation-wide scope of the potential sampling
territory. It was also not certain how much time would be available to set up and take down equipment at
the fields, and whether suitable power supplies would be available. Relatively small amounts of some
analytes were captured with the field wipes and dermal wipes, with some degradation of quality
performance at very low concentrations. The much larger surface area sampled by the drag sled helped
alleviate some of the problems with small analyte amounts for that method. The field dust is a unique
material that may be hard to replicate for preparing suitable quality control samples. The time and
difficulty in collecting dust samples also impacts the ability to collect duplicate samples at fields.
B.4.5 Attempted Measurement ofSVOCs by LC/MS in Field Air, Field Dust, Field Wipe,
Field Drag Sled and Dermal Wipe QC Samples
During the tire crumb rubber sample analyses, tire crumb rubber was extracted using an acetone:hexane
(1:1) solvent mixture for analysis of target SVOC analytes by GC/MS/MS. Extraction was accomplished
using a simple vortex mixing procedure and, due to the relatively high concentrations of most target
analytes, no solvent volume reduction step was required. For tire crumb rubber extracts, a solvent
exchange into methanol was successfully performed to allow analysis of the following analytes in crumb
rubber by LC/MS:
• 2-Mercaptobenzothiazole,
• 2-Hydroxybenzothiazole,
• Cyclohexylamine,
• Dicyclohexylamine,
• N-Cyclohexyl-N-methylcyclohexanamine,
• Diisononylphthalate, and,
• Diisodecylphthalate.
129
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As part of the exposure characterization pilot study, there was interest in learning whether LC/MS
analysis methods could successfully be applied for analysis of SVOCs using the exposure study
environmental and personal samples that were collected and analyzed by GC/MS/MS. All of the air,
wipe, and dust sample media were extracted for GC/MS/MS analysis using an acetone:hexane (1:1)
solvent mixture. Other than for field dust, a solvent volume reduction step was performed to concentrate
the analytes which were present at relatively low levels. Following the GC/MS/MS analyses, the sample
extracts were solvent exchanged into methanol to attempt LC/MS analyses.
The LC/MS quality control results for duplicate samples, field and laboratory blanks, field and
laboratory spiked controls, matrix spike samples, recovery spike samples, and calibration check analyses
were reviewed. Overall, the methods did not meet data quality indicator objectives for any of the target
analytes. Recoveries of spiked analytes in lab and field controls and in matrix spike samples were below
30% in all test samples, and often below 10%. The duplicate samples, when target analytes were
detected, often showed poor reproducibility. Therefore, no exposure characterization pilot study LC/MS
measurement results are included in this report.
Due to the multiple steps needed for extraction, solvent reduction, and solvent exchange to generate
extracts for GC/MS/MS and LC/MS analyses, there are several places where analyte losses could occur
due to volatilization or adsorption to materials. This problem becomes more acute due to the relatively
low amounts of target analytes collected in most samples. In the future, it may be necessary to collect
environmental and personal samples expressly for LC/MS analysis and to develop and test suitable
extraction procedures for those samples.
B.4.6 Field User Questionnaire Quality Control
Field user activity questionnaires were administered to exposure pilot research study participants by
trained interviewers. Interviewers filled out the questionnaire forms during the oral interview.
Questionnaires were reviewed for completeness at the field site. All questionnaires received 100%
duplicate keyed entry; any discrepancies between the two entries were resolved and the data entry was
finalized. Following data entry, the questionnaire results received a data quality review by an
independent staff member. All result compilations for reporting were verified through report table
reviews.
B.4.7 Video Activity Data Analysis Quality Control
B.4.7.1 Publicly-Available Video Data Quality Control
Quality control measures for the publicly available video data acquisition and analysis are described in
Volume 1, Section 3.5.1.
B.4.7.2 Participant Video Quality Control
Quality control measures for the exposure pilot study participant video data acquisition and analysis are
described in Volume 1, Section 3.5.2.
130
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Appendix C
Standard Operating Procedures (SOPs)
for Exposure Characterization Research
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Tables C-l and C-2 list the standard operating procedures (SOPs) that were prepared or used for
the exposure characterization research activities by research area. The SOPs follow the tables
These are research-level SOPs.
Table C-l. Summary of the Exposure Characterization Sample and Data Collection Standard
Operating Procedures (SOPs)
Analytes/Sample Type
SOP Title
EPA SOP Identification Number
Field Metadata
Collection of Field and Activity Metadata
During Exposure Characterization Pilot Study
Field Sampling
D-SED-IEMB-030-SOP-01
Air PUF
Collection of Semi-Volatile Organic Compound
(SVOC) Air Samples at Activity Fields
Involving Tire Crumb Rubber
D-EMMD-SSAB-012-SOP-01
Active air sampling
Collection of Tire Crumb Active Field Ambient
Air Samples for VOCs using Thermal
Desorption Tubes and Low-Flow Pumps
D-EMMD-AQB-024-SOP-01
Passive Air sampling
Radiello Carbopack X Diffusive Sampler
Handling: Field Deployment and Shipping for
Tire Crumb Exposure Studies
D-EMMD-AQB-019-SOP-01
Surface Wipe
Collection of Surface Wipe Samples from
Synthetic Turf Fields
D-SED-IEMB-026-SOP-01
Dermal Wipe
Collection of Dermal Wipe Samples
D-SED-IEMB-028-SOP-01
Field Dust
Collection of Dust Samples from Synthetic Turf
Fields
D-SED-IEMB-029-SOP-01
PM filter sampling
Collection of Particulate Matter (PM) Air
Samples at Activity Fields Constructed using
Crumb Rubber
D-EMMD-SSAB-007-SOP-01
Human activity data
collection
Standard Operating Procedure for Collecting and
Using Extant Publicly- Available Video
D-SED-EHC AB-001 -SOP-01
Human activity data
collection
Videography of Activity Characterization Study
Participants
D-SED-EHCAB-005-SOP-01
Child User
Questionnaire data
Procedure for administering the facility child
user questionnaire
D-SED-EHCAB-004-SOP-01
Adult User
Questionnaire data
Procedure for administering the facility adult
user questionnaire
D-SED-EHCAB-003-SOP-01
132
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Table C-2. Summary of the Exposure Characterization Sample Analysis Standard Operating
Procedures (SOPs)
Analytes/Sample Type
SOP Title
EPA SOP Identification Number
Air sample analysis
Determination of Volatile Organic Compounds
Desorbed from Sorbent Tubes Using the Markes
International Ultra/Unity Thermal Desorption
System
D-EMMD-AQB-018-SOP-01
(Updated Identification Number:
D-EMMD-AQB-SOP-3465-O)
SVOC Air Samples by
GC/MS
Standard Operating Procedure for Preparation of
Air Samples Collected on PUF Plugs for
GC/MS Analysis
D-EMMD-PHCB-036-SOP-01
SVOC Air Samples by
LC/MS
Determination of Selected Organic
Contaminants in Tire Crumb Rubber
Subsamples for Multi-Residue Characterization
by Ultra Pressure Liquid Chromatography/
Tandem Mass Spectrometry (UPLC-MS/MS)
D-EMMD-PHCB-SOP-2327-O
TCR SVOC Extraction
and Analysis by
GC/MS '
Extraction and Analysis of SVOCs in Tire
Crumb Rubber Samples
D-EMMD-PHCB-033-SOP-01
SVOC Field Dust
Samples by
GC/MS/MS
Preparation of Synthetic Field Dust Samples for
SVOC Analysis
D-EMMD-PHCB-068-SOP-01
SVOC Field Wipe
Samples and Dermal
Wipe Samples by
GC/MS
Preparation of Dermal and Surface Wipe
Samples for SVOC Analysis
D-EMMD-PHCB-067-SOP-01
PM filter and dust
metals analysis by HR-
ICP/MS
Extraction of Filter Media for Ion
Chromatography and High Resolution
Inductively Coupled Plasma Mass Spectrometry
D-EMMD-PHCB-071 -SOP-01
(Updated Identification Number:
D-EMMD-AQB-SOP-3465-O)
Metals Extraction for
Solid Samples
Total Nitric Acid Extractable Metals from Solid
Samples by Microwave Digestion
D-EMMD-ECB-003-SOP-01
Metals Extraction for
Wipe Samples
Total Nitric Acid Extractable Metals from Wipe
Samples by Microwave Digestion
D-EMMD-ECB-013-SOP-01
ICP/MS analysis
Operation and Maintenance of the Element
High-Resolution Inductively Coupled Plasma
Mass Spectrometry Instrument
D-EMMD-PHCB-042-SOP-03
133
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U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for the Collection of Field and Activity Metadata During
Exposure Characterization Pilot Study Field Sampling
Number: D-SED-IEMB-030-SOP-01
Effective Date: August 21, 2017
SOP was Developed 0 In-house ~ Extramural
Alternative Identification:
SOP Steward
Name: Kent W. Thomas
Signature: Date:
Approval
Name: Caroline Stevens
Title: Branch Chief, NERL/SED/ffiMB
Signature: Date:
Concurrence*
Name: Christine Alvarez
Title: NERL QA Manager, NERL/SED/IO
Signature: Date:
For Use by QA Staff Only:
SOP Entered into QA Track:
Initials Date
* Optional Field
NERL-SOP.l (7/2003)
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D-SED-IEMB-030-SOP-01
SOP:
Date: August 21, 2017
Page: 2 of 15
STANDARD OPERATING PROCEDURE FOR
COLLECTION OF FIELD AND ACTIVITY METADATA DURING EXPOSURE
CHARACTERIZATION PILOT STUDY FIELD SAMPLING
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 3
5.0 RESPONSIBILITIES 4
6.0 MATERIALS AND REAGENTS 4
7.0 PROCEDURES 4
8.0 RECORDS 88
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 8
10.0 REFERENCES 8
Appendix A. Data and Information Collection Record Forms 9
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
Page: 3 of 15
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) describes the collection of 'meta data' to describe activities
and conditions at a field during exposure characterization pilot field study activities in the tire crumb
rubber research study (TCRS).
2.0 SUMMARY OF THE METHOD
Several types of information will be collected on structured forms regarding activities and conditions
that may be relevant for interpreting measurement results obtained from the TCRs exposure
characterization pilot field sampling events. The general categories of information include:
Meteorological information
Collected on each sampling day
Appendix A pg.
10
General field observations and information
Collected on each sampling day
Appendix A pg.
11
General activity information for the field
Collected on each sampling day
Appendix A pg.
12
Specific information for participant activities
Collected for each research participant
Appendix A pg.
13
Field sampling location record
Collected for each air and field wipe sampling day
Appendix A pg.
14
Field environment record
Collected once
Appendix A pg.
15
Field staff are responsible for recording information on the forms included in this protocol. One form
allows for open-ended observational information to be collected regarding any condition or activity
that might be important in understanding and interpreting results at the specific field or across fields in
the study.
3.0 DEFINITIONS
SOP - Standard operating procedure
TCRS - Tire Crumb Rubber Research Study
CDC - Centers for Disease Control and Prevention
QC - Quality Control
RTP - Research Triangle Park
4.0 CAUTIONS
4.1 No photography is to be performed by any field staff member other than the planned participant
video recordings. No GPS coordinate information will be collected or recorded. All information is to
be based on visual observations and written information on the forms provided with this SOP.
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
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5.0 RESPONSIBILITIES
5.1 The EPA project staff will prepare the SOP and the data collection record forms.
5.2 The field coordinator will assign data collection responsibilities for field staff members, will
review the collected information for content and completeness, and will transmit completed records to
the EPA WACOR.
5.3 The EPA contractor field staff will be responsible for collection and recording data and
observations on these forms:
Meteorological information (pg. 10)
General field observations and information (pg. 11)
Field sampling location record (pg. 14)
Field environment record (pg. 15)
5.4 CDC/ATSDR has agreed to have their field staff record information for the General Field Activity
(pg. 12) and Participant Information (pg. 13) forms. The forms will be provided by the field
coordinator to CDC/ATSDR staff prior to the monitored activities and obtained from CDC staff at the
end of research activities at a field.
6.0 MATERIALS AND RESOURCES
6.1 Meteorological Conditions data collection form
6.2 General Field Information/Observations information collection form
6.3 General Activity Information collection form
6.4 Participant Information collection form
6.5 Field Sampling Location Record Form
6.6 Field Environment Record Form
6.7 Kestrel 5500 or equivalent handheld meteorological measurement device
6.8 Compass
6.9 Portable wind direction vane or streamer
6.10 Ink pen with black ink
6.11 Stopwatch or watch with stopwatch function
7.0 PROCEDURES
7.1 General Data and Information Collection Information
Information regarding field conditions, field environment, and activities will be collected as part of the
exposure characterization pilot field study conducted at each participating fields. Information will be
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
Page: 5 of 15
collected on structured record forms, but will allow for open-ended observations to be recorded. Data
and information collection procedures are described below for each of the six categories of
information.
7.2 Meteorological Conditions Data Collection
7.2.1 Select meteorological information will be measured and recorded at three time points around the
monitored participant activities each day at each field. The three time points include the approximate
start of monitored participant activities, the approximate middle time point of the monitored participant
activity, and at the approximate end time of participant activities. If field staff must prioritize their
time, the priority should be in deploying and collecting participant samples. Meteorological
information can be measured and recorded shortly before or after working with participants, if
necessary. Meteorological measurements should be performed on the synthetic turf field and as close
to the participant activities as is practical and safe.
7.2.2 At each time point, use the Kestrel 5500 handheld meteorological measurement device.
7.2.2.1 Record the time of day the observations were begun for each time period.
7.2.2.2 Power on the device by pressing and holding the 'on' button.
7.2.2.3. Allow the device to equilibrate to current conditions at 1 m above the field surface for five
minutes.
7.2.2.4 Press the 'mode' button to obtain the temperature reading in °C and record the temperature
measurement at a 1-m height above the field. Note: the Kestrel 5500 will be shaded during this
measurement period to avoid direct sunlight causing and incorrect reading of ambient air temperature.
7.2.2.5 Power the device off by holding the 'on' button. Determine the prevalent wind direction at a 1-
m height using a portable vane or streamer. Aim the wind meter rotor at the prevalent wind direction at
a 1-m height above the field. Turn the device on, and after 60 seconds press the 'mode' button until the
average wind speed is displayed. Record the average 60-second wind speed. Press the 'mode' button
again to get the peak wind speed during the 60-second period and record the peak wind speed. Record
wind speeds in units of km/h.
7.2.2.6 Use a compass to determine the predominant direction the wind is coming from. Record the
direction the wind is coming from in compass degrees from magnetic north.
7.2.2.7 Place the device flat on the surface of the field in an exposed location for five minutes to
measure the field surface temperature. After five minutes, and while the device is still on the field,
cycle through the 'mode' button to obtain the temperature reading. Record the field surface
temperature in °C.
7.2.2.8 By observation, record whether the field surface is wet from dew (yes/no), whether the field is
wet from rain or other source of water besides dew (yes/no), and the current general sky conditions
(sunny, partly cloudy, cloudy, drizzle, rain).
7.2.9 7.2.9For each day of meteorological data collection, record the field ID number, date, and
whether the field is an indoor or outdoor field.
7.3 General Field Information/Observations
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
Page: 6 of 15
7.3.1 Use the General Field Information/Observations collection form to record information about the
field and surrounding environment that may be useful for understanding and interpreting the exposure
characterization pilot study measurement results. This is an open-ended observational record form that
should be completed on each day of monitored participant activities.
7.3.2 The form lists several examples of types of observations of interest as examples. However, the
field staff should record information for any observations they believe should be communicated.
7.3.3 The form can be partially completed prior to or after monitored participant activities if the
observations are about something that will not change or vary during the monitored activities.
However, observed conditions potentially affecting or relevant to measurements performed should be
recorded during the monitored participant activities. For example, the level of traffic on adjacent roads
or parking areas could be relevant to the air sample collection measures.
7.3.4 Depending upon the type of observation, it may be necessary to also include the time or time
interval that you observed the condition or activity. Such examples might include a car, truck or bus
idling in the parking lot or road; precipitation conditions or construction activities.
7.3.5 For each day of information collection, record the field ID number and date.
7.4 General Activity Information
7.4.1 Use the General Activity Information collection form to record information about the overall
activities (types and estimated numbers of people) that occur on the participant activity field and
surrounding fields during the monitored participant activity. A new form should be used for each day
of monitored participant activities at each field.
7.4.2 Information should be collected at three time points including the approximate start of monitored
participant activities, the approximate middle time point of the monitored participant activity, and at
the approximate end time of participant activities.
7.4.3 The structured form lists specific types of information to collect.
7.4.4 For each day of information collection, record the field ID number and date.
7.5 Participant Information
7.5.1 Use the Participant Information collection form to record information about each participant
during their monitored activity at the synthetic turf field. A new form should be used for each
participant. The form should be completed for all participants, including those that are participating in
the video recording portion of the study. The research team plans to have participants wear pinnies
with unique participant identifiers (1 - 8) to differentiate the participants. A maximum of four
participants per day is expected.
7.5.2 Information about participant activities should be at the start, at approximately 30-minute
intervals, and at the end of their monitored activity. Information about participant clothing and
equipment should be collected once during the monitored activity; if the clothing or equipment
changes then that should be recorded as well.
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
Page: 7 of 15
7.5.3 The structured form lists specific types of information to collect.
7.5.4 For each participant information collection record, record the field ID number, date, and
participant number.
7.6 Field Sample Location Record
7.6.1 Use the Field Sample Location Record form to record the sample collection location for each
type of sample collected. The form should not be used for quality control samples. Only one form
should be completed for each field even if samples are collected on more than one day.
7.6.2 A single letter code should be used for type of sample:
Field SVOC wipe locations S
Field metals wipe locations M
Field SVOC drag sled locations D
Air sample station locations A
7.6.3 On the field diagram, write the sample type code at each place on the field where samples are
collected. For the upwind off-field air sample station, place the code in the correct direction for the
field orientation, and write down an estimate of the distance (in meters) from the center point of the
field.
7.6.4 In the upper right corner box, draw a directional arrow representing magnetic north using a
compass.
7.6.5 Record the field ID number and sample collection date (or the first day of sample collection if it
is performed over more than one day; for example, if air samples are collected on one day and wipe
samples on another).
7.7 Field Environment Record Form
7.7.1 Use the Field Environment Record form to sketch and label the built and natural structures
within approximately 100 meters of the field in each direction. The form needs to be completed only
one time, and can be completed during times that don't involve participant activities.
7.7.2 Of interest are parking areas, other fields, buffers, buildings, roads and other natural and built
features.
7.7.3 Note the approximate off-field sampling station location.
7.7.4 In the upper right corner box, draw a directional arrow representing magnetic north using a
compass.
7.7.5 Record the field ID number and sample collection date (or the first day of sample collection if it
is performed over more than one day; for example, if air samples are collected on one day and wipe
samples on another).
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
Page: 8 of 15
8.0 RECORDS
The data and information will be collected on the forms described above and shown in Appendix A.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE
The field coordinator should collect all forms at the end of each sample collection day to verify
completeness and to ensure the content meets the data and information requirements described in this
SOP.
10.0 REFERENCES
No references are cited for this SOP.
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21, 2017
Page: 9 of 15
Appendix A
Data and Information Collection Forms
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21,2017
Page: 10 of 15
Meteorological Conditions
TCRS Exposure Characterization Study
Meteorological Conditions
Note: Complete this form for each day of monitored participant activities at each field. DRAFT
Field ID Number
Date
Outdoor or Indoor Field
Near Start of
Near Middle of
Near End of
Metric/Information
Participant Activities
Participant Activities
Participant Activities
Time of Day (Military time format)
Field AirTemperature at 1 m (°C)
Field Surface Temperature (°C)
Wind 1-minute average speed (km/h)
Wind 1-minute maximum speed (km/h)
Wind direction (compass degrees,
where wind is coming from)
Dew on field (yes/no)
Field wet from rain or watering (yes/no)
Conditions (sunny, partly cloudy,
cloudy, drizzle, rain)
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21,2017
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DRAFT
TCRS Exposure Characterization Study
General Field Information/Observations
Use this form to record observations that may be relevant to the research study.
Examples include, but are not limited to, condition of field, field maintenance, construction on/nearfield,
adjacent high traffic on roads or parking areas, ventilation information for indoor fields, other relevant information.
Use a different row for each type of observation.
Field ID Number
Date
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21,2017
Page: 12 of 15
TCRS Exposure Characterization Study General Activity Information
Note: Complete this form for each day of monitored participant activities at each field. DRAFT
Field ID Number
Date
At Start of
Near Middle of
At End of
Metric/Information
Participant Activities
Participant Activities
Participant Activities
Approx. Number People in Active Play
on Study Field
Approx. Number People as Bystanders
on Study Field
Sport Name on Study Field (soccer,
football, etc.)
Type of Active Play on Study Field (1)
Type of Active Play on Study Field (2)
Type of Active Play on Study Field (3)
Type of Active Play on Study Field (4)
Type of Active Play on Study Field (5)
Adjacent Synthetic Fields in Use
(yes/no)
Approx. Number People at Adjacent
Synthetic Fields
Adjacent Grass Fields in Use (yes/no)
Approx. Number People at Adjacent
Grass Fields
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D-SED-IEMB-030-SOP-01
SOP:
Date: August 21,2017
Page: 13 of 15
TCRS Exposure Characterization Study Participant Information
DRAFT
Note: Complete this form for each participant at each field.
Field ID Number
Date
Participant ID
(from 1 to 8)
At Sta rt of
Approx. 30 minutes Into
Approx. 60 minutes Into
Approx. 90 minutes Into
Approx 120minutes Into
At End of
Metric/Information
Participant Activities
Pa rti cipant Activities
Parti cipa nt Activities
Participant Activities
Pa rti cipant Activities
Pa rti ci pa nt Activities
Time of Day (military time format)
Activities
Sport Name (soccer, football, etc.)
Sport Position (goal keeper, soccer
field player, football receiver, etc)
Type of Activities on Study Field
Physical Activity Level (low,
medium, high)
Contacting Turf (yes/no)
Types of Turf Contact (hands,
arms, legs, face, body)
Frequency of Turf Contact (>
1/min; > l/5min; < l/5min)
Clothing/Equipment Types (record only once - not at each time period)
Shirt (yes/no; long/short)
Pants (long/short)
Socks (yes/no; high/mid/low)
Gloves (yes/no and type)
Head Gear (yes/no and type; hat,
helmet, other)
Mouth Guard (yes/no)
Pads (yes/no and type; shoulder,
hip, leg, other)
Wearing sunscreen
Wearing bug repellent
Other Information
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21,2017
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Field Sampling Location Record Form
Field ID Number
Field SVOC wipe locations S
Field metals wipe locations M
Field SVOC drag sled locations D
Air sample station locations A
(For off-field upwind air sample station estimate and record
distance from field center; record type of ground surface)
Draw Magnetic North Direction Arrow Here
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SOP: D-SED-IEMB-030-SOP-01
Date: August 21,2017
Page: 15 of 15
Field Environment Record Form
Field ID Number
Sketch and label features within approx.. 100 m of field
Include roads, parking areas, other fields, buffers, buildings
or other natural and built features
Record approximate off-field sampling station location
Draw Magnetic North Direction Arrow Here
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Crumb Rubber SVOC Sampling
D-EMMD-SSAB-012-SOP-01
Page 1 of22
8/21/2017
U.S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
National Center for Computational Toxicology
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Procedure for the Collection of Semi-Volatile Organic Compound
(SVOC) Air Samples at Activity Fields Involving Tire Crumb Rubber
Number: d-emmd-ssab-012-sop-oi
Effective Date: August 21, 2017
SOP was Developed
In-House
~ Extramural
Alternative Identification:
SOP Steward
Name: Andrea Clements
Signature/Date:
Approval
Name: Chandra Giri
Title: SSAB Branch Chief
Signature/Date:
Concurrence
Name: Sania Tong Argao
Title: EMMDQAM
Signature/Date:
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Crumb Rubber SVOC Sampling
D-EMMD-SSAB-012-SOP-01
Page 2 of22
8/21/2017
PROCEDURE FOR THE COLLECTION OF SEMI-VOLATILE ORGANIC COMPOUND
(SVOC) AIR SAMPLES AT ACTIVITY FIELDS INVOLVING TIRE CRUMB RUBBER
Table of Contents
1.0 Scope and Application 3
2.0 Summary of Method 3
2.1 Definitions 3
3.0 Prerequisites Prior to Field Sampling 3
3.1 Equipment and Supplies 4
3.2 Training Requirements 5
4.0 Cautionary Notes or Special Considerations 5
5.0 Procedures 6
5.1 Pump and Sampling Set-up 6
5.2 Pre- and Post-Sampling Flow Rate Measurement 8
5.3 Sample Collection 9
5.4 Labeling the Samples 11
5.5 Pump/Equipment Take Down 12
5.6 Return Filter Samples to the EPA Laboratory 12
6.0 Quality Control 13
6.1 Field Blanks and Field Controls 14
6.2 Duplicate Samples 14
6.3 BIOS Flow Calibrator Calibration 14
7.0 General Sampling Precautions 15
8.0 Possible Corrective Actions for Observed Problems During Sampling 15
8.1 Pump Failure 15
8.2 Possible Contamination of Filters or Supplies 15
9.0 Recordkeeping 15
9.1 Datasheets 15
9.2 Calculations 15
9.3 Chain-of-Custody 16
Appendix I. SVOC Air Samples Data Collection Sheet and Chain of Custody Forms 17
Appendix II. Battery Tender - Portable Battery Chargers - Owner's Manual 22
Appendix III. BIOS DryCal DC-Lite Flow Calibrator Manual 22
NOTICE
This Analytical Procedure has been prepared for use by the Sensing and Spatial Analysis Branch
of the U.S. Environmental Protection Agency, Research Triangle Park, North Carolina and may
not be specifically applicable to the activities or objectives of other organizations. This procedure
has not been fully validated and should be used for research purposes only. Adequate QA/QC
measures must be implemented with this procedure to allow assessment of data quality.
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Crumb Rubber SVOC Sampling
D-EMMD-SSAB-012-SOP-01
Page 3 of22
8/21/2017
1.0 Scope and Application
This method applies to the collection of semi-volatile organic compounds (SVOCs) from
ambient air at activity fields that utilize crumb rubber and/or artificial turf. Samples will be
analyzed for a suite of SVOCs.
2.0 Summary of Method
Portable, battery operated, air sampling pumps equipped with polyurethane foam (PUF)
cartridges will be used to absorb gas-phase and particle-phase SVOCs from ambient air.
2.1 Definitions
COC - chain-of-custody
Field Blank - sampling media that travels with and is handled like regular sampling media
with the exception that it is never opened and exposed to the environment for sampling
Field Control - sampling media that has been spiked with a known concentration of select
compounds. This media also travels with and is handled like regular sampling media with
the exception that it is never opened and exposed to the environment for sampling
PUF - polyurethane foam
QAPP - quality assurance project plan
SOP - standard operating procedure
SVOCs - semi-volatile organic compounds
VOC - volatile organic compounds
OD - outer diameter
ID - inner diameter
lpm - liters per minute
3.0 Prerequisites Prior to Field Sampling
JTI will test sampling pumps. Use the procedure outlined in Section 5.2 to verify the
sampler can achieve and maintain a flow rate of 20 lpm. EPA has provided a number
of working pumps including spares. If a pump is not working, switch out the pump with
one that can.
JTI will replace the Tygon tubing (V2 inch OD, 5/16 inch ID, 3/16 inch wall) if visually
dirty, sticky, or occluded in order to protect the pump only. It does not need to be
replaced after each field study. EPA provided new, clean tubing at the start of the study
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Crumb Rubber SVOC Sampling
D-EMMD-SSAB-012-SOP-01
Page 4 of 22
8/21/2017
and it should last for the duration.
JTI will charge batteries. EPA has supplied a working 4-Bank Battery Charger (Battery
Tender P/N 022-0148-DL-WH). After connecting the charger to power and connecting
the batteries to the charger using the attached cords, charging will be automatic and
lights will turn solid green when battery charging is complete. More charging
information is available in the user's manual (Appendix II).
JTI will test the flow meter. EPA has supplied a working BIOS DryCal DC- Lite (Model
DCL-H Rev. 1.08) and JTI should only need to charge the unit using the power cord
supplied. If needed, a manual including operating, charging, maintenance, calibration,
and leak check procedures is available (Appendix III).
EPA will clean and prepare PUF cartridges, including blanks.
EPA will spike field control PUF cartridges.
EPA will print and label resealable bags containing sample media. Section 5.4 covers
the naming convention for the samples.
JTI will pack all field supplies listed in Section 3.1. Most equipment loaned by the EPA
has transportation enclosures. All equipment should be packed so as to avoid damage.
Equipment and Supplies
Sampling Media (University Research Glassware URG- 2000-25 Personal Pesticide
Sampler)
o PUF filter media (URG-2000-25CC) - qty. 7+ per sampling day
o Glass tubes (URG-2000-25D) - qty. 7+ per sampling day
o Cartridge caps (URG-2000-25J and H) - qty. 2 per cartridge
o Cartridge plugs (URG-2000-DUSTCAP and DUSTPLUG) - qty. 2 per cartridge
¦ For these experiments, the clean PUF media will be installed in the glass
tubes which will be stored inside the cartridge caps, plugged on the ends
with orange cartridge plugs, wrapped in clean aluminum foil, and placed
in a resealable bag for transport to and from the field.
Sampling Setup
o Protective enclosure (e.g., 18 in X 18 in X 12 in) for pumps/batteries - qty. 5
o Sampling pumps - SKC AirCheck HV30 pump - qty. 5
o Flathead screwdriver for adjusting pump flowrate
o Battery - 12V DC, 17Ah sealed lead-acid battery or equivalent - qty. 5
o Battery Power Adapter - qty. 5
o Sampling stand (vertical rod that connects to the enclosure) - qty. 5
o Three pronged clasps for the ring stand - qty. 5
o Tygon flexible plastic vacuum tubing (V2 inch OD, 5/16 inch ID, 3/16 inch wall)
o Measuring tape
Flow Measurement
o Flowmeter - BIOS DryCal DC- Lite (Model DCL-H Rev. 1.08) or equivalent
o PUF cartridge flow adapter (PUF cartridge with tubing for connecting to BIOS)
Sample Handling and Storage
o Brown cardboard shipping box for sample tubes (a box roughly 7"x5"x5" will
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hold a day's worth of samples)
o Bubble wrap or bubble envelopes for sample protection during shipment
o Sample cooler for storing samples (lOqt or larger as needed to hold sample
shipping box(s) and ice packs)
o Re-freezable ice packs
o Zip closure bags for storage/shipment of PUF cartridges
Sample Tracking
o SVOC Air Samples Data Collection Sheet and Chain of Custody Form (see
Appendix I)
o Pen (Black, Permanent Ink)
o Time enabled device - cell phone is ok
o Shipping labels
Spare and other potentially useful supplies
o Plastic kitchen size garbage bag (non-scented)
o Aluminum foil
o Packaging tape
o Kimwipes
o Scotch tape
o Extra labels
3.2 Training Requirements
All training required is provided by the US EPA. Sample collection will be conducted by
qualified scientific staff trained in the use of the specific field monitoring equipment.
Training will include a demonstration and hands-on training by qualified persons with air
sampling expertise. At a minimum, all SOPs and operating instructions will be reviewed,
understood, and followed exactly by the field staff. Training records will be maintained by
the exposure study project lead (Kent Thomas).
4.0 Cautionary Notes or Special Considerations
The sampling systems are powered by sealed lead acid batteries (gel cell). The battery and
pump system should be protected from excessive heat or cold (<50 °F, >104 °F). Pumps
and batteries are shielded from direct exposure by means of an outer protective enclosure
(see Figure 1). Precautions must be taken against shorting across the battery terminals or
reversing polarity of the power leads. Shorting of the battery may cause a rapid discharge
that will generate excessive heat and may result in a fire or severe burns. Reversing the
polarity (attaching positive to negative) may damage the pump or battery. Red (+) wires
should be attached to the red (+) battery terminal and black (-) wires should be attached to
the black (-) terminal.
Sampling may take place outside and personnel should be equipped to shield the samples
from possible weather events. Plastic trash bags or a tarp or other plastic bin can be used to
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cover the pumps/batteries. If sampling is stopped, the entire apparatus may be covered,
simply stop the pump and put the cap back onto the PUF sampler.
Sampling stands should be set-up so that they are provided protection from tampering.
Sampling stands must also be placed and secured such that no harm will come to children
or others playing in the vicinity of the equipment. Protective enclosures and plastic fencing
are provided and should be used to insure safety.
5.0 Procedures
The following procedures are listed below for Section 5.0.
1. Pump and Sampling Set-up
2. Pre- and Post-Sampling Flow Rate Measurement
3. Sample Collection
4. Labeling the Samples
5. Pump/Equipment Take Down
6. Return Filter Samples to the EPA Laboratory
NOTE: Set up the pump system at the correct location in advance of the anticipated on-field
activity so all sampling stations will be ready prior the beginning of the monitored on-field
activity.
5.1 Pump and Sampling Set-up
5.1.1 Transport the sampling setup and flow measurement equipment to the field location.
This will include protective enclosures, sampling pumps, batteries, power cords,
sampling stands, 3-pronged clasps, vacuum tubing, small screwdriver, and
measuring tape to the field location along with the data collection sheets, PUF
cartridge flow adapter, flow meter, pen, and any materials needed to secure the
monitoring site.
5.1.2 Three sampling sites will be identified for each field location and positioning of the
SVOC samplers is defined in the project Quality Assurance Project Plan (QAPP).
Two sites will be located next to or as close as possible to the activity field. One
site will be located off of the field, in an upwind position if possible. One sampler
will be located at each site and an additional sampler will be positioned at one of the
on-field locations to collect a duplicate sample. The project QAPP provides
guidance for drawing a map of the field to document the position of samplers. (See
D-SED-IEMB-030-SOP-01 Collection of Field and Activity Metadata During
Exposure Characterization Study Field Sampling for details.)
5.1.3 Figure 1 shows the sampler configuration and the major components are identified.
Use this diagram to setup each sampling location. Note that only part of the URG-
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2000 cartridge is being used to collect the SVOC sample (the larger cap containing
the impactor plate has been removed).
Battery
I
Vacuum
Pump
Tubing
Protective
Enclosure
Battery
Power
Adapter
3-Prong
Clasp
-Vacuum
Tubing
(do not pinch)
PUF
Cartridge
Figure 1: SVOC Sampler Configuration
Sampling
Stand
Sampling
Stand
Holder
5.1.3.1 Open the metal protective case and set it on the ground.
5.1.3.2 Setup the sampling stand by inserting one end of the sampling stand into the
holder on the metal protective enclosure and attaching the 3-prong clasp to the
other end of the sampling stand.
5.1.3.3 Adjust the placement of the clamp on the ring stand until the measured
distance between the ground and the clamp is approximately 1 meter.
5.1.3.4 Open the pump, remove the tubing tucked inside the lid, and connect one end
to the hose barb found on the right rear of the pump unit. The attached hose
should be snug and not easily removed without use of applied force. Set the
pump into the protective enclosure on its side so that the hose is positioned
straight up.
5.1.3.5 The vacuum tubing will connect to the PUF cartridge once installed. Fornow,
loop the tubing up and over into the clasp. The upper loop of tubing will
ensure the tubing will not kink once the sampler is attached. (Note: If the
tithing kinks, secure the tubing with a zip tie (not tape) to the sampling stand
to maintain the upper loop.)
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5.1.3.6 Place the battery into the lid of the protective enclosure. Attach the battery
power adapter to the pump unit by inserting the adapter into the 12V input
jack on the right rear of the pump unit near the hose barb. Attach the battery
adapter leads to the appropriate terminals of the battery. Attach the red lead to
the positive (+) red terminal and the black lead to the negative (-) black
terminal. Make sure good contact is made.
Pre- and Post-Sampling Flow Rate Measurement
Note: Flow rate measurement will take place before and after field
sample collection.
5.2.1 A "dummy" PUF cartridge and tubing (collectively referred to as the SVOC flow
adapter) will be sent along in a bag marked "flow adapters for SVOC sampling."
5.2.2 Remove the SVOC flow adapter and remove the orange/red plug from the end of the
"dummy" PUF cartridge. Inset this end into the vacuum tubing connected to the
sample pump.
5.2.3 The other end of the "dummy" PUF cartridge will be connect to a piece of tubing.
Connect this tubing to the bottom barb (outlet) on the BIOS flowmeter.
5.2.4 Turn on the pump by opening the pump lid and sliding the on/off switch located on
the pump deck to the "on" position (up). Allow the pump to run for 3-5 minutes to
warm-up and stabilize.
Note: The pump flow rate should be close to 20 1pm because the flow
rate was adjusted to this point using the flow adjustment screw
in the laboratory prior to field deployment. This will minimize
the amount of time required to fine adjust the pump flow after
the PUF sampler is attached.
5.2.5 After the stabilization period, press the "on" button of the BIOS unit.
5.2.6 Press and hold the "Read" button for approximately 3 seconds. This will activate the
unit to make continuous measurements and automatically average 3 replicate
readings.
5.2.7 Observe the flow rate values being displayed.
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5.2.8 If needed, adjust the flow rate to 20.0 ±1.0 1pm. While observing the calibrator
display, use a small screwdriver to adjust the flow adjustment screw (located just to
the left of the on/off switch) to adjust the flow rate. Adjustment should be made by
gently turning the screw clockwise or counterclockwise to increase or decrease the
pump flow rate. Make adjustments in partial turns.
5.2.9 Once adjusted to 20.0 ±1.0 1pm allow the flow to stabilize for one minute. After 3
readings, record the average flow rate on the SVOC Air Samples Data Collection
Sheet and Chain of Custody Form in the 'Flow' column. There is space for the
measurement before and after sample collection (Appendix I).
5.2.10 Turn off the pump, remove the "dummy" PUF cartridge from the sample pump
tubing and move-on to check the flow on the other sampling setups.
Sample Collection
5.3.1 The PUF cartridge will be sent wrapped in aluminum foil and stored in a resealable
bag labeled with the sample ID (see Section 5.4 for details). Prior to the anticipated
start of the monitored on-field activity, determine the appropriate sample ID and
retrieve the appropriate bag. Section 5.4 gives details about how the sample media
is labeled. Briefly, the ID numbers will have the form TCRS-R-VV-W-X-Y-Z
where position W (F for field or D for duplicate) and Y (on-field position 1, on-field
position 2, off-field position 8) will help you identify the appropriate filter media for
each sampling station.
Note: The next step will begin handling of the PUF cartridge. Please clean
your hands to the best of your ability using water and kimwipes. For
SVOC sampling, technicians should use clean hands and minimize
contact with the sample cartridge rather than don gloves as most nitrile
gloves contain phthalates that can contaminate these samples.
Technicians can use the aluminum foil that comes wrapped around the
cartridge as a barrier to minimize contact with the sample cartridge.
5.3.2 Remove and unwrap the PUF cartridge being sure to retain the bag and place the
aluminum foil inside to keep it clean. {If the foil becomes soiled, throw it away.)
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Figure 2: PUF filter cartridge
5.3.3 Looking at the PUF cartridge, you will see that the caps are two different sizes.
Remove the longer orange/red plug from the smaller/shorter cap and place it into the
resealable bag.
5.3.4 Insert the open end of the PUF cartridge into the vacuum tubing attached to the
sample pump. Secure the PUF cartridge on the sampling stand using the 3-prong
clasp being sure that the clasp is centered on the upper, shorter cartridge cap (see
Fig. 1).
Note: The next step will expose the PUF filter media. DO NOT touch the PUF
plug (white foam-like piece). If you MUST touch the glass tube, do so
with a clean, dry kimwipe or gloves if you must. Gloves should NOT be
worn unless absolutely necessary for cleanliness as compounds from the
gloves may interfere with this SVOC measurement.
5.3.5 Remove the bottom, longer cartridge cap (with the smaller orange plug) and place it
back into the resealable bag. Place the resealable bag in or under the pump or pump
box for safe keeping until sample retrieval. DO NOT separate the resealable bag
from the sampling media as this will increase the likelihood that samples will be
mixed up.
5.3.6 The sampling setup should now look exactly like Figure 1. Double check the length
of tubing and remove any kinks. Adjust the clamp so the inlet to the PUF cartridge
is at 1.0 ± 0.1 meters
5.3.7 Sample collection should be initiated prior to the start of the monitored on-field
activity so that sampling at all three locations is underway at the time the on-field
activity begins. Ideally, sample collection will be initiated within 30 minutes of the
start of the monitored activity (with a maximum time of 60 minutes prior). To
collect field samples, turn on the pump by opening the pump lid and sliding the
on/off switch located on the pump deck to the "on" position (up).
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5.3.8 Record the sample start time on the SVOC Air Samples Data Collection Sheet and
Chain of Custody Form (Appendix I)
5.3.9 Close the pump lid and settle it into the protective case with the vacuum tubing
pointing up. Double check the tubing for kinks and correct if necessary.
5.3.10 Sampling may continue for a period after participant on-field activities are
completed so that all personal participant samples can be collected as quickly as
possible. Ideally, sample collection will be completed within 30 minutes of the
completion of the monitored activity (with a maximum time of 60 minutes after).
As soon as feasible following the monitored on-field activity, open the pump lid and
turn off the pump by sliding the on/off switch located on the pump deck to the "off
position (down).
5.3.11 Record the sample stop time on the SVOC Air Samples Data Collection Sheet and
Chain of Custody Form (Appendix I).
5.3.12 Retrieve the original resealable bag containing the aluminum foil, cartridge cap, and
orange plug. Double check the sample ID to be sure the sample is appropriately
labeled. Remove the longer cartridge cap from the bag and press it on to the open
end of the PUF cartridge. Detach the PUF cartridge from the vacuum tubing and
insert the long orange plug onto the shorter cartridge cap. Wrap the entire cartridge
back in the aluminum foil (if clean and available, otherwise omit) and place it in the
resealable bag with the sample ID.
5.3.13 Place the sample in the cooler chilled with frozen ice packs until placed into freezer
storage (no higher than -4°C) until they are shipped to the EPA Laboratory (see
Section 5.6).
5.3.14 Repeat the flow rate measurement (described in Section 5.2) and record the stop
flow on the SVOC Air Samples Data Collection Sheet and Chain of Custody Form
(Appendix I).
Labeling the Samples
5.4.1 Labels for these samples will be generated at the EPA lab (using the convention
outlined in Section 5.4.2) and placed on the resealable bags containing the clean
PUF cartridges before they are transported to the field. At the end of sampling
period, the sampled PUF will be returned to this bag in accordance with Section 5.3.
5.4.2 Samples are labeled according to the convention:
TCRS-R-V V - W-X-Y-Z
where:
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TCRS designates the tire crumb rubber research study.
R designates the participant identification number
Use 0 for these samples as they are not associated with a specific
participant.
VV designates the field ID
This two-digit code will be a unique identifier for each field
numbered in the range of 70-79.
W designates the sample type
F = sample
D = duplicate sample
B = field blank
C = field control
X designates the analysis method
Use B to denote field air SVOC sampling.
Y designates the sample collection location
1 or 2 will be for on-field air locations
8 will be for the off-field air location
Z designates the parent/sub-sample as needed
Use 0 to designate these samples as the parent sample.
Use L to designate laboratory QC samples.
5.5
5.6
Pump/Equipment Take Down
5.5.1 Remove the sample pump from the protective enclosure.
5.5.2 Disconnect the tubing from the sample pump and store it inside the pump box.
5.5.3 Disconnect the power adapter from the sample pump and battery. Store the adapter
inside of the pump box.
5.5.4 Re-pack all supplies into their original shipping containers and prepare for departure
and transport of all supplies to the EPA laboratory.
Return Filter Samples to the EPA Laboratory
5.6.1 All filter media should be stored at the field location in a cooler chilled with frozen
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ice packs until they can be shipped to EPA. The samples should be shipped back to
the EPA laboratory within two days following sample collection. Samples may be
driven back to the laboratory provided they are stored in a cooler with frozen ice
packs.
5.6.2 For sample shipment, pack the cooler just prior to shipping as follows:
5.6.2.1 Pack the PUF sample cartridges in bubble wrap inside a brown cardboard
box. Tape the box shut and add it to the bottom of the cooler.
5.6.2.2 Add a layer of frozen ice packs to completely cover the storage boxes.
5.6.2.3 Repeat the previous 2 steps as needed until all filter media has been packed
for transport.
5.6.2.4 As available and as necessary to keep the exposed filter media from shifting
and breaking during transport, add any available ice packs to the cooler
followed by unexposed filter media and any padded packing material.
5.6.2.5 Snap a photo of the sample data collection and COC forms (retain in case of
damage during shipping, discard after they are recorded by EPA) and then
add the data collection and COC forms to a resealable bag. Place the bag on
top of the cooler contents and then seal the cooler.
5.6.3 Mail the packed cooler to the EPA laboratory using next day air FedEx or similar
overnight delivery service. Address the shipment to:
US EPA Chemical Services
Kent Thomas or Scott Clifton
109 T.W. Alexander Drive
Building E Loading Dock, Rm El78
Research Triangle ParkNC 27709-0002
Telephone:919-541-7939
5.6.4 Immediately notify Kent Thomas (thomas.kent@epa.gov) or Scott Clifton
(clifton.matthew@epa.gov) of the incoming shipment via email. Include the
shipment tracking number.
Quality Control
The quality control requirements will allow assessment of the quality of the samples
collected. Determination of possible contamination and reproducibility of the method will
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be targeted as data quality indicators.
6.1 Field Blanks and Field Controls
A minimum of 1 field blank and 1 spiked field control will be collected each sampling day.
The project's quality assurance project plan will detail the quality control sample types,
numbers, and deployment plan (see Section B5 of Quality Assurance Project Plan
Addendum for the Tire Crumb Research Study - Exposure Characterization Pilot Study (D-
SED-IEMB-006-QAPP-02)).
6.1.1 As stated in Section 5.2.1, the PUF cartridge will be sent plugged with orange
fittings, wrapped in aluminum foil, and stored in a resealable bag. Resealable bags
containing PUF cartridges meant for field sampling and for field blanks and controls
will be marked with the sample ID (see Section 5.4)
6.1.2 Field blank(s) and field control(s) will be taken to the synthetic turf field along
with the sample filters. The field blank(s) and field control(s) will NOT be
opened or deployed but should be handled just like field samples in that they
should be transported to the field and put into cold storage at the same time as
the field samples. These blanks will NEVER be removed from the resealable
storage bags.
6.1.3 The field blank(s) and field control(s) will be stored and shipped along with the
sample filters.
6.2 Duplicate Samples
Duplicate samples shall be collected at a single on-field location during each day of field
measurement. Two sampling systems (pump/inlets) shall be positioned within 2 meters of
each other and operated as specified in Section 5. The purpose of duplicate samples is to
determination of precision of the sampling method in its entirety.
6.3 BIOS Flow Calibrator Calibration
The BIOS flow meter will be used to determine the flow rate through the sampling media.
Because the unit is equipped with a mass flow controller and because of sampling conditions
(pump not operated at max flow and pressure drop sufficiently low), the flow rate can be
considered stable during sampling.
This BIOS flow meter was calibrated by the manufacturer and no adjustment or additional
calibration of this device is needed. The flow meter should be sent back to the manufacturer
or to another source for re-calibration if it has been greater than 1 year since the calibration
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certification date or if flow meter is not operating properly.
7.0 General Sampling Precautions
o Pumps should never be operated without a filter in-line.
o Pumps should be calibrated against the reference BIOS. Calibration should take
place just prior to sampling initiation and after sampling as noted in section 5.2.
o The flow rate will be used in conjunction with the total elapsed sampling time to
calculate total air volumes sampled and integrated analyte concentrations observed
during the sample capture period.
8.0 Possible Corrective Actions for Observed Problems During Sampling
8.1 Pump Failure
o If a pump fails, correct any obvious errors such as kinked lines, battery not fully
charged, etc. If possible, replace the pump or battery,
o Document any pump failures in the data collection sheet.
8.2 Possible Contamination of Filters or Supplies
Clean resealable bags and aluminum foil will be available. Simple replace the contaminated
items being sure to transfer the sample ID sticker to a new resealable bag.
When possible, a spare PUF sampling cartridge will also be sent along. This PUF cartridge
may be used in place of a contaminated cartridge if a field sample cartridge is contaminated
prior to sample collection.
Contact the NERL-EMMD staff scientists for possible replacement items or directions for
decontamination. Be sure to document in the data collection sheets any suspicion of possible
contamination of filters or supplies.
9.0 Recordkeeping
9.1 Data Sheets
All information concerning sample collection will be recorded by the appropriate operator
on the SVOC Air Samples Data Collection and COC form attached in Appendix I.
9.2
Calculations
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The sample flow rate is directly measured using the average of the pre and post BIOS flow
measurements. The elapsed time in minutes is the sum total of minutes the pump operated
during the sampling episode. A normal 3 hour run period should have approximately 3 hours
X 60 min/hour =180 minutes. Sample volume calculations will be made during data
processing, not as part of the field sampling activities.
Chain-of-Custody
The original of the SVOC Air Samples Data Collection Sheet and Chain of Custody Form
will accompany the filter samples back to the NERL-RTP laboratory. A copy of the SVOC
Air Samples Data Collection Sheet and Chain of Custody Form is attached in the Appendix
I.
Sample collection, shipping, receipt, and analysis will be indicated on the sample COC form
by responsible parties. Original copies of all data forms will be returned to the EPA project
coordinator Kent Thomas (thomas.kent@epa.gov) and maintained in the NERL TCRS
project files.
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Appendix I. SVOC Air Samples Data Collection Sheet and Chain of
Custody Forms
Each form included in this appendix has been given a unique form number (COC-XX) at the
request of JTI so that all sample collection forms for this study can be more easily tracked.
Four forms are attached and are differentiated by the Field Location ID and the sub-header
referring to field or blank samples. For air samples, locations 1 and 2 designate on-field air
sampling locations and 8 designates the off-field air location. The lasts form has a sub-header
designating its use for blanks/controls.
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TIRE CRUMB EXPOSURE STUDY- AIR SAMPLING DATA AND COC SHEET
COC-08
Field Locations - Active PM & SVOC Air Samples
/ \
is V\
vSzz!
Deployment
Recovery
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
1
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PM Filter ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
TCRS-0-98-F-B-1-0
Field air SVOCs - Loc 1
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- AIR SAMPLING DATA AND COC SHEET
COC-09
Field Locations - Active PM & SVOC Air Samples
/ —~ \
IsSzl]
Deployment
Recovery
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
2
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PM Filter ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
TCRS-0-98-F-B-2-0
Field air SVOCs - Loc 2
Field notes:
Receipt notes:
Analysis notes:
;iIIIIIllll
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- AIR SAMPLING DATA AND COC SHEET
COC-IO
Field Locations - Active PM & SVOC Air Samples
Csfizl
Deployment
Recovery
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
8
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PM Filter ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- AIR SAMPLING DATA AND COC SHEET
COC-12
Active SVOC Air Field/Lab Blanks and Controls
k jQi,
Deployment | Recovery
Study Name:
PKC'*'
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID |
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOC
Initials
Date
Initials
Date
Initials
Date
Wmm
mmi
Field notes:
Receipt notes:
Analysis notes:
"0^/7x7x70/7x7x70000//
000000000000.
000000000000/,
00000000000%.
02000000000000,
0000000000000k
000000000000%
020000000000%
000000000000,
000000000000,
$0000000000/
00000000000/
00000000000/
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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Crumb Rubber SVOC Sampling
D-EMMD-SSAB-012-SOP-01
Page 22 of 22
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Appendix II. Battery Tender - Portable Battery Chargers - Owner's
Manual
(4B ankB attery ChargerU serManual. pdf attached)
Appendix III. BIOS DryCal DC-Lite Flow Calibrator Manual
(DryCalDCLiteFlowCalibratorManual.pdf attached)
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Portable Battery Chargers
Designed for six cell lead-acid batteries
from 1.2 - 200Ah.
IMPORTANT SAFETY INSTRUCTIONS
CAREFULLY READ AND
SAVE THESE INSTRUCTIONS
DOWNLOAD MANUAL
This manual can be read or downloaded from the BATTERY TENDER®
website @ www.battervtender.com
WARNING AND CAUTION LABEL DEFINITIONS:
WARNING indicates a potentially hazardous situation which, if not
avoided, could result in serious injury or death.
A CAUTION
CAUTION indicates a potentially hazardous situation which, if not
avoided, may result in minor or moderate injury.
CAUTION
CAUTION used without the safety alert symbol indicates a
potentially hazardous situation, which if not avoided, may result
in property damage.
GENERAL PRECAUTIONS
WARNING
Always charge the battery in a well ventilated area. Explosive
hydrogen gas may escape from the battery during charging. Keep
open flames, electrical sparks and smoking materials away from
the battery at all times. Failure to do so could result in serious
injury or death.
NOTE:
Gas hot water heaters are a source of open flame to be avoided.
CAUTION
Locate the charger as far away from the battery as is allowed by
the length of the output cable harness. NEVER set the charger
above or below the battery. Gasses or fluids from the battery may
corrode and damage the charger.
CAUTION
Do not set the charger on a combustible surface. Locate in a well
ventilated area to dissipate heat generated by the charger.
P/N 3 92-0215-RC
CAUTION
NEVER use a battery charger unless the battery voltage matches
the output voltage rating of the charger. For example, do not use
a 12-volt charger with a 6-volt battery and vice versa.
A WARNING
Do not expose the charger to rain or snow to avoid risk of electric
shock or fire.
A WARNING
Do not use attachments or accessories that are not recommended
or sold by the battery charger manufacturer. Doing so may cause
electric shock, fire, or other unforeseen situations resulting in
serious injury or death.
A CAUTION
When handling electric power cords, always pull by the plug
rather than by the cord. This reduces the risk of damage to both
the plug and cord, and minimizes the likelihood of electric shock.
CAUTION
Make sure all electric power cords are located so that they cannot
be stepped on, tripped over, or otherwise subjected to damage or
stress.
CAUTION
Study all of the battery manufacturer's precautions and specific
recommendations for safe operation such as not removing cell
caps while charging and the recommended rates of charge
(charger output current). This is important to avoid damage to the
battery.
CAUTION
When leaving a battery charger connected to a non-sealed,
flooded battery for extended periods of time (weeks, months,
etc.), periodically check individual cell fluid levels against
manufacturer's recommendations for safe operation.
CAUTION
If the battery releases an excessive amount of gas or if the battery
gets hotter than 130°F (55°C) during charging, disconnect the
charger and allow the battery to cool. Overheating may result in
plate distortion, internal shorting, drying out or other damage.
2
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A WARNING
NEVER disassemble the charger or attempt to do internal repairs. Take
it to a qualified service technician. Assembling the charger incorrectly
may result in the risk of electric shock or create a fire hazard. If the
supply cord is damaged, it must be replaced by the manufacturer, its
service agent or similarly qualified persons in order to avoid a hazard.
PERSONAL PRECAUTIONS
WARNING
Battery posts, terminals and related accessories contain lead and
lead components, chemicals known to the State of California to
cause cancer and birth defects or other reproductive harm. Wash
hands after handling.
1. Someone should be within range of your voice or close enough to come to
your aid when you work near a lead-acid battery;
2. Have plenty of fresh water and soap nearby in case battery acid contacts skin,
clothing, or eyes;
3. Wear complete eye protection and clothing protection. Avoid touching eyes
while working near battery;
4. If battery acid contacts skin or clothing, wash immediately with soap and
water. If acid enters an eye, immediately flood eye with running cold water for
at least 10 minutes and get medical attention immediately;
5. NEVER smoke or allow a spark or flame in vicinity of battery or engine.
6. Be extra cautious to reduce risk of dropping a metal tool onto battery. It might
spark or short-circuit battery or other electrical part that may cause an
explosion;
7. Remove personal metal items such as rings, bracelets, necklaces, and
watches when working with a lead-acid battery. A lead-acid battery can
produce a short-circuited current high enough to weld a ring or the like to
metal, causing a severe burn;
8. Use the charger for charging a lead-acid battery only. It is not intended to
supply power to an extra low-voltage electrical system or to charge dry-cell
batteries. Charging dry-cell batteries may cause them to burst and cause
injury to persons and damage to property;
NOTE
There are some wet, non-spillable, lead acid batteries on the market whose
manufacturers' make the claim that they are dry-cell batteries. These batteries are
sealed, gas-recombinant, starved electrolyte, possibly with AGM (Absorbed Glass
Matte) type construction. It is perfectly safe to use the INTERNATIONAL
BATTERY TENDER® to charge these types of batteries. The dry-cell battery
warning is intended for non-rechargeable, alkaline and other similar types of
batteries. If you have any doubt about the type of battery that you have, please
contact the battery manufacturer before attempting to charge the battery.
9. NEVER charge a visibly damaged or frozen battery.
10. Do not recharge non-rechargeable batteries.
3
PREPARING TO CHARGE
1. If it is necessary to remove battery from vehicle to charge it, always
remove grounded terminal from battery first. Make sure all accessories in
the vehicle are off in order to prevent an arc;
2. Be sure area around battery is well ventilated while battery is being
charged. Gas can be forcefully blown away by using a piece of cardboard
or other nonmetallic material as a fan;
3. Clean battery terminals. Be careful to keep corrosion from coming in
contact with eyes;
4. Add distilled water in each cell until battery acid reaches level specified by
battery manufacturer. This helps purge excessive gas from cells. Do not
overfill. For a battery without cell caps, carefully follow manufacturers'
recharging instructions;
5. Study all battery manufacturers' specific precautions such as removing or
not removing cell caps while charging and recommended rates of charge;
6. Determine voltage of battery by referring to owner's manual and make
sure it matches output rating of the battery charger.
7. Locate charger:
a. Locate the charger as far away from battery as the DC cables
permit;
b. Never place the charger directly above or below the battery
being charged. Gases or fluids from the battery will corrode
and damage the charger;
c. Never allow battery acid to drip on the charger when reading
gravity or filling battery;
d. Do not operate the charger in a closed-in area or restrict
ventilation in any way.
e. Do not set a battery on top of the charger.
8. Connect and disconnect DC output clips only after setting any charger
switches to the off position and removing AC cord from the electric outlet.
Never allow clips to touch each other.
9. Follow these steps when battery is installed in a vehicle. A spark near
battery may cause a battery explosion. To reduce risk of a spark near
battery:
a. Position AC and DC cords to reduce risk of damage by hood,
door, or moving engine parts like fan blades, belts, and
pulleys.
b. Check polarity of battery posts. A positive (pos, p, +) battery
post may have a larger diameter than a negative (neg, n, -)
post;
c. Determine which post of battery is grounded (connected) to
the chassis. If negative post is grounded to the chassis (as in
most vehicles), see item (d). If positive post is grounded to
the chassis, see item (e);
d. For a negative-grounded vehicle, connect the positive (red)
clip from the battery charger to the positive (pos, p, +)
ungrounded post of battery. Connect the negative (black) clip
to the vehicle chassis or engine block away from battery. Do
not connect the clip to carburetor, fuel lines, or sheet-metal
parts. Connect to a heavy gauge metal part of the frame or
engine block;
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e. For a positive-grounded vehicle, connect the negative (black)
clip from battery charger to negative (neg, n, -) ungrounded
post of battery', connect the positive (red) clip to the vehicle
chassis or engine block away from battery. Do not connect
clip to carburetor, fuel lines, or sheet-metal parts. Connect to
a heavy gauge metal part of the frame or engine block;
f. Connect charger AC supply cord to an electric outlet;
g. When disconnecting the charger, turn switches to off,
disconnect AC cord, remove clip from vehicle chassis, and
then remove clip from battery terminal.
10. Follow these steps when battery is outside the vehicle. A spark near the
battery may cause a battery explosion. To reduce risk of a spark near battery:
a. Check polarity of battery posts. A positive (pos, p,+) battery
post may have a larger diameter than a negative (neg, n, -)
post;
b. Attach at least a 24 inch long 6-gauge (AWG) insulated
battery cable to the negative (neg, n, -) battery post;
c. Connect the positive (red) charger clip to the positive (pos, p,
+) post of battery;
d. Position yourself and the free end of cable as far away from
battery as possible, then connect negative (black) charger clip
to free end of cable;
e. Do not face battery when making final connection;
f. Connect charger AC supply cord to an electric outlet;
g. When disconnecting the charger, always do so in reverse
sequence of connecting procedure and break first connection
while standing as far away from the battery as is practical.
USER INSTRUCTIONS
AUTOMATIC CHARGING AND BATTERY STATUS MONITORING: All
BATTERY TENDER® chargers are completely automatic and may be left
connected to both AC power and to the battery that it is charging for long
periods of time. The charger output power, voltage, and current depends on
the condition of the battery it is charging. BATTERY TENDER® chargers have
2 status indicator lights that provide a visual means to determine the operating
mode of the charger and hence the condition of the battery connected to the
charger.
The two-colored status indicator lights are available to determine whether the
charger is operating in one of the 3 primary charge modes: the bulk mode (full
charge, constant current, battery is 0% to 85% charged), the absorption mode
(high constant voltage, battery is 85% to 100% charged), or the storage/float
maintenance mode (low constant voltage, battery is 100% to 103% charged).
When the battery is fully charged, the green status indicator light will turn on
and the charger will switch to a storage/maintenance charge mode. The
BATTERY TENDER® charger will automatically monitor and maintain the
battery at full charge.
5
ELECTRICAL CONNECTIONS BETWEEN THE CHARGER AND THE
BATTERY: Before charging, connect the alligator clips or ring terminals to the
battery terminals. Then connect the charger AC power cord to the AC power outlet.
When you want to disconnect the charger from the battery, first disconnect the charger
AC power cord from the AC power outlet. Then disconnect the charger leads from the
battery terminals.
A WARNING
Always unplug or turn OFF the battery charger before connecting or
disconnecting the charger clamps to the battery. Connecting or disconnecting
clamps with the charger on could cause a spark resulting in a battery explosion.
A battery explosion may rupture the battery case causing a discharge or spray of
sulfuric acid which could result in serious injury or death.
CONNECTIONS FOR ALL LEAD-ACID BATTERY TYPE: (See item 10 under
General Precautions.)
< In General: First connect the red positive (+) charger output lead to the
positive terminal of the battery. Then connect the black negative (-) charger
output lead to the negative terminal of the battery. However, pay particular
attention to the next two items and the instructions under item 18 under
General Precautions.
< As an added measure of safety, particularly when working with standard,
flooded, lead acid batteries, UL recommends that the second, negative (-)
charger output lead connection be made to the grounded equipment chassis
rather than directly to the negative battery post.
< In similar fashion, for positive ground systems, the positive post of the battery
is now at the same electrical potential as the grounded equipment chassis.
Therefore UL recommends that the positive (+) charger output lead
connection be made at the grounded equipment chassis rather than directly
to the positive battery post.
ATTENTION: BATTERY TENDER® CHARGERS HAVE A SPARK FREE
CIRCUITRY. The output alligator clips or rina terminals will not spark when they are
touched together. The BATTERY TENDER chargers will not produce an output
voltage until it senses at least 3 volts from the battery. It must be connected to a battery
with the correct polarity before it will start charging a battery. Therefore, if you plug the
AC power cord into an AC power outlet, and if the output alligator clips or ring terminals
are not connected to a battery, and if you touch the alligator clips or ring terminals
together, there will be no electrical spark.
NOTE:
THE OUTPUT CLIPS OR RING TERMINALS MUST BE CONNECTED TO A
BATTERY BEFORE THE CHARGER CAN PRODUCE AN OUTPUT VOLTAGE.
If the charger is hooked up backwards, the amber light will continue flashing
(International Plus and EUR0400), indicating that a charge has not been initiated
(WP800 does not show any light at all). The alligator clips or accessory ring terminals
must be connected to the battery, with the proper polarity, Red to Positive (+ output to
+ battery post) and Black to Negative (- output to - battery post), before the charger will
generate any output voltage.
6
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WORKING WITH A DEAD BATTERY OR A BATTERY WITH A VERY
LOW VOLTAGE:
If you try to charge a dead battery having a voltage below 3 Volts, BATTERY
TENDER® chargers will not start. An internal safety circuit prevents the
BATTERY TENDER® chargers from generating any output voltage unless it
senses at least 3 Volts at the charger output. In this situation, the amber light will
continue to flash (International Plus and EURO400), indicating that a charge has
not been initiated (WP800 does not show any light at all).
NOTE:
If a 12 Volt, Lead-Acid battery has an output voltage of less than 9 volts when it is
at rest, when it is neither being charged nor supplying electrical current to an
external load, there is a good chance that the battery is defective. As a frame of
reference, a fully charged 12-Volt, Lead-Acid battery will have a rest-state, no-load
voltage of approximately 12.9 volts. A fully discharged 12-Volt, Lead-Acid battery
will have a rest-state, no-load voltage of approximately 11.4 volts. That means
that a voltage change of only 1.5 volts represents the full range of charge 0% to
100% on a 12-Volt, Lead-Acid battery. Depending on the manufacturer, and the
age of the battery, the specific voltages will vary by a few tenths of a volt, but the
1.5-volt range will still be a good indicator of the battery charge %.
STATUS INDICATING LIGHTS: If neither light is lit, then the battery is not
properly connected and/or the charger is not plugged into AC power. The
following describes light operation:
< AMBER LIGHT FLASHING - The amber light flashing indicates that the
battery charger (International Plus and EUR0400) has AC power available
and that the microprocessor is functioning properly. If the amber light
continues to flash, then eitherthe battery voltage is too low(less than 3volts)
or the output alligator clips or ring terminals are not connected correctly.
< AMBER LIGHT ON STEADY - Whenever the amber light is on steady, a
battery is connected properly and the charger is charging the battery. The
amber light will remain on until the charger completes the charging stage.
< GREEN LIGHT FLASHING - (International Plus and EUR0400 only) When
EUR0400 shows a green light flashing, the battery is 80% charged and may
be used if necessary. When the green light is flashing, and the amber light is
on (International Plus), the battery is greater than 80% charged and may be
removed from the charger and used if necessary. Whenever possible, leave
the battery on charge until the green light is solid.
< GREEN LIGHT ON STEADY - All chargers: When the green light stops
flashing and burns steady, the charge is complete and the battery can be
returned to service if necessary. It can also stay connected to maintain the
battery for an indefinite period of time
STATUS INDICATING SYMBOLS: The following symbols are located next to the
status indicator lights.
—1=1 1=1— The symbol next to the AMBER light represents a partially charged
battery. The solid band across the bottom is green in color. The
background is yellow. The green area indicates the charged portion of
the battery and the yellow area represents the uncharged portion.
—1=1 1=1— The symbol next to the GREEN light represents a fully charged
battery. The entire area inside the battery outline is green.
7
TROUBLESHOOTING CHECK LIST:
1. CHARGER LIGHTS DO NOT TURN ON:
a. Remove the charger from the AC outlet and recheck
that the battery charger clamps are connected to the
correct terminals and are making a clean tight
connection.
b. Check to make sure AC outlet is supplying power by
plugging in a lamp, an appliance, or a voltage meter.
2. THE GREEN LIGHT GOES ON IMMEDIATELY WHEN
CHARGING A DISCHARGED BATTERY:
a. The battery may be defective, take battery to the dealer
to be tested.
3. CHARGER IS CHARGING BUT THE GREEN LIGHT DOES
NOT GOON:
a. The battery may be defective, take battery to the dealer
to be tested.
b. The battery has an excessive current draw, remove
battery from equipment.
4. THE AMBER LIGHT COMES ON WHEN STORAGE
CHARGING BATTERIES:
a. The battery may be defective, take battery to the dealer
to be tested.
b. The battery has an excessive current draw, remove
battery from equipment.
This appliance can be used by children aged from 8 years
and above and persons with reduced physical, sensory or
mental capabilities or lack of experience and knowledge if
they have been given supervision or instruction concerning
use of the appliance in a safe way and understand the
hazard involved.
Children shall not play with the appliance. Cleaning and user
maintenance shall not be mad by children without supervision.
The supply cord cannot be replaced. If the cord is damaged
the appliance should be scrapped.
Examine the battery charger regularly for damage, especially
the cord, plug and enclosure, if the battery charger is damaged,
it must not be used until it has been repaired.
This symbol indicates separate collection for electrical
and electronic equipment
8
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Bios International Corporation
10 Park Place
Butler, New Jersey, USA 07405
Phone (973) 492 8400
Toll Free (800) 663 4977
Fax (973) 492 8270
Email sales@biosint.com
Web www.biosint.com
BIOS
© 2003 ~ Bios International Corporation
MK01-1 Rev. C 1.09
DryCal® DC-Lite Manual
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DryCal DC-Lite Specifications
Size 5" x 5" x 2.75" • 127 mm x 127 mm x 70 mm
Weight 42 oz • 1200 g
Flow Ranges | Air Flow Accuracy Specifications based on averaged readings.
Lower limit is based on self-tested maximum leakage.
Model Optimum Flow Range (±1%) Extended Flow Range
L
10-500 ml/min
1 ml/min-500 ml/min
ML
50 ml/min-2 L/min
5 ml/min-5 L7min
M
100 ml/min-7 L/min
10 ml/min-12 L7min
MH
200 ml/min-20 L/min
20 ml/min -20 L/min
H
500 ml/min-30 L/min
50 ml/min-30 L/min
Contact Bios for extended flow range specifications, or visit our website
at www.biosint.com/products/dclite_models.htm
Battery System 6V rechargeable, sealed lead-acid, 6-8 hours typical operation
AC Battery Charger | Power Adapter Wall-mounted, single-station charge,
input: 100 to 120 VAC, 60 Hz., output: 12 VDC. Optional input: 200 to 240 VAC,
50 Hz., output 12 VDC.
Operating Modes Single reading, 10 readings, or auto-mode.
Temperature Range 0-55 °C
Humidity Range 0-70% non-condensing
Printer Port Standard parallel (Not compatible with printers that require
Microsoft1 Windows")
Warranty Product, 1 year; battery, 6 months
The annual recalibration program offered by Bios is elective and is not included
as a warranty item. All specifications are subject to change.
Please contact Bios or visit our web site at www.biosint.com for the most
current information.
Table of Contents
1.0 DC-Lite Features
2.0 Unpacking Checklist
3.0 General Description
4.0 Theory of Operation
5.0 Operating Instructions
5.1 DC-Lite Button Panel
5.2 Turning the Power On
5.3 Disabling & Re-Enabling the 5-Minute Auto-Shutoff Feature
5.4 Taking Readings
5.5 Resetting the Averaging Sequence
5.6 Printing
5.7 Stop & Reset
5.8 Resetting a Printed Sequence
5.9 Printing to a PC
5.10 Hard Reset Button
6.0 Battery System
6.1 Charging the Battery
6.2 Battery Maintenance & Storage
7.0 Isolating the DryCal from Other Instruments
7.1 Use with Instruments that Contain Internal
Mass Flow Controllers (MFCs)
7.2 Use with Personal Air Samplers
7.3 Calibrating Rotameters
7.4 Use with Magnehelic Manometers
8.0 Maintenance, Quality Assurance
8.1 Maintenance
8.2 Leak-Test Procedure
8.3 Air Containing Particulates
8.4 Return Authorization
8.5 Shipment
8.6 Long-Term Storage
8.7 Calibration
9.0 Calibration Statement
10.0 Limited Warranty
2
3
3
3-4
4
4
5
5
5-6
6
6-7
7
7
8
8
8
9
9
9-10
10
10
10
10-11
11
11
11-12
12
12
12
12-13
13
13-14
14
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1.0 DC-Lite Features
0
0*
Front and Side
Charging Jack
Cell Viewing Window
Inlet Port
Connect tubing here for
pressure applications
Outlet Port
Connect tubing here for
suction applications
Back and Side
x
Parallel Printer Port
Reset Button
2
2.0 Unpacking Checklist
Your DryCal DC-Lite has been packaged with care and includes all components
necessary for operation. Please take a moment to check that you have received
the following items. If you believe you have not received a full shipment or have
any other questions, please contact Bios immediately.
Your DryCal DC-Lite Includes
• Single-Station Battery Charger
• Tubing Kit
• Additional High FlowTubing (with DCL-MH and DCL-H only)
• Certificate of Calibration
• Instruction Manual
• Registration Card
3.0 General Description
The DryCal DC-Lite is a field-portable primary flow calibrator used for industrial
hygiene, environmental and laboratory flow measurement applications.
The DC-Lite uses patented dry piston technology and infrared sensors to obtain
volumetric flow rates quickly and accurately.
Housed in a small, sturdy case, each unit employs a variety of popular user con-
veniences such as push-button read and auto-read functions, a large alphanumeric
display, battery level indicator, 5-minute automatic shut-off and a parallel printer
port for data-logging.
4.0 Theory of Operation
The DryCal DC-Lite can be used to measure air flow rates for either a vacuum flow
source (connected to the outlet port) or a pressure flow source (connected to the
inlet port). Before a reading is initiated, or between readings, a computer-directed
valve performs a bypass function.This allows the air to pass through the DryCal
valve, bypassing the flow-measuring cell which is then able to reset.
As a reading is initiated (by pressing the Read button) the internal valve closes
and the flow source evacuates or pressurizes the air in the flow-measuring cell.The
piston rises at the rate of evacuation or pressurization. A precision encoder system
provides two finely collimated light beams with a known distance between the
beams.
After a suitable acceleration interval the piston breaks the first infrared light beams
as it passes.The flow reading is completed when the second infrared beam
3
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is broken. A crystal clock measures the time interval as the piston passes the two
infrared light beams. The internal computer then calculates the volumetric flow
based upon these parameters.
After a completed cycle, the valve is opened by the computer and the piston
resets. The flow measurement is instantly displayed on the LCD in milliliters
per minute (ml) or liters per minute (L).
Any time the valve is open, the air flow is allowed to pass through the DryCal
valve, bypassing the flow-measuring cell.
5.0 Operating Instructions
The following pages will guide you through the operation of your DC-Lite primary
flow calibrator.
5.1 DC-Lite Button Panel
Single Flow Reading
O
Charging
Muw*
Avg. ~
Print Status
Off • Turns off Parallel Port output
10 • Prints 10 readings and stops
All • Prints all readings
1997
1997
nL-
Hold Tor
Auto Mode
ML #01 i
Nirmtir:r In Avcrugn
uS-
Front
Unit Indicator
ml • Milliliters per minute
L • Liters per minute
Average Flow in
Sequence
(10 readings maximum)
Battery Status
* Full
* Mid-Level
* Low
5.2 Turning the Power On
The DC-Lite has an energy saving 5-minute auto shut-off feature.
1 Press the On button to turn the DC-Lite on.
2 An initializing screen will display the microprocessor revision number,
then the standard screen will be displayed.
5.3 Disabling & Re-Enabling the 5-Minute
Auto-Shutoff Feature
5-minute auto-shutoff is the default setting for the DC-Lite.This feauture can be
disabled if your application requires a longer standby time.The 5-minute
auto-shutoff feature must be disabled each time the unit is powered on or reset.
The DC-Lite features protective circuitry that prevents the battery from becoming
over-depleted. If the battery is allowed to become too weak, the DC-Lite may
automatically shut off due to low battery voltage.This is more likely to occur more
if the 5-minute auto-shutoff feature is disabled.
Disabling the 5-minute auto-shutoff feature
1 Press and hold the Read button, then press the On button (or the Reset
button if the unit is already on).
2 The display will read, "Auto-Off Disabled" until the Read button is released.
Re-enabling the 5-minute auto-shutoff feature
With the unit on, push the Reset button.
5.4 Taking Readings
Taking Single Readings
The inlet and outlet ports are located on the right side of the unit.The lower
port is for suction (outlet) and the upper port is for pressure (inlet). All successive
readings will automatically be used to calculate the average flow. The unit
will automatically clear the average after ten readings and begin averaging
a new sequence.
A reading has been initiated when the green LEDs in the flow cell viewing
window turn on, the valve can be heard closing and the piston begins to move
up the flow cylinder.
1 Connect tubing between the flow source and the DC-Lite with sampling
medium in-line if the application requires it.Turn the DC-Lite and
flow source on.
5
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2 Press and release the Read button to obtain a single flow measurement.
The flow measurement will appear on the LCD.
3 Continue this procedure to obtain the required number of flow readings.
Taking Auto-Repeat Readings
Readings can be taken continuously in the auto-repeat mode for hands-free
operation. The unit will automatically clear the average after ten readings
and begin averaging a new sequence.
1 Press and hold the Read button until a reading starts then release.
This will begin a continuous read session.
2 To stop the continuous read session, press the Stop button once.
The display will indicate the current flow reading (Flow), the average flow
value (Average) and the number of readings in the average (Number
in Average) up to 10.
5.5 Resetting the Averaging Sequence
The number of readings in an averaging sequence can be reset to (00) at any time
by pressing and holding the Stop button for 2 full seconds.
5.6 Printing
The DC-Lite must be turned on prior to connecting a printer cable to the back
of the unit. Failure to do so will result in the display reading "Nexus Control."
If this occurs, remove the printer cable and reset the unit using the white recessed
Reset Button located on the back of the unit as described in Section 5.10.
The DC-Lite does not support any printers except those supplied by Bios.The DC-
Lite sends basic ASCII text in IBM/Centronics parallel format to a printer. Although
it may work with older and some stand-alone, IBM-compatible office printers
(printers that do not require drivers to be installed on an attached computer in
order to operate), we do not recommend their use.
If you wish to experiment nonetheless, try the "Wide 1" and "Wide 2" formats to
test compatibility. You may get one page per line or other incompatible results.
Bios offers the BP-1 stand-alone battery powered printer for hard copy output of
DryCal data.This printer is small, portable, convenient and easy to use. It makes an
excellent dedicated printer for use with Bios products.
Bios cannot guarantee compatibility with any printer other than the Bios BP-1
portable thermal printer.
6
Print Setup
1 The flow source should be turned on and connected to the appropriate
air boss on the right side of the DC-Lite.
2 Turn the DC-Lite on before connecting the printer cable. Failure to do so will
result in the display reading "Nexus Control'.' If this occurs, remove the printer
cable and reset the unit using the white recessed Reset Button located on
the back of the unit as described in Section 5.10.
3 Plug the printer cable into the parallel printer port located on the back of
the DC-Lite. Make sure DC-Lite and the printer are on.
Selecting a Print Setting
After the printer setting selection has been made a print mode selection
(All, 10 or Off) must also be made to initiate printing. The Print button will toggle
between three print settings.
1 The default setting is "Off." When the power is turned on the printer
setting will always be in the "Off" position.
2 To engage the printer, press the Print button once for the "Print 10" setting
(this will allow the printer to print ten readings and stop). Press the Print
button twice for the "Print All" position (to print continuously).
3 After the printer setting selection has been made, a Read mode selection
(single or auto) must also be made to initiate the flow measurement process
as described in Section 5.4.
5.7 Stop & Reset
A flow reading can be stopped at any time by pressing and releasing the Stop
button. This process opens the valve and allows air to bypass the flow-measuring
cell. The piston will fall to the bottom of the flow-measuring cell.
The DC-Lite can be reset by pressing and holding the Stop button for two full
seconds. During a reset, the display is cleared and the number of readings in an
averaging sequence is reset to zero.
5.8 Resetting a Printed Sequence
When connected to a printer, the reset process initiates a printed heading for a
sequence of readings and resets the number of readings in an averaging sequence
to zero. The printed heading includes a column for each flow reading (Flow), the
running average (Average) and the number of samples in the average (# Samples).
7
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5.9 Printing to a PC
Bios International offers a parallel-to-serial converter kit, part PSC-1, that allows
the information from a DC-Lite to be printed to a computer via the HyperTerminal
TM
utility included with Microsoft1 Windows .
This information can be imported into many commonly used spreadsheet
programs, such as Microsoft Excel or Quattro Pro.The DryCal parallel-to-serial
converter kit includes everything you will need to print flow readings from your
DryCal to a Windows-based PC.
Bios International only guarantees compatibility with parallel-to-serial converters
purchased through Bios International. Bios International does not offer technical
support on serial port configuration. For assistance with determing the correct
Com Port number or port configuration, please contact your IT professional.
5.10 Hard Reset Button
If for any reason the DC-Lite does not respond to push-button commands, it may
be necessary to reset the instrument. For this purpose there is a white recessed
button on lower right side of the back panel near the parallel printer port.The but-
ton resets the unit back to the initializing screen and the printer setting will revert
to the "Off" position. Before resetting, be sure to remove the printer cable from
the back of the DC-Lite. Failure to do so will result in the display reading "Nexus
Control." If this occurs, remove the printer cable and reset the unit again.
6.0 Battery System
The DryCal DC-Lite is powered by an internal lead-acid battery.The battery will
power the instrument for 6-8 hours of continuous use and has a typical service life
of approximately 2-5 years, depending on use. The DC-Lite provides a convenient
5-minute automatic shut-off feature to extend battery life. Use of a printer does not
affect the battery life.
The DC-Lite can be charged by the Bios single-station charger when plugged into
a standard 115V AC power source outlet (220V AC optional). Provided that the
battery has sufficient charge to operate the DC-Lite, the DC-Lite can be charged
indefinitely using the AC wall adapter provided.
Although the DC-Lite may be plugged into AC power, if the battery is exceptionally
weak the DC-Lite may not function. Please read all setup and charging instructions
indicated in this manual before using equipment.
8
6.1 Charging the Battery
Before using your DryCal DC-Lite, be sure that the battery system has been fully
charged to ensure that unit will perform without interruption. Using the DC-Lite
with a low battery will not affect the product's accuracy.
The DC-Lite is equipped with a battery indicator that provides battery charge
indication at three levels. When the battery indicator on the display is empty the
unit will continue to operate for a limited period of time before shutting itself off.
To Charge the DC-Lite
To view the actual charging status during the charging period, disconnect the
battery charger and wait 3-5 minutes. When the indicator is solid black the battery
is fully charged. Bios recommends leaving the DC-Lite on charge when not in use
to prevent battery degradation.
1 Connect only the appropriate Bios 12VDC charger, provided with the DC-Lite
calibrator, into a standard wall outlet.
2 Insert the charger barrel plug into the charging jack located on the right side
of the DC-Lite housing above the inlet and outlet air bosses. A green Charge
LED will illuminate while the unit is charging. Full charge takes 8 to 12 hours,
and the DryCal can charge while being used.
6.2 Battery Maintenance & Storage
The DC-Lite's lead-acid battery will not exhibit the memory effect common to
nickel-cadmium batteries. It may be left on charge for an indefinite time period
without damage.
Long-term storage without charging can damage the battery pack,
therefore if the DC-Lite cannot be left charging continuously, it should be
fully charged at least once every three months and should be placed in
storage only after achieving a full charge.
7.0 Isolating the DryCal from Other Instruments
The DryCal DC-Lite will mimic the flow source being used.Therefore, if the flow
source exhibits air flow pulsation, Bios recommends the use of an isolation device.
Use of a 25mm, 0.8m filter cassette makes a suitable load for most flow rates used
in industrial hygiene applications.This method stabilizes variations in flow due
to the slight pulsation caused by the stroke of the pump's piston.
In addition, when taking flow readings with the DryCal DC-Lite, an internal valve
closes, placing an insertion pressure spike into the flow stream. Generally, the
9
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pressure spike is invisible to the flow source; however, it can cause an interaction
with some instruments (example: some mass flow controllers, Magnehelic
manometers and rotameters). The most common solution is to isolate the DryCal
with a restriction as described in Sections 7.1-7.4.
7.1 Use with Instruments that Contain Internal
Mass Flow Controllers (MFCs)
For some flow instruments with MFCs and large dead volumes (example: some
PM 2.5 monitors) results may not correlate between the instrument's display and
the DryCal.To eliminate these discrepancies, Bios offers an active regulation
device, part DC-IR-H, to provide a constant insertion pressure.
7.2 Use with Personal Air Samplers
The DryCal DC-Lite may be used to calibrate or check the flow rate of personal air
samplers.To ensure accurate flow calibrations, Bios recommends the use of an
isolating flow restriction as described in Section 7.0. A standard MSHA approved
respirable dust filter or equivalent 25-37 mm 0.5 micron casette should be suffi-
cient to provide an appopriate isolation.
7.3 Calibrating Rotameters
When calibrating rotameters the DryCal DC-Lite should be used as a transfer
standard only. Do not use the DC-Lite in series with a rotameter. For optimum
accuracy, use a rotameter over its mid-range.
1 Attach an isolating load or sample medium, with a pressure drop of about
8 to 12 inches of water column, in series with a stable pump and a DryCal.
2 Calibrate the sampling pump at the desired flow setting (ie: 2.00 Lpm)
with the DryCal. When the desired flow setting is obtained, disconnect the
DryCal and attach the tubing to the outlet boss of the rotameter.
3 When the rotameter ball stabilizes, mark the rotameter for the true flow
rate (2.00 Lpm for example) using tape and a permanent marker to denote
the calibrated flow setting or note the point on a rotameter flow chart.
Repeat this procedure for any additional flow settings.
7.4 Use with Magnehelic Manometers
High-capacitance spring-loaded gauges such as Magnehelic manometers can
cause vibration of the DryCal piston.This is not a defect in the DryCal. The piston is
10
accurately mirroring the transient internal vibrations of the gauge. This type of
gauge must be isolated from the DryCal by inserting a suitable restriction between
the gauge and the calibrator
8.0 Maintenance, Quality Assurance
Although the DryCal DC-Lite is a rugged instrument, certain care and maintenance
requirements must still be met.
Current service and calibration information and pricing can be found at
www.biosint.com/service/dclite.htm.
8.1 Maintenance
When not in use always store your DC-Lite in a clean, dry environment. When
possible leave the unit on charge. Wipe only with a damp cloth and do not spray
with liquid solvents or use abrasive cleaners.
8.2 Leak-Test Procedure
A quality assurance self-test feature is provided to verify proper integrity
of the flow cell. It is recommended that the self-check leakage test be conducted
periodically as part of an on-going quality assurance program.
Passing the leak test does not ensure proper function of the DC-Lite. It does
ensure that total leakage is within the product's allowable limits. To ensure proper
function of the DC-Lite annual factory calibration is recommended.
To Initiate the Leak-Test
The leak-test tubing accessory is a short piece of latex tubing with a red plug
that is found in the tubing kit shipped with your DC-Lite. Place the leak-test
tubing accessory over the top (inlet) air boss.The low flow range DC-Lite requires
a miniature leak-test tubing accessory that is supplied in addition to the
standard tubing kit. Any maintenance to the DryCal must be performed by Bios
maintenance personnel.
1 Press and hold the Stop button while pressing the On button. If the DC-Lite
is already on, press and hold the Stop button while pressing the hard reset
button on the back of the unit as described in Section 5.10. After a leak-test is
initiated, the display will read "LeakTest, Invert & Push Read."
2 Invert the DC-Lite so the piston moves to the top of the cell. While the piston
is resting at the top of the cell press the Read button and the internal
11
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valve will close. Return the unit to an upright position and it will time the
descent of the piston.
3 Place the DC-Lite on a flat, vibration-free surface.
4 Observe the location of the piston to ensure that it is at the top of the cell
when the test begins (the test may take as long as 15-20 minutes). If the
test is completed successfully, the display will read: "Test OK Push Read."
5 Push the Read button as directed and the internal valve will open
and the piston will fall.
6 Repeat the test with the leak-test tubing accessory connected to the
lower (outlet) air boss. If the unit fails the Leak-test, the display will
read: "Maintenance Reqd Push Read."
8.3 Air Containing Particulates
As of January 1, 2001, the DryCal DC-Lite comes standard with either a 5-micron or
30-micron inlet filter inside the inlet fitting (depending on model ordered).
Additionally, all older DC-Lites sent in for calibration will be retrofitted with new
style inlet filters, free of charge. However, air containing cigarette smoke or other
excessive dust and particulates should be additionally pre-filtered. An additional
particulate filter, part AF-516, is available for this purpose. The filter should be
placed ahead of the DryCal in the flow stream, on the inlet side.
8.4 Return Authorization
Prior to returning your DryCal for repair or recalibration, please contact Bios
International for technical support, troubleshooting assistance and an RMA
number if necessary.
You can telephone Bios at (800) 663 4977 or (973) 492 8400, or send an email to
service ® biosint.com.
8.5 Shipment
When shipping the DryCal DC-Lite please ensure that the packaging is adequate
to protect the instrument. When possible the DC-Lite should be shipped in
the original packaging. Bios International Corp. is not responsible for damage that
occurs during shipment.
8.6 Long-Term Storage
DryCal calibrators can remain on charge until needed without causing damage
to the battery. If the DryCal is stored for long periods of time the battery should be
12
charged at least once every three months.
Always store DryCal calibrators in a clean, dry environment and recharge
the unit prior to use after long-term storage.
8.7 Calibration
As a quality assurance measure, Bios recommends annual calibration of all meas-
urement instruments, although how often you have your DryCal calibrated is
an internal quality control decision. The determining factors are whether the unit
passes the internal leak-test, quality system requirements if applicable, and
the conditions in which the unit is used. Units used in a laboratory setting may
require calibration less frequently than a unit that is used in a dusty environment.
The annual calibration program is an elective and is therefore not included as
a warranty item. "As received" flow test data and expedited "48 hour" turnaround
service are also available at an additional cost. Please contact the factory for more
information on available calibration services and pricing.
Calibration Includes
• Cleaning (if required)
• Valve adjustment (if required)
• Battery capacity test
• Internal computer program upgrade as necessary
• Mechanical upgrades as necessary
• Dynamic Performance Test
• NIST-Traceable Calibration Certificate
9.0 Calibration Statement
The DC-Lite is dynamically tested by comparing it to a Laboratory Standard pri-
mary piston prover of much higher accuracy (±0.25%), but of similar operating
principles. Flow generators of ±0.01% stability (included in prover accuracy) are
used for the comparison. Use of provers of similar construction to the devices
under test assures the validity of the flow generator as a transfer standard.
The primary Laboratory Standards are qualified by direct measurement of their
dimensions (diameter, length of measured path, time base) against NIST-traceable
gauges and instruments. A rigorous analysis of their accuracy in accordance with
the International Guide to Uncertainty in Measurements has been performed,
assuring their traceable accuracy.Test procedures assure temperature matching of
the Laboratory Standards to the devices under test.
The calibration dates of the laboratory standards for each parameter (diameter,
13
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encoder spacing, time base) are included in our calibration reports, along with
identification of the devices used for calibration, their calibration dates and NIST
calibration numbers.
10.0 Limited Warranty
The Bios DryCal DC-Lite is warranted to the original end user to be free from
defects in materials and workmanship under normal use and service for a period
of one year from the date of purchase as shown on the purchaser's receipt.The
DC-Lite's battery is warranted for 6 months from the original purchase date. If the
unit was purchased from an authorized reseller a copy of an invoice or packing
slip showing the date of purchase may be required to obtain warranty service.
The obligation of Bios International Corporation under this warranty shall be lim-
ited to repair or replacement (at our option), during the warranty period, of any
part which proves defective in material or workmanship under normal use and
service provided the product is returned to Bios International Corporation, trans-
portation charges prepaid.
Notwithstanding the foregoing, Bios International Corporation shall have no
liability to repair or replace any Bios International Corporation product:
1 Which has been damaged following sale, including but not limited to damage
resulting from improper electrical voltages or currents, defacement, misuse,
abuse, neglect, accident, fire, flood, act of God or use in violation of the
instructions furnished by Bios International Corporation,
2 When the serial number has been altered or removed or
3 Which has been repaired, altered or maintained by any person or party
other than Bios International Corporation's own service facility or a Bios
authorized service center.
This warranty is in lieu of all other warranties, and all other obligations or liabilities
arising as a result of any defect or deficiency of the product, whether in contract or
in tort or otherwise. All other warranties, expressed or implied, including any
implied warranties of Merchantability and fitness for a particular purpose, are
specifically excluded.
In no event shall we be liable for any special, incidental or consequential damages
for breach of this or any other warranty, express or implied, whatsoever.
14
Notes
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/ Q \
W
U. S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Exposure Methods and Measurements Division
Air Quality Branch
STANDARD OPERATING PROCEDURE
SOP Title: Standard Operating Procedure for the Collection of Tire Crumb
Active Field Ambient Air Samples for VOCs using Thermal Desorption Tubes
and Low-Flow Pumps
SOP ID: D-EMMD-AQB-024-SOP-01 Effective Date: August 23, 2017
SOP was Developed: IE] In-house ~ Extramural: enter organization
SOP Discipline*: Field Collection
Alternative Identification:
SOP Contact Signature
Name: Karen Oliver
Signature/Date:
Karen D Oliver
Digitally signed by KAREN OLIVER
DN: c=US, o=U.S. Government, ou=USEPA,
ou=Staff, cn=KAREN OLIVER,
dnQualifier=0000034610
Date: 2017.08.23 16:04:48 -04'00'
Management Signature
Name: Surender Kaushik
Title: AQB Branch Chief
Signature/Date:
TADEUSZ
KLEINDIENST
Digitally signed by TADEUSZ
KLEINDIENST
Date: 2017.08.23 16:27:15 -04'00'
QA Signature
Name: Sania W. Tong Argao
Title: EMMD QA Manager Sania W. TOPig
Signature/Date: Argao
Digitally signed by Sania W. Tong Argao
DN: cn=Sania W. Tong Argao, o=US EPA, ou=ORD/
NERL/EMMD, email=Tong-Argao.Sania@epa.gov,
c=US
Date: 2017.08.23 15:58:26 -04'00'
* See discipline descriptions on the NERL Scientific & Technical SOP intranet site
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
August 23,2017
Page 1 of 20
Standard Operating Procedure for the Collection of Tire
Crumb Active Field Ambient Air Samples for VOCs using
Thermal Desorption Tubes and Low-Flow Pumps
Contributors
Don Whitaker and Karen Oliver
Exposure Methods and Measurement Division
National Exposure Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC
Peter Egeghy
Computational Exposure Division
National Exposure Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC
Tamira Cousett, Matthew Allen and Zora Drake-Richman
Jacobs Technology, Inc.
Research Triangle Park, NC
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
August 23,2017
Page 2 of 20
Contents
Section Page
I.0 Scope and Application 3
2.0 Summary of Method 3
3.0 Definitions 3
4.0 Precautions 3
5.0 Personnel Qualifications 3
6.0 Sampling Media and Supplies 4
6.1 Sampling Media 4
6.2 Sampling Setup 4
6.3 Flow Measurement 4
6.4 Sample Handling and Storage 4
6.5 Sample Tracking 5
6.6 Spare and other potentially useful supplies 5
7.0 Quality Control and Quality Assurance 5
7.1 Field Blanks and Field Controls 5
7.2 Duplicate Samples 5
7.3 Mesa Labs Defender Flow Calibrator 5
8.0 Procedures 6
8.1 General Sampling Considerations 6
8.2 Pre Deployment Preparation 6
8.3 Pump and Sampling Equipment Set-up 6
8.4 Sample Setup 7
8.5 Conducting Active Sample Collection 8
8.6 Labeling the Sample 10
8.7 Pump/Equipment Take Down 11
8.8 Return Samples to the EPA Laboratory 11
9.0 Possible Corrective Actions for Observed Problems During Sampling 12
9.1 Pump Failure 12
9.2 Possible Contamination of Filters or Supplies 12
10.0 Recordkeeping 12
10.1 Datasheets 12
10.2 Calculations 12
10.3 Chain-of-Custody 12
II.0 References 13
Appendix A: Data Collection and COC Record Forms for Fields 1, 2, and 8 14
Appendix B: SKC PocketPump Quick Guide 18
Appendix C: Field Sampling Location Record Form 19
NOTICE
This Analytical Procedure has been prepared for use by the Air Quality Branch of the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina and may not be
specifically applicable to the activities or objectives of other organizations. This procedure has
not been fully validated and should be used for research purposes only. Adequate QA/QC
measures must be implemented with this procedure to allow assessment of data quality.
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
August 23,2017
Page 3 of 20
1.0 Scope and Application
This method applies to the collection of air samples from stationary locations on or near synthetic
turf fields with crumb rubber infill. Samples will be analyzed for a suite of volatile organic
compounds (VOCs). This SOP incorporates many of the procedures previously detailed in standard
operating procedure (SOP) D-EMMD-ABQ-004-SOP-01 (Formerly ECAB-152.1) "SOP for
Carbopack X Sorbent Tube Handling: Field Deployment and Shipping." The streamlined field
deployment checklist in this SOP will be useful to field operators.
2.0 Summary of Method
Portable, battery operated, air sampling pumps attached to 3.5-inch x % inch o.d. stainless steel
thermal desorption (TD) tubes packed with Carbopack X adsorbent are used to capture gas-phase
VOCs from ambient air. Air samples are collected from two stationary locations (duplicate samples
at one of these locations) at each synthetic field as close as possible to where activities occur
without posing an obstruction or safety hazard. A third location will be sampled upwind and at a
sufficient distance from the field to represent background.
3.0 Definitions
COC chain of custody NERL
EMMD Exposure Methods and Measurement PTFE
Division
FEP fluorinated ethylene propylene qty
ID identification TD
National Exposure Research
Laboratory
polytetrafluoroethylene
quantity
thermal desorption
4.0 Precautions
The sampling systems are powered by internal battery packs. The battery pack must be completely
charged before operating the pump. The battery and pump system should be protected from
excessive heat or cold (<-4 °F, >104 °F) as specified in the operator's manual.
Sampling will take place at outside and inside activity fields. Equipment should be shielded as
much as possible from moisture and should not be used during periods of heavy rain (protective
enclosures are not provided). Sampling stands should be set up so that they are provided protection
from tampering. Sampling stands must also be placed and secured such that no harm will come to
children or others playing in the vicinity of the equipment.
5.0 Personnel Qualifications
Required training is provided by the US EPA. Sample collection will be conducted by qualified
scientific staff trained in the use of the specific field monitoring equipment. Training will include
a demonstration and hands-on training by qualified persons with air sampling expertise. At a
minimum, all SOPs and operating instructions will be reviewed, understood, and followed exactly
by the field staff. Training records will be maintained by the EPA exposure study project lead
(currently Kent Thomas).
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
August 23,2017
Page 4 of 20
Sampling Media and Supplies
6.1 Sampling Media
Supelco FLM Carbopack X deactivated 89-mm (3.5 in. x 0.25 in. o.d.) stainless steel
thermal desorption tube (part no. 28686-U, Millipore Sigma, St. Louis, MO) fitted with
0.25-in. brass Swagelok fittings with combined (one-piece) polytetrafluoroethylene
(PTFE) ferrules (Note: Conditioned TD tubes will be capped and stored inside the glass
culture tubes, which will be stored inside sealed metal cans for transport to and from the
sampling site.)
6.2 Sampling Setup
• Sampling pumps - SKC Pocket Pump (Cat. No. 210-1000) - qty. 4
• Charging System - SKC Pocket Pump Multi-charger (Cat. No. 223-247)
• Tripod sampling stand - custom modified - qty. 3
• Tygon flexible vacuum tubing (5/16 in. o.d., 3/16 in. i.d.)
• % in. Swagelok stainless steel straight union with PTFE ferrules and a knurled nut for
holding sampling tube—qty. 4 each
• % in. o.d. "U" shaped acrylic adapter for attaching Swagelok fitting to Tygon tubing -
qty. 4 each
• Measuring tape (at least 6 ft length)
6.3 Flow Measurement
• Flowmeter - MesaLabs flow calibrator, low-flow (or equivalent) (Defender 520 model,
Lakewood, CO)
6.4 Sample Handling and Storage
• Powder-free nitrile gloves
• Kimwipes
• Metal tray
• Clean forceps (e.g., Teflon coated, 5 in. stainless steel)
• CapLok tool (part no. C-CPLOK, Markes International, Gold River, CA)
• Glass culture tubes (part no. 45066A-25150, Kimble/Kontes, Vineland, NJ) - qty. 12
per sampling day (10 for TD tube storage and 2 for spares)
• Unlined caps for glass culture tubes (custom order, Scientific Specialties Service, Inc.,
Randallstown, MD) - qty. 1 per tube
• Septrseal Septa and Teflon liners for culture tube caps (part no. B69800-24 and
B68800-24, Scientific Specialties Service, Inc.) - qty. 1 each type per tube fluorinated
ethylene propylene (FEP) Teflon tubing, 0.25 in. o.d
• Clean unlined gallon metal cans with lids (part no. 5501-07B, SKS Bottle and
Packaging, Inc., Mechanicville, NY)
Note: Conditioned TD tubes will be capped and stored inside the glass culture tubes,
which will be stored inside sealed metal cans for transport to and from the sampling site.
• Cooler (example part no. 5248-5286-5296, Coleman Products, Inc., Wichita, KS)
• Foam inserts for coolers (Instapack quick foam packaging, Sealed Air Corporation,
Danbury, CT)
• Rex protective sleeves, 1.021 in. i.d. by 5.750 in. length with wall thickness of 0.125
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
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Page 5 of 20
in. (custom order, Yazoo Mills, Inc., New Oxford, PA)
• Closed cell foam, assorted thicknesses
6.5 Sample Tracking
• Data Collection and Chain of Custody (COC) Record forms (see Appendix A) and
meta data form shown in Appendix C
• Pen (Black, archival quality Ink)
• GPS and time enabled device - Garmin or cell phone with GPS capabilities
• Shipping labels
6.6 Spare and other potentially useful supplies
• Paint can opener
• Resealable closure bags
• Packaging tape
• Extra labels
Quality Control and Quality Assurance
The quality control requirements will allow assessment of the quality of the samples collected.
Determination of possible contamination and reproducibility of the method will be targeted as data
quality indicators.
7.1 Field Blanks and Field Controls
A minimum of one field blank and one field control will be collected on each sampling day.
As stated in Section 8.4.2, the thermal desorption tubes will be sent sealed with brass
fittings, secured in glass culture tubes, and stored in a metal can. Metal cans containing
thermal desorption tubes meant for field sampling and for field blanks will be pre-labeled
with sample ID codes.
Field blanks and controls will not be removed from their packing in the metal can; they
will remain sealed and returned to the laboratory.
7.2 Duplicate Samples
Duplicate samples will be collected at a single on-field location during each day of field
measurement. Two sampling systems (pump/inlets) shall be positioned on the same
sampling tripod and operated as specified in Section 8.3. The purpose of duplicate samples
is to determine the precision of the sampling method in its entirety.
7.3 Mesa Labs Defender Flow Calibrator
The Mesa Labs Defender flow calibrator will be used at the beginning and end of each
sampling period to measure the pump flow rate. The flow calibrator should have been
certified within the past year by the manufacturer or the flow rates verified against a unit
that is under current certification and deemed appropriate (within 2%). The sampling pump
is equipped with a flow controller and the flow rate is stable during sampling.
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
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Page 6 of 20
Procedures
8.1 General Sampling Considerations
• Samplers must be placed in an area representative of the average ambient conditions (i.e.,
away from roadways, parking lots or high traffic areas).
• Pump flow rates are measured using the Mesa Labs Defender. Flow measurements should
take place immediately prior to and immediately after sampling as noted in sections 8.5.5
through 8.5.14.
• The flow rate will be used in conjunction with the total elapsed sampling time to calculate
total air volumes sampled and integrated analyte concentrations observed during the
sample capture period.
8.2 Pre-Deployment Preparation
• Charge batteries and flow meter
• Test sampling pumps
• Clean field supplies (forceps, glass culture storage tubes, trays, etc.)
• Condition TD tubes for use
• Prepare spiked tubes for use as field controls and lab controls
• Pre-label glass culture tubes and data collection forms with sample codes.
• Pack all field supplies
8.3 Pump and Sampling Equipment Set-up
8.3.1 Transport the sampling setup and flow measurement equipment to the field location (listed
in sections 6.1-6.6). This will include sampling pumps, sampling stands, vacuum tubing,
and measuring tape along with the data collection sheets, flow meter, pen, and any
materials needed to secure the monitoring site.
8.3.2 Three sampling sites will be identified for each location. Two sites will be located on the
activity field. One site will be located off of the field, in an upwind position if possible.
One sampler will be located at each site and an additional sampler will be positioned at one
of the on-field locations (using same tripod stand) to collect duplicate samples.
Note: Ensure that the information regarding specific site locations and conditions have
been recorded as meta data (on the sheet shown in Appendix C) according to SOP D-SED-
IEMB-005-SOP-01.
8.3.3 Figure 1 shows the sampler configuration with major components identified. Use this
diagram to setup each sampling location.
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Crumb Rubber VOC Active Sampling
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Page 7 of 20
Figure 1: VOC Sampler Configuration
1. Set up the sampling stand by spreading the tripod base and extending the vertical rod
The tripods are each outfitted with a TD tube holder, a Radiello passive tube holder
(see SOP D-EMMD-AQB-019-SOP-01 for Radiello deployment procedures) and a
metal plate to mount the pump.
2. Connect one end of the tubing to the hose barb found on the pump. The attached hose
should be snug and not easily removed without the use of applied force. Attach the
pump to the metal plate on the tripod such that the pump is between the plate and the
tripod post. This will provide some shielding to the pump.
3. Turn the pump on by sliding down the protective cover, pressing any keypad button to
activate the pump, and using the up (A) or down (V) arrow buttons simultaneously to
toggle from "Hold" to "Run:' Allow the pump to run while the rest of the equipment
is being set up.
4. Adjust the tripod so the TD tube inlet is at a height of 1.0 - 0.1 meters (35.4 in. - 43.3
in.) above ground level.
8.4 Sample Setup
8.4.1 Refer to SOP D-EMMD-ABQ-004-SOP-01 for instructions on handling the TD tubes.
8.4.2 The TD tubes will be sent with the inlets capped with brass fittings, sealed in glass culture
tubes, and stored in a metal can. Thermal desorption tubes meant for field blanks and
controls will be labeled as such. Tubes meant for sampling will be pre-labeled with the
appropriate sample ID codes. Spare sampling tubes will be shipped to the sampling
locations and can be used in the event of damage to the pre-labeled sampling tubes. Be sure
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to retain the fittings, culture tubes, cans, and packaging for return to the laboratory for
future use.
8.4.3 To set up sampling, determine the appropriate sample code and sampling location. Enter
the TD tube ID number of the pre-labeled tube on the corresponding Data Collection and
COC Record Form.
8.4.4 Immediately before sampling is set to begin, don a pair of nitrile gloves and remove the
glass-enclosed TD tube from the metal can labeled with the field sampling date. Remove
the vial cap and then the Teflon strips from the culture tube one at a time. Remove the
Teflon strips using forceps and place them on a clean surface such as a laboratory tissue or
clean aluminum foil. Next remove the TD tube from the glass culture tube and return the
Teflon strips to the glass culture tube.
8.4.5 Remove the brass fitting from the outlet side (non-grooved end) of the TD tube and insert
this end into the vacuum tubing. Gently place the brass fitting back into the glass culture
tube. Secure the TD tube to the sampling stand using the clamp. Ensure that the other end
of the vacuum tubing is attached to the pump inlet.
8.4.6 Remove brass fitting from the inlet side (grooved end) of the TD tube and place it back
into the glass culture tube, and then return the glass culture tubes to the metal can. The
sampling setup should now look exactly like Figure 1. Double check the length of tubing
and remove any kinks.
8.5 Conducting Active Sample Collection
8.5.1 To collect field samples, turn on the pump by sliding down the protective cover, press any
keypad button to activate the pump, and then press both the up (A) and down (V) keys
together to turn the pump on. Allow the pump to run for at least five minutes to warm-up
and stabilize.
Note: The up (A) and down (V) keys pressed at the same time toggle from "Hold" to "Run"
and from "Run" to "Hold".
8.5.2 The pump flow rate should be set to 100 mL/min in the laboratory prior to field
deployment. This will minimize the amount of time required to fine adjust the pump flow
after the TD tube is attached.
Note: Refer to the pump manual for complete instructions on how to adjust flows. Basic
flow adjustment instructions are shown on the PocketPump Quick Guide in Appendix B.
8.5.3 Insert the non-grooved end of the TD tube into the Swagelok fitting of the Tygon tubing
sample train and tighten the knurled nut finger tight. Insert the TD tube into the mounting
bracket on the sampling stand by inserting the grooved end of the TD tube into the "ears"
of the mounting bracket. This is the sample start time.
8.5.4 Record the sample 'Start Time' on the Data Collection and COC Record Form (Appendix A).
8.5.5 Measure the air sampling flow rate through the TD tube by attaching the grooved end of
the TD tube to a length of Tygon tubing that is then attached to the upper port (suction) of
the Mesa Labs Defender flow calibrator. Press the "ON" button (lower right corner) of the
flow calibrator and hold for approximately one second until the display lights up and the
optical light in the cell illuminates.
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Note: If the on button is depressed too long it will turn the unit off and you must then press
the "ON" button again to turn on.
8.5.6 The display should show the Defender information and highlight the word "Measure."
Press the Enter button twice to begin flow measurements. This will activate the unit to
make continuous measurements and automatically average 3 replicate readings.
Note: Be sure that the Defender unit is set up to measure the volumetric flow rate in units
of mL/min. Do not measure as STP. Refer to the manual on how to change the setup
features.
Note: If the Defender unit is used in bright sunlight, the flow cell may need to be shielded
in order for the sensors to work properly. Simply hold the unit close to your body or hold
the unit in a shaded area while taking the readings.
8.5.7 Observe the flow rate values being displayed. Flow rates should be 100 ± lOmL/min.
8.5.8 If needed, adjust the flow rate to 100 ± 10 mL/min. While observing the calibrator display,
use the up and down arrow buttons on the pump keypad to adjust the flow. The security
code A V ~" must be pressed in sequence within 10 seconds to change operating
parameters (refer to Appendix B for full details).
8.5.9 Once adjusted to 100 ± 10 mL/min allow the flow to stabilize for one minute, reset the
calibrator by pressing the "Stop" button followed by holding the "Read" button for three
seconds. The unit will automatically collect three flow readings and average them. Record
the average flow rate of the three readings on the datasheet in the 'Start Flow' column of
the Data Collection and COC Record Form (Appendix A).
8.5.10 Remove the flow calibrator tubing from the TD tube and attach the TD screen inlet to the
grooved end of the TD tube.
8.5.11 Close the protective sliding cover on the pump and attach it into the bracket near the bottom
of the sampling stand with the vacuum tubing pointing out. Double check the tubing to
verify there are no kinks.
8.5.12 After sampling for the desired time period (presumed to be an approximate three-hour
duration), re-check the flow and record the average flowrate in the 'Stop Flow' column of
the Data Collection and COC Record Form. To do so, simply remove the inlet screen from
the TD tube, attach the flow calibrator with the Tygon tubing, turn on the flow calibrator,
measure three readings, and record the average reading on the form. No stabilization wait
time is required as the pump has been running continuously.
8.5.13 Open the pump protective sliding cover and turn off the pump by pressing the up (A) and
down (V) keys simultaneously to toggle pump mode to "Hold." The pump enters "sleep"
mode after five minutes in "Hold" without activity (there is no manual off option).
8.5.14 Record the sample 'Stop Time' on the Data Collection and COC Record Form (Appendix A).
8.5.15 Retrieve the glass culture tubes containing the brass fittings from the metal can. Make sure
the label on the glass vial and the TD tube ID (etched on the TD) match those shown on
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the data sheet. Don a clean pair of nitrile gloves. Remove the TD tube from the mounting
bracket and remove the inlet screen. Place the brass fitting caps on the TD tube. Hand
tighten the brass fittings and then tighten an additional one-eighth turn using the CapLok
tool. Perform the tug test described in SOP D-EMMD-ABQ-004-SOP-01 to ensure that the
caps are properly tightened.
Note: Do not overtighten the brass nuts as it may distort the metal body of the TD tube or
be hard to remove. Only a small fraction past finger tight is required.
8.5.16 Open the glass culture tube and place the lid onto the metal tray or clean surface.
8.5.17 Retrieve the TD tube. Gently transfer the TD tube to the labeled glass culture tube (Figure
2) being sure that the glass culture tube has a Teflon chip in the bottom to provide
cushioning. Insert the two Teflon strips into the glass culture tube one at a time in order to
minimize stress on the glass.
t & m)
Figure 2: Thermal desorption tube in a glass culture tube
8.5.18 Replace the cap to the glass culture tube.
8.5.19 Place the glass culture tube (containing TD tube) into the cardboard sleeves in the metal
can and place the two foam discs at the top of the can between the metal lid and the culture
tube tops. Securely place the metal lid back on the can.
8.5.20 Samples should be stored at room temperature and shipped back to EPA the day of or the
day after collection (see Section 8.8).
8.6 Labeling the Sample
8.6.1 Labels for these samples will be generated at the EPA lab (using the convention outlined
in Table 1.). The labels will be placed on the glass culture tubes and on the data collection
fonns before they are transported to the field
Table 1. Sample Identification Scheme
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ID Code
Example
Code
Description
Sample Identification: TCRS-R-W-W-X-Y-Z
TCRS
tire crumb rubber research study
R
0
participate identification number
(Use 0 for these samples as they are not associated
with a specific participant.)
VV
70-79
two-digit code will be a unique identifier for each field
numbered in the range of 70-79.
W (sample type)
F
sample
D
duplicate sample
B
field blank
C
field control (spiked blank)
X (analysis method)
D
field air VOC sampling
Y
sample collection location
1 or 2
on-field air locations
8
off-field air location
Z
0
parent/ sample
8.7 Pump/Equipment Take Down
1. Remove the sample pump from the tripod stand.
2. Disconnect the tubing from the sample pump and return pump to its protective case.
3. Re-pack all supplies into their original shipping containers and prepare for transport of
all supplies to the EPA laboratory.
8.8 Return Samples to the EPA Laboratory
1. All samples should be shipped back to the EPA laboratory as soon after sampling is
complete as possible.
2. Pack the sample cooler immediately prior to shipping by placing as many as three metal
cans into the cooler and replacing the associated packing material on top of the cans to
prevent the contents of the cooler from shifting. Photocopy or photograph the Data
Collection and COC Record Forms (retain in case of damage during shipping, discard
after they are recorded by EPA) and then add the completed forms to a zipper storage
bag. Place the bag on top of the cooler contents and then seal the cooler.
3. Ship the packed cooler to the EPA laboratory using next day air UPS or similar
overnight delivery service. EPA generally will prepare and provide a return shipping
label. If applicable, address the shipment to:
US EPA Chemical Services
Attn: Karen Oliver/Lillian Alston (919-541-2337)
Bldg E Loading Dock, Room E-178
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D-EMMD-AQB-024-SOP-01
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Page 12 of 20
109 T.W. Alexander Drive
Durham, NC 27711
4. Immediately notify Karen Oliver (oliver.karen@epa.gov) of the incoming shipment
via email. Include the shipment tracking number.
9.0 Possible Corrective Actions for Observed Problems During Sampling
9.1 Pump Failure
• If a pump fails, correct any obvious errors such as kinked lines, battery not fully charged,
etc. If possible, replace the pump.
• If a replacement pump is unavailable, stop data collection immediately and contact the
NERL/EMMD supervising scientist. Examples of pump failure include: failure to reach
desired flow rate; or failure to maintain the desired flow rate.
• Document any pump failures in the Data Collection and COC Record Form.
9.2 Possible Contamination of Filters or Supplies
Contact the NERL/EMMD staff scientists for possible replacement items or directions for
decontamination. Be sure to document any suspicion of possible contamination of filters
or supplies in the Data Collection and COC Record Form.
10.0 Recordkeeping
10.1 Data Sheets
All information concerning sample collection will be recorded by the appropriate operator
on the VOC Data Collection and COC Record Form and on the Field Sampling Location
Record Form (see SOP D-SED-IEMB-005-SOP-01). Examples are attached in Appendices
A and C, respectively.
10.2 Calculations
The sample flow rate is directly measured using the average of the pre- and post-sampling
Mesa Labs flow calibrator measurements. The elapsed time in minutes is the sum total of
minutes the pump operated during the sampling episode. A normal 3-hour run period
should have approximately 180 minutes.
Collected air volume is calculated as follows:
1000
Where, V = Sample volume in liters
T = Elapsed time in minutes
F = Average flow in mL/min
10.3 Chain-of-Custody
The original Data Collection and COC Record Form will accompany the filter samples
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August 23,2017
Page 13 of 20
back to the NERL-RTP laboratory. A copy of this form is attached in Appendix A.
Subsequent analysis (i.e. thermal desorption/GC-MS analysis) will be indicated on the
sample Data Collection and COC Record Form by responsible parties. Original copies of
all data forms will be maintained in the NERL project files.
11.0 References
D-EMMD-ABQ-004-SOP-01. (Formerly ECAB-152.1.) Standard Operating Procedure for
Carbopack X Sorbent Tube Handling: Field Deployment and Shipping. 2015.
D-EMMD-AQB-019-SOP-01. Standard Operating Procedure for Radiello Carbopack X Diffusive
Sampler Handling: Field Deployment and Shipping for Tire Crumb Exposure Studies. 2017.
D-SED-IEMB-005-SOP-01. Standard Operating Procedure for the Collection of Field and
Activity Metadata During Exposure Characterization Pilot Study Field Sampling. 2017.
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Appendix A: Data Collection and COC Record Forms for Fields 1, 2, and 8
TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
Field Locations - Passive (Radiello) and Active VOC Samples
JL
Deployment
Recovery
(S « \\
Study Name:
11 ^77 SI
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
l
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Radiello Tube ID
Holder ID
Start Time
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
PETube ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
August 23,2017
TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
Field Locations - Passive (Radiello) and Active VOC Samples
/o
Deployment
Recovery
is « \\
Study Name:
11 ^77II
TCRS
Date
VK mT^tA
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
2
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Radiello Tube ID
Holder ID
Start Time
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
PE Tube ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Form Rev 06/21/2017 da»
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Crumb Rubber VOC Active Sampling
D-EMMD-AQB-024-SOP-01
August 23,2017
TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
Field Locations - Passive (Radiello) and Active VOC Samples
Deployment
Recovery
[1 ^
^7 1)
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
8
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Radiello Tube ID
Holder ID
Start Time
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
PETube ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY-- VOC MONITORING DATA AND COC SHEET
Active (PE) VOC Field/Lab Blanks and Controls
s *
* %
Deployment
Recovery
Itss
r/z J J
Study Name:
% c#
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PE Tube ID
Initials
Date
Initials
Date
Initials
Date
yfy/,yfyfyfyryfyry/-yr y/,yfyfyfyfyfyfyryryfysy/ yfysyryf
//Js//'y/ysy/Js's/syry/',/y/ysyyf/'y/Jsy/y/ysJs,'sy/,y/Js'
/-***********************y
-'***********************''
^*******^***************-'
Place Field/Lab Blank ID Label
Here
Field notes:
Receipt notes:
Analysis notes:
y/'y/yfy/yfyfyryfyf'yfyfyfyfyfyr,yry/yfyfysyr,y/ yr y/yr yf
J/J/-,/J/y/ys'sysJs//J/JsysJsy/Jsys'sysysy/'fs's's'sJs<
******* * ** **** * * ****** ****'
************************4
Place Field/Lab Blank ID Label
Here
Field notes:
Receipt notes:
Analysis notes:
PE Tube ID
Initials
Date
Initials
Date
Initials
Date
**************************************************-£
Place Field/Lab Control ID Label
Here
Field notes:
Receipt notes:
Analysis notes:
TTTTVTTT'CyTT'/yTTTTTTT'f 7 TTT7T 'i- — " fV " V -
**************************************************5
**************¦£-***********************************•£
*^****^A**A*A«e
Place Field/Lab Control ID Label
Here
Field notes:
Receipt notes:
Analysis notes:
Form Rev 06/21/2017 daw.
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D-EMMD-AQB-024-SOP-01
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Appendix B: SKC PocketPump Quick Guide
froc\r(Kv>\y>\\n.a
focket/ump »
• To change the pressure in Constant Pressure mode.
W«tn pjrrp nr\cn press|A ~ Nr e a ~ • *~] t*v-
» To change temperature scale Irom F to C or C to F,
WBifvmcfu'wg p^3s[AV! then • ihen|eT]
• To change beck pressure units from mm to ins or ins
to mm,
VAhpunpanrwg prewjAV] men • A ~ • «x>n IA • I
locket lump
Personal Low Flow Sampler
Clmi
cX
»
r^amssn tt« SKC me. 863 Valley View Road, Eighty Four. PA 15330
iocketfump Te-rfrvS »
Keypad >s located toreaffi me sit»ng cover
Star button •
• To scroll mrough displays or, «itn other buttons to sen
pump oporasons
Up «nd down arrow buttons A ~
• To increase or (teceam flow or pressure Ounng setup
and to set up pump ope/aura
Button sequence
• To enter commands corrocfly during pump set up, they
must ce « sequence
Underlined sequence • ~ A •
• To be pressed wthm to seconds oI previous command
Bracketed sequence {A ~]
• lo oe pressed simultaneous^
Security code • A ~ •
• To prevent gnauthon/eo changes to the pump 3 sarnjy ng
program
frocjrt\,v>\tn,in(j
focket fump He.PjiAe.ncei »
• To activate pump (e g to change pump from SLEEP
to HOLD).
Press any Duttor
• To change pump from MOLD to RUN or RUN to HOLD,
PfSSS|A
• To dear old data.
Wo pump mnnng . press |A ~! rhen • A ~ • tnen • •
• To select operating mode (switch from constant flow
to constant pressure).
Wo pump running, press | A Tj then • A ~ • men
• ~ A •
• To chango the (low rale in Constant Flow mode
With pump m how. pres.-. | A ~) then • A ~ • fSCT
lashes) P-ess A ck ~ to change J»ow we When done
press • •
• To calibrate the flow in Constant Flow mode
With pump m ho»d. p'ass 1A ~] men • A ~ • than •
(ADJ flashes) Press AhTIq acftus! 'tow unfci pump
and CMHWOf are *r» ag-eement When done, press •
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Appendix C: Field Sampling Location Record Form
Field Sampling Location Record Form
Field ID Number
Field SVOC wipe locations S
Field metals wipe locations M
Field SVOC drag sled locations D
Air sample station locations A
(For off-field upwind air sample station estimate and record
^distance from field center; record type of ground surface)
Draw Magnetic North Direction Arrow Here
-------
U.S Environmental Protection Agency
\ Office of Research and Development
mj National Exposure Research Laboratory
Exposure Methods and Measurements Division
Air Quality Branch
STANDARD OPERATING PROCEDURE
SOP Title: Standard Operating Procedure for Radiello Carbopack X Diffusive
Sampler Handling: Field Deployment and Shipping for Tire Crumb Exposure
Studies
SOP ID: D-EMMD-AQB-019-SOP-01
Effective Date: August 23, 2017
SOP was Developed: IE] In-house ~ Extramural: enter organization
SOP Discipline*: Field Collection
Alternative Identification:
SOP Contact Signature
Name: Karen Oliver Digitally signed by KAREN OLIVER
DN: c=US, o=U.S. Government,
ix * DCM n I l\/^— E3 OU-USEPA, ou-Staff, cn-KAREN
Signature/Date: f\AKtN U. ULIVtK OLIVER, dnQualifier=0000034610
Date: 2017.08.23 16:06:18 -04W
Management Signature
Name: Surente KausWk Digi(a||y sjg(led by TADEUSZ
Title: AQB Branch Chief KL EIN DIE N ST
signature/Date TADEUSZ KLEINDIENST Date: 2017.08.23 16:24:08
-04'00'
QA Signature
Name: Sania W. Tong Argao
Digitally signed by Sania W. Tong Argao
Title: EMMD QA Manager Qonjo \/\/ Tnnn DN: cn=Sania W. Tong Argao, o=US EPA,
ocai Ilea VV. I Ul ly ou=ORD/NERUEMMD, email=Tong-
Siffnatnre/Date' A man Argao.Sania@epa.gov, c=US
Signature/Date. MigdO Date: 2017.08.23 16:00:55-04'00'
* See discipline descriptions on the NERL Scientific & Technical SOP intranet site.
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Standard Operating Procedure for Radiello Carbopack X
Diffusive Sampler Handling: Field Deployment and
Shipping for Tire Crumb Exposure Studies
Contributors
Don Whitaker and Karen Oliver
National Exposure Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC
Tamira Cousett, Zora Drake-Richman, Matt Allen and Stacy Henkle
Jacobs Technology
Durham, NC
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Revision History
Version
No.
Name
Date of
Revision
Description of Change(s)
1
EPA and JTI,
listed on cover
page
August 18,
2017
Original SOP.
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Contents
Section Page
I.0 Scope and Application 4
2.0 Summary of Method 4
3.0 Definitions 4
4.0 Health and Safety Warnings 4
5.0 Cautions/Interferences 5
6.0 Personnel Qualifications 5
7.0 Equipment and Supplies 5
8.0 Quality Control/Quality Assurance 7
9.0 Procedures 7
10.0 Data and Records Management 19
II.0 References and Supporting Documentation 19
Appendix A: Shipment Chain of Custody Form 21
Appendix B: Tube Field Monitoring Data and Chain of Custody Sheet 22
Appendix C: Field Procedure for Diffusive Sample Collection Using Radiello Samplers - Deployment and Return
Shipping 26
Appendix D: Field Packing Checklist for Laboratory Staff 30
Appendix E: Incoming Field Sample Checklist for Laboratory Staff 31
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1.0 Scope and Application
This standard operating procedure (SOP) describes sample handling techniques for Carbopack X
Radiello Samplers that are used for diffusive sample collection of volatile organic compounds
(VOCs) in ambient air for Tire Crumb Exposure Studies. Direction is provided for field deployment
and shipping.
2.0 Summary of Method
Ambient and personal air samples are collected using Radiello radial diffusive samplers containing
Carbopack X sorbent. Prior to sampling, the Radiello stainless steel mesh cartridges containing
Carbopack X are conditioned according to D-EMMD-AQB-008-SOP-01, "Standard Operating
Procedure for Carbopack X Sorbent Tube Conditioning Using the Markes International Model TC-
20 Sample Tube Conditioner" by placing each Radiello cartridge into an empty industry standard
PerkinElmer-style stainless steel thermal desorption (TD) tube. Conditioned tubes are sealed with
0.25-in. Swagelok caps with combined polytetrafluoroethylene (PTFE) ferrules and are stored in
glass culture tubes with Teflon-lined caps in a refrigerator until needed. The culture tubes are then
placed in protective sleeves in a metal can and stored in a refrigerator until the time ofshipment.
(Note: TD tubes containing Radiello cartridges are visually denoted by one of the two end caps
having a stainless steel nut substituted for a brass nut to differentiate the tubes containing
Radiello cartridges from standard TD tubes that have all brass caps and nuts.)
In the field, the Radiello cartridges are removed from the TD tubes, placed in polypropylene
diffusive bodies and deployed for sampling for a designated time period. The samplers are then
retrieved and prepared for return shipment to the analytical laboratory where they are analyzed
according to either D-EMMD-AQB-006-SOP-01, "Standard Operating Procedure for Desorbing
Volatile Organic Compounds from Carbopack X Sorbent Tubes Using the PerkinElmer
TurboMatrix ATD.' or D-EMMD-AQB-014-SOP-01, "Standard Operating Procedure for
Desorbing Volatile Organic Compounds from Carbopack X Sorbent Tubes Using the PerkinElmer
TurboMatrix ATD 650" and D-EMMD-AQB-003-SOP-01, "Standard Operating Procedure for
Determination of Volatile Organic Compounds Desorbed from Carbopack X Diffusive Sampling
Tubes Using the Agilent 6890N/5975 GC-MSD.'
3.0 Definitions
4.0 Health and Safety Warnings
Glass vials might occasionally break during shipment. The field and laboratory staff should
exercise caution when packing and unpacking the glass vials from the shipping containers.
COC chain of custody
DI deionized
DQO data quality objective
FEP fluorinated ethylene propylene
PTFE polytetrafluoroethylene
PVC polyvinyl chloride
QAPP quality assurance project plan
SOP standard operating procedure
TD thermal desorption
VOC volatile organic compound
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5.0 Cautions/Interferences
5.1 The operator should handle the TD tubes and Radiello yellow diffusive bodies only while
wearing clean nitrile or cloth gloves so that the tubes do not become contaminated with
body oils, hand lotions, perfumes, etc.
5.2 To maintain sample integrity, labels should not be attached to the TD tubes or Radiello bodies
and ink markings should not be made on the TD tubes or Radiello bodies (see section 9.4).
5.3 Only combined (one-piece) PTFE ferrules should be used with the 0.25-in. storage end
caps as other types of ferrules might not seal adequately or might score the tube.
5.4 A CapLok tool should be used to tighten the fittings one-eighth to one-quarter turn past
finger tight so that they are neither too tight nor too loose.
5.5 Care must be taken when transferring the Radiello Carbopack X cartridge from the TD
tube to the Radiello diffusion body. The cartridge must be gently pushed out of the TD
tube using the supplied "push rod" so as not to damage the wire screen containing the
sorbent. Care must also be taken when transferring the cartridge back into the TDtube.
5.6 Sorbent material can sometimes leak from the Radiello Carbopack X cartridge, most likely
due to a damaged cartridge or improper handling. Laboratory and field personnel should
watch for any significant loss of sorbent material when end caps are changed. Any suspect
tube should be removed from the sampling/analysis queue.
5.7 Since the Radiello Carbopack X cartridge itself does not have a unique identifier, it is
important that each tube be returned to its assigned uniquely identified TD tube when
transferred from the diffusion body back to a TD tube.
5.8 The tubes should be shipped in an airtight, non-VOC-emitting container to minimize their
exposure to possible contaminants in the ambient air.
5.9 The refrigerator in which the tubes are stored should be free of solvents and chemicals to
prevent possible contamination of the tube samples.
5.10 The laboratory in which the tubes are handled should be free of VOCs to prevent possibility
of contamination.
5.11 Depending on the data quality objectives (DQOs) for a particular study, Radiello bodies
and TD tubes may be cleaned after each use to minimize any chance of contamination.
6.0 Personnel Qualifications
Field study personnel should have experience handling TD tubes and collecting trace-level VOC
samples using TD tubes.
7.0 Equipment and Supplies
In general, all sampling equipment and supplies, excluding the VOC-free refrigerator and vacuum
oven, are shipped to sampling sites in packaged field kits prepared by the VOC laboratory. The
following equipment and supplies are needed:
• Refrigerator, VOC free
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• Precision vacuum oven (model 19, Precision Scientific Inc., Chicago, IL)
• Radiello Carbopack X cartridges (part no. RAD 141, Millipore Sigma, St. Louis, MO) loaded
in empty stainless steel 89-mm stainless steel TD tubes (part no. 21822-U, Millipore Sigma)
and fitted with precleaned and assembled 0.25-in. brass Swagelok fittings with combined (one-
piece) PTFE ferrules (part no. 23094-U, Millipore Sigma) Note: TD tubes containing
Radiello cartridges are visually denoted by one of the two end caps having a stainless steel
nut substituted for a brass nut to differentiate the tubes containing Radiello cartridges
from standard TD tubes that have all brass caps and nuts.
• Radiello yellow diffusive body (part no. RAD 1201, Millipore Sigma), triangular support plate
(part no. RAD 121, Millipore Sigma), and vertical adapter for personal sampling (part no. RAD
122 Millipore Sigma)
• Nitrile gloves (part no. 55091, 55092, or 55093, Kimberly-Clark, Neenah, WI orequivalent)
• CapLok tool (part no. C-CPLOK, Markes International, Gold River, CA)
• Glass vials (part no. 45066A-25150, Kimble/Kontes, Vineland, NJ)
• Unlined caps for glass vials (custom order, Scientific Specialties Service, Inc., Randallstown, MD).
• Septrseal Septa and Teflon liners for glass vial caps (part no. B69800-24 and B68800-24,
Scientific Specialties Service, Inc.)
• Clean, unlined gallon metal cans with lids (part no. MET-03098, 1195 Qorpak Inc.,
Washington Pike Bridgeville, PA 15017)
• Cooler (example part no. 5248-5286-5296, Coleman Outdoor Products, Inc., Wichita,KS)
• Foam inserts for coolers (Instapack quick foam packaging, Sealed Air Corporation, Danbury, CT)
• Rex protective sleeves, 1.021-in. i.d. by 5.750-in. length with wall thickness of 0.125 in.
(custom order, Yazoo Mills, Inc., New Oxford, PA)
• Closed cell foam, assorted thicknesses
• Assorted tools, including but not limited to metal forceps or tweezers, wrenches of various
sizes, and paint can openers
• Fluorinated ethylene propylene (FEP) Teflon tubing, 0.25-in. o.d.
• 600-mL Pyrex beaker (part no. 1000)
• Tech Wipes, three-ply tissue (part no. 350/50353, Horizon Industries, Tyler, TX)
• Zipper storage bags, 5 x 7-in. 3 mil (model #S-14444, 100/carton, Uline, Pleasant Prairie, WI)
- used to store and ship the diffusion caps
• Zipper storage bags, 16 x 16-in. 3 mil (model #S-10835, 100/carton, Uline, Pleasant Prairie,
WI) - to contain COC forms, data sheets, and labels when shipped to the field)
• Aluminum foil, food service grade (Western Plastics, Calhoun, GA) - for baking out diffusion caps
• Cable ties
• Bubble wrap
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• Paper tape and sample ID labels
• Shipment chain of custody (COC) forms (Appendix A), field monitoring data and COC sheets
(Appendix B), and laminated field deployment procedure (Appendix C)
8.0 Quality Control/Quality Assurance
8.1 Before storing, before and after shipping, and before and after sample collection, the end
caps on the TD tubes should be checked for tightness by tugging simultaneously on each
of the end caps in opposite directions to verify that the tubes are properly sealed.
8.2 TD tubes containing Radiello cartridges are visually denoted by one of the two end caps
having a stainless steel nut substituted in for a brass nut to differentiate the tubes containing
Radiello cartridges from standard TD tubes that have all brass caps and nuts.
8.3 Staff must handle all sampling media with gloves to ensure there is no contamination.
8.4 Staff must inspect Radiello diffusive bodies to ensure they are free of debris prior to
deployment.
9.0 Procedures
9.1 Preparation of TD tubes for outgoing field shipments
1. Retrieve the conditioned TD tubes and "tug test" tubes as described in section 8.1 to
ensure end caps are secure.
2. Use paper tape or generated labels on the outside of the appropriate glass vials to
clearly label "Field Spikes," "Field Blanks," and "Spares" (Figure 1). (Refer to the
project-specific Quality Assurance Project Plan (QAPP) to determine how field spikes
and field blanks are prepared and used for the current project.)
Figure 1. Labeled field blank and field spike.
3. Record the TD tube number of all outgoing tubes in the designated laboratory notebook.
4. Record the conditioning date next to each outgoing tube and the exposure dates next
to the field spikes.
5. Make a copy of the laboratory notebook page to be sent to the field (Figure 2).
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Page 8 of 33
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Packaging TD Tubes for Shipment to or from the Field
Note: Prior to the first use wash all metal shipping cans with soap and deionized (DI)
water. Wipe them down with Tech Wipes and let them air dry.
1. Insert a short piece of 0.25-in. FEP Teflon tubing as a protective chip in the bottom of a
glass vial to prevent the TD tube from bouncing around and possibly breaking the glass.
Perform the tug test (see section 8.1), and then place the sealed TD tube into the glass vial.
2. Use forceps or tweezers to insert two 5.5-in. pieces of 0.25-in. o.d. FEP Teflon tubing
strips into the glass vial beside the TD tube one at a time to prevent the TD tube from
bumping the sides of the glass vial and cracking or breaking the glass (Figure 3).
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Figure 3. Protective Teflon tubing inserted into glass vial.
3. Screw the cap, which is fitted with a septum and Teflon liner, onto the glass vial.
4. Attach a sample ID label to the glass vial and to the field data sheet; this step
streamlines the sample deployment process for the field operators.
5. Line the bottom of a metal can with a 6-in.-diameter foam disk, and then insert 19
cardboard protective sleeves (1.021-in. i.d. by 5.75-in. length) to cushion the glass vials.
6. Place the glass vial(s) into the metal can inside the protective sleeves, and insert a piece
of loam cut roughly the size of a cardboard sleeve into the metal can to ensure that the
protection sleeves fit snugly inside the can, as shown in Figure 4. (Note: The seven
protection sleeves in the center are preassembled with bubble wrap and bound together
with cable ties, which allows for easy insertion or removal of the outer band of tubes,
as shown in Figure 5.)
Figure 4. Tubes packed in metal Figure 5. Tubes packed in inner
can. protective sleeve.
7. Place two pieces of round foam (6.5-in. and 6-in. diameter) in the top of the metal can
and seal the metal can with the lid (Figure 6).
Figure 6. Foam inserts in shipping canister.
8. Store the metal can in a refrigerator at 4 °C until the tubes are to be sent to the field for
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sample collection or back to the laboratory for analysis.
9. Ensure that any tubes that were removed from the metal canisters are repackaged as
described in Section 9.2 steps 1-2 and that all procedures in section 9.2 for packing and
sealing the metal cans are followed.
10. Pack the diffusive bodies in a zipper storage bag and place it inside a metal shipping
canister.
13. Place the metal cans in coolers (three cans per cooler) fitted with foam packaging, as
shown in Figure 7
Figure 7. Metal cans packed in cooler for shipment.
12. Pack field data sheets and COC forms, spare preprinted sample ID labels, and return
shipping labels inside a large (16 in. m 16 in.) zipper storage bag and place inside the
cooler before shipping. Be sure to sign and date the COC form prior to shipping the
cooler to the field.
Cleaning and Preparing Diffusive Bodies for Shipment to the Field
Laboratory personnel should inspect diffusive bodies for overall integrity prior to each
return shipment to the field and should clean them as necessary using the following
procedure. Compromised diffusive bodies should be discarded by VOC laboratory staff.
When handling diffusive bodies, both field and laboratory personnel must wear cotton or
nitrile gloves at all times to ensure the caps are not contaminated with body oils. Use the
following procedure to clean the diffusive bodies:
1. Immerse the diffusive bodies in a beaker with mild laboratory detergent and DI water
and sonicate for 20 minutes. (Note: Be sure the diffusive bodies remain submerged by
weighting down with a smaller beaker.)
2. Rinse the diffusive bodies with plenty of tap water followed with DI water.
3. Lay diffusive bodies on several layers of laboratory tissues and air dry. Store the clean
diffusion bodies in clean zipper storage bags.
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Receiving Sample Media
(Note: Steps 1-10 are "check-in" steps that may be completed in an office or laboratory
upon receipt of sampling media to ensure the integrity of the media and provide time for
organization prior to deployment to the field. Alternatively, these steps may be completed
in the field immediately prior to deployment.)
1. Remove the shipping canisters from the cooler.
2. Unpack the glass vials containing the tubes from the shipping canister by opening the
lid of the can with a flathead screwdriver or paint can opener.
3. Remove the foam pieces from the top of the can, and remove the bound inner unit of
tubes from the can.
4. Check in the TD tubes one by one by verifying that the glass vials are not cracked and
that the caps are on the glass vials. Verify that the storage end caps are still in place on
the TD tube and then check the TD tube numbers against the COC form. If any of the
TD tubes have end caps that have slipped off or if the glass vials are broken, the
operator should select a different tube for field deployment.
5. While wearing clean nitrile or cloth gloves, uncap the glass vial and remove the two
Teflon tubing strips using tweezers, forceps, or small pliers one strip at a time so as not
to crack or break the glass vial (Figure 8). Remove the cap from the glass vial and inspect
the inside of the cap to ensure the cap septa and liner are in place. Replace if necessary.
Figure 8. Removing TD tube from the glass vial.
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6. Remove the TD tube from the vial and perform the tug test to ensure the storage end caps
are not loose (Section 8.0). If a problem is noted, choose a different TD tube for field
deployment. Return the tube to the glass vial being sure that the protective Teflon chip is
still on the bottom of the vial. (Note. Since the glass vials provide secondary containment,
if a situation arises where all of the spare diffusive sampling tubes are used, then a tube can
be selected for which the glass vial was broken or cracked. All relevant information on tube
selection must be recorded on the field monitoring data sheet should this situation arise.)
7. Slide the Teflon strips into the glass vial, cap the vial, and place the glass vial holders in
the shipping can. Repeat these steps for each TD tube that has been received and then
place the foam pieces and lid on the can and seal. (Note. If these check in steps are being
performed in the field at the time of deployment, the operator will not be placing the
tubes or associated Teflon pieces back in the glass vials and metal shipping containers.)
8. Inspect all Radiello yellow diffusive bodies prior to use. Do not deploy any Radiello
yellow diffusive bodies that have holes in them or have debris on the surface. Spare
Radiello yellow diffusive bodies are provided in every shipment and should be used in
these instances. Compromised Radiello yellow diffusive bodies should be returned by
field staff to the VOC laboratory along with notes detailing concerns or problems
regarding suspect Radiello yellow diffusive bodies. (Note. Cloth or nitrile gloves are
to be worn for all activities involving handling of the diffusive body and/or TD tube
and Radiello cartridge.)
9. Store the container(s) of TD tubes, tools, spare supplies, pens, diffusion caps, and a
notebook containing the field data sheets in a storage box that can be transported easily
to the field site.
10. List any observations regarding condition of sample media upon receipt on the field
monitoring data and COC sheet (Appendix B) that accompanied the tube shipment.
11. If the tubes have been stored in a refrigerator, allow them to come to room temperature
(~ 30 min to 1 h) before using them for sample collection.
Deployment of Radiello Diffusive Samplers
1. Assembly of the sampler for fixed site monitoring requires a tripod sampling stand
(Figure 9A), a triangular support plate that has been modified to fit the tripod, a yellow
diffusive body, a 1/8-inch diameter push rod, and a Radiello Carbopack X cartridge
contained within the TD tube (Figure 9B).
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A B
Figure 9. Tripod Sampling Stand (A); Radiello yellow diffusive body, support
plate, push rod and TD tube containing a Radiello Carbopack X cartridge (B).
2. For fixed site sam pling, the triangular support plate should be mounted on the top of the
tripod with the threaded portion of the support plate that holds the diffusive body facing
the base of the tripod (Figure 10). Extend and lock the sections of the tripod and place at
the designated sampling area.
m
Figure 10. Assembly of support plate on tripod.
3. For each tube, ensure that the preprinted sample ID label is on the field data sheet and
the other on the glass vial (Figure 11A). Record the field sample TD tube number, the ID
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code of the corresponding triangular support plate and the sampling location information
on the field data collection fonn (Figure 1 IB) The field data collection fonn is located in
Appendix B.
Figure 11 A. Retrieve TD tube packed Figure 11B. Verifying labels on the
inside of glass vial from shipping vial and field data collection form
container.
4. Record the TD tube number(s) of the field blank(s) and field spike(s) on the field data
sheet. For QA samples, place one of the preprinted sample ID labels on the field data
sheet and the other on the glass vial. Field blanks and field spikes must remain sealed
with the storage end caps and are deployed alongside field samples.
5. To deploy field samples, using the CapLok tool, remove the end caps from both ends
of the TD tube (Figure 12).
Figure 12. Remove end caps with Caplok tools.
6. Insert the 1/8-inch push rod in the grooved end of the TD tube and carefully push the
Radiello Carbopack X cartridge out of the TD tube (A) and into the opening of yellow
diffusive body (B) (See Figure 13). (Note: A correctly centered cartridge should not
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stick out even by half a millimeter. If it does, the cartridge is not correctly positioned
and is out of axis).
mt*? r
Push Rod
•Til r
I TD Tube
Radiello ' '
» ^ M
A B
Figure 13. Push rod (A) used to push Radiello cartridge into the Radiello
diffusive body (B).
7. Place the empty TD tube, end caps and Teflon strips and chip back into the glass vial
and replace the vial cap.
8. Screw the yellow diffusive body containing the Radiello cartridge into the triangular
support plate mounted on the top of the tripod. The diffusive body should be
positioned underneath the support plate facing the ground (Figure 14). (Note: Be sure
to minimize contact with the diffusive body and gloved hands to prevent
contamination.)
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Figure 14. Screw the Radiello diffusive body onto the triangular support plate.
9. Attach the sampler to the person (Figure 15A) or sampling tripod (Figure 15B).
During personal sampling, ensure the sample body is not covered by clothing or hair.
A B
Figure 15. Radiello samplers deployed for personal monitoring (A) or
stationary monitoring (B).
10. Record the start time and additional sampling details on the field monitoring data
sheet. An example data sheet entry is shown in Figure 16 (Note: The sample ID
code will vary according to the design of a particular field study.
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Figure 16. Enter sample ID code and tube number on data sheet.
11. Deploy for 3 hours (nominal).
12. At the end of the 3-hour deployment period, record the stop date and time on the field
monitoring data sheet and any additional sampling/field comments (Figure 16).
13. Unscrew the yellow diffusive body from the triangular support plate.
14. Retrieve the exposed Radiello cartridge from the diffusive body using a pair of
stainless steel forceps (Figure 17A). Carefully place the end of the Radiello cartridge
into the non-grooved end of the TD tube and use the 1/8-inch push rod to gently push
the cartridge completely into the TD tube (Figure 17B). (Note: Be sure the Radiello
cartridge is returned to its original TD tube. TD tube numbers must be verified against
the information recorded on the field data monitoring form).
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A B
Figure 17. Radiello Cartridge (A) inserted back into the original PE tube
using push rod (B).
15. Use CapLok tools as show in Figure 12 to tighten end caps on each end of the TD
tube and perform the "tug test" to ensure end caps are tight. Place the TD tube back
into the appropriate glass vial as shown in Figure 18. Ensure the Teflon chip and two
Teflon strips are also packed inside of the glass vial to provide stability (Figure 18A).
The tube should not move in the glass vial when packed correctly (Figure 18B).
B
TD Tube
U
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Figure 18. Tube packed into glass vial with Teflon chip and strips (A) and capped (B).
16. Return glass vials containing TD tubes back to the shipping canister. Place used
Radiello diffusive bodies in a bag marked "Used" and return with samples for
assessment for reuse.
17. Record tube numbers for any spare or unused tubes. In the comments section of the field
data sheet indicate if the tube was a spare and/or was unused (Figure 16). Ensure that
all entries on the field monitoring sheet are filled on correctly with start times, dates and
sampling notes as well as stop dates, times and sampling notes. (Note: All tubes shipped
from the field must be documented on the field data sheet by field staff.).
18. Prepare the tubes for return shipment to the laboratory according to the procedure
outlined in section 9.2. Field staff can also refer to the "Field Procedure for Diffusive
Sample Collection Using Radiello Samplers - Deployment and Shipping" in
Appendix C. A laminated version of this procedure will be shipped to field sites at the
start of a study.
10.0 Data and Records Management
10.1 Details of the tube deployment (start/stop times, date, sample ID code, TD tube serial
number, and operator's name) are listed on the field deployment data sheet (AppendixB).
10.2 Data sheets are returned to the laboratory with samples for analysis where they are placed
in designated three-ring binders.
10.3 For large studies, field staff might be asked to populate electronic versions of field data
sheets and send them to the laboratory manager.
10.4 Information from the field data sheets is combined with the corresponding analytical data
in either Excel format or by a data manager as appropriate to a particular study and outlined
in that study's QAPP.
10.5 Laboratory staff should refer to the Field Packing Checklist (Appendix D) and the
Incoming Field Sample Checklist (Appendix E) when preparing outgoing field shipments
and checking in incoming field samples.
11.0 References and Supporting Documentation
D-EMMD-AQB-008-SOP-01 (formerly ECAB-156.0E). 2013. Standard Operating Procedure for
Carbopack X Sorbent Tube Conditioning Using the Markes International Model TC-20 Sample
Tube Conditioner. U.S. Environmental Protection Agency, National Exposure Research
Laboratory.
D-EMMD-AQB-006-SOP-01 (formerly ECAB-154.1). 2015. Standard Operating Procedure for
Desorbing Volatile Organic Compounds from Carbopack X Sorbent Tubes Using the PerkinElmer
TurboMatrix ATD. U.S. Environmental Protection Agency, National Exposure Research
Laboratory.
D-EMMD-AQB-014-SOP-Ol. 2016. Standard Operating Procedure for Desorbing Volatile
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Organic Compounds from Carbopack X Sorbent Tubes Using the PerkinElmer TurboMatrix ATD
650. U.S. Environmental Protection Agency, National Exposure Research Laboratory.
D-EMMD-AQB-003-SOP-01 (formerly ECAB-151.1). 2016. Standard Operating Procedure for
Determination of Volatile Organic Compounds Desorbed from Carbopack X Diffusive Sampling
Tubes Using the Agilent 6890N/5975 GC-MSD. U.S. Environmental Protection Agency, National
Exposure Research Laboratory.
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Appendix A: Shipment Chain of Custody Form
| v© I CHAIN-OF-CUSTODY DECLARATION FORM
EST I
GENERAL INFORMATION
Monitoring Project:
Date of Initiation:
Sample Collection Date:
Total No. of Samples for Custody Transfer:
THE FOLLOWING TRANSFER OF CUSTODY DECLARATIONS APPLY TO ALL SAMPLES
THAT ARE LISTED DIRECTLY IN EACH DESCRIPTION AND ONLY TO THOSE SAMPLES.
TO THE FIELD
DESCRIPTION OF SHIPMENT (Number and type of samples covered by this declaration):
Relinquished by:
Received by:
(Print Name and Organization)
(Print Name and Organization)
(Signature, Date and Time}
(Signature, Date and Time)
Condition Acceptable? Yes No
FROM THE FIELD
DESCRIPTION OF SHIPMENT (Number and type of samples covered by this declaration):
Relinquished by:
Received by:
(Print Name and Organization)
(Print Name and Organization)
(Signature, Date and Time)
(Signature, Date and Time)
Condition Acceptable? Yes No
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Appendix B: Tube Field Monitoring Data and Chain of Custody Sheet
TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
Field Locations - Passive (Radiello) and Active VOC Samples
Deployment
Recovery
!? ** flf
Study Name:
" II
TCRS
Date
Si
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
1
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Radiello Tube ID
Holder ID
Start Time
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
PE Tube ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
Field Locations - Passive (Radiello) and Active VOC Samples
Deployment
Recovery
6 « 4\
Study Name:
13. 1
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
2
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Radiello Tube ID
Holder ID
Start Time
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
PETube ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Form Rev 06/21/2017 daw
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TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
Field Locations — Passive (Radiello) and Active VOC Samples (f \
Deployment
Recovery
11 *^Lf)
Study Name:
g "J!
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
8
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Radiello Tube ID
Holder ID
Start Time
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
PE Tube ID
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
Place Sample ID Label Here
Field notes:
Receipt notes:
Analysis notes:
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Radiello Samplers Field Deployment
D-EMMD-AQB-019-SOP-01
August 23, 2017
Page 25 of 33
TIRE CRUMB EXPOSURE STUDY-- VOC MONITORING DATA AND COC SHEET
Active (PE) VOC Field/Lab Blanks and Controls
(i *
* -*\
p- m
Deployment
Recovery
\% '
Study Name:
V. #
TCRS
Date
m " * r™1
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PETube ID
Initials
Date
Initials
Date
Initials
Date
Field notes;
Place Field/Lab Blank ID Label
Here
Receipt notes:
Analysis notes:
Field notes:
Place Field/Lab Blank ID Label
Here
Receipt notes:
Analysis notes:
PE Tube ID
| | Initials
Date
Initials
Date
Initia Is
Date
Field notes:
Receipt notes:
Analysis notes:
Place Field/Lab Control ID Label
Here
r rr»
1 1 1 1 1
Place Field/Lab Control ID Label
Here
Field notes:
Receipt notes:
Analysis notes:
Form Rev 06/21/2017 daw
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Page 26 of 33
Appendix C: Field Procedure for Diffusive Sample Collection Using Radiello
Samplers - Deployment and Return Shipping
Health and Safety Warnings
Glass vials containing TD tubes might occasionally break during shipment. Exercise caution when
packing and unpacking the glass vials from the shipping containers.
Cautions/Interferences
• The operator should handle the TD and diffusive bodies only while wearing clean cloth or
nitrile gloves.
• Labels should not be attached to the TD tubes or Radiello diffusive bodies, and ink
markings should not be made on the TD tubes or Radiello diffusive bodies. Markers should
not be used around the TD tubes or Radiello diffusive bodies.
• Radiello cartridges must be seated properly in the diffusive body. They should not stick
out of the diffusive body by even a millimeter. Any protrusion from the diffusive body
indicates the Radiello sampling cartridge is not properly seated.
• When sampling is complete, a CapLok tool should be used to tighten the storage end caps
one-eighth to one-quarter turn past finger tight so that they are neither too tight nor too
loose. A tug test should be performed to ensure adequate end cap tightness.
• The laboratory/area in which the samples are stored and handled should be free of VOCs
to prevent any possibility of contamination.
Procedure
1. Diffusive Sample Collection
Note: Steps 1 through 5 are usually performed in the lab/office upon receipt of the
sampling media to facilitate organization of the field deployment of the TD tubes. Steps
6 through 15 are performed in the field.
1. Unpack the TD tubes from the shipping can by opening the lid of the can with a screwdriver
as necessary, remove the foam pieces from the top of the can, remove the inner tube
holder of glass vials from the can, and remove the remaining glass vials from the shipping
can if applicable.
2. Check in the TD tubes one by one by verifying that the glass vials are not cracked and
that the caps are on the glass vials. Verify that the storage end caps are still in place on
the TD tube. If any of the TD tubes have storage end caps that have slipped off or if the
glass vials are broken, the operator should select a different tube for field deployment.
3. Check the TD labels against the labels on the field data sheet.
4. While wearing clean nitrile gloves, uncap the glass vial and remove the two Teflon tubing
strips using tweezers, forceps, or small pliers one strip at a time so as not to crack or break
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Page 27 of 33
the glass vial.
5. Remove the TD tube from the vial and perform the tug test to ensure the storage end caps
are not loose. If a problem is noted, choose a different TD tube for field deployment. Return
the tube to the glass vial being sure that the protective Teflon chip is still on the bottom of
the vial.
6. Slide the Teflon strips into the glass vial, cap the vial, and place the glass vial holders in
the shipping can. Repeat these steps for each TD tube that has been received and then
place the foam pieces and lid on the can and seal.
7. Inspect all Radiello yellow diffusive bodies prior to use. Do not deploy any Radiello yellow
diffusive bodies that have holes in them or have debris on the surface. Spare Radiello
yellow diffusive bodies are provided in every shipment and should be used in these
instances. Compromised Radiello yellow diffusive bodies should be returned by field staff
to the VOC laboratory along with notes detailing concerns or problems regarding suspect
Radiello yellow diffusive bodies.
8. Store the container(s) of TD tubes, tools, spare supplies, pens, diffusion caps, and a
notebook containing the field data sheets in a storage box that can be transported easily
to the field site.
Note: Perform the following steps at the field site beginning immediately prior to
deployment of the Radiello Sampler tubes while wearing clean gloves and working
steadily:
9. Following the procedures above, allow tubes to warm up for 30 minutes prior to
deployment.
10. Remove a TD tube from a glass vial and use a CapLok tool to loosen and remove the
storage end cap from the sampling end of the tube. Place the Teflon chip and strips, and
storage end cap (as applicable) back into the glass storage vial and cap the glass vial.
11. Record the appropriate TD tube number on the field data sheet next to its corresponding
sample ID label. Store the glass vial as appropriate.
12. Using the 1/8-inch push rod, insert in the grooved end of the TD tube and carefully push
the Radiello Carbopack X cartridge out of the TD tube and into the opening of yellow
diffusive body. (Note. A correctly centered cartridge should not stick out even by half a
millimeter. If it does, the cartridge is not correctly positioned and out of axis).
13. Attach the Radiello sampler to the person or sampling tripod. During personal sampling,
ensure the sample body is not covered by clothing or hair
14. Follow steps 8 through 12 for each TD tube to be deployed for sample collection.
15. Do not uncap the field blanks or field spikes, but instead hang them in place with both of
the storage end caps still sealing the TD tube. Record the TD tube serial number for the
field blank(s) and field control(s) on the field data sheet. (Note. This deployment procedure
will depend on the design of a particular study; some studies might specify that the field
blank(s) and field spike(s) travel to the field and then are returned to the field office for
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storage during the sampling period.)
16. Once all Radiello samplers are positioned, mount the tripod as appropriate at the site.
Record the start time and additional sampling details and/or comments on the field
monitoring data sheet.
Note: Perform the following steps at the field site at the end of the sampling cycle.
17. At the end of the 3-hour deployment period, record the stop date and time on the field
monitoring data sheet and any additional sampling/field comments.
18. Retrieve the exposed Radiello cartridge from the diffusive body using a pair of stainless
steel forceps. Carefully place the end of the Radiello cartridge into the non-grooved end
of the TD tube and use the 1/8-inch push rod to gently push the cartridge completely into
the TD tube. (Note. Be sure the Radiello cartridge is returned to its original TD tube. TD
tube numbers and labels must be verified against the information recorded on the field
data monitoring form.)
19. Use CapLok tools to tighten storage end caps on each end of the TD tube and preform
the "tug test" to ensure end caps are tight.
20. Place the TD back into the appropriate glass vial. Ensure the Teflon chip and two Teflon
strips are also packed inside of the glass vial to provide stability.
21. Return glass vials containing TD tubes back to the shipping canister. Place used
Radiello diffusive bodies in a bag marked "Used" and store appropriately for cleaning.
22. Verify that the field sample ID label and TD tube number on the vial match those recorded
on the field monitoring data sheet. Record the stop time and any additional sample
collection data on the field monitoring data sheet beside the appropriate field ID label/TD
tube serial number.
23. Return all TD tubes and supplies to the storage box/cooler for return to the field office.
2. Shipment to the Laboratory
1. To prepare the TD tube shipment to the laboratory, check to see that the Teflon tubing
chip is in the bottom of each glass vial to prevent the TD tube from bouncing around and
possibly breaking the glass.
2. Use tweezers/forceps to insert two Teflon tubing strips into each glass vial beside the TD
tube to prevent the TD tube from bumping the sides of the glass vial and cracking or
breaking the glass.
3. Screw the vial cap onto the glass vial after checking the vial cap to be sure that the liner
and septum are in place. Replace with a spare liner or septum if necessary.
4. Place the glass vial(s) into the metal can(s) loaded with cardboard protection sleeves to
cushion the glass vials. Insert the piece of foam that is cut roughly the size of a cardboard
sleeve into the metal can to ensure that the protection sleeves fit snugly inside the metal
can. Place the center tube holder insert into the middle of the can.
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5. Place the two pieces of round foam in the top of the metal can and seal the metal can with
the lid.
6. Place the metal cans in the same shipping box or container that they were originally
shipped in and fill the container with bubble wrap or other packaging material to cushion
the contents.
7. Fill out the COC form and return it along with the field data sheets in this shipment. Note:
Make a photocopy of these documents for retention at the field office prior to shipping.
8. Seal the box securely for shipment, attach the return shipping label for delivery, and be
sure that the package will not be in transit over a holiday or weekend.
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Appendix D: Field Packing Checklist for Laboratory Staff
It is helpful to perform these activities a week or two before the next shipment.
Activity
Performed
Count how many clean TD tubes are in the fridge and ready for deployment. This will give
you an idea of how many batches you might need to analyze this week to free up tubes for
the next shipment.
r
Count how many glass vials and vial caps are currently available for field use.
r
Be sure you have enough coolers.
r
Be sure you have enough tubes for the field spike exposures. It is always a good idea to
ask if there is a need for any additional field spikes outside the norm before starting the
field spike exposures.
r
Check to see if you have enough hang tag packets for shipping the coolers. The sooner
you know the better in case more need to be ordered.
r
Be sure you have enough protective Teflon strips and chips to pack into each vial. You
might need to check incoming shipments stored in the fridge for extra Teflon strips/chips if
you do not have enough for outgoing shipments.
r
Before you start packing, check to see if any additional sites have been added or if sites
have been removed for each field location. It is also helpful to pass this information along
to the staff member who is preparing the sample ID labels.
r
Be sure you have enough clean Radiello diffusive bodies. Write down how many you pack
per shipment and ensure they are clean.
r
Always write down the TD tubes numbers packed in each batch in the designated lab
notebook. Include the exposure date for field spikes and lab controls and the conditioning
dates for all other tubes packed.
r
QA packed shipments and any inventory forms that are shipped to ensure tube numbers
are typed correctly. Templates for inventory sheets are on the desktop of the spare
computer in D260 in the folder labeled "Packing Lists".
r
Always pack field spikes and field blanks in vials labeled with paper tape: "Field Spike,"
"Field Blank," or "Spare."
r
Store outgoing shipments on the top shelf on the right-hand side of the refrigerator.
r
Copy outgoing COC signature pages and tube inventory lists and store in designated field
study COC binders.
r
Store all emails/correspondence relevant to a particular batch with copies of the COC.
r
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Appendix E: Incoming Field Sample Checklist for Laboratory Staff
Activity
Performed
Be sure all check-in notes, signatures, and date are recorded on the original COC in
permanent waterproof black pen.
r
Sign and date the signature page of the COC as well as the boxes next to each received
sample.
r
If any additional tubes are received that are not listed on the COC by field operators,
record those tube numbers on the COC and initial/date receipt of those tubes as well.
r
In general, one unused/unexposed tube is sent back with each shipment. This tube is
considered the shipping blank* Write "shipping blank" in the "Receipt Comments"
section and assign the appropriate Sample ID to this tube on the COC in the box where the
sample ID label is placed according to the format designated in the associated QAPP.
Examples of recently used Sample ID number formats for shipping blanks are shown
below:
For Reaional Shiooina Blank/Spare Tube
Region-Site-Week-Type
##-99-##-SB
Example: 06-99-12-SB
Region 6, Site 99, Week 12, Shipping Blank
Note: The designated site for the shipping blank sample is 99.
The newly assigned sample ID should also be written on paper tape and placed on
the vial that the tube is stored in.
For Phillv Shiooina Blank/Spare Tube
Site-Week-Type-PHL
99-##-SB-PHL
Example: 99-25-SB-PHL
Site 99, Week 25, Shipping Blank, Philly
Note: The designated site for the shipping blank sample is 99.
The newly assigned sample ID should also be written on paper tape and placed on
the vial that the tube is stored in.
Label the glass vial with the shipping blank sample code before storing.
*lf multiple spare/unused TD tubes are shipped back, select only one as the shipping blank
and assign an appropriate Sample ID. The remaining unused tubes should be conditioned
prior to reuse.
r
Cross-check TD tube numbers and Sample IDs on the tubes against those on the COC.
r
Note any observations in the "Receipt Comments" section. The following are some
suggestions of the info to enter so that everyone checking in samples is making the same
types of check-in comments, which helps when flagging data in the database.
• "SE loose" - the sampling end cap on the grooved end of the tube is loose;
tightened
• "RE loose" - the rear end cap is loose; tightened
• "Vial cracked"
• "Cap off vial"
• "SE end cap off'/ "SE end cap nut off'
r
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• "RE end cap off/ "RE end cap nut off
• "Tube dirty"
• "SE ferrule missing/RE ferrule missing"
• "Tube number incorrect"; "Correct tube number is
• "Sample ID is incorrect"; "Correct sample ID is...."
• "Tubes switched in vial; switched tubes to match COC"
• "Tube invalid no analysis"
Remove all protective Teflon tubing strips and chips to ensure they are available for the
next outgoing shipments. If any strips or chips are dirty, they can be wiped off with lint-free
Kimwipes, and in extreme cases can be rinsed with Dl water and dried with house air.
Never use solvents.
r
Remove white lined vial caps/black lined vial caps and replace them with white vial caps
that are not shipment-ready before they are stored.
r
Set all tubes to the side that are considered invalid and will not be analyzed. These are
usually tubes that are found on the ground. Inform the VOC lab manager of these tubes
and verify that they will not be analyzed.
r
Store all checked-in tubes inside their glass vials, place them in a cardboard box, and
place them in the fridge. Labels from the incoming canisters can be placed on the
cardboard box to identify the samples in the box.
r
Clean any used Radiello diffusive bodies. Discard those that are torn or unfit for additional
use.
r
Immerse the diffusive bodies in a beaker with mild laboratory detergent and Dl water and
sonicate for 20 minutes. Note: Be sure the diffusive bodies remain submerged by
weighting down with a smaller beaker.
r
Rinse the diffusive bodies with plenty of tap water followed with Dl water. Lay diffusive
bodies on several layers of laboratory tissues and air dry. Store the clean diffusion bodies
in clean zipper storage bags.
r
Copy the COC after check-in is complete and place the original COC in the designated
binder with any correspondence regarding that particular batch. Place the copy aside in the
designated space so that the Excel tube tracking sheet can be updated. In addition, store a
copy of the COC with the tubes that are refrigerated for future analysis.
r
Acknowledge receipt of all incoming shipments for the day and any important
notes/findings in the designated laboratory notebook.
r
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U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure (SOP) for Collection of Surface Wipe Samples from
Synthetic Turf Fields
Number: D-SED-IEMB-026-SOP-01
Effective Date: August 21, 2017
SOP was Developed 0 In-house ~ Extramural
Alternative Identification:
SOP Steward
Name: Kent W. Thomas (with Dan Vallero Contribution)
Signature:
Approval
Name: Caroline Stevens
Title: Branch Chief, NERL/SED/ffiMB
Signature: Date:
Concurrence*
Name: Christine Alvarez
Title: NERL QA Manager
Signature: Date:
For Use by QA Staff Only:
SOP Entered into QATS:
Initials Date
* Optional Field
NERL-SOP.l (7/2003)
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D-SED-IEMB-026-SOP-01
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Page: 2 of 22
STANDARD OPERATING PROCEDURE (SOP) FOR
COLLECTION OF SURFACE WIPE SAMPLES FROM SYNTHETIC TURF FIELDS
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 4
5.0 RESPONSIBILITIES 4
6.0 MATERIALS AND REAGENTS 4
7.0 PROCEDURES 5
8.0 RECORDS 10
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 11
10.0 REFERENCES 12
Appendix A. Sample Collection Record for a Surface Wipe Sample 13
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1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) describes the method for collecting wipe samples from
synthetic turf field surfaces to measure semivolatile organic compounds (SVOCs) and metals for the
United States Environmental Protection Agency (EPA) exposure characterization pilot tire crumb
rubber research study (TCRS).
2.0 SUMMARY OF THE METHOD
Dermal, inhalation, and ingestion of dust at synthetic turf fields may represent important pathways of
exposure to chemicals associated with tire crumb rubber, other synthetic field materials, and
environmental dust deposited on the field. The concentrations of metals and semivolatile organic
compounds (SVOCs) on field surfaces available for dermal transfer must be measured to determine
human exposures and to compare these to the various exposure pathways and to biologic markers in
blood and urine.
Surface wipe samples for metals analysis will be collected at synthetic turf field sites using a wet
(water) wipe (Environmental Express, Ghost Wipe No. 4210) conforming to American Society for
Testing and Materials (ASTM) E1792 (ASTM-03, 2016a) requirements. Surface wipe samples for
SVOC analysis will be collected using cleanroom twill wipes (M.G. Chemicals, cotton, pre-cleaned),
using a dry 30.5 cm x 30.5 cm wipe attached to a drag sled and a wipe wetted with 1:1 isopropyl
alcohol:water with dimensions of 4 inch x 4 inch (10 cm x 10 cm).
3.0 DEFINITIONS
ASTM - American Society for Testing and Materials
CDC - Centers for Disease Control and Prevention
COC - Chain-of-custody
EPA - Environmental Protection Agency
FB - Field Blank
FC - Field Control spiked with target analytes
Metals - Includes both metals and the metalloid, arsenic
QAPP - Quality Assurance Project Plan
QC - Quality Control
RTP - Research Triangle Park
SOP - Standard Operating Procedure
SVOC - Semivolatile Organic Compound (generally, a compound with vapor pressure = 10"5 - 10"2
kilopascals)
TCRS - Tire Crumb Rubber Research Study
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4.0 CAUTIONS
4.1 Nitrile gloves and eye protection should be worn during sample collection for metals wipe samples.
Silver Shield gloves and eye protection should be worn during sample collection for SVOCs.
4.2 Field staff should keep the sampling materials and the samples out of the reach of children.
4.3 Do not wipe the template demarcating a sampling area.
4.4 Collect samples at times when it was safe to do so with regard to any activities occurring on the
field. Sample collection time is not critical for these samples, but the samples should be collected at a
convenient time during the overall exposure measurement activities at each field.
4.5 No photography will be performed of any activities at the fields.
5.0 RESPONSIBILITIES
5.1 The EPA project staff will prepare the surface wipe sample collection equipment and materials and
deliver them to the field coordinator. EPA will provide the spiked field controls.
5.2 The field coordinator will receive the surface wipe sample collection equipment and materials. The
field coordinator will create a strategy and schedule to deploy or collect the appropriate percentage of
each type of field quality control (QC) samples as defined in the QAPP addendum. The field
coordinator will communicate the schedule for QC samples to the field staff and distribute any
additional QC sample materials. The field coordinator will distribute surface wipe sample collection
equipment and materials to the field staff. Upon collection of the surface wipe samples, the field
coordinator will be responsible for returning the samples with their collection records and Chain-of-
custody (COC) sheets to the EPA in Research Triangle Park (RTP), NC for analysis.
5.3 The field staff will be responsible for obtaining the collection equipment and materials from the
field coordinator, collection of the surface wipe sample, entering relevant information on the sample
collection record sheets, and returning collected surface wipe samples and records to the field
coordinator.
6.0 MATERIALS AND REAGENTS
6.1 Wipe media for SVOCs (M.G. Chemicals, Cleanroom Twill wipes, 10 cm x 10 cm and 30.5 cm x
30.5 cm, cotton, pre-cleaned)
6.2 Wipe media for metals (Environmental Express SC 4210 (or similar) Ghost Wipes, 15 cm x 15 cm,
packaged pre-moistened with deionized water)
6.3 Pre-cleaned and certified amber glass jars with Teflon-lined lids, 2 oz. straight-sided (Thermo I-
Chem Part No. 340-0060 or equivalent)
6.4 Plastic digestion cups, (50 mL, Environmental Express P/N SC475 or equivalent)
6.5 Masking tape
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6.6 Disposable nitrile gloves
6.7 Disposable Silver Shield gloves
6.8 Protective glasses
6.9 Frozen ice packs
6.10 Cooler
6.11 Aluminum or stainless steel template for SVOC wipes (with 12" x 12" interior dimension wiping
area)
6.12 Paper sampling template for metal wipes (with 12" x 12" interior dimension wiping area)
6.13 25' measuring tape
6.14 Ink pen with black ink
6.15 Isopropyl alcohol (ACS reagent grade or better)
6.16 Disposable pre-wetted isopropanol wipes for cleaning sampling equipment
6.17 Stainless steel or aluminum tray (10" x 13" or similar)
6.18 Stainless steel and plastic forceps
6.19 Sample collection and COC record sheets
6.20 Sample ID labels
6.21 Field waste bag
6.22 DAWser 2016 drag sled (custom built by EPA) consisting of a 10 kg aluminum block (25.4 x
25.4 x 5.1 cm), clamps for securing wipe material, and an attached handle
7.0 PROCEDURES
7.1 SAMPLE COLLECTION
Wipe samples will be collected from synthetic turf fields to support characterization of chemical
constituents.
7.1.1 Identification of Field Sampling Location
Individual wipe and drag sled samples will be collected from three locations at each field (see Figure
1). A separate set of samples will be collected at each location including: one wipe sample for SVOC
analysis, one wipe sample for metals analysis, and one drag sled sample for SVOC analysis. It is
important that the surface SVOC, surface metals, and drag sled SVOC not be collected from the exact
same spots on the field. They should be collected in proximity to each other at the three locations but
their sampling areas must not overlap (Figure 1).
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Figure 1. Surface wipe and drag sled sample collection locations on athletic fields.
7.1.2 Gloves
Prior to collecting metals surface wipe samples, put on clean, powderless nitrile gloves and keep them
on during the entire sampling period. Prior to collecting surface wipe SVOC and drag sled SVOC
samples, put on Silver Shield gloves.
7.2 Field Surface Wipes for Metals
Samples will be collected at positions #1, #2, and #5 as shown in Figure 1, for a total of three separate
samples. No background sampling location wipe sample will be collected.
Use surface wipes to collect samples for metals analysis at synthetic turf field sites. Samples are
collected with a wet (water) wipe material conforming to ASTM E1792 (ASTM-03, 2016a)
requirements (Ghost Wipe No. 4210, Environmental Express).
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Collect samples following the ASTM El 728 sample collection method (ASTM 1728-16, 2016b), a
standard wet-wipe method for collecting dust from indoor floor surfaces that use water as the wetting
agent. Specifically, a 929 cm2 (1-ft2) template is placed on the surface of the field.
Remove the wet wipe from the foil packet. Using one side of the wipe, wipe the turf surface in a S or
Z-shaped pattern within the template area. After folding the wipe in half to get a fresh wipe surface,
wipe the area again in a S or Z-shaped pattern perpendicular to the first wipe pattern (see Figure 2).
Next, fold the wipe in half again and wipe the edges of the sampling area near the interior portion of
the template. Prior to placing the wipe in a storage tube, use plastic forceps to remove full size tire
crumb rubber infill granules, synthetic grass blades, and other large debris or litter. Finally, fold the
wipe and place it a pre-cleaned 50-mL polyethylene tube (Environmental Express, Disposable
Digestion Cup No. SC475 or equivalent) for storage. Tightly cap the tube and transport at ambient
temperature or lower to the laboratory, where the samples are placed in a freezer at -20 °C.
Figure 2. Wiping the turf surface in a S or Z-shaped pattern within the 929 cm2 template area.
7.3 Field Surface Wipe Samples for SVOCs
Ensure that you have a sufficient number of previously pre-cleaned SVOC wipes for the field team
staff for transport to the field location.
Two types of field surface wipe samples will be collected for SVOCs analysis. One method uses a dry
wipe material attached to a drag sled. The second uses an isopropanol:water-wetted wipe.
7.3.1 Drag Sled Dry Wipe Method: Collect surface wipe drag sled samples for SVOC analysis at
synthetic turf field sites using a dry wipe material (Texwipe TX312 Cleanroom Twill, 30.5 cm x 30.5
cm, cotton) that has been cleaned by pre-extraction using a series of solvents including acetone and
hexane prior to use.
Collect samples only at times when it was safe to do so with regard to any activities occurring on the
field. Sample collection time is not critical for these samples, but the samples should be collected at a
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convenient time during the overall exposure measurement activities at each field.
Collect samples at positions #1, #2, and #5 as shown in Figure 1, for a total of three separate samples.
Samples will be collected from different areas than the areas used for metals wipe sample collection.
Ensuring that there is no area overlap can be accomplished by placing templates and marking the drag
sled area prior to sampling. No background sampling location wipe samples will be collected.
Using clean, Silver Shield gloves, remove the wipe material from its storage container and clamp it to
a wipe sampling push sledge device (see Figure 3). The device has a 10 kg aluminum block of the
dimensions 25.4 x 25.4 x 5.1 cm with clamps on one side for securing the wipe material and an
attached handle for pushing the devi ce. Secure the wipe materi al so that the 645 cm2 bottom face of the
block is completely covered by the wipe material.
Using a tape measure, mark a 5 m x 1 m area (5 m2) on the synthetic turf field. The area may be
marked with masking tape or surveyor flags; existing field lines may also be used to denote one or
more area boundaries. With the wipe sampler starting in one corner of the marked area, drag the sled
down the 5-m length and then back again. Move the drag sled one width over in the collection area.
Drag the sled down the 5-m length and then back again. Repeat this until the entire 5 m2 has been
wiped with one up and one back pass. When pushing or pulling the drag sled, keep the handle at or
below waist level to minimize the vertical force of the handle on the drag sled body - the goal is to
achieve consistency by having the majority of the force resulting from the weight of the drag sled
body.
Prior to placing the wipe back into the storage container, remove as much as possible of any synthetic
grass blades, large tire crumb rubber pellets, and other large debris or litter on the sides of the wipe
material that did not contact the field. With forceps, remove any large (> 1 mm) tire crumb rubber
pellets from the portion of the wipe material that contacted the synthetic turf field. Do not attempt to
rem ove any grass blades from the field-facing side of the filter.
Finally, fold the wipe and place it in the clean 500 mL amber glass wide mouth storage bottle with
Teflon cap liner. Tightly cap the bottle and transport at 4 °C or lower to the laboratory, where the
samples are placed in a freezer at -20 °C.
Figure 3. Wipe sampling push sledge device with cotton dry wipe material attached.
7.3.2 Wetted Wipe Method: Collect wetted samples at synthetic turf field sites using a wipe material
(Texwipe TX312 Cleanroom Twill, 10 cm * 10 cm, cotton) that has been cleaned by pre-extraction
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using a series of solvents including acetone and hexane prior to use. In the laboratory, prior to
shipment to the field site, each wipe will be placed in a clean 60-mL wide-mouth amber jar, and 3 mL
of 1:1 isopropanol:water will be added directly to the wipe material in the j ar, dispersed across the
folded wipe material as evenly as possible. The jar will then be tightly capped with Teflon-lined lids.
Sample labels will be affixed to the jars, and the jars will be transported to the field site.
Collect samples at times when it was safe to do so with regard to any activities occurring on the field.
Sample collection time is not critical for these samples, but the samples should be collected at a
convenient time during the overall exposure measurement activities at each field.
Collect samples at posi tions #1, #2, and#5 as shown in Figure 1, for a total of three separate samples.
Collect samples from different areas than the areas used for previous wipe sample collection. Ensuring
that there is no area overlap can be accomplished by placing templates and marking the drag sled area
prior to sampling. No background sampling location wipe samples will be collected.
Place a 929 cm2 (1 ft2) aluminum template on the surface of the field.
Using clean, Silver Shield gloves and, if needed, clean tweezers, remove the pre-wetted wipe material
from its storage container. Using one side of the wipe, wipe the turf surface in a S or Z-shaped pattern
within the template area (see Figure 4). After folding the wipe in half to get a fresh wipe surface, wipe
the area again in a S or Z-shaped pattern perpendicular to the first wipe pattern. Next, fold the wipe in
half again and wipe the edges near the interior portion of the template. Prior to placing the wipe back
into its sample jar, use forceps to remove full size tire crumb rubber infill granules (>1 mm), synthetic
grass blades, and other large debris or litter. Finally, fold the wipe and place it back into its 60-mL
amber wide-mouth glass jar. Tightly cap the jar and transport at 4 °C or lower to the laboratory, where
the samples are placed in a freezer at -20 °C.
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Figure 4. Wiping the turf surface in a S or Z-shaped pattern within the 929 cm2 template area. (Note:
Silver Shield gloves will be used instead of the nitrile gloves shown in this photo).
7.4 HANDLING AND PRESERVATION
7.4.1 Complete the sample collection records and COC records for the samples (Appendix A).
7.4.2 After collection and during transport from the collection site, store the surface wipe samples in a
cooler with frozen ice packs.
7.4.3 Store the samples on frozen ice packs or in a refrigerator or freezer until shipment. Ship samples
by overnight delivery service in a shipping cooler with frozen ice packs. SOP EMAB-185.0 Standard
Operating Procedure (SOP) for Storage and Shipping of Multimedia Samples for post-collection
handling, storage, and shipment of surface wipe samples may be consulted for additional information.
7.4.4 Ship samples and their sample collection data/COC sheets to:
US EPA Chemical Services
Kent Thomas or Scott Clifton
109 T.W. Alexander Drive
Building E Loading Dock, Rm El78
Research Triangle ParkNC 27709-0002
Telephoned 19-541-7939
8.0 RECORDS
A data collection system will be used to capture information associated with the collection of all
samples. For the surface wipe samples, the sample collection information to be recorded will include
the following, as a minimum: the sample ID, the date and time of the sample collection, the sampling
location, initials or ID number of the field staff member responsible for the sample collection, and any
comments regarding collection (Appendix A). Other information shall be collected as needed to ensure
successful collection and interpretation of data. Please see D-SED-IEMB-030-SOP-01 for recording
sample collection locations on the proper field diagram.
Section B3 in the QAPP addendum details the sample code information. Sample codes used for the
EPA Tire Crumb Rubber Research Study will follow the general naming scheme used by the EPA for
the tire crumb rubber characterization study.
The specific coding information for field wipe samples is extracted from the QAPP addendum:
TCRS-R-YY-W-X-Y-Z
Where:
TCRS
Designates the tire crumb rubber research study
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R - Participant identification number
1-8; each number assigned to a unique participant where participant-specific ID is required
(personal air, dermal)
0 for all samples not associated with a specific participant
VV - Field ID number
Two-digit code unique to each field (We will use a different unique code for each
field/participant group combination. We will not try to match to any previous field numbers so
we can pre-print all labels. Numbers will go from 70 to 79).
W - Sample type designator
F = sample
D = duplicate sample
B = field blank
C = field control (spike)
X - Method type designator
E = field wet wipe metals
F = field wet wipe SVOCs
J = field drag sled SVOCs
Y - Sample collection location character
1, 2, or 5 for on-field wipe, sled, or dust sample location (corresponds to field sketch SI, S2, S5
locations in Figure 1)
Z - Parent/subsample designation character
We will use a value of zero (0) for all parent samples.
We will use the character L to designate laboratory QC samples.
Additional digits may be assigned if any sub-samples are generated.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE
9.1 Field blank (FB) and field control spikes (FC) samples will be prepared and used according to the
schedule outlined in the QAPP addendum Table B-3. For storage, shipping, analysis and quantitation
procedures, FB and FC samples will be prepared and treated in the same manner as the wipe samples.
9.2 FB will be deployed to monitor background contamination during storage and analysis. FB samples
will be prepared by opening the container with wipe while wearing Silver Shield (drag sled and wet
SVOC wipes) or nitrile (metals wipes) gloves, unfolding, folding, and placing into a labeled sample
container. FB samples shall otherwise be treated in the same manner as the surface wipe samples.
9.3 FC will be deployed to assess recovery of target analytes from the wipe medium under the same
storage and transportation conditions as the field samples. FC will be prepared by adding known
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amounts of target compounds to matrix blanks which is stored in a sealed container. The container is
shipped to the field and returned without opening/handling. It is stored under the same conditions as
field collected samples.
9.4 At least one FB and FC should be included with each batch of wipe samples shipped to the EPA
laboratory.
9.5 A duplicate sample will be collected for each of the three sample types at each field. Duplicates
will be collected from a previously unsampled field area directly adjacent to its matching sample, using
all of the same procedures that are used for the samples.
10.0 REFERENCES
ASTM E1792-02. (2016a). Standard method for wipe sampling materials for lead in surface dust. ASTM
International, West Conshohocken, PA, USA.
ASTM E1728-16. (2016b). Standard practice for field collection of settled dust samples using wipe sampling methods
for subsequent lead determination. ASTM International, West Conshohocken, PA, USA.
ASTM D5116-10. (2010). Standard guide for small-scale environmental chamber determinations of organic
emissions from indoor materials/products. ASTM International, West Conshohocken, PA, USA.
ASTM D7706-11. (2011). Standard practice for rapid screening of VOC emissions from products using micro-scale
chambers. ASTM International, West Conshohocken, PA, USA. Quality Assurance Project Plan, An EPA Pilot
Study Evaluating Personal, Housing, and Community Factors Influencing Children's Potential Exposures to
Indoor Contaminants at Various Lifestages (EPA Pilot Study Add-On to the Green Housing Study), Exposure
Measurements and Analysis Branch, National Exposure Research Laboratory, Research Triangle Park, N.C., 2015.
Celeiro, M. et al. (2014). Investigation of PAH and other hazardous contaminant occurrence in recycled tyre rubber
surfaces: case study: restaurant playground in an indoor shopping centre. International Journal of Environmental
Analytical Chemistry. 94(12): 1264-1271.
Dye, C; Bjerke, A; Schmidbauer, N; Mano, S. (2006). Measurement of Air Pollution in Indoor Artificial Turf Halls.
Norwegian Pollution Control Authority/Norwegian Institute for Air Research, State Programme for Pollution
Monitoring. http://www.isss-sportsurfacescience.org/downloads/documents/SIlHPZNZPS_NILUEngelsk.pdf.
Highsmith, R; Thomas, KW; Williams, RW. (2009). A Scoping-Level Field Monitoring Study of Synthetic Turf and
Playgrounds; EPA/600/R-09/135. National Exposure Research Laboratory, U.S. Environmental Protection
Agency.
http://cfpub.epa.gov/si/si_public_record_report.cfm7dirEntrykH215113&simpleSearch=l&searchAll=EPA%2F6
00%2FR-09%2F 135.
Stout II, Daniel M., TenBrook, Patti L. DRAFT Combined Workplan/Quality Assurance Project Plan (WP/QAPP);
Development of a Simple Approach to Check for Pesticide Drift at Schools. v2. 2014.
Procedure for the Field Collection of Surface Wipe Samples from Hard Flooring, HUD, 2004.
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Appendix A.
Sample Collection and COC Records for Field Surface Wipe and Drag Sled Samples
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TIRE CRUMB EXPOSURE STUDY- WIPE SAMPLING DATA AND COC SHEET
COC-13
Field Locations - Metals & SVOC Field Wipe Samples
T - ^
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
1
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
iiiiiiiiiiiii
WMMSSSt*,
ifilllllllllllll
Sample ID
Field notes:
Receipt notes:
Analysis notes:
¦mum
wmm
¦Mil
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Collect Time
Initials
Date
Initials
Date
Initials
Date
Bililii
llllllllllllll
111®®®!
Sample ID
Field notes:
Receipt notes:
Analysis notes:
'sy0s0y0s0y0s0y/ys/si'
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- WIPE SAMPLING DATA AND COC SHEET
COC-14
:ield Locations - Metals & SVOC Field Wipe Samples
11 1/
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
2
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
0000000000000^
^000000000000^,
^0000000000000/,
tf00000000000^
00000000000W
Sample ID
Field notes:
Receipt notes:
Analysis notes:
'warn,
1111^
¦warn,.
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
00000000000001'
'000000000000$'
00000000000V,
00000000000%
^0000000000000/,
00000000000W
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- WIPE SAMPLING DATA AND COC SHEET
COC-15
Field Locations - Metals & SVOC Field Wipe Samples
T -
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
5
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
iiiiiiiiiiiii
WMMSSSt*,
ifilllllllllllll
Sample ID
Field notes:
Receipt notes:
Analysis notes:
¦mum
wmm
¦Mil
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Collect Time
Initials
Date
Initials
Date
Initials
Date
Bililii
Sample ID
Field notes:
Receipt notes:
Analysis notes:
'sy0s0y0s0y0s0y/ys/si'
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- WIPE SAMPLING DATA AND COC SHEET
COC-16
Metals Field Wipe Field/Lab Blanks and Controls
fs £\
|ssjzz?j
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID |
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
WSSSSI-,
illllllilll
1111111111111
Illllllilll
Sample ID
Field notes:
Receipt notes:
Analysis notes:
¦Ml
¦Mi
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
§1111111
1111111111111
Illllllilll
Sample ID
Field notes:
Receipt notes:
Analysis notes:
WM/////////////M
Sample ID
Field notes:
Receipt notes:
Analysis notes:
-------
COC-17
Study Name:
TCRS
Field ID No:
Field Location ID
D-SED-IEMB-026-SOP-01
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TIRE CRUMB EXPOSURE STUDY- WIPE SAMPLING DATA AND COC SHEET
SVOC Field Wipe Field/Lab Blanks and Controls
Collection
Date
Operator
Sample Chain of Custody
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOCs
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOCs
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY - DRAG SLED SAMPLING DATA AND COC SHEET
COC-18
Field Locations - SVOC Drag Sled Samples
/ - \
fi *v\
liSBi]
Collection
Study Name:
TCRS
Date
vV. /
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
l
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOC Drag Sled
Collect Time
Initials
Date
Initials
Date
Initials
Date
wrnrn,
Sample ID
Field notes:
Receipt notes:
Analysis notes:
MMHI
¦MB
Field notes:
Receipt notes:
Analysis notes:
Sample ID
iiiiiiiiiiii
'WMMMm
7777777777777777777777777
iiiiiii
y//////////y////////y
wmmm
Iffflif
illlM
WSMB/
jffllBB
IIIIIII*
^0000000000V,
W///////////Zm»&
liiiiiii
IIIIIIIIIIII
IllllillllP
y//////////////////,S.
liliii
m^m^m.
v////////////////////^.
111111
1111111111P
'mmmmm,
Wmmm#'
WmMmm?
WmMMw/
I1111111111P
WMMMMMk
IPPPPPPPPP1
w/ssWssswyyyyyyy/y,
/ZwZflwZwytfw//
illllllii
vZwZflW/ZvZw//
llllllli
,v////ywWy0y//y/yyyyy/
iiiiiiiii
illllllllill
iiiiiil
Illlllllill
iiiiiiiii
iiiiiiiiiiii
llllllli
'SMIlm
mmmmrn,
lllllllill
iiiii*
iiiiiii
mmmmrn,
'wmmm
'Smmrnrn
-
illllllii
rnlmm,
-¦¦///////////////////////
V/VVVVVVVVVVVVVVVVVVVVV'.
::::
wMMmm,
iiiiiimil
Ilieili
W/S/SSSMjW/^^
mill
mmmw,
iiiiiiiiiii
W/SSSSSSSSSSs%
llllll
mmmmM.
iilii
mmlm,111
iiiiiiii
SMMmmM
¦¦¦
mmmwm
iiliil
'$$ffi0000000>
mmmmwi
liiiii
y///////////////////y
iilii
iiiiiii
wmmmB,
'mmmflm
W/////////////M
¦fllllllllllll
^—p
1
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COC-19
TIRE CRUMB EXPOSURE STUDY - DRAG SLED SAMPLING DATA AND COC SHEET
Field Locations - SVOC Drag Sled Samples
| Collection ~|
Study Name:
TCRS
Field ID No:
Field Location ID
Date
Operator
Sample Chain of Custody
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOC Drag Sled
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
y0000000000/y/0sA
V0000000000000,
Sample ID
Field notes:
Receipt notes:
Analysis notes:
'0000000000%' *0000000000
W////////////zWM
ws000000ss00//
1111111
V0000000000// W000000000/
W0000000000/ ^0000000000
'00000000000/ ^0000000000/
Illlllll1111111
W0000000000/ ^0000000000/
W0000000000/ ^0000000000/
^00000000000^ 0000000000/
V0000000000/ W000000000W
llllllll 11111111
.. " : : :
: :
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COC-20
TIRE CRUMB EXPOSURE STUDY - DRAG SLED SAMPLING DATA AND COC SHEET
Field Locations - SVOC Drag Sled Samples
| Collection ~|
Study Name:
TCRS
Field ID No:
Field Location ID
Date
Operator
Sample Chain of Custody
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOC Drag Sled
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
^W/7///////^
Y000/0//////////000/'/
'W///0W////////////Z,
WWWWWWWWWsssssst
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY - DRAG SLED SAMPLING DATA AND COC SHEET
COC-21
SVOC Drag Sled Field/Lab Blanks and Controls
fs V;
IsEzJ
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID |
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOC Drag Sled
wmmmm
'wmmmm
'wwmmm
Collect Time
Initials
Date
Initials
Date
Initials
Date
wmmmm,
wmmmm,
Field notes:
Receipt notes:
Analysis notes:
Jllllll1111
Sample ID
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC Drag Sled
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
mrnrnm,
ii!
Field notes:
Receipt notes:
Analysis notes:
Sample ID
-------
U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure (SOP) for
Collection of Dermal Wipe Samples
Number: D-SED-ffiMB-028-SOP-Ol
Effective Date:
SOP was Developed
0 In-house
~ Extramural
Alternative Identification:
SOP Steward
Name: Kent Thomas
Signature:
Date:
Approval
Name: Caroline Stevens
Title: Branch Chief, IEMB
Signature:
Date:
Concurrence*
Name: Christine Alvarez
Title: NERL QA Manager
Signature:
Date:
For Use by QA Staff Only:
SOP Entered into QATS:
Initials
Date
* Optional Field
NERL-SOP.l (7/2003)
-------
SOP:
Date:
Page:
SED-IEMB-028-SOP-01
Draft August 21,2017
2 of 15
STANDARD OPERATING PROCEDURE (SOP) FOR
COLLECTION OF HAND WIPE SAMPLES
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHODS 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 4
5.0 RESPONSIBILITIES 4
6.0 MATERIALS AND REAGENTS 4
7.0 PROCEDURES 5
8.0 RECORDS 8
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 9
10.0 REFERENCES 10
Appendix A: Sample Collection Record for a Dermal Wipe Sample 11
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SOP: SED-IEMB-028-SOP-01
Date: Draft August 21,2017
Page: 3 of 15
1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) describes the method for collecting dermal wipe samples
from a participant's skin in order to measure semi-volatile organic compounds (SVOCs) and metals on
the skin for the EPA pilot tire crumb rubber research study (TCRS).
2.0 SUMMARY OF THE METHODS
Dermal, inhalation, and ingestion of dust at synthetic turf fields may represent important pathways of
exposure to chemicals associated with tire crumb rubber, other synthetic field materials, and
environmental dust deposited on the field. The concentrations of metals and SVOCs on the skin of
TCRS participants must be measured to determine dermal exposures and to compare these to the other
pathways and to biologic markers in blood and urine.
Each participant's skin will be wiped in the following manner:
Metals: Three dermal wipe samples will be collected for metal analysis from each participant
following an on-field sports activity in the exposure characterization pilot study. One sample will be a
hand wipe sample, the second sample will be from a defined area of the forearm, and the third sample
will be collected from a defined area of the leg (either calf or thigh depending on which area had more
exposed skin area during the sports activity). Wipe samples for metals will be collected from one hand,
one arm, and one leg on the left side of the participant's body.
Semivolatile Organics: Three dermal wipe samples will be collected for SVOC analysis from each
participant following an on-field sports activity in the exposure characterization study. One sample will
be a hand wipe sample, the second sample will be from a defined area of the forearm, and the third
sample will be collected from a defined area of the leg (either calf or thigh depending on which are had
more exposed skin area during the sports activity). Wipe samples for SVOCs will be collected from
one hand, one arm, and one leg on the right side of the participant's body.
3.0 DEFINITIONS
CDC - Centers for Disease Control and Prevention
COC - Chain-of-custody SOP - Standard operating procedure
FB - Field Blank TCRS - Tire Crumb Rubber Research Study
FC - Field Control (spiked control)
Metals - Includes both metals and the metalloid, arsenic QC - Quality Control
QAPP - Quality Assurance Project Plan
RTP - Research Triangle Park
SVOC - semivolatile organic compound (generally, compound with vapor pressure ~ 10"5 - 10"2
kilopascals)
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4.0 CAUTIONS
4.1 Field staff will keep all sampling materials out of reach of children.
4.2 Standard laboratory protective gloves are required for this procedure to eliminate transfer of
chemicals from the technician's hands onto the wipe media and to provide hygiene for participant
contact. Nitrile gloves should be worn during sample collection for metals wipe samples. Silver Shield
gloves should be worn during sample collection for SVOCs.
5.0 RESPONSIBILITIES
5.1 The EPA project staff will provide wipe media, digestion cups, and glass jars (collection materials)
and deliver them to the field coordinator. EPA will provide the spiked field controls.
5.2 The field coordinator will receive the dermal wipe sample collection equipment and materials. The
field coordinator will create a strategy and schedule to deploy or collect the appropriate percentage of
each type of quality control (QC) samples. The field coordinator will communicate the schedule for
QC samples to the field staff and distribute any additional QC sample materials. The field coordinator
will distribute the collection materials to the field staff. Upon collection of the dermal wipe samples,
the field coordinator will be responsible for returning the samples with their collection records and
COC sheets to the EPA in Research Triangle Park (RTP), NC for analysis.
5.3 The field staff will be responsible for obtaining the collection equipment and materials from the
field coordinator, collection of the dermal wipe samples, entering relevant information on the sample
collection record and COC sheets (Appendix A) and returning collected hand wipe samples to the field
coordinator.
6.0 MATERIALS AND REAGENTS
6.1 Wipe media for SVOCs (M.G. Chemicals, Cleanroom Twill wipes, 10 cm x 10 cm, cotton, pre-
cleaned)
6.2 Wipe media for metals (Environmental Express SC 4210 (or similar) Ghost Wipes, 15 cm x 15 cm,
packaged pre-moistened with deionized water)
6.3 Isopropanol, ACS Reagent Grade
6.4 Deionized water
6.5 Plastic digestion cups, (50 mL, Environmental Express P/N SC475 or equivalent)
6.6 Pre-cleaned and certified amber glass jars with Teflon-lined lids (2 oz. Straight-sided amber glass
jars, I-Chem Part # 340-0060 or equivalent)
6.7 Disposable gloves (nitrile)
6.8 Disposable Silver Shield gloves
6.9 Stainless steel forceps
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SOP: SED-IEMB-02 8-SOP-01
Date: Draft August 21,2017
Page: 5 of 15
6.10 Stainless steel or aluminum tray
6.11 Easy to remove bandage tape (3M Nexcare 1" Gentle Paper Tape or equivalent)
6.11 Cooler
6.12 Frozen ice packs
6.13 Ink pens
6.1 Sample collection and COC record sheets
6.15 Sample ID labels
6.16 Rectangular flexible Teflon sheet template with outer dimensions of 11.5 x 19.0 cm and inner
dimensions of 7.5 x 15 cm dimensions to provide a wipe surface area of 112 cm2. Two templates are
needed for each participant, one for metals wipe collections and one for SVOC wipe collections.
(Note: if insufficient templates are available, a single template may be used for both metals and
SVOCs by first cleaning the template with a wetted wipe).
7.0 PROCEDURES
7.1 SAMPLE COLLECTION
Sample collection will follow the procedures for 7.1.1 "metals" collection, followed by the procedures
for 7.1.2 "SVOC" collection.
7.1.1 Collection of dermal wipe samples from participants for metals:
7.1.1.1 Timeline: Dermal wipes will be collected from each person, as soon as possible following
his/her activity on a field.
7.1.1.2 Before starting sample collection, briefly describe the dermal wipe sampling procedures that
will be used to the participant. Ask the participant if it is OK to collect the dermal wipe samples on
their hands, arms, and legs. Make sure there is at least one other adult field team member present
during the sample collection (parents of child participants may also be present if they wish).
7.1.1.3 Prior to collecting metals wipe samples, put on clean, powderless nitrile gloves and keep them
on during the entire sampling period. New gloves should be worn for each participant.
7.1.1.4 For metal analysis, use wet (water) wipe material (Environmental Express, Ghost Wipe No.
4210) conforming to American Society for Testing and Materials (ASTM) El792 requirements
(ASTM-03, 2016a).
7.1.1.5 Hand wipe sample: Remove a wet wipe from the foil packet and unfold it to its full dimensions.
With moderately firm pressure, wipe the left hand, including the back, front, and sides of the hand,
fingers, and thumb. Next, fold the wipe with the exposed (contacted) surface on the inside and place
into a pre-cleaned 50-mL polyethylene tube (Environmental Express, Disposable Digestion Cup No.
SC475 or equivalent) for storage.
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7.1.1.6 Forearm wipe sample: Select a clean Teflon template. Place it over the underside of the left
forearm. Use a short piece of bandage tape to tape one short end of the template to the left arm, then a
second short piece of tape to secure the other short end to the arm. The template should lay as flat
against the arm as possible once taped down. Remove a wet wipe ("Ghost Wipe") from the foil packet
and unfold it to its full dimensions. Then, fold it into quarters before beginning sample collection. With
moderately firm pressure, thoroughly wipe the bottom (underside) of the left forearm over the entire
112 cm2 area using a rectangular template. Next, fold the wipe one more time, with the exposed
(contacted) surface now on the inside. With moderately firm pressure, thoroughly wipe the bottom
(underside) of the left forearm over the entire 112 cm2 area for a second time. Again fold the wipe with
the exposed (contacted) surface on the inside and place into a pre-cleaned 50-mL polyethylene tube
(Environmental Express, Disposable Digestion Cup No. SC475 or equivalent) for storage.
7.1.1.7: Leg wipe samples: Select the area to sample based on skin that was most exposed during the
participant activity. The lower leg is preferred, but the lower part of the upper leg may be used if it was
the most exposed area. Use the same Teflon template that was used on the forearm. Place the template
over the outer side of the left leg. Use a short piece of bandage tape to tape one short end of the
template to the leg, then a second short piece of tape to secure the other short end to the leg. The
template should lay as flat against the leg as possible once taped down. Remove a wet wipe ("Ghost
Wipe") from the foil packet and unfold it to its full dimensions. Then, fold it into quarters before
beginning sample collection. With moderately firm pressure, thoroughly wipe the left leg over the
entire 112 cm2 area using a rectangular template. Next, fold the wipe one more time, with the exposed
(contacted) surface now on the inside. With moderately firm pressure, thoroughly wipe the left leg
over the entire 112 cm2 area for a second time. Again fold the wipe with the exposed (contacted)
surface on the inside and place into a pre-cleaned 50-mL polyethylene tube (Environmental Express,
Disposable Digestion Cup No. SC475 or equivalent) for storage.
7.1.1.8 Record the sample collection information on the sample collection sheet (Appendix A).
7.1.1.9 Ensure all caps are tightly fitted and transport tubes at ambient temperature or lower to the
laboratory, where the samples are placed in a freezer at -20 °C
7.1.2 Collection of dermal wipe samples from participants for SVOCs:
7.1.2.1 In the laboratory, prior to shipment of materials to the field site, each wipe will be placed in a
clean 60-mL wide-mouth amber jar, and 3 mL of 1:1 isopropanol: water will be added directly to the
wipe material in the jar, dispersed across the folded wipe material as evenly as possible. The jar will
then be tightly capped with Teflon-lined lids. Sample labels will be affixed to the jars, and the jars will
be transported to the field site.
7.1.2.2 Timeline: Dermal wipes will be collected from each person, as soon as possible following
his/her activity on a field.
7.1.2.3 Prior to collecting wipe samples, put on clean, Silver Shield gloves and keep them on during
the entire sampling period. New gloves should be worn for each participant.
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7.1.2.4 Collect wipe samples for SVOC analysis using wetted (1:1 water:isopropanol) cotton wipe
material (M.G. Chemicals, Cleanroom Twill, 10 x 10 cm).
7.1.2.5 Hand wipe sample: Remove the wipe from its glass storage jar to its full dimensions. With
moderately firm pressure, wipe the right hand, including the back, front, and sides of the hand, fingers,
and thumb. Next, fold the wipe with the exposed (contacted) surface on the inside and replace into its
glass storage jar.
7.1.2.6 Forearm wipe sample: Select a clean Teflon template. Place it over the underside of the right
forearm. Use a short piece of bandage tape to tape one short end of the template to the right arm, then a
second short piece of tape to secure the other short end to the arm. The template should lay as flat
against the arm as possible once taped down. Remove a wipe from its glass storage jar and unfold it to
its full dimensions. Then, fold it into quarters before beginning sample collection. With moderately
firm pressure, thoroughly wipe the bottom (underside) of the right forearm over the entire 112 cm2 area
using a rectangular template. Next, fold the wipe one more time, with the exposed (contacted) surface
now on the inside. With moderately firm pressure, thoroughly wipe the bottom (underside) of the right
forearm over the entire 112 cm2 area for a second time. Again fold the wipe with the exposed
(contacted) surface on the inside and place it back into its labeled storage jar and seal the cap tightly.
7.1.2.7: Leg wipe samples: Select the area to sample based on skin that was most exposed during the
participant activity. The lower leg is preferred, but the lower part of the upper leg may be used if it was
the most exposed area. Use the same Teflon template that was used on the forearm. Place the template
over the outer side of the right leg. Use a short piece of bandage tape to tape one short end of the
template to the leg, then a second short piece of tape to secure the other short end to the leg. The
template should lay as flat against the leg as possible once taped down. Remove a wet wipe from its
glass jar and unfold it to its full dimensions. Then, fold it into quarters before beginning sample
collection. With moderately firm pressure, thoroughly wipe the right leg over the entire 112 cm2 area
using a rectangular template. Next, fold the wipe one more time, with the exposed (contacted) surface
now on the inside. With moderately firm pressure, thoroughly wipe the right leg over the entire 112
cm2 area for a second time. Again fold the wipe with the exposed (contacted) surface on the inside and
place it back into its labeled storage jar and seal the cap tightly.
7.1.2.8 Record the sample collection information on the sample collection sheet (Appendix A).
7.1.2.9 Ensure all caps are tightly fitted onto the glass storage jars and place the jars into a cooler with
frozen ice packs. Samples must be stored on ice packs, or in a refrigerator or freezer following
collection. Samples must be shipped to the laboratory in a cooler with frozen ice packs. Upon receipt
at the laboratory, samples are placed in a freezer at -20 °C
7.2 HANDLING AND PRESERVATION
7.2.1 After collection and during transport from the collection site, store the SVOC wipe samples in a
cooler with ice packs. Wipe samples for metals analysis may remain at ambient temperatures.
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7.2.2 Store pre-cleaned 50-mL polyethylene tube (Environmental Express, Disposable Digestion Cup
No. SC475 or equivalent) with metals wipe samples at ambient temperature at the field site and during
shipment. (Note: metals wipe samples may be stored and shipped in a cooler at lower than ambient
temperatures if that is most convenient). Wipe samples for SVOC analysis must be stored on ice packs,
or in a refrigerator or freezer following collection, and shipped in a cooler on frozen ice packs to the
laboratory. All tubes and jars must be tightly capped. Samples do not need to be shipped each day, and
may be accumulated across sampling days at a field location prior to shipment. Upon receipt at the
laboratory, wipe samples for SVOC analysis must be placed in a freezer at approximately -20 °C.
7.2.3 Ship samples and their sample collection data/COC sheets to:
US EPA Chemical Services
Kent Thomas or Scott Clifton
109 T.W. Alexander Drive
Building E Loading Dock, Rm E178
Research Triangle ParkNC 27709-0002
Telephoned 19-541-7939
8.0 RECORDS
A data collection system will be used to capture information associated with the collection of all
samples. For the technician collected dermal wipe samples, the sample collection information to be
recorded will include the following, as a minimum: the sample ID, the participant ID, the date and time
of the sample collection, initials or ID number of the field staff member responsible for the sample
collection, and any comments regarding collection (Appendix A). Other information shall be collected
as needed to ensure successful collection and interpretation of data. Section B3 in the QAPP addendum
details the sample code information.
The specific coding information for field wipe samples is extracted from the QAPP addendum:
TCRS-R-YY-W-X-Y-Z
Where:
TCRS
Designates the tire crumb rubber research study
R - Participant identification number
1-8; each number assigned to a unique participant where participant-specific ID is required
(personal air, dermal)
0 for all samples not associated with a specific participant
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VV - Field ID number
Two-digit code unique to each field (We will use a different unique code for each
field/participant group combination. We will not try to match to any previous field numbers so
we can pre-print all labels. Numbers will go from 70 to 79).
W - Sample type designator
F = sample
D = duplicate sample
B = field blank
C = field control (spike)
X - Method type designator
N = personal dermal sample metals
L = personal dermal sample SVOCs
Y - Sample collection location character
H for dermal samples collected from hands
A for dermal samples collected from arms
L for dermal samples collection from legs
Z - Parent/subsample designation character
We will use a value of zero (0) for all parent samples.
We will use the character L to designate laboratory QC samples.
Additional digits may be assigned if any sub-samples are generated.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE
9.1 Field blank (FB) and field control spikes (FC) samples will be prepared and used according the
QAPP addendum Table B-3. For storage, shipping, analysis and quantitation procedures, FB and FC
samples will be prepared and treated in the same manner as the hand wipe samples.
9.2 FB will be deployed to monitor background contamination during storage and analysis. The FB
will consist of clean wipes that are removed from the container while wearing nitrile (metals) or Silver
Shield (SVOCs) and handled and folded in the same manner as the actual dermal wipe samples, with
the exception that no skin or other surface is wiped. They are then returned to their containers and
shipped or driven to the EPA laboratory.
9.3 FC will be deployed to assess recovery of target analytes from the wipe media under the same
storage and transportation conditions as the field samples. FC will be prepared by adding known
amounts of target compounds to wipe media, sealed in a sample container which will remain unopened
in the field and returned to the EPA laboratory.
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9.4 At least one FB and FCS should be included with each batch of hand wipe samples shipped to the
EPA laboratory.
9.5 No duplicate dermal wipe samples will be collected due to the increased participant burden and
time they would add.
10.0 REFERENCES
R.A. Fenske, "Dermal exposure assessment techniques." Annals of Occupational Hygiene 37.6 (1993):
687-706.
R. A. Fenske and C. Lu, "Determination of Handwash Removal Efficiency: Incomplete Removal of
the Pesticide Chlorpyrifos from Skin by Standard Handwash Techniques." J Am Ind Hyg Assoc, 55.
1994.
J. C. Chuang, C. Lyu, Y-L Chou, P. J. Callahan, M. Nishioka, K. Andrews, M. A. Pollard, L.
Brackney, C. Hines, D. B. Davis, and R. Menton, "Evaluation and Application of Methods for
Estimating Children's Exposure to Persistent Organic Pollutants in Multiple Media." EPA/600/R-
98/164a (Volume I), 1999.
Standard Operating Procedure for the Collection of Dermal Wipe Samples for Persistent Organic
Pollutants, EPA/NERL SOP EMAB-011.1E (CTEPP 2.15) vl.
T.H. Connor, and J. P. Smith. "New Approaches to Wipe Sampling Methods for Antineoplastic and
Other Hazardous Drugs in Healthcare Settings." Pharmaceutical Technology in Hospital Pharmacy 1.3
(2016): 107-114.
Quality Assurance Project Plan, Addendum for the Tire Crumb Research Study Exposure
Characterization Pilot Study.
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Page: 11 of 15
Appendix A.
Sample Collection and COC Records for Dermal Wipe Samples
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TIRE CRUMB EXPOSURE STUDY- DERMAL WIPE SAMPLING DATA AND COC SHEET
COC-24 Participant - Metals Dermal Wipe Samples
/ -
m
% 1 \4/
| Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
p
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Participant ID
Location
Collect Time
Initials
Date
Initials
Date
Initials
Date
i
Hand
Sample ID
Field notes:
Recei pt notes:
Analysis notes:
Participant ID
Location
Collect Time
Initials
Date
Initials
Date
Initials
Date
i
Arm
Sample ID
Field notes:
Recei pt notes:
Analysis notes:
Participant ID
Location
Collect Time
Initials
Date
Initials
Date
Initials
Date
i
Leg
Sample ID
Field notes:
Recei pt notes:
Analysis notes:
iilii
NOTE: There will be eight of these sheets, one for each participant, with a different
participant ID number from 1-8, with COC sheet ID numbers from COC-24 to COC-31.
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TIRE CRUMB EXPOSURE STUDY-- DERMAL WIPE SAMPLING DATA AND COC SHEET
COC-32
Metals Dermal Wipe Field/Lab Blanks and Controls
ff %
% ifch
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID | p
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
Field notes:
Receipt notes:
Analysis notes:
Sanple ID
SilillB
liiiil®
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
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TIRE CRUMB EXPOSURE STUDY- DERMAL WIPE SAMPLING DATA AND COC SHEET
COC-33 Participant - SVOC Dermal Wipe Samples
I w |J
| Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
p
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Participant ID
Location
Collect Time
Initials
Date
Initials
Date
Initials
Date
i
Hand
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Participant ID
Location
Collect Time
Initials
Date
Initials
Date
Initials
Date
i
Arm
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Participant ID
Location
Collect Time
Initials
Date
Initials
Date
Initials
Date
i
Leg
WSSKk.
¦MR
Sample ID
Field notes:
Receipt notes:
Analysis notes:
illlllllllllll
Jllllllllll
Jiiiiiiiiiiii
JlMllllllll
SmmMm
mlllllll
«111111111
iiiiiiiiii
NOTE: There will be eight of these sheets, one for each participant, with a different
participant ID number from 1-8, with COC sheet ID numbers from COC-33 to COC-40.
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TIRE CRUMB EXPOSURE STUDY-- DERMAL WIPE SAMPLING DATA AND COC SHEET
COC-41
SVOC Dermal Wipe Field/Lab Blanks and Controls
Collection
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID | p
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOC
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
mmmm.
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
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U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure (SOP) for Collection of Dust Samples from Synthetic
Turf Fields
Number: D-SED-IEMB-029-SOP-02
Effective Date: September 7, 2017
SOP was Developed 0 In-house ~ Extramural
Alternative Identification:
SOP Steward
Name: Kent W. Thomas
Signature:
Approval
Name: Caroline Stevens
Title: Branch Chief, NERL/SED/ffiMB
Signature: Date:
Concurrence*
Name: Christine Alvarez
Title: NERL QA Manager
Signature: Date:
For Use by QA Staff Only:
SOP Entered into QATS:
Initials Date
* Optional Field
NERL-SOP.l (7/2003)
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STANDARD OPERATING PROCEDURE (SOP) FOR
COLLECTION OF FIELD DUST SAMPLES FROM SYNTHETIC TURF FIELDS
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 3
5.0 RESPONSIBILITIES 4
6.0 MATERIALS AND REAGENTS 4
7.0 PROCEDURES 5
8.0 RECORDS 9
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 10
Appendix A. Sample Collection Record for a Surface Dust Samples 11
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1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) describes the method for collecting dust from synthetic turf
field surfaces to measure semivolatile organic compounds (SVOCs) and metals for the United States
Environmental Protection Agency (EPA) exposure characterization pilot tire crumb rubber research
study (TCRS).
2.0 SUMMARY OF THE METHOD
Dermal, inhalation, and ingestion of dust at synthetic turf fields may represent important pathways of
exposure to chemicals associated with tire crumb rubber, other synthetic field materials, and
environmental dust deposited on the field. The concentrations of metals and SVOCs on field surfaces
available for dermal transfer must be measured to determine human exposures and to compare these to
the various exposure pathways and to biologic markers in blood and urine.
Dust samples for SVOCs and metals analysis will be collected at synthetic turf field sites by on-field
sieving of bulk dust collected as a composite from three locations on the field using a 120 mesh (150
|iM) stainless steel sieves.
3.0 DEFINITIONS
COC - Chain-of-custody
EPA - Environmental Protection Agency
FB - Field Blank
FC - Field Control spiked with target analytes
Metals - Includes both metals and the metalloid, arsenic
QAPP - Quality Assurance Project Plan
QC - Quality Control
RTP - Research Triangle Park
SOP - Standard operating procedure
SVOC - semivolatile organic compound (generally, a compound with vapor pressure = 10"5 - 10"2
kilopascals)
TCRS - Tire Crumb Rubber Research Study
4.0 CAUTIONS
4.1 Nitrile gloves and eye protection should be worn during sample collection for dust samples for
metals and SVOCs.
4.2 Collect samples at times when it is safe to do so with regard to any activities occurring on the field.
Sample collection time is not critical for these samples, but the samples should be collected at a
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Date: September 7, 2017
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convenient time during the overall exposure measurement activities at each field.
4.3 No photography will be performed of any activities at the fields.
5.0 RESPONSIBILITIES
5.1 The EPA project staff will prepare the dust sample collection equipment and materials and deliver
them to the field coordinator. EPA will provide the spiked field controls.
5.2 The field coordinator will receive the dust sample collection equipment and materials. The field
coordinator will create a strategy and schedule to deploy or collect the appropriate percentage of each
type of field dust quality control (QC) samples as defined in the QAPP addendum. The field
coordinator will communicate the schedule for QC samples to the field staff and distribute any
additional QC sample materials. The field coordinator will distribute dust sample collection equipment
and materials to the field staff. Upon collection of the field dust samples, the field coordinator will be
responsible for returning the samples with their sample collection records and Chain-of-custody (COC)
sheets to the EPA in Research Triangle Park (RTP), NC for analysis.
5.3 The field staff will be responsible for obtaining the collection equipment and materials from the
field coordinator, collection of the dust samples, entering relevant information on the sample collection
record sheets and COC, and returning collected dust samples and records to the field coordinator.
6.0 MATERIALS AND REAGENTS
6.1 Stainless steel sieve assembly, including 120 mesh (150 |iM) screen, stainless steel lid, and
stainless steel pan for SVOCs and metals dust collection (U.S. Standard stainless steel 12" x 3.25"
or equivalent, pre-cleaned with deionized/carbon-filtered water and acetone and hexane rinse)
6.2 40-mL glass jars with Teflon-lined lids, pre-cleaned with acetone and hexane rinse
6.3 Plastic digestion cups, (50 mL, Environmental Express P/N SC475 or equivalent)
6.4 Disposable polypropylene spatula (6 per field in case of breakage)
6.5 Glass and/or metal funnel
6.6 Plastic funnel
6.7 Disposable nitrile gloves
6.8 Protective glasses (safety glasses or sunglasses)
6.9 Stainless steel tweezers or forceps
6.10 40-mL glass jars holding 200, 300, and 400 mg of dust for visual comparison standards
6.11 Frozen ice packs
6.12 Cooler
6.13 Ink pen with black ink
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6.14 Sample collection and COC record sheets
6.15 Sample ID labels
6.16 Synthetic bristle brushes
7.0 PROCEDURES
7.1 SAMPLE COLLECTION
Field dust samples will be collected from synthetic turf fields to support characterization of chemical
constituents.
7.1.1 Identification of Field Sampling Location
Samples will be collected across three locations at each field (see Figure 1). Samples will be collected
as a composite by successive collections at the three locations. Separate samples will be collected for
metals and SVOCs. It is important that the surface SVOC, surface metals, drag sled SVOC, and dust
samples should not be collected from the exact same spots on the field. They should be collected in
proximity to each other at the three locations but their sampling areas should not overlap. Ensuring
that there is no area overlap can be accomplished by placing surface wipe templates and marking the
drag sled area prior to sampling.
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7.1.2 Gloves and Glasses
Prior to collecting metals field dust samples, put on clean, powderless nitrile gloves and keep them on
during the entire sampling period. Put on protective glasses to protect against rubber particles that
might be launched during collection.
7.2 Field Dust Samples for Metals
7.2.1 Composite samples will be collected across positions #1, #2, and #5 as shown in Figure 1, by
successive collection and sieving of tire crumb rubber at each location. No background sampling
location dust sample will be collected.
7.2.2 Remove a new plastic spatula from its wrapper.
7.2.3 Bring the 120 mesh (150 |im) stainless steel sieve and the spatula to the first sampling location.
7.2.4 Attach the receiving pan part of the sieve assembly onto the sieve screen.
7.2.5 Use the spatula to scoop crumb rubber from the field onto the sieve screen, filling the sieve to
approximately 50% capacity.
7.2.6 Place the lid on the sieve screen and shake laterally in a vigorous manner for approximately two
minutes (shaking can be started and stopped as needed for rest, and more than one person may
contribute to the shaking).
7.2.7 Avoid getting large rubber pieces or other materials into the pan; if large pieces enter the pan,
remove them with tweezers.
7.2.8 Remove the lid and sieve screen and dump the bulk rubber from the screen back onto the field
from where it was collected. Do not dump the dust collected in the pan.
7.2.9 Re-distribute the rubber back into the field (this may be done after collection at each location or
after all sampling has been completed).
7.2.10 Move to field sample location #2 on the field and repeat steps 7.2.4 through 7.2.8.
7.2.11 Move to field sample location #5 on the field and repeat steps 7.2.4 through 7.2.8.
7.2.12 Following sieving at the final location, remove the pan from the screen and while tilting the pan
slightly use one hand to bang the side of the pan to bring as much dust as possible to one edge of the
pan (note that due to static electricity it will not be possible to dislodge all dust adhering to the pan).
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7.2.13 Place the plastic funnel above the open plastic digestion cup and carefully tap as much dust as
possible from the pan, through the funnel, and into the digestion cup (note that due to static electricity
it will not be possible to dislodge all dust adhering to the pan). A stand or tube holder may be used to
hold the tube during this process, or a second person may assist in the operation. Tightly cap the plastic
digestion cup after as much dust is transferred as possible.
7.2.14 If visible dust remains adhered to the pan, a synthetic bristle brush may be used to brush
collected dust into one edge of the pan, and then through the funnel into the plastic digestion cup.
7.2.15 Visually evaluate the amount of dust collected. The goal is to collect approximately 300 mg or
more of dust, with a minimum of approximately 200 mg. Sample amounts will be estimated by visual
comparison to containers holding approximately 200, 300, and 400 mg of dust.
7.2.16 If the amount of collected dust is not 200 mg or greater based on visual comparison to the
standards, it will be necessary to repeat sample collection across the three locations until at least 200
mg is collected.
7.3 Field Dust Samples for SVOCs
7.3.1 Composite samples will be collected across positions #1, #2, and #5 as shown in Figure 1, by
successive collection and sieving of tire crumb rubber at each location. No background sampling
location dust sample will be collected.
7.3.2 Remove a new plastic spatula from its wrapper (or the original spatula used for metals can be
used).
7.3.3 Bring the 120 mesh (150 |im) stainless steel sieve to the first sampling location. Note that the
same sieve used for metals sample dust collection may be used for the SVOC dust sample collection.
7.3.4 Attach the receiving pan part of the sieve assembly onto the sieve screen.
7.3.5 Use the spatula to scoop crumb rubber from the field onto the sieve screen, filling the sieve to
approximately 50% capacity.
7.3.6 Place the lid on the sieve screen and shake laterally in a vigorous manner for approximately two
minutes (shaking can be started and stopped as needed for rest, and more than one person may
contribute to the shaking).
7.3.7 Avoid getting large rubber pieces or other materials into the pan; if large pieces enter the pan,
remove them with tweezers.
7.3.8 Remove the lid and sieve screen and dump the bulk rubber from the screen back onto the field
from where it was collected; do not dump the dust collected in the pan.
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Date: September 7, 2017
Page: 8 of 14
7.3.9 Re-distribute the rubber back into the field (this may be done after collection at each location or
after all sampling has been completed).
7.3.10 Move to field sample location #2 on the field and repeat steps 7.2.4 through 7.2.8.
7.3.11 Move to field sample location #5 on the field and repeat steps 7.2.4 through 7.2.8.
7.3.12 Following sieving at the final location, remove the pan from the screen and while tilting the pan
slightly use one hand to bang the side of the pan to bring as much dust as possible to one edge of the
pan (note that due to static electricity it will not be possible to dislodge all dust adhering to the pan).
7.3.13 Place the metal or glass funnel above the open glass sample jar and carefully tap as much dust
as possible from the pan, through the funnel, and into the jar (note that due to static electricity it will
not be possible to dislodge all dust adhering to the pan). A stand or tube holder may be used to hold the
tube during this process, or a second person may assist in the operation. Tightly cap the jar after as
much dust is transferred as possible.
7.3.14 If visible dust remains adhered to the pan, a synthetic bristle brush may be used to brush
collected dust into one edge of the pan, and then through the funnel into the glass sample jar.
7.3.15 Visually evaluate the amount of dust collected. The goal is to collect approximately 300 mg or
more of dust, with a minimum of approximately 200 mg. Sample amounts will be estimated by visual
comparison to containers holding approximately 200, 300, and 400 mg of dust.
7.3.16 If the amount of collected dust is not 200 mg or greater based on visual comparison to the
standards, it will be necessary to repeat sample collection across the three locations until at least 200
mg is collected.
7.4 HANDLING AND PRESERVATION
7.4.1 Complete the sample collection records and COC records for the samples (Appendix A).
7.4.2 After collection and during transport from the collection site, store the dust samples in a cooler
with frozen ice packs.
7.4.3 Store the samples on frozen ice packs or in a refrigerator or freezer until shipment. Ship samples
by overnight delivery service in a shipping cooler with frozen ice packs.
7.4.4 Ship samples and their sample collection data/COC sheets to:
US EPA Chemical Services
Kent Thomas or Scott Clifton
109 T.W. Alexander Drive
Building E Loading Dock, Rm E178
Research Triangle ParkNC 27709-0002
Telephoned 19-541-7939
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8.0 RECORDS
A data collection system will be used to capture information associated with the collection of all
samples. For the dust samples, the sample collection information to be recorded will include the
following, as a minimum: the sample ID, the date and time of the sample collection, the sampling
location, initials or ID number of the field staff member responsible for the sample collection, and any
comments regarding collection (Appendix A). Other information shall be collected as needed to ensure
successful collection and interpretation of data. Please see D-SED-IEMB-030-SOP-01 for recording
sample collection locations on the proper field diagram.
Section B3 in the QAPP addendum details the sample code information. Sample codes used for the
EPA Tire Crumb Rubber Research Study will follow the general naming scheme used by the EPA for
the tire crumb rubber characterization study.
The specific coding information for field dust samples is extracted from the QAPP addendum:
TCRS-R-YY-W-X-Y-Z
Where:
TCRS
Designates the tire crumb rubber research study
R - Participant identification number
1-8; each number assigned to a unique participant where participant-specific ID is required
(personal air, dermal)
0 for all samples not associated with a specific participant
VV - Field ID number
Two-digit code unique to each field (We will use a different unique code for each
field/participant group combination. We will not try to match to any previous field numbers so
we can pre-print all labels. Numbers will go from 70 to 79).
W - Sample type designator
F = sample
D = duplicate sample
B = field blank
C = field control (spike)
X - Method type designator
1 = field dust metals
K = field dust SVOCs
Y - Sample collection location character
C for composite dust samples collected over locations 1, 2, and 5
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SOP: D-SED-IEMB-029-SOP-02
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Z - Parent/subsample designation character
We will use a value of zero (0) for all parent samples.
We will use the character L to designate laboratory QC samples.
Additional digits may be assigned if any sub-samples are generated.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE
9.1 Field blank (FB) and field control spikes (FC) samples will be prepared and used according to the
schedule outlined in the QAPP addendum Table B-3. For storage, shipping, analysis and quantitation
procedures, FB and FC samples will be prepared and treated in the same manner as the field dust
samples. (This step assumes that suitable dust surrogate material can be found for metals blanks and
spiked controls. Diatomaceous earth will be used for SVOC blanks and spiked controls).
9.2 FB will be deployed to monitor background contamination during storage and analysis. FB samples
will be shipped to the field, their caps will be opened and then immediately closed, and returned to the
laboratory with the samples. FB samples shall otherwise be treated in the same manner as the field dust
samples.
9.3 FC will be deployed to assess recovery of target analytes from a dust surrogate medium under the
same storage and transportation conditions as the field samples. FC will be prepared by adding known
amounts of target compounds to surrogate dust material which is stored in a sealed container. The
container is shipped to the field and returned without opening/handling. It is stored under the same
conditions as field collected samples.
9.4 At least one FB and FC should be included with each batch of dust samples shipped to the EPA
laboratory.
9.5 No duplicate samples will be collected.
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Date: September 7, 2017
Page: 11 of 14
Appendix A.
Sample Collection and COC Records for Field Dust Samples
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TIRE CRUMB EXPOSURE STUDY- FIELD DUST SAMPLING DATA AND COC SHEET
COC-50
Field Locations - Metals & SVOC Field Dust Samples
/i*
/S
% U-i
V> r
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Date: September 7, 2017
Page: 13 of 14
TIRE CRUMB EXPOSURE STUDY- FIELD DUST SAMPLING DATA AND COC SHEET
COC-51
Metals Field Dust Field/Lab Blanks and Controls
(s v\
LsSS^d
Collection
Study Name:
K^TSsi
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID |
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
0040000000004
00000000000004,
4400000000000/
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Metals
Collect Time
Initials
Date
Initials
Date
Initials
Date
444444444444444444444444
0040000000004
w004444444440vvv
'444444444444444444444444444,
00000000000004,
444444444440^000004,
44444444444444444444440/
4000000000004
000000044^^^0,
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
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Page: 14 of 14
TIRE CRUMB EXPOSURE STUDY- FIELD DUST SAMPLING DATA AND COC SHEET
COC-52
SVOC Field Dust Field/Lab Blanks and Controls
(i O '^i
Collection
Study Name:
ih>
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
SVOCs
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOCs
Collect Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
¦¦¦
'wmm,
Sample ID
Field notes:
Receipt notes:
Analysis notes:
-------
J Q \
W
U. S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Exposure Methods and Measurement Division
Sensing and Spatial Analysis Branch
STANDARD OPERATING PROCEDURE
SOP Title: PROCEDURE FOR THE COLLECTION OF PARTICULATE MATTER (PM)
AIR SAMPLES AT ACTIVITY FIELDS CONSTRUCTED USING CRUMB RUBBER
SOP ID: D-EMMD-SSAB-007-SOP-01
Effective Date: 08/21/17
SOP was Developed
In-house
~ Extramural
SOP Discipline: Field Collection
Alternative Identification:
SOP Contact Signature
Name: Ron Williams
Title: Author
Signature/Date:
RONALD
WILLIAMS
Digitally signed by RONALD WILLIAMS
DN: c=US, o=U.S. Government,
ou=USEPA, ou=Staff, cn=RONALD
WILLIAMS, dnQualifier=0000013874
Date: 2017.08.22 08:11:26 -04'00'
Management Signature
Name: Chandra Giri
Title: SSAB Chief
Signature/Date:
CHANDRA
GIRI
Digitally signed by CHANDRA
GIRI
Date: 2017.08.21 13:50:36
-04'00'
QA Signature
Name: Margie Vazquez
Title: EMMD QA manager |\/| AR |
Signature/Date:
VAZQUEZ
Digitally signed by MARGARITA VAZQUEZ
DN: c=US, o=U.S. Government,
ou=USEPA, ou=Staff, cn= MARGARITA
VAZQUEZ, dnQualifier=0000018558
Date: 2017.08.21 11:39:22 -04'00'
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Crumb Rubber Particulate Sampling
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Page 2 of 19
TITLE: PROCEDURE FOR THE COLLECTION OF PARTICULATE
MATTER (PM) AIR SAMPLES AT ACTIVITY FIELDS
INVOLVING TIRE CRUMB RUBBER
SOURCE: USEPA
NERL/EMMD/SSAB
109 TW Alexander Dr., MD-E205-04
Research Triangle Park, NC 27709
AUTHORS:
for (WitfiamS Date: 8/21/2017
Ron Williams
Annroved BY:
SSAB Branch Chief Date:
Chandra Giri
QA Manager Date:
Sania Tong-Argao
Notice
This Analytical Procedure has been preparedfor use by the Sensing and Spatial Analysis Branch of the U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina and may not be specifically applicable to
the activities or objectives of other organizations. This procedure has not been fully validated and should be used for
research purposes only. Adequate QA/QC measures must be implemented with this procedure to allow assessment of
data quality.
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Revision History
Version
No.
Name
Date of
Revision
Description of Change(s)
1
Ron Williams
08/21/17
Original version
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PROCEDURE FOR THE COLLECTION OF PARTICULATE MATTER (PM) AIR
SAMPLES AT ACTIVITY FIELDS CONSTRUCTED USING CRUMB RUBBER
TABLE OF CONTENTS
1.0 Scope and Application 5
2.0 Summary of Method 5
3.0 Prerequisites 5
3.1 Equipment and Supplies 5
3.2 Training Requirements 5
4.0 Cautionary Notes or Special Considerations 6
5.0 Procedures 6
5.1 Loading Filters in the Harvard Impactors for use 6
5.2 Labeling the Sample 7
5.3 Pump Set-up 8
5.4 Initial Pump Flow Measurement for Sample Start 9
5.5 Final Pump Flow Measurement for Sample End 10
5.6 Pump/Equipment Take Down 10
5.7 Removal of Filters from HI Units 11
6.0 Quality Control 11
6.1 Field Blanks 12
6.2 Duplicate Samples 12
6.3 BIOS Flow Calibrator Calibration 12
7.0 General Sampling Precautions 12
8.0 Possible Corrective Actions for Observed Problems During Sampling 12
8.1 Pump Failure 12
8.2 Possible Contamination of Filters or Supplies 13
9.0 Recordkeeping 13
9.1 Datasheets 13
9.2 Calculations 13
9.3 Chain-of-Custody 13
10.0 References 13
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1.0 Scope and Application
This method applies to the collection of particulate matter (collected as total suspended
particulate or TSP) from outdoor air at activity fields that utilize crumb rubber and/or artificial
turf. Samples will be analyzed for particle mass and metals.
2.0 Summary of Method
Portable battery operated air sampling pumps equipped with Harvard Impactor (HI)
particulate matter (PM) without size selective inlets will be used to collect particle phase outdoor
ambient air samples. Particulates will be collected on pre-weighed Teflon filters.
3.0 Prerequisites
• Tared Teflon filters (37 mm, 2.0 |i) prepared in advance of their needed deployment time
period
3.1 Equipment and Supplies
NERL (National Exposure Research Laboratory) prepared/supplied items:
• Clean lab supplies (e.g. forceps, plastic Petri dishes, Harvard Impactors, SV-30 pumps,
calibrated BIOS flow meters etc.)
• Harvard Impactors (HI), 20 LPM, pre-cleaned, pre-oiled
• HI filter cassettes with tared Pallflex 37 mm 2 |im porosity Teflon filter and Millipore AP
1003700 cellulose backing filter
• 12V DC, 18 Ah sealed lead acid battery or equivalent
• SKC HV-30 air sampling pump with inlet stand and security box
• Protective enclosure
• BIOS International Dry Cal-DC Lite air flow calibrator or equivalent, high flow detection
cell
• Powder-free nitrile gloves
• Tygon flexible plastic vacuum tubing (V2 inch OD, 5/16 inch ID, 3/16 inch wall)
• Sampling labels
• Screwdriver for adjusting air pump flow rate
• Zip lock bags for storage/shipment of new or used filter cassettes
• Teflon tape
• HI flow calibration cap
• Data collection forms
Field Personnel supplied items:
• Time piece, synchronized to local cell towers
• Pen (Black, Permanent Ink)
3.2
Training Requirements
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All training required is provided by the US EPA. Sample collection should be conducted
by qualified scientific staff trained in the use of the specific field monitoring equipment. If
sampling is conducted by non-scientists, a scientist should oversee the monitoring effort. Training
should include a demonstration and hands-on training by qualified persons with air sampling
expertise. At a minimum, all standard operating procedures (SOPs) and operating instructions
should be reviewed, understood, and followed exactly by the field staff.
4.0 Cautionary Notes or Special Considerations
The sampling systems are powered by sealed lead acid batteries (gel cell). The battery and
pump system should be protected from excessive heat or cold (<50 °F, >104 °F). Pumps and
batteries are shielded from direct exposure by means of an outer protective enclosure. This
enclosure should be used at all times. Precautions must be taken against shorting across the battery
terminals or reversing polarity of the power leads. Shorting of the battery may cause a rapid
discharge that will generate excessive heat and may result in a fire or severe burns. Reversing the
polarity (attaching positive to negative) may damage the pump or battery. Red (+) wires should
be attached to the red (+) battery terminal and black (-) wires should be attached to the black (-)
terminal.
Sampling will take place outside and equipment should be shielded from possible weather
events. Sampling stands should to be set-up so that they are provided protection from tampering.
Sampling stands must also be placed and secured such that no harm will come to children or others
playing in the vicinity of the equipment. Protective enclosures are provided and must be used to
insure safety.
5.0 Procedures
5.1 Loading Filters in the Harvard Impactors for use
5.1.1 In a clean laboratory space, unpack the materials shipped by the NERL-EMMD.
Contact Ron Williams (919-541-2957) if any of the materials defined in the
supplies list are missing or if you wish to use an alternative supply.
5.1.2 While wearing powder-free gloves, install one HI cassette into each HI sampler as
defined by the HI Research Operating Procedure (ROP #07-DEARS).
Note: Since the filters are pre-weighed (tared) it is imperative that the
filter Ids be maintained throughout the handling process so
filter loadings can be accurately determined. See Section 5.2 for
labeling instructions.
• This must be done in a low traffic area, where dust is kept to a minimum. A
laminar flow hood would fit this requirement.
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• Install the cassette with the indicated "top" or "up" side facing the top inlet of
the sampler. Be sure that all of the red rubber seals securing the cassette are in
their proper positions.
• Close and seal the HI units by use of the two metal catches located on each unit.
Insure that the alignment pins are engaged and that the base and inlet sections
are parallel prior to snapping the latches closed.
• Keep the zip lock bag that the HI cassette came in.
Note: These bags are labeled with the Id number of the tared filter.
The filter and cassette must be returned to the appropriately
labeled zip lock bag after monitoring.
5.2 Labeling the Sample
Note: Since the filters are pre-weighed (tared) it is imperative that the
filter Ids be maintained throughout the handling process so
filter loadings can be accurately determined when post-weighed.
• Prepare three labels for each sample using the coding system described below:
TCRS-R-VV-W-X-Y-Z
Where:
TCRS
Designates the tire crumb rubber research study
R - Participant identification number
1-8; each number assigned to a unique participant where participant-specific ID is required
(personal air, dermal)
0 for all samples not associated with a specific participant
VV - Field ID Number
Two-digit code unique to each field (We will use a different unique code for each
field/participant group combination. Previously used field numbers will not be duplicated
so we can pre-print all labels. Numbers will go from 70 to 79).
W - Sample type designator
F = sample
D = duplicate sample
B = field blank
C = field control (spike)
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X - Method type designator
A = field air PM/metals
Y - Sample collection location character
1 or 2 for on-field air location; 8 for off-field air location
Z - Parent/subsample designation character
We will use a value of zero (0) for all parent samples.
We will use the character L to designate laboratory QC samples.
• Place one label on the zip lock bag and a second one on the HI unit base at
the time of transfer of the filter cassette from the zip lock bag to the HI unit.
Note: Make sure the three-digit filter code on the zip lock bag matches
the three digit filter code in the full sample code. This number
tracks the tared filter through the post weighing
• Place the assembled HI unit in a clean large zip lock bag for transport to the
monitoring location.
• Place the third label on the data collection sheet that will be used to record
the collection information. (See Appendix I for data collection sheet format).
(Note: as an option, the TCRS sample code may be pre-entered on the sheet
instead of using a label).
5.3 Pump Set-up
5.3.1 Transport the assembled HI unit along with their air sampling pump boxes to the
monitoring location along with the data collection sheets, BIOS calibration unit,
calibration cap, GPS unit and any materials needed to secure the monitoring site.
5.3.2 One pump will be set-up at each monitoring location associated with each site with
one exception. A single location will have duplicate monitoring systems so that
precision can be established. The pump set up will be identical for each sampling
filter type.
5.3.3 Select a site that will enable you to place the two near-field sampling stations as near
to the field as safety allows, on different sides of the field (possibly adjacent sides)
and in a downwind position where possible or applicable.
• Because some fields might be irregular in shape, some compromises might
have to be afforded to the siting of the stations relative to perfect placement.
• Each pump box should be placed as flat on the ground as possible, even so,
the units will operate in any angle of deflection. An upright (0° angle is best
relative to the HI units built-in weather shielding).
• Draw the locations on the site map (using black permanent ink) (see D-SED-
IEMB-005-SOP-01 meta-data collection SOP) with sufficient detail to
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indicate relative positions of each sampling box, their distance from the field
and any other details worth noting (position of any nearby trees or playground
equipment, roadways, etc.).
• Secure the metal rod to the HI air pump system.
• Attach the ring to the rod at the indicated mark.
• Open the pump box, remove the tubing and connect one end to the hose barb
found at the base of the HI unit and the other end to the barb on the right rear
of the pump unit. Remove any kinks in the hose.
• Slide the hose sufficiently onto the barb so that it is secure (a minimum of
3/8th of an inch). It may be necessary to lightly dampen the tubing to aide
with sliding the tubing onto the barbs.
• The attached hose should be snug and not easily removed without use of
applied force.
• Secure the HI unit upside down on the metal rod by inserting the small end of
the impactor head downward through the opening of the ring with the base
resting upside down on the ring. Verify the inlet opening of the impactor is
1.0 ± .1 meter from the ground. Alternatively, a finger clamp may be used to
secure the HI unit.
• Attach the battery power adapter to the pump unit by inserting the adapter
into the 12V input jack on the right rear of the pump unit.
• Attach the battery adapter leads to the appropriate terminals of the battery.
Attach the red lead to the positive (+) red terminal and the black lead to the
negative (-) black terminal. Make sure good contact is made.
• Turn on pump by sliding the on/off switch located on the pump deck to the
"on" position.
Note: The pump flow rate should be "roughed in" to 20 LPM prior to
attaching the HI unit. This will minimize the amount of time
required to fine adjust the pump flow after the HI unit is
attached.
Initial Pump Flow Measurement for Sample Start
5.4.1 Allow the pump to run for 3-5 minutes to warm-up and stabilize.
5.4.2 Attach the HI calibration cap to the Bios DryCal Calibrator using the supplied
tubing. Secure the tubing to the bottom (outlet) barb on the calibrator and to the barb
on the calibrator cap.
5.4.3 Press the "on" button of the BIOS unit.
5.4.4 Press and hold the "Read" button for approximately 3 seconds. This will activate the
unit to make continuous measurements and automatically average 3 replicate
readings.
5.4.4 Remove the top inlet portion of the HI unit by firmly grasping the red center portion
with one hand and with the other hand firmly grasp the top inlet portion and gently
twist and pull the top off. Do not block the inlet openings during this process. Place
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the inlet on a clean surface (zip lock bag) to avoid contamination.
5.4.5 Attach the HI calibration cap to the HI unit by gently pressing the top onto the red
portion of the HI unit. A slight twisting motion may be necessary to allow the
calibration cap to slide over the O-rings. Be careful not to cut or tear the O-rings
during this process.
5.4.6 Observe the flow rate values being displayed.
5.4.7 Adjust the flow rate to 20.0 ± 1.00 LPM if necessary. While observing the calibrator
display, use a screwdriver to adjust the flow adjustment screw to adjust the flow rate.
Adjustment should be made by gently turning the screw clockwise or
counterclockwise to increase or decrease the pump flow rate. Make adjustments in
partial turns.
5.4.8 Once adjusted to 20.0 ±1.0 LPM allow the flow to stabilize for one minute, reset
the calibrator by pressing the "Stop" button followed by holding the "Read" button
for three seconds. After three readings, record the average flow rate on the datasheet.
5.4.9 Without turning the pump off, immediately remove the calibration cap.
5.4.10 Re-attach the HI inlet to the HI unit.
5.4.12 Record the time and date of the flow measurement in the appropriate section of the
datasheet.
5.4.13 Record the Teflon filter ID number, attached to the outside of the HI unit, in the
appropriate section of the datasheet
5.4.14 Secure pump and place protective enclosure around pump system to prevent
tampering and for safety reasons.
5.5 Final Pump Flow Measurement for Sample End
5.5.1 After sampling for the desired time period, presumed to be ~ three-hour duration,
attach the BIOS calibrator to the HI unit and measure the flow rate at the end of
monitoring period.
5.5.2 Repeat steps 5.4.1through 5.4.6
5.5.3 Do not adjust the pump flow rate at the end of monitoring, simply record the average
value of three measurements as the ending flow rate on the datasheet.
5.5.4 Immediately turn off the HV-30 pump using the on/off switch on the pump deck.
5.5.5 Record the date and time that the pump was turned off on the datasheet.
5.5.6 Remove the BIOS calibration cap from the HI and replace it with its HI inlet.
5.5.7 Remove the tubing from the HI unit and place the HI unit in a zip lock bag and seal.
Ensure that the HI unit is returned to the zip lock bag with the correct sample code
label.
5.5.8 Transport the HI unit to a clean environment for removal of the filter cassette.
5.6 Pump/Equipment Take Down
5.6.1 Disconnect the tubing from the pump unit.
5.6.2 Disconnect the battery leads from the battery and remove the adapter from the pump.
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5.6.3 Pack all supplies and prepare for departure.
5.6.4 Transport/ship all supplies to the laboratory.
5.7 Removal of Filters from HI Units
5.7.1 In the same clean environment used in 5.1, remove the HI units from their zip lock
bags.
5.7.2 Wearing the powder-free gloves, open the HI units and remove the filter cassette,
returning it to the previously-assigned zip lock bag.
Note: The bags are labeled with the Id number of the tared filter. The filter
and cassette must be returned to the appropriately labeled zip lockbag
after monitoring.
5.7.3 Wipe down all of the equipment that went to the field using lint-free laboratory
wipes that are just slightly moistened to remove immediately transferrable dust.
Repackage all of the materials into their original shipping containers and prepare the
necessary shipping paperwork. All materials should be returned to: Ron Williams,
US EPA, 4930 Page Road, Durham, NC, 27703 (919-541-2957) using next day Fed
Ex or similar overnight delivery service. The kits will contain sealed gel cell
batteries and the NERL Safety and Health Office (541-4307) can assist with any
specialized shipping papers.
5.8 TSP (Total Suspended Particulate) Option
In the event that TSP (total suspended particulate) measurements are being performed (no
PM2.5 size fractionation required), the sampler shall be operated with the oiled impactor stage
removed from the HI. This is how the sampler will be used in support of the Tire Crumb Rubber
Study. This is accomplished by separating the inlet from the impactor stage, removing the oiled
impactor insert and reassembly of the HI. All other aspects of the sampling protocol remain as for
the PM2.5 sample collection (filter selection, duration, gravimetric analysis, etc). It should be noted
that TSP mass collection is not dependent upon a 20 LPM flow rate. It is important to establish an
initial flow rate and a final flow rate with the average being the flow rate used to calculate total
collected air volume. The HI should be operated in a vertical orientation (inlet facing skywards) if
TSP operation is to be used. No inlet is needed under TSP sampling conditions. An initial flow rate
in the range of 15-25 LPM is acceptable. The HV-30 pumps have an upper limit of 30 LPM so
operating the TSP version of the His at 20 LPM is suggested but not a requirement.
6.0 Quality Control
The quality control requirements will allow assessment of the quality of the samples
collected. Determination of possible contamination and reproducibility of the method will be
targeted as data quality indicators.
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Crumb Rubber Particulate Sampling
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Page 12 of 19
6.1 Field Blanks
• There should be at least one field blank performed for each day of air monitoring. All
field blanks should be assigned as a sample type code B. This sample uses the same
labeling code as described in Section 5.2.
• These should be installed within a HI, carried to the field (but not connected to the
sampling box nor having any air pulled through them).
6.2 Duplicate Samples
Duplicate samples shall be taken at a single location during each day of field measurement.
Two sampling systems (pump/inlets) shall be positioned within 2 meters of each other and operated
as specified in Section 5. The purpose of duplicate samples being the determination of precision for
the sampling method in its entirety.
6.3 BIOS Flow Calibrator Calibration
The BIOS calibrator, as previously described, will be used to determine initial and final
flows so that an average flow rate can be determined. This device has been calibrated annually by
the manufacturer and no adjustment of this device is needed. Review the calibration date on the
BIOS to ensure it has been calibrated within the last one year period.
7.0 General Sampling Precautions
Samplers must be placed in an area representative of the average ambient conditions. HI
units should be kept in sealed bags until just prior to the start of the sampling period. Pumps should
never be operated without a particulate filter in-line or with the sampling train sealed. Pumps should
be calibrated against the reference BIOS. Calibration should take place just prior to and
immediately after sampling. The average of initial and final flow rates will be used in conjunction
with the total elapsed sampling time to calculate total air volumes sampled and integrated analyte
concentrations available during the capture period. Air volume calculations will be performed at a
later stage and will not be performed as part of the field sample collection.
8.0 Possible Corrective Actions for Observed Problems During Sampling
8.1 Pump Failure
• If a pump fails, correct any obvious errors such as kinked lines, battery not fully
charged. If possible, replace the pump.
• If a replacement pump is unavailable, stop data collection immediately and contact the
EPA's tire crumb rubber study lead (Kent Thomas @ 9195417939) for instructions.
Examples of pump failure include: failure to reach desired flow rate; or failure to
maintain the desired flow rate.
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8.2 Possible Contamination of Filters or Supplies
Contact the EPA's tire crumb rubber study lead (Kent Thomas @9195417939) for
instructions concerning possible replacement items or directions concerning decontamination
procedures.
9.0 Recordkeeping
9.1 Data Sheets
All data concerning the data collection will be recorded by the appropriate operator on the
Sample Collection and COC Data Sheets shown in Appendix I. After the data is collected, copies
of the original shall be made and these copies will be labeled and stored in a separate notebook for
safekeeping. The originals are to be returned to the NERL-EMMD supervising scientist along with
the collected samples.
9.2 Calculations
Flow rates are direct readings from the BIOS. Average flow rate is the sum of the initial and
final flow rate divided by 2. The elapsed minutes is the sum total of minutes the pump operated
during the sampling episode. A normal 3 hour run period should have approximately 3 hours X 60
min/hour =180 minutes.
9.3 Chain-of-Custody
Chain of Custody (COC) record forms are shown in Appendix I for samples and QC
samples. The instrument operator will sign-off that the filter is being utilized in the field. The
original of the COC will accompany the filter back to the NERL-EMMD (the originator should
retain a copy for their own records).
Subsequent analysis (i.e. gravimetric analysis, etc.) will be indicated on the sample form by
responsible parties. Original copies of all data forms will be maintained in the NERL EMMD
project files.
10.0 References
Research Operating Procedure 07 (version 3) for Use and Preparation of the Harvard Impactor for
Collection of Particulate SVOC Matter in the DEARS. 12/17/2005.
D-SED-IEMB-005-SOP-01. Standard Operating Procedure for the Collection of Field and
Activity Metadata During Exposure Characterization Pilot Study Field Sampling. 2017
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Appendix I. Air PM/Metals Sample Data Collection Sheet and Chain of Custody Form
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Crumb Rubber Particulate Sampling
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Page 16 of 19
TIRE CRUMB EXPOSURE STUDY- VOC MONITORING DATA AND COC SHEET
COC-08
Field Locations -- Active PM & SVOC Air Samples
/ 'A
7
Deployment
Recovery
—
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
1
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PM Filter ID
Start Ti me
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
svoc
Start Ti me
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sanple ID
Field notes:
Receipt notes:
Analysis notes:
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Crumb Rubber Particulate Sampling
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Page 17 of 19
TIRE CRUMB EXPOSURE STUDY-- VOC MONITORING DATA AND COC SHEET
COC-09
Field Locations -- Active PM & SVOC Air Samples
/ - ^ \
i 45b 'A
LUSE'J
Deployment
Recovery
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
2
Shipped to EPA, RTP
Received & Stored at EPA,
RTP
Analyzed
PM Filter ID
Start Ti me
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Start Ti me
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Satriple ID
Field notes:
Receipt notes:
Analysis notes:
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D-EMMD-SSAB-QQ7-SOP-01
Crumb Rubber Particulate Sampling
Effective date 08/212017
Page 18 of 19
TIRE CRUMB EXPOSURE STUDY-- VOC MONITORING DATA AND COC SHEET
COC-10
Field Locations -- Active PM & SVOC Air Samples
Deployment
Recovery
11 fl
Study Name:
TCRS
Date
Field ID No:
Operator
Sample Chain of Custody
Field Location ID
8
Shipped to EPA,RTP
Received & Stored at EPA,
RTP
Analyzed
PM Filter ID
Start Ti me
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
SVOC
Start Time
Start Flow
Stop Flow
Stop Time
Initials
Date
Initials
Date
Initials
Date
Sample ID
Field notes:
Receipt notes:
Analysis notes:
Sample ID
Field notes:
Receipt notes:
Analysis notes:
-------
U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for Collecting and Using Extant Publicly-
Available Video
Number: D-SED-EHCAB-OOl-SOP-Ol
SOP was Developed
Alternative Identification: EHCAB-
Name: Marsha K. Morgan
Signature/Date:
Name: Kent W. Thomas
Title: Tire Crumb Leader
Signature/Date:
Name: Brittany Stuart
Title: QA Manager, Systems Exposure Division
Effective Date: November 14,2016
~ Extramural
0 In-house
-001-01
SOP Steward
Approval
Concurrence*
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TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 3
5.0 RESPONSIBILITIES 3
6.0 MATERIALS 4
7.0 PROCEDURES 4
8.0 RECORDS 8
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 8
10.0 REFERENCES 9
Appendix A. Standardized List of Extant Video Search Terms 10
Appendix B. Participant Activity Information on Extant Video 11
Appendix C. List of VIDs Sorted by Scenario and Age Group 12
Appendix D. Activity Template - Frequencies of selected subject activities on extant video 13
Appendix E. Activity Template - Number of selected subject activities on extant video 14
Appendix F. Activity Template - Duration (minutes) of selected subject activities on extant video
15
Appendix G. Template for Tabulation of Extant Video Activity Data 16
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1.0 SCOPE AND APPLICATION
Using publicly available videos (e.g. content posted on YouTube), videography is being used to collect
activity pattern data on children and adults while playing/practicing on artificial turf fields that contain
tire crumb infill at athletic facilities. The purpose of the extant videography is to provide an objective
assessment of user activity patterns potentially impacting exposure to chemicals found in crumb rubber
infill that are difficult to capture consistently using questionnaires.
2.0 SUMMARY OF THE METHOD
Using study acceptance criteria, trained EPA technicians shall identify and download publicly-available
internet videos (e.g., YouTube) of 30 children and 30 adults engaging in activities on artificial turf fields
that contain tire crumb infill. EPA technicians shall document from each downloaded video a description
and image of the selected subject, the type of activity/sport, the type of field (e.g., indoor or outdoor),
and the duration of the activity/sport.
EPA technicians shall record the selected activities of each person on tape for a total of 15 minutes for field
hockey and soccer and 10 minutes for football using three types of paper templates. These activities include
frequency of hand-to-mouth, object-to-mouth, hand-to-turf, and body-to-turf events; number of fingers
in mouth per hand-to mouth event; and activity level duration (i.e., time spent at resting, low, medium,
or high). The activities of each person recorded on the paper templates shall be manually transferred
(using double key entry) into a spreadsheet in MS Excel and a copy of these files made using a thumb
drive.
3.0 DEFINITIONS
SOP - Standard operating procedure
COC - Chain-of-custody
VID - Video identification number
4.0 CAUTIONS
The videography requires the collection of images that may be considered to be personally identifiable
participant data. Also, it is likely that the video footage will include other players and bystanders that are
not the focus of activity data collection, as well as inclusion of field or geographic features that may
make the video location discernible. No personal or site identifying information shall be recorded as
research data as part of the data activity transcription. Any and all human subjects protections
requirements as specified by the Institutional Review Board shall be followed.
5.1 RESPONSIBILITIES
5.2 EPA laboratory technicians shall be responsible for using video websites (e.g. YouTube) or
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general search engines (e.g. Google) to identify, download, and securely save acceptable extant
videos of children or adults playing or practicing on artificial turf fields with crumb rubber infill.
They shall also be responsible for extracting data from the downloaded extant videos and
recording selected activities onto three types of paper templates (see Appendices D-F). They
shall be responsible for manually transferring these data into a Microsoft Excel spreadsheet
(using double key entry) and making a copy using a thumb drive.
5.3 The EPA Principal Investigator shall be responsible for maintaining custody of the EPA non-
networked laptop computer and one copy of the extant video files. He or she shall also be
responsible for signing out the non-networked laptop computer and video files to laboratory
technicians to code people's selected activities while playing on synthetic turf fields. In addition,
he or she will be responsible for providing the EPA Database Manager with a copy of the activity
pattern data recorded from the extant video files in an MS Excel file.
5.4 The EPA Database Manager shall be responsible for maintaining one copy of the extant video
files. He or she shall also be responsible for converting the activity data in the MS Excel file into
a SAS database.
6.1 MATERIALS
6.2 Networked, password-protected laptop computer
6.3 Non-networked, password-protected laptop computer at EPA-RTP facility
6.4 Microsoft Internet Explorer or Google Chrome (most recent version of either Web browser)
6.5 Windows Media Player, version 12
6.6 Microsoft Excel software, version 2007 or newer
6.7 Microsoft Word software, version 2007 or newer
6.8 Printer
6.9 Hardcopy of example standardized list of search terms (Appendix A)
6.10 Hardcopies of activity templates (Appendices B-F)
6.11 Individual digital copies of Appendices A-F as Word file templates (e.g. Appendix A.docx)
6.12 Pen
6.13 Adob e Acrob at XI Pro
6.14 Encrypted, portable USB thumb drives (see Reference section)
6.15 Hardcopy file folder
6.16 Scanner
6.17 External hard drive
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7.1 PROCEDURES
7.2 Collection of Extant Publicly-Available Videos
7.2.1 Sign out the non-networked laptop computer (for up to 7 days) from the EPA Principal
Investigator by printing with a pen your name, date, and time on the hard copy sign out
sheet.
7.2.2 Turn on and log onto your networked laptop computer using your LAN ID and password. Insert
an encrypted thumb drive and create a folder on it called Tire Crumb Extant Video. Open
Appendix A (List of Example Search Terms), Appendix B (Participant Activity Information on
Extant Video), and Appendix C (List of VIDs by Scenario and Age Group) using Microsoft
Word.
7.2.3 Open Internet Explorer or Chrome on the laptop computer. Use the address bar to navigate to a
video site (e.g. YouTube) or a general search engine (e.g. Google). Using the Example List of
Search Terms (Appendix A), select and type a phrase (e.g., "children's soccer game turf') into
the search area of this website to find a target video. (Note that the search terms will be refined
as experience is gained in determining the types and quality of extant synthetic field-related
video. For example, different sport, practice, or training activities may be identified for
searching).
7.2.4 Select a video from among the search results of 30 minutes or greater length, watch the entire
video, and determine whether it meets the study's acceptance criteria for extant video data.
Acceptance criteria include 1) resolution of taped activity (which must be high enough in quality
to discern when a participant makes contact with the field), 2) continuity of person on tape
(viewer must be able to see 1 participant on video for a minimum of 1 5 minutes for field
hockey and soccer and 10 minutes for football), and 3) applicability for research goals (the
participant and activity must correspond with the scenarios and age groups targeted for high-
end exposure characterization, per the study QAPP). Note: If all acceptance criteria are obtained
(above), up to three individuals can be used per videotape.
7.2.5 If the selected video meets all of the acceptance criteria, type the letters "ss" following the HTTP
text and in front of the website name (e.g. "https://www.ssyoutube.com/watch_") on the address
bar. Press the Enter key to initiate a download of the video as an MP4 audio and video file. Click
on the MP4 file and save it in the Tire Crumb Extant Video folder on the thumb drive. Label the
filename and description as e.g. "Tire Crumb Extant Video VID.mp4," using a number 01
through 60 as the VID based on the sequence in which the videos are retrieved.
Save a copy of Appendices A and C in the Tire Crumb Extant Video folder on the thumb drive.
(Note: The thumb-drive versions of Appendices A and C can be usedfor every video downloaded
and VID assigned during the extant videography.) On Appendix B, type the VID in the top cell
where indicated and save a copy of the file in the Tire Crumb Extant Video Folder on the thumb
drive as e.g. "Appendix B FZD.docx" and continue to step 7.1.6.
If the selected video does not meet the acceptance criteria, repeat steps 7.1.2 through 7.1.4. Apply
the standardized search terms on other video sites or search engines if desired or necessary.
7.2.6 Safely eject the thumb drive containing the saved video file and appendices. Navigate to the
Downloads folder on the networked laptop and delete the MP4 file downloaded in step 7.1.5.
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Empty the laptop's Recycle Bin folder to eliminate the file from the networked computer. Log
off and shut down the networked laptop.
7.2.7 Turn on and log onto the non-networked laptop computer by clicking on the "Administrator"
icon, and typing in the generic password "Welcome 1", then insert the thumb drive containing
the saved video file. On the external hard drive, create or locate a folder called Tire Crumb
Extant Video. Copy the downloaded MP4 file, along with Appendices A, B, and C, from the
thumb drive to the Tire Crumb Extant Video folder on the C drive. Safely eject the thumb drive.
7.2.8 Using Windows Media Player, open and play the transferred video file from the Tire Crumb
Extant Video folder. Using Microsoft Word, open the participant information file (e.g.
"Appendix BFZD.docx").
Type the following information on the participant information file (Appendix B) where indicated:
the duration of the video file in hours, minutes, and seconds; the start and stop times (in hours,
minutes, and seconds from the beginning of the video) for the 15 or 10-minute period, respectively,
to be viewed for activity coding; a description of the video subject being followed (i.e., gender
and jersey color and number); and the type of sport or activity (e.g. football, soccer). Take a
screen capture of the videotaped participant using Windows Media Player by pausing the video
on a frame showing the subject, pressing Alt + Print Screen on the keyboard, and pasting the
image into the Appendix B table where indicated. Record the time of the screen shot on the
videotape in Appendix B.
Based on the subject's visual age group (based on other players) and the sport or activity filmed,
type the VID number in a cell under the appropriate column on the List of VIDs by Scenario and
Age Group sheet (Appendix C). (Note: At the conclusion of the extant videography, each of the
three exposure scenarios should have 20 VIDs associated with them, 10 with child subjects and
10 with adult subjects.)
Close Windows Media Player.
7.2.9 Repeat Steps 7.1.2 to 7.1.8 to locate and obtain additional video files.
When extant video collection is ceased at the end of each workday, and also once all study
requirements for extant video collection are fulfilled, print out hardcopies of Appendices B, and
C. Place the printed sheets in a file folder, label the folder "Tire Crumb Extant Video" along with
the current date (e.g. Tire Crumb Extant Video, May 2, 2016), and log off and shut down the
non-networked laptop. Place the thumb drive, laptop computer, and file folder in a locked cabinet
when you are away from your office during the day or at the end of the workday. A f t er
s e ar chi ng for vi de ot ape s for a thr ee da y peri od, return the thumb drive, laptop
computer, and file folder to the EPA Principal Investigator and print with a pen your name,
date, and time on the sign out sheet.
**Once all 60 video files have been selected, place all of the video files onto a thumb drive and
print out final hardcopies of Appendices B and C and give them to the EPA Principal Investigator.
7.3 Data Extraction from Extant Publicly-Available Video
7.3.1 Sign out the non-networked laptop computer from the EPA Principal Investigator. Turn on and
log onto the laptop computer. Open the Tire Crumb Extant Video folder on the C drive. Print out
a hardcopy of each of the 3 Activity Templates for frequencies, number, and duration of selected
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subject activities on extant video (Appendices D-F). Select a completed Appendix B document
with a VID, participant description, sport/activity type, and duration listed.
7.3.2 Open the MP4 file with the corresponding VID in the filename, saved in the Tire Crumb Extant
Video folder, using Windows Media Player. Before playing the video, write the VID of the video
on the upper-left of each activity template.
7.3.3 Watch the entire video and familiarize yourself with the participant's activities on videotape.
During the second playback, code the person's activities using Appendix D. On this paper
template, with a pen record with tally marks how many times the participant made hand-to-
mouth, object-to-mouth, hand-to-turf, and body-to-turf contact during the 30-minute time period
Write the date of the analysis on the upper-right of the template where indicated.
7.3.4 Log off and shut down the non-networked laptop. Scan the completed activity templates and
email them as PDF files to the EPA Principal Investigator. Return the laptop and give the
completed hardcopy activity templates to the EPA Principal Investigator. (Note: This procedure
will be completedfor all 60 video files before other selected activities on videotape will be coded
using the two other paper templates, Appendices E and F.)
7.3.5 Repeat steps 7.2.1 through 7.2.4 using the Appendix E Activity Template. For each hand-to-
mouth event seen on the video, make a tally mark in the bottom row of cells under the column
which indicates the number of fingers in mouth (one through five). At the conclusion of the
playback, add the tally marks to determine the total number of times the videotaped participant
was seen with one finger in mouth, two fingers in mouth, etc. in the same cells used for tallying.
7.3.6 Repeat steps 7.2.1 through 7.2.4 using the Appendix F Activity Template. For each of the four
activity levels listed (resting, low, moderate, and high), record the time intervals that the subject
spends at each activity level. For example, if the subject is seen sprinting from 0:15:00 to 0:15:30,
write "0:00:30" to indicate 30 seconds of high activity. At the conclusion of the video, add the
time intervals for each activity level to determine the total duration of time spent by the subject
at each level.
7.4 Electronic Tabulation of Data Extraction Results
7.4.1 Sign out (via sign out sheet) the non-networked laptop computer and the file folder containing
the completed paper Activity Templates (Appendices D-F) from the EPA Principal Investigator.
7.4.2 Turn on and log onto the non-networked computer. Insert a portable thumb drive. Create a MS
Excel spreadsheet and format the spreadsheet according to the template provided in Appendix G
for all VIDs, 01 through 60. Use the keyboard to enter the handwritten activity data from the
paper templates for each person followed on extant video.
7.4.3 Save the spreadsheet as "ExtantActivityData" in the Tire Crumb Extant Video folder on the C
drive. Include the EPA technician's name and the date of data entry at the top of the spreadsheet
above the column headings. Copy the spreadsheet onto the thumb drive in the Tire Crumb Extant
Video folder.
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7.4.4 Safely eject the thumb drive. Log off and shut down the non-networked computer. Return the
computer and thumb drive to the EPA Principal Investigator and check-in the materials using
sign out sheet.
7.4.5 The EPA Principle Investigator will upload the MS Excel spreadsheet via the thumb drive onto
a secured EPA server (private L drive folder: TCRS/Activity Data).
7.4.6 The EPA Database Manager will convert the MS spread sheet into a SAS database. The SAS
database will be housed at this location: private L drive folder: TCRS/ActivityDatabase.
8.0 RECORDS
Unique VIDs for each downloaded video are recorded on the video filenames and on the activity
templates for video data extraction. No names or personal information shall be collected if they can be
discerned from the video. No data extraction shall be performed for non-participants. No organization
name, team name, or location information shall be collected in the information extraction. The electronic
video files shall be treated as personally identifiable data and will be managed and secured to allow
access and use only by trained study staff for the intended purpose of turf field activity data collection.
No video or still images shall be publicly released as part of the research effort and research reporting.
Double key data entry, in which the EPA Principal Investigator shall compare the technician's
transcriptions of the same MS activity data file, will be used to verify the accuracy of the electronic data
acquired from the extant videography. Any discrepancies between the two data files will be resolved by
the EPA Principle Investigator by reviewing the original hardcopy version and making necessary
changes as needed to the data file. The EPA Principal Investigator or equivalent will also copy the
downloaded extant video files onto a portable USB drive or external hard drive to be kept in a locked
cabinet.
9.1 QUALITY CONTROL AND QUALITY ASSURANCE
9.2 Extant video quality checks: See section 7.1.4.
9.3 Data and records management: About 10% of the downloaded videos shall be re-coded by the
same trained laboratory technician. In addition, this same subset of videos (10%) shall also be
coded by a second trained staff member or contractor. The EPA Principal Investigator will use
this double key data entry to assess comparability and intra/inter-reviewer consistency for the
subjects' activity data recorded using each type of paper template. The goal is 90% intra-reviewer
and 85%) inter-reviewer accuracy of activity data coding for laboratory technicians. If the coder
fails the intra- and/or inter-reviewer accuracy test(s), he/she will recode a person's activity data
on a video file until they can pass the test.
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
10.0 REFERENCES
Quality Assurance Project Plan, Activity Characterization for the Tire Crumb Research Study, National
Exposure Research Laboratory, Research Triangle Park, N.C., 2016.
How to securely encrypt a USB flash drive, http ://www. online-tech-tips. com/computer-tips/encrypt-
usb-flash-drive/ (accessed on June 24, 2016).
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix A: Example Standardized List of Extant Video Search Terms
Scenario 1 (Soccer)
Scenario 2 (Football)
Scenario 3 (Field hockey/P.E.)
Children soccer game artificial
turf
Children football game
artificial turf
Children field hockey game
artificial turf
Children soccer full practice
artificial turf
Children football practice
artificial turf
Children field hockey practice
artificial turf
Adult soccer game artificial turf
Adult football game turf
Adult field hockey game turf
Adult soccer full practice artificial
turf
Adult football practice
artificial turf
Adult field hockey practice
artificial turf
MLS soccer game artificial turf
NFL football game turf
NCAA field hockey game turf
MLS soccer practice artificial turf
NFL football full practice
artificial turf
NCAA field hockey practice
artificial turf
NASL soccer game artificial turf
NCAA football game turf
USA Field Hockey game turf
NASL soccer practice artificial
turf
NCAA football full practice
artificial turf
USA Field Hockey practice
artificial turf
USL soccer game artificial turf
Arena Football League game
artificial turf
High school men's field
hockey game artificial turf
USL soccer practice artificial turf
Arena Football League
practice artificial turf
High school women's field
hockey game artificial turf
NWSL women's soccer game
artificial turf
Women's football league
game artificial turf
Indoor field hockey game
artificial turf
NWSL women's soccer practice
artificial turf
Women's football league
practice artificial turf
Indoor field hockey practice
artificial turf
NCAA men's soccer game
artificial turf
Indoor football game artificial
turf
US men's international field
hockey game artificial turf
NCAA men's soccer practice
artificial turf
Indoor football practice
artificial turf
US women's international
field hockey game turf
NCAA women's soccer game
artificial turf
Flag football game artificial
turf
Field hockey goalkeeper game
artificial turf
NCAA women's soccer practice
artificial turf
Flag football practice artificial
turf
Field hockey goalkeeper
practice artificial turf
Indoor soccer game artificial turf
Touch football game turf
Ultimate Frisbee game turf
Indoor soccer practice turf
Touch football practice turf
Ultimate Frisbee practice turf
Soccer goalkeeper game turf
Boys football game turf
Athletic drills artificial turf
Soccer goalkeeper practice
artificial turf
Girls football game artificial
turf
Boys field hockey game or
practice artificial turf
US men's international soccer
game artificial turf
Boys football practice
artificial turf
Girls field hockey game or
practice artificial turf
US women's international field
hockey game artificial turf
Girls football practice
artificial turf
Physical education artificial
turf
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix B: Participant Activity Information on Extant Video
Technician Name
VID
Video Duration
Start and stop times for 30-minute
activity coding period
Start: 0:00:00
Stop: 0:00:00
Child or adult
Sex
Type/color of clothing
Main position or activity on field
Screen capture of participant and
record time of screen shot
Time 0:00:00
Type of field (indoor or outdoor)
Type of sport or activity (e.g.,
soccer, football)
Notes:
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix C: List of VIDs by Scenario and Age Group
Number
Scenario 1 (Soccer)
Scenario 2 (Football)
Scenario 3 (Field
hockey/P.E.)
Child
Adult
Child
Adult
Child
Adult
1
2
3
4
5
6
7
8
9
10
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix D: Activity Template - Frequencies of selected subject activities on extant video
Technician Name:
VID: Analysis Date: - -
Hand-to-mouth
Object-to-mouth
Hand-to-turf
Body-to-turf
(excludes hands)
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix E: Activity Template - Number of selected subject activities on extant video
Technician Name:
VID: Analysis Date:
Fingers in mouth (per
hand-to-mouth event)
One
Two
Three
Four
Five
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix F: Activity Template - Duration (minutes) of selected subject activities on extant video
Technician Name:
VID: Analysis Date:
Resting
(e.g., sitting/standing)
Low activity
(e.g.., walking)
Moderate activity
(e.g., jogging)
High activity
(e.g., running)
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix G: Template for Tabulation of Extant Video Activity Data
VID
Scenario
Adult
Sex
Indoor
Hand-
Object-
Hand-
Body-
Times
Times
Times
Times
Times
(1, 2, 3)
or
or
to-
to-
to-turf
to-turf
with 1
with 2
with 3
with 4
with 5
or sport
Child
Outdoor
mouth
mouth
events
events
finger
fingers
fingers
fingers
fingers
Field
events
events
(excl.
in
in
in
in
in
hands)
mouth
mouth
mouth
mouth
mouth
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
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Standard Operating Procedure for Collecting and Using Extant Publicly-Available Video
Appendix G: Template for Tabulation of Extant Video Activity Data (continued)
VID
Duration
Duration
Duration at
Duration
at rest
at low
moderate
at high
(min.)
activity
activity
activity
(min.)
(min.)
(min.)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
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U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for Videography of Activity Characterization
Study Participants
Number: D-SED-EHCAB-005-SOP-01
Effective Date: August 21, 2017
SOP was Developed
In-house
~ Extramural
Alternative Identification: EHCAB-005-01
SOP Steward
Name: Marsha K. Morgan
Signature Date:
Approval
Name: Kent W. Thomas
Title: Tire Crumb Leader
Signature Date:
Concurrence
Name: Christine Alvarez
Title: QA Manager, Systems Exposure Division
Signature Date:
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 3
5.0 RESPONSIBILITIES 4
6.0 MATERIALS 4
7.0 PROCEDURES 5
8.0 RECORDS 8
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 8
10.0 REFERENCES 9
Appendix A. List of Required Videotaping Equipment 10
Appendix B. Activity Template - Frequencies of selected activities on study participant video... 11
Appendix C. Activity Template - Number of selected activities on study participant video 12
Appendix D. Activity Template - Duration (minutes) of selected activities on study participant
video 13
Appendix E. Template for tabulation of study participant activity data 14
Appendix F. Chain-of-custody form for the participant's videotapes 16
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
1.0 SCOPE AND APPLICATION
Videography is being used to collect activity pattern data on child or adult participants who routinely
play on artificial turf fields that contain tire crumb infill at athletic facilities. The purpose of the video
data collection is to quantify selected activity patterns of children and/or adults while they play/practice
on artificial turf fields to provide objective information on potential exposures to tire crumb rubber
constituents through inhalation, dermal, and ingestion pathways.
2.0 SUMMARY OF THE METHOD
Field technicians shall record child and adult participants that participate in the exposure characterization
component of the Tire Crumb Research Study (TCRS). Field technicians shall videotape these
participants playing/practicing on artificial turf fields for 1.5-hours using a video camera (containing
two video data (SD) cards) that is attached to a monopod.
Laboratory technicians shall translate the selected micro-activities of participants by using a
non-networked laptop computer and a large computer monitor. The technicians shall record the
selected activities of each person on tape for 1,5-hours using three types of paper templates. These micro-
activities include frequency of hand-to-mouth, object-to-mouth, hand-to-turf, and body-to-turf events;
number of fingers in mouth per hand-to-mouth event; and activity level duration (i.e., time spent at
resting, low, medium, or high). The activities of each person recorded on the paper templates shall
be manually transferred (using double-key entry) into a spreadsheet in MS Excel and a copy of these
files made using a thumb drive.
3.0 DEFINITIONS
SOP - Standard operating procedure
COC - Chain-of-custody
PID - Participant identification number
CDC - Centers for Disease Control and Protection
4.0 CAUTIONS
The videography requires the collection of images that may be considered to be personally identifiable
participant data. Also, it is likely that the video footage will include other players and bystanders that
are not videography participants, as well as inclusion of field or geographic features that may make the
video location discernible. Any and all human subjects protections and training requirements as
specified by the Institutional Review Board shall be followed (currently stated in the Work Assignment).
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
5.1 RESPONSIBILITIES
5.2 CDC research staff shall be responsible for recruiting eligible children and/or adults and obtaining
their assent/informed consent before videotaping their activities while playing/practicing on
artificial turf fields.
5.3 The contractor staff shall be responsible for attending an EPA pre-pilot testing activity and training
their field technicians to videotape study participants while playing/practicing on artificial turf
fields as well as code selected micro-activity data from the videotapes of participants.
5.4 Contractor field technicians shall be responsible for videotaping the study participants
while playing/practicing on the artificial turf fields for up to 1.5 hours (target time is 1.5 hour
per participant) at the enrolled facilities.
5.5 The contractor staff shall be responsible for coding selected activity data from the participant
SD cards using three types of paper templates (Appendices B-D). They shall be responsible
for manually transferring and checking these data into a Microsoft Excel spreadsheet (using double-
key entry) and making a copy using a thumb drive. In addition, contractor staff shall be
responsible for providing an electronic version of the selected micro-activity data (in MS Excel
files) to the EPA Principle Investigator.
5.6 The EPA Principal Investigator shall be responsible for signing in/out the SD cards to laboratory
staff. In addition, he or she will be responsible for providing the EPA Database Manager with
a copy of the activity pattern data recorded from the study participant video files in an MS Excel
file.
5.7 The EPA Database Manager shall be responsible for maintaining one copy of the study
participant video files. He or she shall also be responsible for converting the activity data in the
MS Excel file into a SAS database.
6.1 MATERIALS
6.2 Two 27-inch computer monitors
6.3 One networked, password-protected laptop or desktop computer
6.4 Two non-networked, password-protected laptop computers
6.5 Videotaping equipment (see Appendix A)
6.6 COC sheets (see Appendix F)
6.7 Microsoft Word software, version 2007 or newer
6.8 Microsoft Excel software, version 2007 or newer
6.9 Hardcopies of Activity Templates (Appendices B-D)
6.10 Individual digital copies of Appendices B-E as Word file templates (e.g. Appendix B.docx)
6.11 Pens (acid-free)
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6.12 Windows Media Player, version 12
6.13 Adob e Acrob at XI Pro
6.14 Scientific calculator (physical or virtual)
6.15 Encrypted, portable USB thumb drives (see Reference section)
6.16 Hardcopy file folder
6.17 Paper scanner
6.18 White dry erase board (8.5 x 11 inch) with pen
6.19 Aluminum video monopod
7.0 PROCEDURES
7.1 Videotaping Study Participants at Enrolled Facilities
7.1.1 CDC research staff shall obtain assent/informed consent to videotape a subset of study
participants that are participating in the activity characterization and exposure measurement
component of the TCRS. This assent/informed consent shall be requested as part of the
eligibility screening interview for users of TCRS-enrolled facilities. When CDC research staff
is not present at a field site, they shall provide contractor field technicians with written hardcopy
documentation and contact information on which participants (by field location) have consented
to have their activities videotaped for 1.5 hours. Note: If CDC research staff is present at the
field site when the participant activity is scheduled, they shall provide the contractor field
technicians with contact information (verbally) on which participants (by field location) have
consented to have their activities videotaped for 1.5 hours.
7.1.2 Contractor field technicians shall attend pre-pilot testing activities to observe a demonstration on
how EPA would like to videotape the selected micro-activities of individual participants while
playing/practicing on synthetic turf fields. The signed names of the field technicians, including
attendance date, shall be recorded onto a sheet of white paper and a copy provided to the EPA
Principal Investigator. This document will be stored in a locked cabinet in the EPA Principal
Investigator's office located in D-576.
7.1.3 EPA staff and/or contractors shall contact study participants who have given informed
consent (via CDC) to be videotaped and arrange the scheduled times to videotape the adults
and/or children while playing/practicing on artificial turf fields.
7.1.4 Contractor field technicians shall videotape individual study participants during the scheduled
appointment times. Perform equipment checks on the camcorder to assure that it is
functioning properly before entering the field. Turn on the camcorder and verify that it
works and then check that the inserted battery is sufficiently charged (> 75%). Place
two new SD cards into the camcorder. Verify the date and time is accurate and is being recorded
on the two SD files. Remove the lens cap and then open the LED screen. Select the recording
option to write a real-time copy of the video files on both SD cards inserted into the camera (i.e.
"Rec Set - Simultaneous Rec"). Attached the camcorder to the monopod. Using a dry erase
board (8.5" x 11") with attached pen, write the participant's PID on it (2-inch size).
7.1.5 Set up the monopod (with camcorder) at one end of the playing field (nearest to the participant
being filmed). Use zoom as needed when videotaping the participant (use 50% frame height).
Move the monopod a few feet (left or right) as needed to obtain unobstructed views of the
participant. To start videotaping the participant, press the Record button on the video camera. At
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the beginning of the video, place the dry erase board (with the participant's PID) in front of the
camera lens for five seconds. (Note: If the participant spends less than 1.5-hours
playing/practicing on artificial turffields at the enrolled facilities then videotape for the entire
available playing practice period). Videotape the study participant for 1.5 total hours while
they are playing/practicing on artificial turf fields at the enrolled facilities. This time period
may include on-field breaks for water and/or food. Throughout the videotaping period, be as quiet
as possible and keep a low profile. Concentrate on filming the participant's selected micro-activities
including hand-to-mouth, hand-to-turf, object-to-mouth, and body-to-turf contacts. Do not
videotape the participant at inappropriate times (e.g., changing clothes, bathing, using the
restroom, going to the locker room, leaving the facility); stop the video camera and wait until the
participant has returned to the field and then resume videotaping their activities.
7.1.6 After videotaping the participant for 1.5 total hours, press the Record button on the
camcorder to stop recording. Put on the lens cap. Remove the camcorder from the monopod.
Using the camcorder, review both SD cards to verify that the participant was recorded for the
entire time period (including that the date and time of filming is correct) and that the selected
micro-activities can be clearly observed on these video files (press the "Thumbnail" button and
navigate the contents of each SD card, "A" and "B" to find the files; fast-forward through the
playback to minimize time spent on-site). Then, remove the two SD cards and place them into
the SD card cases. Affix a white label to the SD card case (not directly to the SD card) and write
on it with a pen the PID, field ID, and date. Place the camcorder, SD cards cases containing the
SD cards, and other accessories into the camera bag. Do not leave the video camera, SD cards,
and other accessories in an unlocked car or in a car if the weather is hot (i.e., temperature is
greater than 90°F). Repeat sections 7.1.4 - 7.1.6 for each scheduled participant. Leave the facility
and return to the contractor duty station (keep all items secured in a locked room or cabinet).
7.1.7 After returning to the office in RTP, NC, contractor field technicians s h a 11 turn on and log
onto the non-networked, password-protected laptop computer using your LAN ID and
password. For each study participant, remove the two SD card cases from the camera bag. Store
one of the SD cards (in a plastic case) in a locked cabinet. For the other one, remove
the SD card and insert in into the laptop.
7.1.8 Locate the participant's video files on the SC card (SD/Private/AVCHD/BDMV/STREAM/mts).
Use Windows Media Player to play the video files on the inserted SD card. Rename the video
files to include the participant's PID e.g. "Tire Crumb Field Video (PID).mts and place a copy
of the participant's video files on the C drive, under the folder name: TCRS Video Files." Obtain
a blank COC form (Appendix F) and complete the form using information on stop/start times
from the video player. Eject the SD card from the laptop after all video files have been
appropriately renamed. Place the SD card back into the plastic case. Give this SD card and filled
out/signed COC to the EPA principal investigator (D-576). Repeat section 7.1.7-7.1.8 for each
filmed participant.
7.2 Data Extraction from Study Participant Videos
7.2.1 To code the participant activities on the video files, turn on and log onto the non-networked
laptop computer. Open the TCRS Video Files folder on the C drive. For each participant, do
the following procedures. Print out a hardcopy of the Activity Template - Frequencies of
selected micro-activities on study participant video (Appendix B). Open one of the video files
saved in the TCRS Video Files folder using Windows Media Player. Before playing the video,
write the PID of the video on the upper-left of each activity template. Write the date of the
analysis on the upper-right of the template.
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7.2.2 Watch the entire video and familiarize yourself with the participant's micro-activities on videotape.
7.2.3 During the second playback, code the person's micro-activities using Appendix B. On this
paper template, with a pen record with tally marks how many times the participant made
individual hand-to-mouth, object-to-mouth, hand-to-turf, and body-to-turf contacts during
the 1.5-hour time period. Also provide the specific time that each selected micro-activity
occurred by the participant on this template e.g. 00:45:26 (hours, minutes, and seconds after the
start). In addition, record whether the participant was using a mouthguard or wearing gloves (one
or two) on this template. The video may be paused or rewound as necessary to verify types of
contact and specific times. At the conclusion of the video, record the total counts of each micro-
activity at the bottom of the same cells used for tallying. Log off and shut down the non-
networked laptop. Scan the completed activity templates and place them onto an encrypted
thumb drive. Return the thumb drive, and give the completed hardcopy paper activity
templates to the EPA Principal Investigator; The EPA principle investigator will store these
items in a locked cabinet in his/her office. (Note: This procedure will be completed for all 24
video files before other selected activities on videotape will be coded using the two other paper
templates, Appendices C and D.)
7.2.4 Repeat steps 7.2.2 through 7.2.4 using the Appendix C Activity Template. For each hand-to-
mouth event seen on the video, make a tally mark in the bottom row of cells under the column
which indicates the number of fingers in mouth (one through five). At the conclusion of the
playback, add the tally marks to determine the total number of times the videotaped participant
was seen with one finger in mouth, two fingers in mouth, etc. Record the totals at the bottom of
the same cells used for tallying.
7.2.5 Repeat steps 7.2.2 through 7.2.4 using the Appendix D Activity Template. For each of the four
activity levels listed (resting, low, moderate, and high), record the time intervals that the subject
spends at each activity level. For example, if the subject is seen sprinting from 0:15:00 to 0:15:30,
write "0:00:30" to indicate 30 seconds of high activity. At the conclusion of the video, add the
time intervals for each activity level to determine the total duration of time spent by the subject
at each level. Record the total duration of time (in hh:mm:ss format) at the bottom of the
appropriate column for each of the four listed activity levels.
7.3 Electronic Tabulation of Data Extraction Results
7.3.1 Sign out (via the sign-out sheet) the file folder in abinder containing the completed paper Activity
Templates (Appendices B-D) from the EPA Principal Investigator.
7.3.2 Turn on and log onto the non-networked laptop computer. Insert a portable thumb drive. Create
a MS Excel spreadsheet and format the spreadsheet according to the template provided in
Appendix E for all PIDs referenced in the Activity Templates. Use the keyboard to enter the
handwritten activity data from the paper templates for each person followed on video. Perform
a 100% check that all the data entered from individual activity templates into the spreadsheet are
correct.
7.3.3 Save the spreadsheet as "FieldActivityData" in the Tire Crumb Participant Video folder on the
C drive. Include the EPA technician's name and the date of data entry at the top of the spreadsheet
above the column headings. Copy the Tire Crumb Participant Video folder and all its contents
from the C drive onto the inserted thumb drive.
7.3.4 Safely eject the thumb drive. Log off and shut down the non-networked computer. Return the
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thumb drive to the EPA Principal Investigator and check-in the materials using the sign-out sheet.
7.3.5 The EPA Principal Investigator will upload the MS Excel spreadsheet via the thumb drive onto
a secured EPA server (private L drive folder: TCRS/Activity Data).
7.3.6 The EPA Database Manager will convert the MS Excel spreadsheet into a SAS database. The
SAS database will be housed at this location: private L drive folder: TCRS/Activity
Database.
8.0 RECORDS
Unique PIDs previously assigned to each participant and his/her activity video are recorded on the video
filenames (as transferred via SD card) and on the Activity Templates. The videographer shall attempt to
minimize videotaping other players or bystanders as much as possible. No names or personal information
will be collected from non-participants. No data extraction will be performed for non-participants. The
electronic video files will be treated as personally identifiable data and will be managed and secured to
allow access and use only by trained study staff for the intended purpose of field-related activity data
collection. No video or still images will be publicly released without the written consent of the study
participant.
Contractor staff shall provide th e EPA Principal Investigator or equivalent with electronic video files
(SD cards) of each study participant. The EPA Principle Investigator will also make a copy of the
participant's video files by placing them on an external hard drive and storing them in a locked cabinet in
his/her office. Individual contractor technicians shall perform double-key data entry of each Activity
Template (B-D) onto separate FieldActivityData electronic files (a and b). Any discrepancies between
the two data files will be resolved by the EPA Principal Investigator by reviewing the original
hardcopy version and making necessary changes as needed to the electronic data files. The EPA
Principal Investigator or equivalent will also make a copy of the participant's data files by placing them
on an external hard drive and storing them in a locked cabinet in his/her office. All records will be archived
by EPA for a minimum of 10 years.
9.1 QUALITY CONTROL AND QUALITY ASSURANCE
9.2 Video camera and accessories checks: See section 7.1.4.
9.3 Data and records management: About 10% of the downloaded videos shall be viewed again
and the selected micro-activities will be quantified (re-coded) onto the hardcopy Activity
Template by the same trained laboratory technician. In addition, this same subset of videos
(10%) shall also be coded by a second trained staff member or contractor. The EPA Principal
Investigator will use this double-key data entry to assess comparability and intra/inter-reviewer
consistency for the subj ects' activity data recorded using each type of paper template. The goal is
90% intra-reviewer and 85% inter-reviewer accuracy of activity data coding for laboratory
technicians. If the coder fails the intra- and/or inter-reviewer accuracy test(s), he/she will recode
a person's activity data on a video file until they can pass the test.
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
10.0 REFERENCES
Quality Assurance Project Plan, Activity Characterization for the Tire Crumb Research Study, National
Exposure Research Laboratory, Research Triangle Park, N.C., 2016.
Standard Operating Procedure for Administering the Facility Adult User Questionnaire, Activity
Characterization for the Tire Crumb Research Study, National Exposure Research Laboratory, Research
Triangle Park, N.C., 2016.
Standard Operating Procedure for Administering the Facility Child User Questionnaire, Activity
Characterization for the Tire Crumb Research Study, National Exposure Research Laboratory, Research
Triangle Park, N.C., 2016.
How to securely encrypt a USB flash drive, http://www.online-tech-tips.com/computer-tips/encrvpt-
usb-flash-drive/ (accessed on June 24, 2016).
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix A: List of Required Videotaping Equipment
Item
Manufacturer
Quantity
Sony HXR-NX100 Full HD NXCAM Camcorder
Sony
1
Sony 32GB High Speed UHS-I SDHC U3 Memory Card (Class 10)
Sony
34
Pearstone Microfiber Cleaning Cloth, 18% Gray (7 x 7.9")
Pearstone
1
Arco Video Dr. Bag 30
Arco
1
Ruggard Desiccant Silica Gel Pack - Metal Case (40 g)
Ruggard
1
Ruggard Memory Card Case for 12 SD Cards and 12 microSD Cards
Ruggard
1
Ruggard Memory Card Case for 2 SD cards
Ruggard
10
Sony NP-F970 L-Series Info-Lithium Battery Pack (6300mAh)
Sony
1
White labels (for SD Card Cases)
1
White dry erase board with black pen
Sparco
1
Manfrotto aluminum video monopod
Manfrotto
1
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix B: Activity Template - Frequencies of selected micro-activities on study participant video
Technician Name:
VID: Analysis Date: - -
Wearing Mouthguard: Yes or No (circle one) Wearing Gloves: None 1 2 (circle one)
Hand-to-mouth
Object-to-mouth
Hand-to-turf
Body-to-turf
(excludes hands)
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix C: Activity Template - Number of selected micro-activities on study participant video
Technician Name:
VID: Analysis Date:
Fingers in mouth (per hand-to-mouth event)
One
Two
Three
Four
Five
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix D: Activity Template - Duration (minutes) of selected micro-activities of study participant on video
Technician Name:
PID:
Analysis Date:.
Resting
(e.g., sitting/standing)
Low activity
(e.g.., walking)
Moderate activity
(e.g., jogging)
High activity
(e.g., running)
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix E: Template for Tabulation of Study Participant Activity Data
PID
Sport
Adult
or
Child
Sex
Indoor
or
Outdoor
Field
Hand-
to-
mouth
events
Object
- to-
mouth
events
Hand-
to-turf
events
Body-
to-turf
events
(excl.
hands)
Times
with 1
finger
in
mouth
Times
with 2
fingers
in
mouth
Times
with 3
fingers
in
mouth
Times
with 4
fingers
in
mouth
Times
with 5
fingers
in
mouth
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix E: Template for Tabulation of Study Participant Activity Data (continued)
PID
Duration
at rest
(min.)
Duration
at low
activity
(min.)
Duration at
moderate
activity
(min.)
Duration
at high
activity
(min.)
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Standard Operating Procedure for Videography of Activity Characterization Study Participants
Appendix F. Chain-of-custody form for the participant's videotapes
Tire Crumb Research Study
i Q \
v-si
Site location:
Site Information (field number, indoor or outdoor field):
(Do not include facility name or location here):
Type of sport, adult or child, and sex:
Videotape ID
Description: Total recording time on videotape and
recording stop/start times
Comments: Weather conditions, problems with videotaping equipment,
reasons for stopping subject recoding (e.g., bathroom break, injuries)
Collected by (Full name):
Date collected:
Collection start time:
Collection end time:
Shipped by (Full name):
Date shipped:
Received by (Full Name):
Date received:
Storage:
Relinquished by (Full name):
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U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for Administering the Facility Child User
Questionnaire
Number: d-sed-ehcab-oo4-sop-oi
Effective Date: August 15,2016
SOP was Developed 0 In-house D Extramural
Alternative Identification: EIB-004-01
SOP Steward
Name: Marsha K. Morgan
MARSHA MORGAN August 9, 2016
OliilldlLll C . Date: 2016.08.09 1S:29:19-04'00' -L'dlC .
Digitally signed by MARSHA MORGAN
Approval
Name: Kent W. Thomas
Title: Tire Crumb Leader
Digitally signed by KENT THOMAS
c. „ KENT THOMAS August 10,2016
Signature; DaiWoaio 07:5*09-04W Date:
Concurrence^
Name: Brittany Stuart
Title: QA Manager, Systems Exposure Division
Digitally signed by BRITTANY STUART
, BRITTANY STUART , August 15,2016
Signature: d,*™,Date: a
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TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 3
5.0 RESPONSIBILITIES 3
6.0 MATERIALS 4
7.0 PROCEDURES 4
8.0 RECORDS 5
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 4
10.0 REFERENCES 5
Appendix A. Facility Child User Questionnaire 6
Appendix B. Questionnaire COC form 15
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1.0 SCOPE AND APPLICATION
The Facility Child User Questionnaire is used to collect data on children (< 13 years old) who routinely
play on artificial turf fields that contain tire crumb infill at athletic facilities. The purpose of the
questionnaire is to collect information on the child's activity patterns that may impact the magnitude and
frequency of their exposures to chemicals found in crumb tire infill.
2.0 SUMMARY OF THE METHOD
Research staff administer the Facility Child User Questionnaire to the parents of child participants who
routinely play on artificial turf fields using a computer-assisted interview (CAI) method. The
questionnaire is used to record specific types of data about the participating children including
demographics (i.e., age, gender, and race), education levels, activity-levels, types and frequency of sports
played on fields, frequency and duration of field use, hygiene practices (e.g., hand washing and eating
events), types of clothing worn, and contact rates on turf for different types of activities. Using a laptop
computer, research staff open the Facility Child User Questionnaire via the Epi Info software program
and ask parents each question about their children and record their responses. Research staff save all
responses recorded in the questionnaires prior to exiting the Epi Info software program. They also make
a backup copy of all questionnaire responses using a portable flash drive.
3.0 DEFINITIONS
SOP - Standard operating procedure
CAI - Computer-assisted interview
COC - Chain-of-custody
PID - Participant identification number
4.0 CAUTIONS
Research staff must keep all completed participant questionnaires on the laptop computer and portable
flash drive in a secure location at all times.
5.0 RESPONSIBILITIES
5.1 The EPA Database Manager will be responsible for providing the questionnaire (Epi Info and PdF
versions) to the EPA Tire Crumb Team Leader.
5.2 The EPA Tire Crumb Team Leader will be responsible for providing the questionnaire to the
appropriate research staff responsible for questionnaire administration.
5.3 The field technicians will be responsible for completing the participant questionnaires. They are
also be responsible for returning the completed questionnaires (via portable flash drives), including
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Standard Operating Procedure for Administering the Facility Child User Questionnaire
chain-of-custody (COC) forms, to the EPA Tire Crumb Team Leader.
6.0 MATERIALS
6.1 Laptop computer
6.2 Epi Info software, version 7.1.5
6.3 Adobe Acrobat XI Pro
6.4 Encrypted, portable USB thumb drives (see Reference section)
6.5 COC sheets
7.0 PROCEDURES
7.1 Administration of the Questionnaire (See Appendix A)
7.1.1 Turn on the designated laptop computer (password protected) assigned to this project.
7.1.2 Open the Epi Info software program located on the desktop of the laptop computer. On the main
screen of this software program, click on the "Enter Data" button. At the top of the screen, click on
"Open Form" and then click on the button (with three dots) to open a current project folder. Next, find
the Tire Crumb Child Questionnaire folder located under Epi Info 7 Projects Folder. In this folder,
select the Childlnfo.pij file, click the "Open" button, and then the "OK" button.
7.1.3 At the top of the screen, click on the "New Record" button. This questionnaire has a total of 20
questions. Record the child participant identification number (PID; obtained from the EPA Tire Crumb
Research Leader), facility name, interview date, study ID number, facility location, and interviewer ID
number at the top of the questionnaire form.
7.1.4 Begin the questionnaire. Ask the child's parent the first question and record his/her response to
the question. Repeat this procedure for each question.
7.1.5. After the questionnaire is completed go to the top of the screen, select "File" and click on the
"Save" button and save the file as "ChildQuestionnairePIDXX (example: ChildQuestionnaireOl).
7.1.6 For the next child participant, repeat steps 7.1.3 - 7.1.5.
7.1.7 Exit the Epi Info software program by selecting "File" at the top of the screen and then click on
"Exit".
7.1.8 Make a backup copy of the Tire Crumb Child Questionnaire folder using only the study
designated portable flash drive. Label the flash drive with a unique identifier (example: TCRS:Child
Questionnaire). *A11 questionnaire files will be uploaded to this one flash drive.
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8.0 RECORDS
COC forms (Appendix B) will be used to document the transfer of the participant questionnaire data.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE
Proper COC records shall be kept documenting the transfer and receipt of all questionnaire data
by EPA's Tire Crumb Team Leader at the EPA laboratory in Research Triangle Park, NC.
10.0 REFERENCES
Quality Assurance Project Plan, Activity Characterization for the Tire Crumb Research Study,
National Exposure Research Laboratory, Research Triangle Park, N.C., 2016.
Epi Info 7 User Guide. 2016. https://wwwn.cdc.gov/epiinfo/user-auide/
How to securely encrypt a USB flash drive, http://www.online-tech-tips.com/computer-tips/encrypt-
usb-flash-drive/ (accessed on June 24, 2016).
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Appendix A: Facility Child User Questionnaire
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Standard Operating Procedure for Administering the Facility Child User Questionnaire
Form Approved
OMB No. 0923-xxxx
Exp. Date xx/xx/201x
Youth/Child Field User Questionnaire
PID
Site ID Number
Facility Name
Facility Location
Interview Date
Interviewer ID
Interviewer: I would like to ask you some questions about activities that may affect your child's
exposures to, and contact with synthetic turf fields that contain crumb rubber materials.
Field Contact Frequency and Duration Questions
Interviewer: I have several questions about the time your child spends on synthetic turf fields at this
facility
Bl. How long has your child been coming to this facility?
(years)
(months)
B2. Specifically on the synthetic fields at this facility, what sports, physical education classes, or other
activities has your child actively participated in by season (specify) over the past year?
Season
Sport
Specify Other
ATSDR estimates the average public reporting burden for this collection of information as 30 minutes per response,
including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data
needed, and completing and reviewing the collection of information. An agency may not conduct or sponsor, and a
person is not required to respond to collection of information unless it displays a currently valid OMB control
number. Send comments regarding this burden estimate or any other aspect of this collection of information
including suggestions for reducing this burden to CDC/ATSDR Reports Clearance Officer; 1600 Clifton Road, MS
D-74, Atlanta, GA 30333, ATTN: PRA (0923-XXXX).
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B3. Over the past year, how many days per week by season has your child
typically spent on synthetic fields at this facility?
Spring
Summer
Fall
Winter
(days per week)
(days per week)
(days per week)
(days per week)
B4. Over the past year, how many hours per day by season has your child typically spent on the
synthetic fields at this facility?
Spring
Summer
Fall
Winter
(hours per day)
(hours per day)
(hours per day)
(hours per day)
B5. Over the past year, what was the longest period of time that your child has spent on the
synthetic fields at this facility during a single day?
(number of hours)
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Contact Types and Scenarios per Each Type of Field Use
Interviewer: I have several questions about the kinds of activities that your child takes part in specifically
on synthetic turf fields installed at this facility.
For the following question, please use one of the three responses (often, sometimes, and rarely/never).
"Often" means > 50% of the time and "sometimes" means < 50%.
B6. How frequently does your child do the following activities on synthetic fields at this facility each season?
Dive on Fallon Sit on turf Eat snacks Drink
ground ground
Spring
Summer
Fall | | | | | | | | |
Winter
Inhalation Exposure-Related Questions
B7. When using synthetic fields at this facility:
What % of the time is your child highly active, for example, running?
What % of the time is your child moderately active, for example, jogging?
What % of the time does your child have low activity, for example, walking?
What % of the time is your child resting, for example, sitting or standing?
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Dermal and Non-Dietary Ingestion Exposure-Related Questions
For the following questions, please use one of the four responses (every time, often,
sometimes, or rarely/never):
B8. When using synthetic turf fields at this facility:
Every Time Often
Some Rarely/
times Never
How often does your child chew gum?
3
2
0
How often does your child use a mouth guard?
3
2
0
How often does your child eat?
3
2
0
How often does your child drink?
3
2
0
How often does your child play in the rain?
3
2
0
How often does your child wipe their hands with a hand wipe
before eating?
3
2
0
How often does your child sweat heavily?
3
2
0
How often does your child touch the turf (with their hand)?
3
2
0
How often does your child touch the turf with their body excluding
hands?
3
2
0
How often does your child sit on turf with bare skin wearing shorts?
3
2
0
How often is your child barefooted on the turf?
3
2
0
How often does your child play with the turf materials or rubber
granules?
3
2
0
How often does your child touch their mouth with their hands or
fingers?
3
2
0
How often does your child place non-food objects in their mouth
every time like toothpicks, or pens or use their mouth to hold an
object? If rarely/never, skip next.
3
2
0
What type of object does your child most often places in their
mouth while at this facility?
How often does your child get cuts or abrasions from contact with
the turf?
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If rarely/never, skip next.
What is the body part that usually has the most cuts or abrasions:
knee, elbow, hand, thigh, shin, or other?
B9. What clothing does your child typically wear in this facility during each season (check all that apply)?
Spring
Summer
Fall
Winter
Shorts
~
Short-sleeve shirt
~
Long pants
~
Long-sleeve shirt
~
Gloves
~
Socks
~
Helmet
~
Hat
~
Pads
~
Tire Crumb Take-Home Questions
For the following questions, please use one of the four responses (every time, often, sometimes, or
rarely/never):
BIO. After using this facility:
How often do you notice tire crumbs, dirt, or debris
Every Time Often Sometimes
on your child's body? 3 2 1
Rarely/Never
0
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Standard Operating Procedure for Administering the Facility Child User Questionnaire
in your car?
in your home?
In your laundry room/mudroom?
in living room?
in your child's bedroom?
in your bathroom(s) your child uses?
0
0
0
0
0
0
Post-Use Hygiene Practices Questions
For the following questions, please use one of the four responses (every time, often,
sometimes, or rarely/never):
Bll. After using this facility:
How often does your child shower and change
clothes immediately after engaging in activities on
the synthetic turf at this facility?
Every Time Often Sometimes Rarely/Never
3 2 1 0
How often does your child's shoes/equipment get
wiped or removed before entering your home?
For the following questions, please use one of the six responses (never, once a month, 2 to 3 times a month,
once a week, 2-3 times a week, or four or more times a week).
B12. At other locations:
Never
Once a 2 to 3 Once a
month times week
a
month
How often has your child played on any other synthetic
turf fields during the past year?
2 to 3 4 or
times more
a week times
a week
How often has your child played on any synthetic turf 0 1 2 3 4 5
fields in the last five years?
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Standard Operating Procedure for Administering the Facility Child User Questionnaire
How often has your child played on any natural grass 0 12 3 4
fields during the past year?
How often has your child played on any natural grass
turf fields in the last five years?
How often has your child played on playgrounds with 0 12 3 4
rubber mulch, mats or synthetic turf during the past
year?
How often has your child played on playgrounds with 0 12 3 4
rubber mulch, mats or synthetic turf during in the last
five years?
General Hygiene Questions
B13. How many times in general does your child wash their hands per day?
B14. How many times in general does your child bathe or shower per week?
General Demographic Questions
Dl. How old is your child?
D2. Is your child male or female? U Male U Female 'J Refused
D3. Do you consider your child to be Hispanic or Latino? (J Yes J No O Refused
D4. Which of the following categories best describes your child's race? (select one or more)
q Native American
Indian or Alaska
Native
q Asian
Q Black or African
American
ij Native Hawaiian or
Other Pacific
Islander
White
q Refused
q Don't know
D5. How tall is your child?
(ft)
in
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D6. How much does your child weigh?
(lbs)
D7. What is your child's current grade in school?
ij Other
i 1 Refused
o
2nd
o
6th
o
3rd
o
7th
o
4th
o
8th
o
5th
o
gth
Specify other grade
That concludes the surve
y. Thank you for your time. I know that your time is valuable.
If you have any questions or concerns, please, refer to the contact sheet for information
on who to contact.
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Appendix B: Questionnaire COC form3
FD IDb
Site ID
PID
Received
Comments
Date
Initials
a For hardcopy versions, place n/a in the flash drive ID column
bFlash drive ID
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D-SED-EHCAB-003-SOP-01
U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for Administering the Facility Adult User
Questionnaire
Number: d-sed-ehcab-oo3-sop-oi
Effective Date: August 15,2016
SOP was Developed 0 In-house D Extramural
Alternative Identification: EIB-003-01
SOP Steward
Name: Marsha K. Morgan
Digitally signed by MARSHA MORGAN
MARSHA MORGAN „ August 9,2016
Signature: D„ Date:
Approval
Name: Kent W. Thomas
Title: Tire Crumb Leader
Digitally signed by KENT THOMAS
DN: c=US, o=U.S. Government, ou=USEPA, ou=Staff,
-i=KEN T TH OM AS, d nQual i fi er=0000015 373
C - ¦ , KENl THOMAS cn=KtNMHuMA5,dr,'ju3 litier=00000l 5 575 , A..«..~+ -1 n inic
Signature: Date: August 10,2016
Concurrence^
Name: Brittany Stuart
Title: QA Manager, Systems Exposure Division
Signature: BRITTANY STUART - Date: August 15, 2016
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TABLE OF CONTENTS
1.0 SCOPE AND APPLICATION 3
2.0 SUMMARY 01 THE METHOD 3
3.0 DEFINITIONS 3
4.0 CAUTIONS 3
5.0 RESPONSIBILITIES 3
6.0 MATERIALS 4
7.0 PROCEDURES 4
8.0 RECORDS 5
9.0 QUALITY CONTROL AND QUALITY ASSURANCE 5
10.0 REFERENCES 5
Appendix A. Facility Adult User Questionnaire 6
Appendix B. Questionnaire COC form 15
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
1.0 SCOPE AND APPLICATION
The Facility Adult User Questionnaire is used to collect data from adults and older children (> 13 years
old) who routinely play on artificial turf fields that contain tire crumb infill at athletic facilities. The
purpose of the questionnaire is to collect information on the participants' activity patterns that may
impact the magnitude and frequency of their exposures to chemicals found in crumb tire infill.
2.0 SUMMARY OF THE METHOD
Research staff administer the Facility Adult User Questionnaire to adults/older children who routinely
play on artificial turf fields using a computer-assisted interview (CAI) method. The questionnaire is used
to record specific types of data about the participants including demographics (i.e., age, gender, and
race), education levels, activity-levels, types and frequency of sports played on fields, frequency and
duration of field use, hygiene practices (e.g., hand washing and eating events), types of clothing worn,
and contact rates on turf for different types of activities. Using a laptop computer, research staff open
the Facility Adult User Questionnaire via the Epi Info software program and ask the participants each
question and record their responses. Research staff save all responses recorded in the questionnaires
prior to exiting the Epi Info software program. They also make a backup copy of all questionnaire
responses using a portable flash drive.
3.0 DEFINITIONS
SOP - Standard operating procedure
CAI - Computer-assisted interview
COC - Chain-of-custody
PID - Participant identification number
4.0 CAUTIONS
Research staff must keep all completed participant questionnaires on the laptop computer and portable
flash drive in a secure location at all times.
5.0 RESPONSIBILITIES
5.1 The EPA Database Manager will be responsible for providing the questionnaire (Epi Info and PdF
versions) to the EPA Tire Crumb Team Leader.
5.2 The EPA Tire Crumb Team Leader will be responsible for providing the questionnaire to the
appropriate research staff responsible for questionnaire administration.
5.3 The research staff member(s) designated to administer the questionnaire will be responsible for
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
completing the participant questionnaires. They are also be responsible for returning the completed
questionnaires (via portable flash drives), including chain-of-custody (COC) forms, to the EPA Tire
Crumb Team Leader.
6.0 MATERIALS
6.1 Laptop computer
6.2 Epi Info software, version 7.1.5
6.3 Adobe Acrobat XI Pro
6.4 Encrypted, portable USB thumb drives (see Reference section)
6.5 COC sheets
7.0 PROCEDURES
7.1 Administration of the Questionnaire (See Appendix A)
7.1.1 Turn on the designated laptop computer (password protected) assigned to this project.
7.1.2 Open the Epi Info software program located on the desktop of the laptop computer. On the main
screen of this software program, click on the "Enter Data" button. At the top of the screen, click on
"Open Form" and then click on the button (with three dots) to open a current project folder. Next, find
the Tire Crumb Adult Questionnaire folder located under Epi Info 7 Projects Folder. In this folder,
select the Adultlnfo.prj file, click the "Open" button, and then the "OK" button.
7.1.3 At the top of the screen, click on the "New Record" button. This questionnaire has a total of 21
questions. Record the participant identification number (PID; obtained from the EPA Tire Crumb
Research Leader), facility name, interview date, study ID number, facility location, and interviewer ID
number at the top of the questionnaire form.
7.1.4 Begin the questionnaire. Ask the participant the first question and record his/her response to the
question. Repeat this procedure for each question.
7.1.5. After the questionnaire is completed go to the top of the screen, select "File" and click on the
"Save" button and save the file as "AdultQuestionnairePIDXX (example: AdultQuestionnairePIDOl).
7.1.6 For the next participant, repeat steps 7.1.3 - 7.1.5.
7.1.7 Exit the Epi Info software program by selecting "File" at the top of the screen and then click on
"Exit".
7.1.8 Make a backup copy of the Tire Crumb Adult Questionnaire folder using only the study
designated portable flash drive. Label the flash drive with a unique identifier (example: TCRS:Adult
Questionnaire). *A11 adult questionnaire files will be uploaded to this one flash drive.
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8.0 RECORDS
COC forms (Appendix B) will be used to document the transfer of the participant questionnaire data.
9.0 QUALITY CONTROL AND QUALITY ASSURANCE
Proper COC records shall be kept documenting the transfer and receipt of all questionnaire data
by EPA's Tire Crumb Team Leader at the EPA laboratory in Research Triangle Park, NC.
10.0 REFERENCES
Quality Assurance Project Plan, Activity Characterization for the Tire Crumb Research Study,
National Exposure Research Laboratory, Research Triangle Park, N.C., 2016.
Epi Info 7 User Guide. 2016. https://wwwn.cdc.gov/epiinfo/user-auide/
How to securely encrypt a USB flash drive, http://www.online-tech-tips.com/computer-tips/encrypt-
usb-flash-drive/ (accessed on June 24, 2016).
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Appendix A: Facility Adult User Questionnaire
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
Form Approved
OMB No. 0923-0054
Exp. Date 01/31/2017
Adult/Adolescent Field User Questionnaire
PID
Facility Name
Interview Date
Site ID Number
Facility Location
Interviewer ID
Interviewer: I would like to ask you some questions about activities that may affect your exposures to, and
contact with synthetic turf fields that contain crumb rubber materials.
Field Contact Frequency and Duration Questions
Interviewer: I have several questions about the time you spend on synthetic turf fields at this facility.
(years)
Bl. How long have you been coming to this facility?
(months)
B2. Specifically on the synthetic fields at this facility, what sports, physical education classes, or other
activities have you actively participated in by season (specify) over the past year?
Season
Sport
Specify Other
ATSDR estimates the average public reporting burden for this collection of information as 30 minutes per response,
including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data
needed, and completing and reviewing the collection of information. An agency may not conduct or sponsor, and a
person is not required to respond to collection of information unless it displays a currently valid OMB control
number. Send comments regarding this burden estimate or any other aspect of this collection of information
including suggestions for reducing this burden to CDC/ATSDR Reports Clearance Officer; 1600 Clifton Road, MS
D-74, Atlanta. GA 30333, ATTN: PRA (0923-0054).
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
B3. Over the past year, how many days per week by season have you typically spent on the synthetic fields at
this facility?
Spring
Summer
Fall
Winter
(days per week)
(days per week)
(days per week)
(days per week)
B4. Over the past year, how many hours per day by season have you typically spent on the synthetic fields
at this facility?
Spring
Summer
Fall
Winter
(hours per day)
(hours per day)
(hours per day)
(hours per day)
B5. Over the past year, what was the longest period of time that you spent on the synthetic fields at this
facility during a single day?
(number of hours)
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
Contact Types and Scenarios per Each Type of Field Use
Interviewer: I have several questions about the kinds of activities that you take part in specifically on synthetic
turf fields installed at this facility.
For the following question, please use one of the three responses (often, sometimes, and rarely/never). "Often"
means > 50% of the time and "sometimes" means < 50%.
B6. How frequently do you do the following activities while on synthetic fields at this facility each season?
Dive on Fallon Sit on turf Eat snacks Drink
ground ground
Spring
Summer
Fall | | | | | | | | |
Winter
Inhalation Exposure-Related Questions
B7. When using synthetic fields at this facility:
What % of your time are you highly active, for example, running?
What % of your time are you moderately active, for example, jogging?
What % of the time do you have low activity, for example, walking?
What % of the time are you resting, for example, sitting or standing?
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
Dermal and Non-dietary Ingestion Exposure-related Questions
For the following questions, please use one of the four responses (every time, often, sometimes, or
rarely/never):
B8. When using synthetic turf fields at this facility:
Every Time Often Some Rarely
times /Never
How often do you chew gum?
3
2
0
How often do you use a mouth guard?
3
2
0
How often do you eat?
3
2
0
How often do you drink?
3
2
0
How often do you play in the rain?
3
2
0
How often do you wipe your hands with a hand wipe before eating?
3
2
0
How often do you sweat heavily?
3
2
0
How often do you touch the turf with your hand?
3
2
0
How often do you touch the turf with your other body parts
3
2
0
excluding hands?
How often do you sit on the turf with bare skin wearing shorts?
3
2
0
How often are you barefooted on the turf?
3
2
0
How often do you play with the turf materials or rubber granules?
3
2
0
How often do you touch your mouth with your hands or fingers?
3
2
0
How often do you place non-food objects in your mouth like
3
2
0
toothpicks, or pens or use your mouth to hold an object?
If rarely/never, skip next.
What type of object do you most often place in your mouth while at
this facility?
How often to you get cuts or abrasions from contact with the turf? 3 2 10
If rarely/never, skip next.
What is the body part that usually has the most cuts or abrasions:
knee, elbow, hand, thigh, shin, or other?
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
B9. What clothing do you typically wear in this facility during each season (check all that
apply)?
Spring
Summer
Fall
Winter
Shorts
~
Short-sleeve shirt
~
Long pants
~
Long-sleeve shirt
~
Gloves
~
Socks
~
Helmet
~
Hat
~
Pads
~
Tire Crumb Take-Home Questions
For the following questions, please use one of the four responses (every time, often, sometimes, or
rarely/never):
BIO. After using this facility:
How often do you notice tire crumbs, dirt, or debris
on your body?
in your car?
in your home?
In your laundry room/mudroom?
In your living room?
In your bedroom?
In your bathroom(s)?
Every Time
3
3
3
3
3
3
3
Often
2
2
2
2
2
2
2
Some
imes Rarely/Never
0
0
0
0
0
0
0
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
Post-Use Hygiene Practices Questions
For the following questions, please use one of the four responses (every time, often, sometimes,
or rarely/never):
Bll. After using this facility:
Every Time Often Sometimes Rarely/Never
How often do you take shower and change clothes 3 2 1 0
immediately after engaging in activities on the
synthetic turf at this facility?
How often do you take actions to prevent tire 3 2 1 0
crumbs from getting into your car?
How often do you wipe or remove shoes/equipment 3 2 1 0
before entering your home?
For the following questions, please use one of the six responses (never, once a month, 2 to 3 times a month,
once a week, 2-3 times a week, or four or more times a week).
B12. At other locations:
Never
Once a
month
2 to 3
times a
month
Once a
week
2 to 3
times
a week
4 or
more
times a
week
How often have you played on any other
synthetic turf fields during the past year?
How often have you played on any
synthetic turf fields in the last five years?
How often have you played on any natural
grass fields during the past year?
How often have you played on any natural
grass turf fields in the last five years?
How often have you played on
playgrounds with rubber mulch, mats or
synthetic turf during the past year?
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
How often have you played on 0 1 2 3 4 5
playgrounds with rubber mulch, mats or
synthetic turf during in the last five years?
General Hygiene Questions
B13. How many times in general do you wash hands per day?_
B14. How many times in general do you bathe or shower per week?
General Demographic Questions
Dl. How old are you?
D2. Are you male or female? (J Male (J Female O Refused
D3. Do you consider yourself to be Hispanic or Latino? (J Yes No Refused
D4. Which of the following categories best describes your race? (select one or more)
o
Native American
Indian or Alaska
Native
O
Black or African
American
O
White
O
Don't know
o
Asian
O
Native Hawaiian or
Other Pacific
Islander
O
Refused
D5. How tall are you?
(ft)
in
D6. How much do you weigh?
(lbs)
I? yes
D7. Are you still in school? | | yes
If so, what is your current grade in school?
no
O 1011
8th
11th
gth
12th
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
q Technical School Q College q Graduate School
q Other (j Refused
Specify Other Grade
D8. If No, what is your highest education level?
q 11th or less Q High School Graduate/ GED
q Some College Q College Graduate School
(«) Other
D9. What is your occupation?
ij Post High School Training
(j Post-graduate
q Refused
This concludes the survey. Thank you for your time. I know that your time is valuable.
If you have any questions or concerns, please, refer to the contact sheet for information on who
to contact.
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D-SED-EHCAB-003-SOP-01
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Standard Operating Procedure for Administering the Facility Adult User Questionnaire
Appendix B: Questionnaire COC form3
FD IDb
Site ID
PID
Received
Comments
Date
Initials
a For hardcopy versions, place n/a in the flash drive ID column
bFlash drive ID
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[This page intentionally left blank.]
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^'T4%
$ o \
mj
PRO**
U. S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Exposure Methods and Measurements Division
Air Quality Branch
STANDARD OPERATING PROCEDURE
SOP Title: Standard Operating Procedure for Determination of Volatile Organic
Compounds Desorbed from Sorbent Tubes Using the Markes International
Ultra/Unity Thermal Desorption System for the Tire Crumb Research Study
SOP ID: D-EMMD-AQB-SOP-3465-O
Effective Date: October 1, 2016
SOP was Developed: ~ In-house IE] Extramural: Jacobs WA 3-111
SOP Discipline*: Organic Chemistry
Alternative Identification: #D-EMMD-AQB-018-SOP-01
SOP Contact Signature
Name: Karen Oliver
Signature/Date:
Management Signature
Name: Surender Kaushik
Title: Branch Chief
Signature/Date:
(Tad Kleindienst signing on behalf of Surender Kaushik)
QA Signature
Name: Sania Tong Argao
Title: Quality Assurance Manager
Signature/Date:
*See discipline descriptions on the NERL Scientific and Technical SOP intranet site.
-------
Revision History
Revision
No.
Name
Date of
Revision
Description of Change(s)
1
Karen Oliver
11/21/2018
This SOP was revised to reflect current
Division and Branch. Previous EMMD ID #D-
EMMD-AQB-018-SOP-01.
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D-EMMD-AQB-SOP-3465-0
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Standard Operating Procedure for Determination of
Volatile Organic Compounds Desorbed from Sorbent
Tubes Using the Markes International Ultra/Unity
Thermal Desorption System for the Tire Crumb
Research Study
Contributors
Karen Oliver
National Exposure Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC
Tamira Cousett
Jacobs Technology Inc.
Research Triangle Park, NC
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Contents
Section Page
I.0 Scope and Application 3
2.0 Summary of Method 4
3.0 Definitions 4
4.0 Health and Safety 4
5.0 Interferences 5
6.0 Personnel Qualifications 5
7.0 Equipment and Supplies 5
8.0 Reagents and Standards 6
9.0 Quality Control and Quality Assurance 6
10.0 Standards Preparation 7
II.0 Procedures 7
12.0 Data and Records Management 16
13.0 Method Performance 16
14.0 Maintenance and Troubleshooting 17
15.0 References and Supporting Documentation 19
Appendix A: VOC Method Parameters 21
Appendix B: VOC PAH Method Parameters 22
Appendix C: Markes Unity Almsco GC-MS TOF analysis sheet 25
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Scope and Application
1.1 This standard operating procedure (SOP) is applicable to the determination of volatile
organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and non-targeted
compounds of interest using the Markes International gas chromatograph-mass
spectrometer (GC-MS) time-of-flight (TOF) system following desorption from sorbent
tubes using the Markes International thermal desorber 50:50 (TD 50:50) and the Unity 2.
The TD 50:50 serves as an auxiliary thermal desorption unit that is capable of desorbing
up to 100 sorbent tubes in one analytical sequence. Primary tube desorption occurs in the
TD 50:50, and collected analytes are transferred to the Unity 2, focused on the cold trap,
desorbed off the trap, and transferred to the GC for further separation before final
quantitation in the TOF MS. The analysis method for VOCs, Tire Crumb Compounds and
non-targeted compounds is provided in Appendix A.
1.2 This SOP is written as a companion to D-EMMD-AQB-017-SOP-01, "Standard Operating
Procedure for Determination of Volatile Organic Compounds Desorbed from Sorbent
Tubes Using the Markes International BenchTOF-Select GC-MS TOF System for the Tire
Crumb Research Study."
1.3 The following VOCs are the compounds of interest from the EPA Compendium Method
TO-14A target list (U.S. EPA, 1999a), PAHs of interest from the EPA Compendium
Method TO-13A target list (U.S. EPA, 1999b), and target Tire Crumb Research Study
(TCRS) compounds of interest from in-house pilot studies.
VOCs
1.2-Dichloro-1,1,2,2-
tetrafluoroethane
1.3-Butadiene
Trichlorofluoromethane
1,1 -Dichloroethene
1,1,2-Trichloro-1,2,2-
trifluoroethane
1,1 -Dichloroethane
cis-1,2-Dichloroethene
1,2-Dichloroethane
1,1,1 -T richloroethane
Benzene
Carbon tetrachloride
1,2-Dichloropropane
Trichloroethene
Toluene
T etrachloroethene
Chlorobenzene
Ethylbenzene
m,p-X ylene
Styrene
o-Xylene
4-Ethyltoluene
1,3,5-
T rimethylbenzene
m -Dichlorobenzene
/;-Dichlorobcnzcnc
o-Dichlorobenzene
PAHs
Naphthalene
Acenaphthalene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Tire Crumb
fert-butylamine
/ram-2-butcnc
cy.v-2-butcnc
Methyl isobutyl
ketone
Benzothiazole
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2.0 Summary of Method
VOCs are desorbed from sorbent tubes that have been previously exposed using D-EMMD-AQB-
016-SOP-01, D-EMMD-AQB-015-SOP-01, or D-EMMD-AQB-007-SOP-01 and conditioned
using D-EMMD-AQB-008-SOP-01 (Markes TC-20 tube conditioner). The tubes are fitted with a
stainless steel DiffLok cap on the rear end (outlet) of the tube while an inert coated stainless-steel
cap is placed on the grooved end (inlet) of the tube. Tubes are loaded horizontally into the sampling
trays with the fritted (grooved) end of the tube (inlet) pointing toward the right-hand side. An
analytical sequence is created and initiated using the Ultra-TD software to select the appropriate
desorption method and run the sequence. The TD 50:50/Unity 2 method for determining VOCs,
TCRS compounds and non-targeted compounds is summarized in Appendix A.
An additional method has been optimized on the system to desorb VOCs and PAHs from
Carbograph 2 TD and Carbograph 1 TD dual-bed sorbent tubes. This method is referred to
throughout the SOP as the VOC PAH method and is not in the scope of daily laboratory analytical
practices; the operating parameters and compound target lists are specified separately in Appendix
B(VOC_PAH method).
Definitions
D1
duplicate
PAH
polycyclic aromatic hydrocarbon
DQO
data quality objective
ppbv
parts per billion by volume
ECC
electronic carrier control
pptv
parts per trillion by volume
GC
gas chromatograph
psig
pounds per square inch gauge
FB
field blank
PTFE
polytetrafluoroethylene
FS
field spike
SA
sample
ID
identification
SB
shipping blank
in.
inch
SOP
standard operating procedure
MDL
method detection limit
TCRS
tire crumb research study
MFC
mass flow controller
TD
thermal desorber
min
minute
TOF
time of flight
mL
milliliter
VOC
volatile organic compound
MS
mass spectrometer
4.0 Health and Safety
4.1 Gases in high-pressure cylinders are in use in this laboratory. Operators must exercise
extreme care in working with high-pressure gas cylinders.
4.2 Certain areas of the Markes International TD 50:50/Unity 2 are extremely hot, so caution
should be used when attempting to retrieve a hot or jammed tube. Also, the power to the TD
50:50 should be switched off when attempting to retrieve a jammed tube and when
troubleshooting and performing routine maintenance.
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5.0 Interferences
5.1 Prior to sampling, sorbent tubes should be conditioned for 1 hour using the tube
conditioning procedure described in D-EMMD-AQB-008-SOP-01 (Markes TC-20) to
remove any VOC contaminants. This process should remove any contaminants that are
residual from prior sampling or that might have outgassed from the sorbent. Conditioning
specifications for sorbent tubes are provided by the manufacturer and should be executed
per manufacturer protocol.
5.2 Prior to analysis, all sorbent tubes must be loaded with internal standards as described in
SOP D-EMMD-AQB-015-SOP-01.
5.3 Two laboratory blanks should be analyzed at the beginning of every desorption sequence
using a conditioned sorbent tube to remove any VOC contaminants from the trap that might
have been adsorbed from the helium purge gas or outgassed from the sorbent in the trap.
5.4 Leak tests should be performed during each analytical run. If repeated leak test failures
occur, see the Unity 2 Troubleshooting Guide, the Unity 2 Operators' Manual, the Markes
International Leak Locating Guide, and the Markes International Thermal Desorption
Training Guide.
5.5 The O-rings located inside of the DiffLok caps might need to be changed periodically due
to wear. See the thermal desorption training guide for O-ring replacement.
5.6 The Peltier cooling will not function properly if the dry gas supply is not switched on. The
dry gas supply must be set to 50-60 psi and have a dew point of less than -50 °C or ice will
form on the Peltier coolers.
5.7 Tubes and their associated DiffLok caps should be handled by the operator only when
wearing either clean white cotton or nitrile gloves to prevent contamination from skin oils
and the VOCs they contain.
Note: DiffLok caps used on sorbent tubes loaded with only VOCs should not be used
interchangeably with sorbent tubes loaded with VOCs and PAHs to ensure there is no cross
contamination of PAHs.
6.0 Personnel Qualifications
Personnel should have knowledge of the following:
• General laboratory safety practices including appropriate cylinder-handling procedures.
• Sorbents, breakthrough volumes, flowmeters, mass flow controllers (MFCs), computer
spreadsheets, thermal desorption, gas chromatography, mass spectrometry, data analysis and
validation, and general instrument troubleshooting.
7.0 Equipment and Supplies
The following equipment and supplies are needed:
• Markes International Thermal Desorber 50:50 (Markes International, Llantrisant, UK).
• Markes International Unity 2 (Markes International).
• Markes International BenchTOF-Select (Markes International).
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D-EMMD-AQB-SOP-3465-0
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• Markes International TOF-DS Software V 1.3 (Markes International).
• Markes International User Software V 5.1.103 (Markes International).
• Markes International CIA Advantage Software V 5.1.103 (Markes International).
• Computer with Windows 7 64-bit (English edition), Quad core, Intel Xeon E3-1225 v3 or
equivalent processor, 8 GB DDR3 memory, 10 GB free space, 1920 x 1080 resolution graphics
card and 1920 x 1080 monitor.
• TO-15/TO-17 air toxics focusing trap, part no. U0T15ATA-2S, for Unity 2, Markes
International).
• Clean cloth gloves (part no. 11-462-26B, Thermo Fisher Scientific, Waltham, MA) or nitrile
gloves (part no. 55091, 55092, or 55093, Kimberly-Clark, Neenah, WI).
• Peek tubing (part no. SERZ-0108, 1/6" o.d. x 0.03" bore, 1M, Markes International)
• DiffLok Caps, %-inch stainless steel inert coated (part no. C-DLS10, Markes International).
• DiffLok Caps, %-inch stainless steel (part no. DL010, Markes International).
• Assorted wrenches.
• CapLok tools (Markes International).
• Low-emission Viton O-rings, sizes 006, 007, and 010 (part no. U-COV06, U-COV07, and U-
COV10, respectively, Markes International).
• Ultra/TD-100 O-ring insertion tool (part no. SERMTD-1382, Markes International).
• Filter disk, sintered PFTE, 5.11m, pack of 10 (part no. U-DISK1, Markes International,).
8.0 Reagents and Standards
• Cylinder gas, research-grade helium (AirGas, Morrisville, NC).
• Cylinder gas, ultra-high-purity nitrogen (AirGas).
• Daily external check standards loaded diffusively in the exposure chamber (D-EMMD-AQB-
007-SOP-01) or the climate-controlled exposure chamber (D-EMMD-AQB-016-SOP-01).
T014A VOC Standards and internal standards may also be loaded using the active-loading
system (see D-EMMD-AQB-015-SOP-01).
9.0 Quality Control and Quality Assurance
9.1 The TD 50:50/Unity 2 automatically performs a leak test on the tube and the trap prior to
each desorption to verify that the seals at these locations are tight to prevent sample loss.
9.2 The sorbent focusing trap is conditioned by analyzing two laboratory blanks using
conditioned sorbent tubes at the beginning of every desorption sequence to remove
contaminant VOCs.
9.3 Sorbent tubes are conditioned using a 1-hour tube conditioning cycle as described in D-
EMMD-AQB-008-SOP-01 (Markes TC-20) prior to sample collection to remove
contaminant VOCs. Sorbent must be conditioned as specified in protocols provided by the
manufacturer.
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D-EMMD-AQB-SOP-3465-0
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9.4 During diffusive sampling, samples can be exposed alone or in pairs depending on the data
quality objectives (DQOs) of the study. The criteria for acceptable results for duplicate
analytical precision, as defined in Compendium Method TO-17, Section 14, "Performance
Criteria for the Solid Adsorbent Sampling of Ambient Air," require agreement within 20%
for duplicate pairs (U.S. EPA, 1999b).
9.5 Depending on the DQOs of a study, laboratory and/or field blanks may be included at the
beginning of the desorption sequence following the helium blank.
9.6 Depending on the DQOs of a study, two to three daily external check standards are included
in each desorption sequence. These standards are used to gauge filament wear in the mass
spectrometer and system stability. Daily external check standards are compared to the
original external check standards that were analyzed with the initial calibration to
determine if VOC concentrations are within ±30% of the current calibration range.
9.7 Internal standards are manually loaded on to each sorbent tube prior to analysis as
described in D-EMMD-AQB-015-SOP-01, to account for instrument drift. The responses
of the internal standards are used by the GC-MS TOF software for calculation of compound
concentrations and by the operator to monitor changes in the sensitivity of the analytical
system. The responses of internal standard compounds should be monitored daily to ensure
their response remains steady. Decreased response for these compounds indicates the
system might need to be optimized and calibrated. See the Markes International
BenchTOF-Select operators" manual for more information. Internal standards are loaded
onto each tube to be analyzed by the instrument. The internal standard consists of four
components: 4-bromofluorobenzene, chlorobenzene-d5, 1,4-difluorobenzene, and
bromochloromethane.
10.0 Standards Preparation
Standards are loaded diffusively onto the sorbent tubes by using an exposure chamber as described
in D-EMMD-AQB-007-SOP-01 or D-EMMD-AQB-016-SOP-01. Standards may also be prepared
using the active loading system as detailed in D-EMMD-AQB-015-SOP-01.
11.0 Procedures
11.1 Establish Communication with the TD 50:50/Unity 2 Thermal Desorber
Power on the TD 50:50 and Unity 2 by pressing the power switch located on the back of
each instrument. After each instrument is powered on, the following procedures are used
to establish communication between the TD 50:50 and Unity 2, instruments using the TD
50:50 instrument interface screen on the desktop computer designated for instrument
control:
1. Turn on the desktop computer.
2. Double click the Ultra TD-Tubes icon on the desktop.
3. When the Ultra TD dialog box opens, the last sequence table that was analyzed will
appear. On the upper toolbar, click File > New > Sequence or click the New
Sequence icon.
^ I
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Desorbing VOCs on Ultra/Unity TD
D-EMMD-AQB-SOP-3465-0
Revision 0
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4. When the blank sequence table appears on the screen (Figure 1), right click on any
portion of the new sequence table and select Add Set of Tubes (Figure 2).
•v. tirff SiiTjirTC*
Fk-iyck
I
Siqtira'/iiMi
Flip&tfu
St«
1YPE 1 N*»>J
| Tybf |
Figure 1. New sequence table.
Mew Sequence
Open Sequence
Add Sequence
Add Set of Tubes
Delete Item
Figure 2. Adding a set of tubes.
5. When the Select Method dialog box (Figure 3) and "Add New Set" dialogue box
appears on the screen, select the desired method and click Open. (For the scope of
daily laboratory activities, the VOC and non-targeted method is named,
"25tolOS_4min_16mLpurge_Desorb315_CarbopackX_no hit stdl 00416_gc cycle
time 47min.mth.)
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Desorbing VOCs on Ultra/Unity TD
D-EMMD-AQB-SOP-3465-0
Revision 0
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Figure 3. Selecting the desired method.
6. In the Add New Set dialog box (Figure 4), set the first and last tube numbers using the
drop-down menus. For instance, if the operator wishes to analyze 23 tubes in slots 1-23,
the first tube would be " 1" and the last tube would be "23." Note: The No. of Injection
is set to "1".
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7. In the Re-collection field, select "Same" from the drop-down menu to ensure sample is
collected back onto the same sorbent tube from which it was desorbed.
8. Select OK after the first and last tubes have been set.
9. Click the + sign to expand the samples list for the new set of tubes. The sequence table
will populate a row for each sample to be analyzed with the same name and method
(Figure 5).
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D-EMMD-AQB-SOP-3465-0
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10. Iii the Set column of the sequence table, click on the auto-generated sample identification
(ID) code to highlight it in blue, and then enter the tube ID number in this field (Figures
6a and 6b). Be sure to enter the tube ID numbers in the order that the tubes will be
analyzed.
Set
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Figure 6a. Selecting the auto-generated tube ID.
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11. Once the tube numbers have been entered, click File > Save As and enter the sequence
name with the current days" date in the MMDDYY format, and then click Save (Figure
7). Note: If more than one sequence is run on a day, a unique identifier should be placed
at the end of the sequence name such as MMDDYYA or MMDDYYB, as not to
overwrite other sequences run on a particular day.
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11.2 Set and Adjust Initial Flow Rates
Gas flows are set and measured using the electronic carrier control (ECC) function. The
ECC function uses an internal MFC to set and measure gas flows without operator
intervention. Column head pressure is monitored by the GC at the head of the column, and
any variations in pressure are compensated for at the supply. Total flow can be read from
the GC. Flows can be confirmed with a flow meter.
Significant inconsistencies in flows tend to indicate problems with the TD 50:50 or the
Unity 2. Due to the use of MFCs, flow inconsistencies can be more difficult to diagnose as
all flow settings and readouts are digitally controlled. The operator should monitor
chromatography carefully as this is the area in which flow inconsistences will have the
greatest impact.
11.3 Load the Carousel
Although the number and type of samples, blanks, and standards will vary depending on
the DQOs of the project, a rough ordering and brief explanation of tubes on the sample
carousel is as follows:
• Laboratory blank: a conditioned, unexposed sampling tube that has remained in the
laboratory. Two blanks are run at the beginning of the sequence to determine trap
background levels.
• Field blank (FB): conditioned, unexposed sampling tube transported to the field and
back.
• Field Spike (FS): laboratory-exposed 2.0 ppbv sampling tubes transported to the field
and back.
• Laboratory Control (LC): the field.
• Shipping blank (SB): unused spare tube transported to the field and back
• Daily external check standard: a sampling tube passively loaded with the calibration
mixture at a designated concentration level for 24 hours (D-EMMD-AQB-007-SOP-
01 or D-EMMD-AQB-016-SOP-01) actively loaded standards are also available for
use (D-EMMD-AQB-015-SOP-01). Daily check standards are used to monitor
filament wear and system stability. The daily check standards are analyzed at the
beginning, middle, and end of the sample batch to ensure the system remains within
±30% of the calibration range during analysis.
A typical sample batch consists of two laboratory blanks at the beginning of the sequence,
two additional laboratory blanks within the sequence, 18 samples, and three standards for
a total of approximately 27 analyses, which are completed in approximately 27 hours.
Tubes loaded into tube trays for analysis must be QA checked to ensure that tube numbers
are correct and have been loaded in the correct order. The sequence table created in the
TOF-DS software (see D-EMMD-AQB-017-SOP-01) and written on the Markes Unity
Almsco GC-MS TOF analysis sheet (Appendix C) must also be checked for correct tube
order and numbers.
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Use the following procedure to load the carousel:
1. Verify that the cylinder valves and the regulator outlet valves are open and that the
regulator outlet pressure is set at the correct value (research helium = 50-60 psig).
2. Open the TD 50:50 door and remove the first tray to load the first 10 tubes in the
analytical sequence (Figure 8). Note: The door of the TD 50:50 should never be opened
during analysis.
Figure 8. Opening the TD 50:50 door to access tube trays.
3. While wearing either white cotton or nitrile gloves, load the top sample tray labeled 1 -
10, starting with the tube slot in the back of the tray, with the laboratory blanks, sample,
and standard sorbent tubes (with DiffLok caps on both ends) by placing them
horizontally in the numbered slots with the fritted (grooved) end of the tube (inlet)
pointing toward the right-hand side and the rear end of the tube (outlet) pointed towards
the left-hand side of the tube tray (Figure 9).
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Figure 9. Loading sorbent tubes into the TD 50:50 tube tray.
4. When all slots of the first tray have been loaded with tubes, insert the tray back into
the top slot of the TD 50:50. Guide the tray into the slot slowly until a single click is
felt and gently pull back on the tray. This click indicates the tray is properly seated
(Figure 10).
Figure 10. Loading the sample tray into the TD when full.
5. Repeat steps 2-4 with tube trays 2-10 in the TD until all sampling tubes are loaded.
Be sure to remove and load one tray at a time in the order in which tubes trays are
stacked inside the TD.
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11.4 Run the Ultra TD 50:50 and Unity 2 Analysis Sequence
Use the TOF-DS analytical software to create the TOF GC-MS sequence table (sample list)
and initiate an analytical sequence as described in detail in D-EMMD-AQB-017-SOP-01.
Initiate the analysis sequence on the system computer as follows:
1. Follow the steps in section 11.1 to open the software and create the sequence table.
2. Click on the three tabs of the method dialog box: Pre-desorption, Tube/Sample
desorption, and Trap Settings to ensure settings match those specified for the method.
The VOC and non-targeted method parameters are detailed in Appendix A.
3. Once method settings are verified, click the first sample in the sequence table and click
the start icon ([) to begin the TD 50:50 and Unity 2 sequence. An internal schematic
of the Unity 2 system will appear on screen when the sequence begins (Figure 11).
Figure 11. Unity 2 Schematic during desorption.
4. Click on the Sequence Reporter tab of the sequence table to review desorption
parameters as sorbent tubes are desorbed (Figure 12). Throughout the analysis of
samples, it is helpful to view this tab periodically to ensure no tube leak or system leaks
occur. Note: If tube or system leaks do occur, contact the principal investigator to
initiate troubleshooting efforts.
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C:\ProgfamData\Marke5 TD\Methc>d£\051S16.£.eq (Controlling Sequence)
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Note: After the samples have been desorbed, they are stored until data is reviewed. Prior
to re-use, tubes must be conditioned and stored as described in D-EMMD-AQB-008-SOP-
01 (Markes TC-20) prior to use.
12.0 Data and Records Management
12.1 The operator must maintain a laboratory notebook in which the experimental and sample
details are recorded.
12.2 The operator must record the date that each cylinder gas is changed in the Markes
International gas logbook.
12.3 Service on the Ultra TD 50:50 and Unity 2 must be documented in the maintenance
notebook.
13.0 Method Performance
13.1 Method detection limits (MDLs) on the order of 35 pptv for benzene have been achieved
for 24-hour exposures.
13.2 Laboratory experiments to evaluate issues such as reverse diffusion, temperature and
humidity effects, linearity of response, MDLs, and ozone effects, are discussed in
McClenny et al. (2005). These experiments were used to determine the subset of the
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TO-14A VOCs listed in Section 1.0 that can be determined using Carbopack X diffusive
sampling techniques.
14.0 Maintenance and Troubleshooting
14.1 The O-rings in the hot and cold nozzle of the TD 50:50 and the Viton O-rings on the Unity
2 sampling inlet must be periodically changed due to wear. Worn O-rings may result in
leak test failures. See the operators' manual, leak locating guide and thermal desorption
training guide for o-ring replacement.
Note: The TD 50:50 and the Unity 2 must be powered off during routine maintenance.
14.2 The trap O-ring and filter on the cool non-valve end of the trap should be changed when
trap changes occur or if poorly sealing O-rings are determined to be a leak source. Worn
O-rings can result in leak test failures.
14.3 The focusing trap in the Unity 2 may need to be changed periodically due to wear. This
change is generally performed by a Markes International technician during the annual
performance maintenance service call as heated valve seals are also replaced. After
installation of the new trap, trap conditioning is recommended using the parameters listed
in Table 1. Instructions for changing and conditioning the focusing trap are detailed in the
operators' manual.
Table 1. New Trap Conditioning Parameters
Trap Temperature (°C)
Hold Time (min)
200
10
250
10
300
10
350
30
350
30
350
30
14.4 The O-rings located inside of the DiffLok caps might need to be changed periodically due
to wear. See the thermal desorption training guide for O-ring replacement.
14.5 For routine maintenance procedures and suggested troubleshooting procedures for the
Ultra TD 50:50 and Unity 2, refer to the Unity 2 Troubleshooting Guide, the Unity 2
Operators' Manual, the Markes International Leak Locating Guide, and the Markes
International Thermal Desorption Training Guide. A suggested maintenance schedule is
given in Figure 14.
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Suggested maintenance schedule
Suggested maintenance frequencies are given below. However, in
some cases (depending on the application), items may need
replacing more frequently.
UNITY 1 and ?
Condition/change charcoal fitter
(split tube)
Replace/repack cold trap
Replace fused silica transfer line
Change sample tube O-rings/filters
Cold trap seals
TD-lOO
Condition/change charcoal filter
(split tube)
Replace/repack cold trap
Replace fused silica transfer line
Change sample tube O-rings/filters
Cold trap seals
Replace O-rings in DiffLok caps
Change nozzle seals
3 months1
12 months1
12 months
12 months, or if damaged/leaking
12 months, or if damaged/leaking
3 months1
12 months1
12 months
12 months, or if damaged/leaking
12 months, or if damaged/leaking
If damaged/leaking
If damaged/leaking
ULTri A
Replace O-rings in DiffLok caps If damaged/leaking
Change nozzle seals If damaged/leaking
Air Server 3/8, CIA 8 and CIA Advantage
Replace filter disks 12 months
Figure 14. Suggested maintenance schedule.
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15.0 References and Supporting Documentation
15.1 References
D-EMMD-AQB-003-SOP-01 (alternative ID: ECAB-151.1). 2016. Standard Operating
Procedure for Determination of Volatile Organic Compounds Desorbed from
Carbopack X Diffusive Sampling Tubes Using the Agilent 6890N/5975 GC-MSD.
U.S. Environmental Protection Agency, National Exposure Research Laboratory.
D-EMMD-AQB-005-SOP-01 (alternative ID: ECAB-153.0). 2013. Standard Operating
Procedure for Carbopack X Sorbent Tube Conditioning using CDS Analytical Model
9600 Tube Conditioners. U.S. Environmental Protection Agency, National Exposure
Research Laboratory.
D-EMMD-AQB-006-SOP-01 (alternative ID: ECAB-154.1). 2015. Standard Operating
Procedure for Desorbing Volatile Organic Compounds from Carbopack X Sorbent
Tubes Using the PerkinElmer TurboMatrix ATD. U.S. Environmental Protection
Agency, National Exposure Research Laboratory.
D-EMMD-AQB-007-SOP-01 (alternative ID: ECAB-155.1). 2015. Standard Operating
Procedure for Use of the Exposure Chamber for Loading Passive Sampling Devices
with Volatile Organic Compounds. U.S. Environmental Protection Agency, National
Exposure Research Laboratory.
D-EMMD-AQB-008-SOP-01 (alternative ID: ECAB-156.0E). 2013. Standard Operating
Procedure for Carbopack X Sorbent Tube Conditioning Using the Markes International
Model TC-20 Sample Tube Conditioner. U.S. Environmental Protection Agency,
National Exposure Research Laboratory.
D-EMMD-AQB-015-SOP-01. 2016. Standard Operating Procedure for Actively Loading
Sorbent tunes with Volatile Organic Compounds. Environmental Protection Agency.
National Exposure Research Laboratory.
D-EMMD-AQB-016-SOP-01. 2016. Standard Operating Procedure for the Use of the
Climate-Controlled Exposure Chamber for Loading Passive Sampling Devices with
Volatile Organic Compounds. U.S. Environmental Protection Agency, National
Exposure Research Laboratory.
D-EMMD-AQB-017-SOP-01. 2016. Standard Operating Procedure for Determination of
Volatile Organic Compounds Desorbed from Sorbent Tubes Using the Markes
International BenchTOF-Select GC-MS TOF System. Environmental Protection
Agency. National Exposure Research Laboratory.
McClenny, W.A., Oliver, K.D., Jacumin, H.H. Jr., Daughtrey, E.H. Jr., and Whitaker, D.A.
2005. 24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent
followed by thermal desorption/GC/MS analysis-laboratory studies. J. Environ.
Monit. 7:248-256.
U.S. EPA. 1999a. Compendium Method TO-14A: Determination of Volatile Organic
Compounds (VOCs) in Ambient Air Using Specially Prepared Canisters with
Subsequent Analysis by Gas Chromatography. In Compendium of Methods for the
Determination of Toxic Organic Compounds in Ambient Air, 2nd ed., EPA/625/R-
96/010b. Cincinnati, OH: Office of Research and Development.
U.S. EPA. 1999b. Compendium Method TO-17: Determination of Volatile Organic
Compounds in Ambient Air Using Active Sampling onto Sorbent Tubes. In
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Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air, 2nd ed., EPA/625/R-96/010b. Cincinnati, OH: Office of Research and
Development.
Unity 2 Operators' Manual. November 2011. Document no. QUI-1057 Version 1.4.
(Markes International, Llantrisant, UK).
Unity 2 Trouble Shooting Guide. February 2008. Version 1.0. (Markes International).
Thermal Desorption Training Guide. Power Point. (Markes International).
Leak Locating Guide. Power Point. (Markes International).
Unity 2 (Digital MFCs already fitted) Hardware Installation Manual. March 2014.
Document no. QSI-SERUTE-5156. (Markes International).
15.2 Supporting Documentation
Oliver, K.D., Jacumin, H.H. Jr., and Daughtrey, E.H. Jr. 2003. Initial Evaluation of
PerkinElmer Carbopack X Diffusive Sampling Badges for Collection of Toxic VOCs.
TR-4423-03-09. Research Triangle Park, NC: ManTech Environmental Technology,
Inc.
Oliver, K.D., Jacumin, H.H. Jr., Daughtrey, E.H. Jr., and McClenny, W.A. 2000. Sample
Integrity of Volatile Organic Compounds Collected and Stored on Multiadsorbent
Tubes and Analyzed Using an AutoGC/MS System. TR-4423-00-07. Research Triangle
Park, NC: ManTech Environmental Technology, Inc.
TurboMatrix ATD 650/TD Control Software User's Guide. June 2002. Part Number
09934591, Release A, PerkinElmer Instruments LLC, 710 Bridgeport Avenue, Shelton,
CT 06484.
TurboMatrix Thermal Desorbers User's Guide. April 2000. Part Number M041-3331,
Release B, PerkinElmer, Inc., 761 Main Avenue, Norwalk, CT 06859.
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Appendix A: VOC Method Parameters
System: Ultra TD 50:50 and Unity 2
Method Filename: 25to10S_4min_16mLpurge_Desorb315_CarbopackX_no int std_100416_gc
cycle 47min.mth
TD mode: Two-stage desorption
Corresponds to Method: TQ14_Tire Crumb_Finai_100516_variable drops for the TOF-GC-MS
[Unity Method]
Author =
MethodName =
Company =
Notes =
DateCreated =
DateModified = 05/10/201614:24:25
FileName = 25to10S_4min_1 GrnLpurge_Desorb315_CarbopaokX_no int std_10041 G_go cycle 47min
OperatinqMode = Standard Two Stage
IdleSplit = TRUE
MinimumCarrierPressure = 5
PurgeT raplnLine = FALSE
PurgeS plit = TRUE
Standby Flow =20
- AirServerTrapFlow =20
PrePurgeSplitFlow =20
F'rePurgeT rapFlow =20
PrimaryDesorblSplitFlow =20
PrimaryDesorb2SplitFlow =20
PrimaryDesorblTrapFlow =50
PrimaryDesorb2TrapFlow =20
- T rapD esorbS pliFlow =36
PreTrpFirePurgeSplitFlow =36
PreT rpFirePurgeT rapFlow =50
T ubefcondSplitFlow =20
AirServerLinePurge =20
Directs amplingFlow =20
DryPurgeFlow =16
DirectModeFlushSplitFlow =20
StdlnjFlow =50
AirServerTrapF'urge =20
DirectModeTrapPurgeFlow =20
DirectModeFlushTrapFlow =20
PrePurgeTime = .1
AirServerPostSannplePurgeTime = 1
DryPurgeTime = 4
DirectPostSamplePurgeTime = 1
PreTrapFirePurgeTime = 2
AirServerPostSampleTrapPurgeTime = 1
AirServerPostSampleTrapPurgeDirect = 1
DvenTemperaturel =315
DesorbTirnel = 15
Desorbl T raplnLine = TRUE
Desorbl Split = FALSE
0venTemperature2 = 250
DesorbTime2 = 0
Desorb2Split = FALSE
StdlnjTirne = 1
LoopFillTirne = .4
DryPurgeOrStdlnj =DryPurge
T rapLow = 15
TrapHigh = 280
TrapHold = 5
TrapSplit = TRUE
QMBSSarnple = 2
SensorT ernperature = 65
TrapHeatRate = 0
ColumnFlow = 1.5
DesorbFlow = 20
TubeD esorbS plit = 0
TrapD esorbS plit = 36
InletSplitRatio =No Split
OutletsplitRatio =25.0 :1
TotalSplitRatio =25.0 : 1
FlowPathT ernperature = 160
GCCycleTime = 60
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Appendix B: VOC PAH Method Parameters
System: Ultra TD 50:50 and Unity 2
Method file name: PAH and VOCs.mth
TD mode: Two-stage desorption
Corresponds to Method: Method_TQ17d for the TOF-GC-MS
[UnityMethod]
Author =
MethodName =
Company =
Notes =
DateCreated =
D ateM odified = 11/12/2015 11:27:38
FileNarne = C:\PrograrnData\Markes TD\Methods\PAH and VOCs.mth
OperatingMode = Standard Two Stage
IdleSplit = TRUE
MinimumCarrierPressure = 5
PurgeT raplnLine = FALSE
PurgeS plit = TRUE
StandbyFlow =20
AirServerT rapFlow =20
PreF'urgeSplitFlow =20
PreF'urgeT rapFlow =20
PrimaryDesorbl SplitFlow =50
PrimaryDesorb2SplitFlow =20
PrimaryDesorbl T rapFlow =50
PrirnaryDesorb2T rapFlow =20
T rapDesorbSpliFlow =23
PreT rpFirePurgeSplitFlow =23
PreT rpFirePurgeT rapFlow =50
T ubeCondSplitFlow =20
AirServerLinePurge =20
Directs amplingFlow =20
DryPurgeFlow =1S
D irectM odeFlushS plitFlow =20
StdlnjFlow =50
AirServerT rapPurge =20
DirectModeT rapPurgeFlow =20
DireotModeFlushT rapFlow =20
PrePurgeTirne = .1
AirServerPostSamplePurgeTime = 1
DryPurgeTime = 4
DirectPostSamplePurgeTime = 1
PreT rapFirePurgeTime = 1
AirServerPostSarnpleTrapPurgeTirne = 1
AirServerPostSampleTrapPurgeDireot = 1
~ venTemperaturel =340
DesorbTimel = 10
Desorbl T raplnLine = TRUE
Desorbl Split = TRUE
OvenT emperature2 = 250
DesorbTime2 = 0
Desorb2Split = FALSE
StdlnjTime = 3
LoopFillTime = .4
DryPurgeOrStdlnj =Stdlrij
TrapLow =-10
TrapHigh = 315
TrapHold = 4
TrapSplit = TRUE
QMBGSample = 2
SensorT emperature = 65
TrapHeatRate = 0
ColumriFlow = 2
DesorbFlow = 50
TubeDesorbSplit = 50
TrapDesorbSplit = 23
InletSplitRatio =2.0: 1
OutletSplitRatio =12.5 : 1
TotalsplitRatio =25.0 : 1
FlowPathT emperature = 1 SO
GCCycleTime = 26
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Scope and Application
1.1 This appendix applies to the exploration of the desorption of volatile organic compounds
(VOCs) and poly cyclic aromatic hydrocarbons (PAHs) from Carbograph 2TD and
Carbograph 1TD dual-bed sorbent tubes using EPA Compendium Method TO-17 type
procedures (U.S. EPA, 1999a). For this method, the Markes International Ultra TD 50:50
and Unity 2 are interfaced with a Markes International GC-MS TOF system.
1.2 This method is written as a companion to D-EMMD-AQB-017-SOP-01, "Standard
Operating Procedure for Determination of Volatile Organic Compounds Desorbed from
Sorbent Tubes Using the Markes International BenchTOF-Select GC-MS TOF System."
1.3 The standards are prepared by using flash vaporization to load PAHs and active loading to
load VOCs onto sorbent tubes, as described in an SOP that is under development.
1.4 The following VOCs are the compounds of interest from the EPA Compendium Method
TO-14A target list (U.S. EPA, 1999b). Target PAHs are the compounds of interest from
the EPA Compendium Method TO-13A target list (U.S. EPA, 1999c).
Summary of Method
VOCs and PAHs are desorbed from Carbograph 2TD and 1TD dual-bed sorbent tubes that have been
previously loaded using flash vaporization techniques to load tubes with PAHs (SOP under
development) followed by active loading with a gas-tight syringe to load VOCs (D-EMMD-AQB-
015-SOP-01) onto tubes conditioned using the Markes TC-20 (D-EMMD-AQB-008-SOP-01) tube
conditioner. The tubes, with DiffLok caps on both ends, are placed horizontally into the sampling
tray with the fritted (grooved) end of the tube (inlet) pointing towards the right-hand side and the rear
end of the tube (outlet) pointed towards the left-hand side of the sampling tray. An analytical sequence
is created and initiated using the analytical software. The Ultra TD-Tube software is used to create a
desorption sequence by selecting the "PAH and VOCs.mth" desorption method and then initiating
the sequence.
D-EMMD-AQB-008-SOP-01 (alternative ID: ECAB-156.0E). 2013. Standard Operating
Procedure for Carbopack X Sorbent Tube Conditioning Using the Markes International Model
TC-20 Sample Tube Conditioner. U.S. Environmental Protection Agency, National Exposure
Research Laboratory.
VOCs:
Benzene
Toluene
Ethylbenzene
«?,/;-Xvlcnc
Styrene
o-Xylene
4-Ethyltoluene
1,3,5 -T rimethylbenzene
Naphthalene
Acenaphthalene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
PAHs:
References
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D-EMMD-AQB-015-SOP-01. 2016. Standard Operating Procedure for Actively Loading Sorbent
tunes with Volatile Organic Compounds. Environmental Protection Agency. National
Exposure Research Laboratory.
D-EMMD-AQB-017-SOP-01. 2016. Standard Operating Procedure for Determination of Volatile
Organic Compounds Desorbed from Sorbent Tubes Using the Markes International
BenchTOF-SelectGC-MS TOF System. Environmental Protection Agency. National Exposure
Research Laboratory.
U.S. EPA. 1999a. Compendium Method TO-17: Determination ofVolatile Organic Compounds in
Ambient Air Using Active Sampling onto Sorbent Tubes. In Compendium of Methods for the
Determination of Toxic Organic Compounds in Ambient Air, 2nd ed., EPA/625/R-96/010b.
Cincinnati, OH: Office of Research and Development.
U.S. EPA. 1999b. Compendium Method TO-14A: Determination ofVolatile Organic Compounds
(VOCs) in Ambient Air Using Specially Prepared Canisters with Subsequent Analysis by Gas
Chromatography. In Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, 2nd ed., EPA/625/R-96/010b. Cincinnati, OH: Office of Research
and Development.
U.S. EPA. 1999c. Compendium Method TO-13A: Determination of Polycyclic Aromatic
Hydrocarbons (PAHs) in Ambient Air Using Gas Chromatography/Mass Spectrometry
(GC/MS). In Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air, 2nd ed., EPA/625/R-96/010b. Cincinnati, OH: Office of Research and
Development.
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Appendix C: Markes Unity Almsco GC-MS TOF analysis sheet
DATE:
COMMENTS:
Lab D-277
ATD SLOT
ANALYSIS
ANALYSIS DESIG.
TUBE DESIG
POSITION
NUMBER
DATE TYPE # EXT.
#
DETAILS OF ANALYSIS
TUBE# 1
RUN# 1
HB 01 .d
Helium blank - empty glass tube
TUBE# 2
RUN# 2
02 .d
TUBE # 3
RUN# 3
03 .d
TUBE# 4
RUN# 4
04 .d
TUBE# 5
RUN# 5
05 .d
TUBE # 6
RUN# 6
06 .d
TUBE# 7
RUN# 7
07 .d
TUBE# 8
RUN# 8
08 .d
TUBE # 9
RUN# 9
09 .d
TUBE# 10
RUN# 10
10 .d
TUBE# 11
RUN# 11
11 .d
TUBE# 12
RUN# 12
12 .d
TUBE# 13
RUN# 13
13 .d
TUBE# 14
RUN# 14
14 .d
TUBE# 15
RUN# 15
15 .d
TUBE# 16
RUN# 16
16 .d
TUBE# 17
RUN# 17
17 .d
TUBE# 18
RUN# 18
18 .d
TUBE# 19
RUN# 19
19 .d
TUBE # 20
RUN # 20
20 .d
TUBE# 21
RUN# 21
21 .d
TUBE # 22
RUN # 22
22 .d
TUBE # 23
RUN # 23
23 .d
TUBE # 24
RUN # 24
24 .d
TUBE # 25
RUN # 25
25 .d
TUBE # 26
RUN # 26
26 .d
TUBE # 27
RUN # 27
27 .d
TUBE # 28
RUN # 28
28 .d
TUBE # 29
RUN # 29
29 .d
TUBE # 30
RUN # 30
30 .d
TUBE # 31
RUN# 31
31 .d
TUBE # 32
RUN # 32
32 .d
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U.S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for Preparation of Air Samples Collected on PUF Plugs
for GC/MS Analysis
Number: D-EMMD-PHCB-036-SOP-01
Effective Date: 09/08/2016
SOP was Developed
S In-house
~ Extramural
SOP Steward
Name: M. Scott
Signature:
Date: %$//£
Approval
Name: Myriam Medina-Vera
Title: Branch Chief, PHCB
Signature
Date: dj/Q $¦/&#/£
oncurrence*
Name:
Title:
Signature:
Date:
For Use by QA Staff Only:
SOP Entered into QATS:
Initials
Date
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Standard Operating Procedure for Preparation of Air Samples Collected on PUF Plugs for
GC/MS Analysis
Section
I.0 Scope and Application 3
2.0 Summary of Method 3
3.0 Definitions 4
4.0 Health and Safety Warnings 4
5.0 Materials and Equipment 4
6.0 Interferences 6
7.0 Personnel Qualifications 6
8.0 Sample Preservation and Storage 6
9.0 Extraction Procedure - Soxhlet Method 6
10.0 Extraction Procedure - Ultrasonic Method 8
II.0 Records 10
12.0 Quality Control and Quality Assurance 10
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1.0 Scope and Application
This SOP details the extraction and work-up procedures for air samples collected on pre-
cleaned polyurethane foam (PUF) plugs. This method is applicable for extraction of both
indoor and outdoor field samples as well as laboratory generated samples, including
collection from emissions experiments. This SOP is written to encompass a wide range of
analytes and to be applicable across many studies. Analytical performance will need to be
assessed for specific analytes prior to use.
2.0 Summary of Method
There are two acceptable methods for extraction and processing of PUF plugs that will be
detailed in this SOP that involve either Soxhlet or ultrasonic extraction. The method
chosen will depend on availability of materials and equipment, resources, and analytical
performance. For both methods, samples are allowed to equilibrate to room temperature
after removing from freezer storage.
With the Soxhlet extraction method, samples are transferred to clean 150 mL Soxhlet
extractors. Internal standard solution is spiked onto the surface of the samples. Boiling
flasks are filled with 300 mL of 1:1 acetone:hexane along with several boiling chips. The
extractors are assembled on a heating mantle with condensers and heat is applied so the
extraction rate is -20 cycles per hour. The samples are extracted for 16 hours (overnight
is convenient). The extracts in the boiling flasks are allowed to cool and are then
concentrated to 2-5 mL on a rotary evaporator. The concentrated extracts are then
transferred to a 15 mL graduated glass tube along with two 2 mL hexane rinses of the
boiling flask. The extracts are then concentrated to a final volume of 1 mL under
nitrogen. The extracts are then transferred to autosampler vials for analysis.
For ultrasonic extraction, samples are transferred to clean 60 mL amber jars. Internal
Standard solution is added to the PUF. Each jar is filled with 50 mL of 1:1
acetone:hexane and is then sealed with a PTFE-lined cap. The jars are placed in an
ultrasonic cleaner with water level well below the level of the jar cap. The ultrasonic
cleaner is then turned on for 15 minutes. Sample jars are removed from the cleaner and
the extracts are transferred through funnels into 250 mL narrow mouth bottles. The
funnels are rinsed with hexane from a wash bottle after the extracts are added. The
solvent addition, extraction, and transfer is repeated two more times. The extracts in the
bottles are then evaporated to 2-5 mL using a parallel evaporator. The concentrated
extracts are then transferred to a 15 mL graduated glass tube along with two 2 mL hexane
rinses of the bottle. The extracts are then concentrated to a final volume of 1 mL under
nitrogen. The extracts are then transferred to autosampler vials for analysis.
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3.0 Definitions
3.1 PUF - Polyurethane Foam sample media.
3.2 SRS - Surrogate recovery standards which are used to evaluate analyte
recovery.
3.3 IS - Internal standard solution which is used in quantification to establish
response ratios.
3.4 Method Blank - Unfortified media that is extracted to evaluate
interferences and possible contamination in the media or lab.
3.5 Method Spike - Media that is fortified and extracted to evaluate analyte
recovery from the extraction process.
3.6 Recovery Spike - Unfortified media that is extracted and processed like
the Method Blank. The extract is fortified after sample preparation is
complete. This is used to simulate 100% analyte recovery so matrix effects
that can influence the measured concentrations can be evaluated.
4.0 Health and Safety Warnings
4.1 Follow the procedures detailed in applicable Health and Safety Research
Protocols.
4.2 Follow proper operating procedures for all equipment and instruments
used.
4.3 Exercise caution when using syringes and avoid inhalation or dermal
contact with all solvents and solutions used in this procedure.
4.4 Exercise caution when working with and around heating mantles used for
Soxhlet extraction. Perform extractions inside of a fume hood and ensure
that all connections are secure before leaving the extractors unattended.
Allow flasks used in extraction to cool before handling.
4.5 The ultrasonic cleaner and the water bath inside can become very hot, so
exercise caution when removing containers from the bath and allow the
bath to cool or replace the water with cool water before continuing if the
heat is excessive.
5.0 Materials and Equipment
5.1 Soxhlet method
5.1.1 Clean PUF plugs (Supelco 20600-U or equivalent)
5.1.2 Stainless steel forceps
5.1.3 Spiking Solution, applicable to analytes being measured
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5.1.4 Internal Standard Solution (IS), applicable to analytes being
measured
5.1.5 Pipette or syringe capable of accurately delivering 50 |iL of
solution
5.1.6 Soxhlet Extractors with condensers and chillers, 150 mL
5.1.7 Heating mantles
5.1.8 Boiling flasks, 500 mL
5.1.9 Hexane, pesticide grade or equivalent
5.1.10 Acetone, pesticide grade or equivalent
5.1.11 Boiling chips
5.1.12 Rotary evaporator
5.1.13 Glass serological or volumetric pipette capable of 2 mL
5.1.14 Pasteur pipettes - 9"
5.1.15 Graduated tubes, glass, 15 mL
5.1.16 Nitrogen evaporator with heated water bath (N-Evap or equivalent)
or dry block
5.1.17 Autosampler vials, 2 mL, caps with PTFE-lined septa
Ultrasonic Extraction Method
5.2.1 Clean PUF plugs (Supelco 20600-U or equivalent)
5.2.2 Stainless steel forceps
5.2.3 Spiking Solution, applicable to analytes being measured
5.2.4 Internal Standard Solution (IS), applicable to analytes being
measured
5.2.5 Pipette or syringe capable of accurately delivering 50 |iL of
solution
5.2.6 Wide mouth glass jars with PTFE-lined caps, 60 mL
5.2.7 Ultrasonic cleaner with water bath
5.2.8 Hexane, pesticide grade or equivalent
5.2.9 Acetone, pesticide grade or equivalent
5.2.10 Analytical funnels, glass
5.2.11 Narrow-mouth bottles, Boston round, 250 mL
5.2.12 Parallel evaporator, Buchi Multivapor P-6 or equivalent
5.2.13 Glass serological or volumetric pipette capable of 2 mL
5.2.14 Pasteur pipettes - 9"
5.2.15 Graduated tubes, glass, 15 mL
5.2.16 Nitrogen evaporator with heated water bath (N-Evap or equivalent)
or dry block
5.2.17 Autosampler vials, 2 mL, caps with PTFE-lined septa
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6.0 Interferences
Interferences are any component that interferes with the quantitative analysis.
Interferences should be evaluated prior to applying this method to study samples.
This method may be modified to deal with interferences if necessary as long as
modifications are documented and are acceptable within a studies QA Plan. If
interferences not identified during method evaluation are discovered with study
samples, they will be identified and evaluated as part of a studies ongoing QA/QC
plan.
7.0 Personnel Qualifications
This SOP is written to be used by personnel familiar with the equipment and
procedures that will be used. Personnel should be adequately trained and display
proficiency with those techniques prior to using this SOP for sample analysis.
8.0 Sample Preservation and Storage
Study samples will be collected at a field location or laboratory and stored at
freezer conditions (-20°C) until they can be extracted. Sample stabilty should be
assessed for the analytes in a given study if extended (>30 days) storage time is
anticipated. At the time of extraction, the samples will be removed from the
freezer and will be allowed to warm to room temperature. Sample extracts will be
stored under freezer conditions (- 20° C) in cases where analysis cannot be
performed immediately. The extracted PUF plugs will be discarded.
9.0 Extraction Procedure Soxhlet Method
9.1 Remove PUF air samples from the freezer and let warm to room
temperature.
One sample batch will consist of the following:
15 Air samples (from freezer)
1 Lab spike
1 Lab blank
1 Laboratory 100% recovery spike
9.2 While the samples from the freezer are warming to room temperature, the
method spike, method blank and recovery spike can be prepared for
extraction.
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9.3 Method Spike Preparation
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9.3.1 Place a clean PUF plug into a 150 mL Soxhlet extractor so that it's
in a U-shape and sits under the siphon tube on the extractor.
9.3.2 Transfer a 50 |iL aliquot of Spiking Solution to the PUF plug and
allow the solvent to evaporate (~1 minute).
9.3.3 Transfer a 50 |iL aliquot of Internal Standard Solution to the PUF
plug and allow the solvent to evaporate (~ 1 minute).
9.4 Lab blank Preparation
9.4.1 Place a clean PUF plug into a 150 mL Soxhlet extractor so that it's
in a U-shape and sits under the siphon tube on the extractor.
9.4.2 Transfer a 100 |iL aliquot of Internal Standard to the PUF plug and
allow the solvent to evaporate (~1 minute).
9.5 Recovery Spike Preparation
9.5.1 Place a clean PUF plug into a 150 mL Soxhlet extractor so that it's
in a U-shape and sits under the siphon tube on the extractor.
9.5.2 After extraction and concentration, add 50 |iL of spiking solution
to the sample.
9.5.3 Add 100 |iL of internal standard solution, cap and vortex along
with the other samples processed in the sample batch.
9.6 Air Sample Preparation
9.6.1 Place the PUF sample into a 150 mL Soxhlet extractor so that it's
in a U-shape and sits under the siphon tube on the extractor.
9.6.2 Fortify each of the PUF plugs with 100 |iL of Internal Standard
solution and allow the solvent to dry.
9.7 Sample Extraction (Spikes, Blanks and Air Samples)
9.7.1 Label a 500 mL boiling flask for each sample to be extracted.
9.7.2 Add 300 mL of 1:1 acetone: hexane to each flask along with
several boiling chips.
9.7.3 Assemble each Soxhlet extractor with the corresponding boiling
flask and attach the condenser. Verify that each condenser has cool
liquid passing through it. The liquid should be between 10 and 15
°C to prevent water condensation into the extractor and to prevent
vaporization of the solvent.
9.7.4 Place the assembled extraction apparatus onto a heating mantle or
on an extraction bank and begin heating the solvent in the flasks.
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9.7.5 Once the solvent vapor begins condensing and dripping onto the
PUF plugs, adjust the heat so that all of the extractors are working
at approximately the same rate (~ 10-20 cycles/hour).
9.7.6 After the majority of the samples have performed one extraction
cycle, begin timing the extraction. Allow the extraction to continue
for 16 hours.
9.8 Extract Processing
9.8.1 Turn off the mantle or extraction bank providing heat to the
extraction solvent. Turn off cool water supply to the condensers
after the solvent stops boiling. Allow the extracts to cool before
handling (-30 minutes).
9.8.2 Concentrate the extract on a rotary evaporator to a volume of 2-5
mL.
9.8.3 Transfer the concentrated extract to a 15 mL graduated tube. Rinse
the boiling flask twice with 2 mL aliquots of hexane. Transfer the
rinsate to the graduated tube.
9.8.4 Concentrate to a volume of 1 mL under nitrogen.
9.8.5 Transfer the sample solution to an autosampler vial using a Pasteur
pipette.
9.8.6 Cap the autosampler vial and analyze by GC/MS.
9.8.7 If the sample cannot be analyzed immediately, store in a freezer at
-20 °C until they can be analyzed.
10.0 Extraction Procedure - Ultrasonic Method
10.1 Remove PUF air samples from the freezer and let warm to room
temperature.
One sample batch will consist of the following:
24 Air samples (from freezer)
1 Lab spike
1 Lab blank
1 Laboratory 100% recovery spike
10.2 While the samples from the freezer are warming to room temperature, the
method spike, method blank and recovery spike can be prepared for
extraction.
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10.3 Method Spike Preparation
10.3.1 Place a clean PUF plug into a 60 mL wide mouth glass jar.
10.3.2 Transfer a 50 |iL aliquot of Spiking Solution to the PUF plug and
allow the solvent to evaporate (~1 minute).
10.3.3 Transfer a 100 |iL aliquot of Internal Standard solution to the PUF
plug and allow the solvent to evaporate (~ 1 minute).
10.3.4 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
10.4 Lab blank Preparation
10.4.1 Place a clean PUF plug into a 60 mL wide mouth glass jar.
10.4.2 Transfer a 100 |iL aliquot of Internal Standard solution to the PUF
plug and allow the solvent to evaporate (~ 1 minute).
10.4.3 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
10.5 Recovery Spike Preparation
10.5.1 Place a clean PUF plug into a 60 mL wide mouth glass jar.
10.5.2 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
10.5.3 After extraction and concentration, add 50 |iL of spiking solution
to the sample.
10.5.4 Add 100 |iL of internal standard solution, cap and vortex along
with the other samples processed in the sample batch.
10.6 Air Sample Preparation
10.6.1 Place the PUF sample into a 60 mL wide mouth glass jar.
10.6.2 Fortify each of the PUF plugs with 100 |iL of Internal Standard
solution and allow the solvent to dry.
10.6.3 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
10.7 Sample Extraction (Spikes, Blanks and Air Samples)
10.7.1 Place samples into an Ultrasonic cleaner and start the cleaner.
10.7.2 Allow the cleaner to run for 15 minutes.
10.7.3 Carefully remove the samples from the ultrasonic cleaner, drying
the outside of each jar with a paper towel as it is removed.
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D-EMMD-PHCB-036-SOP-01
09/08/2016
Page 10 of 11
10.7.4 Assemble an analytical funnel on a 250 mL glass Boston round
bottle and label one bottle for each sample extract.
10.7.5 Carefully pour the solvent content of each sample jar into the
corresponding bottle through the funnel. Allow the jar to sit in the
funnel until solvent stops dripping.
10.7.6 Carefully remove the jars and add another 50 mL of 1:1
acetone:hexane. Recap the jars.
10.7.7 Rinse the inside of each funnel into its bottle with hexane from a
wash bottle.
10.7.8 Repeat steps 10.7.1 to 10.7.7 two more times, omitting step 10.7.6
after the third extraction.
10.8 Extract Processing
10.8.1 Concentrate the sample extracts inside of the bottles to a volume of
-2-5 mL on a parallel evaporator.
10.8.2 Transfer the concentrated extract to a 15 mL graduated tube. Rinse
the bottle twice with 2 mL aliquots of hexane. Transfer the rinsate
to the graduated tube.
10.8.3 Concentrate to a volume of 1 mL under nitrogen.
10.8.4 Transfer the sample solution to an autosampler vial using a Pasteur
pipette.
10.8.5 Cap the autosampler vial and analyze by GC/MS.
10.8.6 If the sample cannot be analyzed immediately, store in a freezer at
-20 °C until they can be analyzed.
11.0 Records
Chain of custody records will be maintained to document the removal and
extraction of each air sample. Those records will be stored as indicated in the
applicable studies QA plan.
The performance of this procedure will be documented in a NERL laboratory
notebook. This documentation will include details and observations for each
sample batch analyzed.
12.0 Quality Control and Quality Assurance
Data will be reviewed by the EMMD QA Manager. The data quality objectives
and review procedures from the QAPP for the study being conducted will dictate
specific quality assurance practices. All QA practices will be consistent with the
NERL Quality Management Plan.
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D-EMMD-PHCB-036-SOP-01
09/08/2016
Page 11 of 11
The method blank, method spike and recovery spike will serve to measure method
performance for each batch of samples.
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[This page intentionally left blank.]
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U. S Environmental Protection Agency
V Office of Research and Development
National Exposure Research Laboratory
\,t enQ^ Exposure Methods and Measurement Division
Public Health Chemistry Branch
STANDARD OPERATING PROCEDURE
SOP Title: Determination of Selected Organic Contaminants in Tire Crumb
Rubber Subsamples for Multi-Residue Characterization by Ultra Pressure Liquid
Chromatography/ Tandem Mass Spectrometry (UPLC-MS/MS)
SOP ID: D-EMMD-PHCB-SOP-2327-0
Effective Date: 01/29/2018
SOP was Developed: IE! In-house
SOP Discipline*: Organic Chemistry
Alternative Identification:
SOP Contact Signature
Name: Elin Ulrich
Digitally signed by ELIN
, ;n, ELIN ULRICH "L,RIC"
Signature/Date: Date: 2018.03.27 16:28:58
-04'00'
Management Signature
Name: Myriam Medina-Vera
Title: PHCB Chief MYRIAM Digitally signed by MYRIAM
IVI I I \I/-\IVI MEDINA-VERA
Signature/Date: MEDINA-VERA
QA Signature
Name: Margie Vazquez
Title: EMMD QA manager
Signature/Date:
*See discipline descriptions on the NERL Scientific and Technical SOP intranet site.
-------
Revision History
Revision
No.
Name
Date of
Revision
Description of Change(s)
0
Larry McMillan
03/21/2018
Original SOP. Effective date: 3/21/18.
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SOP # D-EMMD-PHCB-SOP-2327-O
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Page 3 of 31
TABLE OF CONTENTS
1. Scope and Applicability 4
2. Summary of Method 4
3. Definitions/Acronyms 4
4. Health and Safety Warnings 4
5. Cautions/Interferences 5
6. Personnel Qualifications/Responsibilities 5
7. Equipment and Supplies 5
8. Reagents and Standards 6
9. Procedures 7
9.1. Mobile Phase Solution Preparation 7
9.2. Standard Solution Preparation #1 8
9.3. Standard solution preparation #2 8
9.4. Tire Crumb Rubber Study Standard Preparation 9
9.5. TCRS LC sample prep 9
9.6. Instrument setup 10
9.7. Quantitation- Setting up Standard Curve 14
10. Data and Records Management 30
11. Quality Assurance/Quality Control 30
12. References 31
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SOP Title: Determination of Selected Organic Contaminants in Tire Crumb
Rubber Subsamples for Multi-Residue Characterization by Ultra Pressure
Liquid Chromatography/ Tandem Mass Spectrometry (UPLC-MS/MS)
1. Scope and Applicability
This standard operating procedure (SOP) describes a method for analyzing Tire Crumb
Research Study (TCRS) subsamples for selected organic contaminants in Dermal Wipes, Air
SVOCs, Field Dust, and Field Wipe.
2. Summary of Method
TCRS samples are extracted with acetone and hexane for gas chromatograph tandem mass
(GCMSMS). After the GCMSMS analysis, approximately one milliliter (mL) is allowed to
evaporate until dryness and reconstituted to lmL with water and acetonitrile. After the extract
is reconstituted, the listed compounds (Table 1) are determined by ultra-performance liquid
chromatograph/tandem mass spectrometer (UPLC7MS/MS, also known as ultra-high pressure
or UHPLC).
3. Definitions/Acronyms
3.1. Internal Standard (IS) A fixed amount of reference compound or solution is added to
each sample and standard solution prior to extraction. The ratio of the detector signal
of the native analyte to the detector signal of the internal standard (IS) is compared to
the ratio obtained from the calibration curves where the IS level remains fixed and the
native analyte levels vary. The internal standard is used to correct for minor sample-
to-sample differences in extraction, purification, injection volume, chromatographic
behavior, and mass spectrometry ionization efficiency.
3.2. Quality Control (QC) Samples Blanks, spikes, and duplicates are used as quality
control measures.
3.2.1. Blanks are prepared with deionized laboratory water.
3.2.2. Spikes, deionized water is spiked with known amounts of reference materials
targeted by each analysis. The concentrations of analytes in these QC samples
are compared to their theoretical values for the determination of the accuracy of
the analysis
3.3. TCRS: Tire Crumb Research Study
4. Health and Safety Warnings
Personnel must be thoroughly acquainted with the potential hazards of the reagents, products,
solvents, equipment, and procedures described in this SOP. The current Material Safety Data
Sheets (MSDS) for the chemicals used in this method should be consulted. The Health and
Safety Research Protocol for this laboratory activity is on file. Care should be observed with
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Effective Date: 01/29/2018
Page 5 of 31
the use of all compounds specified in this protocol as some may be hazardous if used
incorrectly (e.g., Formic Acid).
Waste Management: Solid, liquid, and glass waste are disposed of in separate containers.
Solvents and samples used in this procedure should be disposed according to Health and
Safety regulations and mindful of appropriate labeling and record keeping
5. Cautions/Interferences
Do not wash glass bottles in detergent, with other glasses or in washing unit that may have
detergent residue. Washing glassware in a common dishwashing unit can contaminate it with
detergent residues, which contain polyethylene glycol (PEG) and other sticky substances with
vinyl coated steel racks can be and additional source of contaminations.
Do not perform further filtration on pre-filter solvents additional filtering can introduce
contaminations.
Routine instrument maintenance is critical to achieve optimum sensitivity. All laboratory
materials must be determined to be free of contamination to ensure potential background
interferences are minimized.
User must review Waters Manual: Controlling Contamination in Ultra Performance LC®/MS
and HPLC/MS Systems 715001307. Rev. D.
6. Personnel Qualifications/Responsibilities
This SOP assumes a thorough working knowledge of basic laboratory skills, reagents, and
instrumentation. This document is designed to guide a competent laboratory worker. It is
assumed that the user of this method is very familiar with liquid chromatography / mass
spectrometry, MassLynx software, Microsoft Excel, and computer programs in general (1-2
years of experience).
7. Equipment and Supplies
UPLC-MS/MS system Waters Acquity (UPLC) ultra- performance liquid chromatography
system (Waters Corporation, Milford, MA) with binary pump, auto sampler, column heater, or
other equivalent automated HPLC system suitable for the instrument parameters outlined in
this method.
The characteristics of the UPLC used in this SOP:
All solvent lines are polyether ether ketone (PEEK) tubing
Mobile phase stainless-steel filters.
Sample Syringe (10 [xL)
Injection syringe (250 |iL)
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Sample Loop ASSY EXTENSION LOOP lOOuL; ACQUITY APC
• Waters Xevo TQD Tandem mass spectrometer - Ion source: positive ion electrospray
ionization, ESI+. and negative ion electrospray ionization ESI
• Waters Acquity UPLC BEH CI8 reverse phase UPLC column, 2.1x50 mm, 1.7 [j,m
(P/N 186002350) or equivalent column.
• Waters Acquity UPLC BEH CI8 1.7um VanGuardtm Pre-Column 2.1 X 5 mm column
PN 186003975
• N-EVAP 12 nitrogen evaporator (Organomation Associates INC West Berlin, MA) or
equivalent nitrogen with 10-15 psi nitrogen.
• VWR 24/16 Galaxy 16 DH Centrifuge: rotation speed 3500 ppm. Serial no. R-
104098
• Sonicator- Aquasonic Model 150HT Cat# 21811-804 VWR Scientific Products.
• Vortex mixer. - Maxi Mix II Barnstead/Thermolyze Model No M371615 Dubuque
Iowa
Supplies
1. Microfiber Filters, Ultra Free MC Filters Cat# UFC30LG25 HydrophilicPTFE
Membrane.
2. Sample container, high density polyethylene HDPE, 1000 mL, wide mouth, with screw
top (P/N 2189-0032 24/case Nalgene Labware, Rochester, NY) or equivalent
3. Centrifuge tube and cap, polypropylene, sterile, 15 mL (BD Falcon brand, BD,
Franklin Lakes, NJ, P/N 352096, or equivalent)
4. Pipettor, variable volume, positive displacement, capability of 10 to 100, and 100 to
1000 microliter ranges (Eppendorf, Westbury, NY), or equivalent
5. Disposable polypropylene pipettor tips of various sizes (10, 100, 1000, 5000 uL)
(Genesee Scientific, Research Triangle Park, North Carolina USA) or equivalent
Reagents and Standards
8.1. TCRS Standards 100 ug/ml in dichloromethane (DCM). These compounds were
received from LAB D551.
8.2. Atrazine (Ring-13C3, 99%) 100 ug/ml in nonane -Cambridge Isotope Laboratories
Andover MA.
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8.3. Methanol (MEOH)- A456-4 Optima LC/MS UN1230 Fisher Chemicals
8.4. Acetonitrile(_ACN) - A955-4 Lot 17132 Optima LC/MS Fisher Chemicals
8.5. Mili-Q water, resistivity 18 Mfl-cm (@25°C)
8.6. Formic Acid A117-50 Optima LC/MS Cas 54-18-6 Fisher Chemicals
8.7. Ammonium Formate (NH4COOH) 99% Cas-540-69-2 ACROS
Table 1. Analytes for LC-MS/MS analysis.
Analyte
Molecular Formula
Monisotopic Mass
CAS#
Cyclohexylamine
C6H13N
99.104797 Da
108-91-8
Di cycl oh exyl a mi n e
C12H23N
181.183044 Da
101-83-7
N,N-Di cycl ohexyl methyl a mi ne
C13H25N
195.198700 Da
7560-83-0
2-Hydroxybenzothiazole (benzothiazolinone)
C7H5
151.009186 Da
934-34-9
2-Merca ptobenzothi azol e
C7H5NS
166.986343 Da
149-30-4
Bi s(2,2,6,6-tetra methyl -4pi peri dyl) sebecate
C44H84N
736.632935 Da
52829-07-9
9. Procedures
9.1 Mobile Phase Solution Preparation
Two different methods were developed to analyzed different compounds.
9.1.1. Mohile Phase Preparation For Method #1
Compounds List 1: Cyclohexylamine, 2-Hydroxybenzothiazole, N,N-
Dicyclohexylmethylamine, and Bis(2,2,6,6-tetramethyl-4piperidyl sebecate)
9.1.1.1. Solvent A - preparation of 0.1% formic 90/10 water: acetonitrile solution:
Using 1000 ml graduated cylinder measure 100 ml of acetonitrile and add to a
one-liter mobile phase bottle. Add 100 jj.1 of formic acid. Add 900 ml of
water. Labeled bottle Al- 0.1% FA 90:10 H20/ACN
9.1.1.2. Solvent B - preparation of 0.1% formic acid 90/10 acetonitrile: water solution:
Using 1000 ml graduated cylinder measure 100 ml of water and add to a one-
liter mobile phase bottle. Add 100 jj.1 of formic acid. Add 900 ml of
acetonitrile. Labeled bottle B1 - 0.1% FA 90:10 ACN/Water
9.1.2. Mohile Phase Preparation For Method #2
Compounds List 2: Dicyclohexylamine and 2-mercaptobenzothiazole
9.1.2.1. Solvent A - preparation of 0.4 mM Ammonium Formate 90/10 water:
Acetonitrile solution:
Using 1000 ml graduated cylinder measure 100 ml of methanol and add 25.2
mg of ammonium formate to a one-liter mobile phase bottle. Add 900 ml of
water. Label bottle Al - 0.4 mM NH4COOH 90:10 H20/MEOH
9.1.2.2. Solvent B - preparation of 0.4 mM Ammonium Formate 90/10 Acetonitrile:
water solution:
Using 1000 ml graduated cylinder measure 100 ml of water and add 25.2 mg
of ammonium formate to a one liter mobile. Add 900 ml of methanol. Label
bottle B1 - 0.4 mM NH4COOH 90:10 MEOH/Water
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9.2. Standard Solution Preparation #1
Compounds to be analyzed: Cyclohexylamine, 2-Hydroxybenzothiazole, N,N-
Dicyclohexylmethylamine, and Bis(2,2,6,6-tetramethyl-4piperidyl sebecate)
9.2.1. Add 1 mL of MeOH to an evaporated TCRS standard to give a concentration of
10,000 pg/|iL. The TCRS standard analytes can be found in the SOP titled
Extraction and Analysis of SVOCs in Tire Crumb Rubber Samples (SOP# D-
EMMD-PHCB-033-SOP-01) . From this sample, prepare a series of solutions
to generate a calibration curve. Prepare dilutions in 50:50 ACNiFhO with 0.1%
formic acid. The table below shows the dilutions and constituents of each
sample which are prepared to a final volume of 1 mL.
Table 2. TCR standards for calibration curve
Concentration of
Vol of Std
Vol of IS* @
Vol of solvent
STD (pg/nL)
(nL)
1000 pg/|iL
ACN:H20 (|iL)
200
200
100
700
150
150
100
750
100
100
100
800
80
80
100
820
60
60
100
840
40
40
100
860
20
20
100
880
10
10
100
890
5
5
100
895
*Internal Standard is "CeAtrazine
9.2.2. Prepare vials (1 mL) of blank solvent and of IS (100 pg/|iL) for analysis.
9.3. Standard solution preparation #2
Compounds to be analyzed: Dicyclohexylamine and 2-mercaptobenzothiazole
9.3.1. Add 1 mL of MeOH to an evaporated TCRS standard to give a concentration of
10,000 pg/|iL. From this sample, prepare a series of solutions to generate a
calibration curve. Prepare dilutions in 50:50 MeOH:H20 with 0.1% formic
acid. The table below shows the dilutions and constituents of each sample
which are prepared to a final volume of 1 mL. Note that there is no internal
standard for this procedure.
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Table 3. TCR standards for calibration curve
Concentration of
Vol of Std
Vol of solvent
STD (pg/nL)
(nL)
MeOH:H20 (|iL)
200
200
700
150
150
750
100
100
800
80
80
820
60
60
840
40
40
860
20
20
880
10
10
890
5
5
895
9.3.2 Prepare vials (1 mL) of blank solvent for analysis.
9.4. Tire Crumb Rubber Study Standard Preparation
Two sets of calibration standards were prepared from TCRS Standard mix (1 ng/|iL);
one set was prepared in 50:50 Me0H:H20 and the other was prepared in in 50:50
ACN:H20. Table 4 below displays the volumes of solvents used to prepare the
standards.
Standard
Concentration (pg/jiL)
Volume of TCR mix
(1 ng/jiL)
Volume of solvent / jiL
MeOH:H20 or ACN:H20
5
5
995
10
10
990
20
20
980
40
40
960
60
60
940
80
80
920
100
100
900
150
150
850
200
200
800
250
250
750
Table 4. Calibration Standards prepared from the Tire Crumb Rubber standard mix.
9.5. TCRS LC sample prep
9.5.1. Organize TCRS samples per batch according to earlier Gas Chromatography
preparations. Prepare 0.1% Formic Acid (FA) by adding 100 |iL of FA in 100
mL of H20 and 100 mL of ACN separately.
9.5.2. Prepare a stock solution of methyl paraben 13C6 by adding 50 |iL of 1,000,000
pg/ |iL methyl paraben 13C6 to 5 mL of MeOH for a resulting concentration of
10,000 pg/|iL.
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9.5.3. Prepare a stock solution of atrazine 13C3 by adding 200 |iL of 100,000 pg/|iL
atrazine 13C3 to 20 mL of MeOH for a resulting concentration of 1,000 pg/|iL.
9.5.4. Prepare 150 mL of the IS by mixing 1.5 mL of 10,000 pg/|iL methyl paraben
13C6 with 15 mL of 1,000 pg/|iL atrazine 13C3 and diluting to a final volume
of 150 mL using 50:50 0.1 % FA in H20:ACN, resulting in 100 pg/|iL
solution.
9.5.5. Add 1 mL of IS to each TCRS sample and vortex. Some samples contain
particulate matter after shaking and will need to be filtered before LC analysis.
9.5.6. Pipette the samples into centrifuge tube containing a filter (microcon-10
centrifugal filter, regenerated cellulose 10,000 NMVL).
9.5.7. Centrifuge the samples for 25 min at 13000 rpg. If the full volume of the
sample does not fit entirely into the filter, repeat the process until the entire
sample is filtered.
9.5.8. After filtering, transfer the samples into labeled amber vials for LC analysis
9.6. Instrument setup
General operation and maintenance of the UPLC-MSMS system are not detailed here.
Users show follow Waters® Xevo® TQD ACQUITY UPLC® System Customer
Familiarization Guide 1 for UPLC-MSMS and manufacturers recommendations. User
must be familiar with MassyLnx 4.1 operational software.
Start un:
9.6.1. Double click to startup Masslynx from Icon in Desktop
9.6.2. At the default sample list go to file and open project
9.6.3. Select TCR1172017.PRO or Desired Project
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SOP # D-EMMD-PHCB SOP-2327-O
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Page 11 of 31
9.6.4. Single Click on MS Instrument Console
I**/] MaiiLyru - TCR11172Q17 - in5tfument,;larlup^^J
E'le Kiew Bun Help
aS • I LJ U I | ~ a BR II
Instrument
Spectrum chrorr
P
1 pA_M E OH_Q110
Ed»t shutdown or Startup
Shutdown
9.6.5. Select System startup for MS Console Window
Sti &rwy Schwx
• Sampte Manag# PTN
Hi POAOtteHr
;t'i Xevo TOO
Pkau
Warterunc* Cftrtm
Log«
Start up syrtsm
Piwre A8 t-sK«ra
Piitw ««d
Colurr £ld£yt#&
»&r&$C4«»n
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9.6.6. Check all
9.6.7. Select BSM, check all and set Duration for 10 min
System Startup
Prime Solvents | ptiona :t arac1
| sr« bsm|
Binary Solvent Manager
[V) Prime A! gj Prime B1
[7] Prime Seal Wash
[g Prime A2 gfj Prime B2
Duration of prime:
110.0 | min
[ Set Defaults..
Start ] Close
9.6.8. From MS Console Window Click on flow ml/min and set to flow =0.250,
Al=50, B1 =50
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9.6.9. Turn on PDA Lamp, Collison gas, API Gas and Operate by clicking the Icons
on the let of MS Console Page. The lights will turn form red to green.
9.6.10. Select Binary Solvent Manager from MS Console Page. The Delta shown
should be below 25.
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9.6.11. System is ready for use
9.7. Quantitation- Setting up Standard Curve
9.7.1. Choose a mid-point in the standard range i .e 500 pg/|il by clicking to highlight
row 6.
ito * to sto
ParaOMW i*TD 1 *
tnjM
in I'M
1
i» 7« sea
iM OM Too tlo
• to ' ?to ' »to
1»
i
rto »fe
100 700 149
390 600 too ten
•1
t-=e
*toT«
ell's
T "S3
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9.7.2. On the chromatogram screen select: Display Remove
9.7.3. Select remove all and click OK
Remove Chromatogram
Remove Chromatogram
i-43-r
Chromatograms: J
Chtomalograms:
OK
A
7:071 SI5_5 Mix Paraben$_ISTDJ_36 -
6:071815 5 Mix Parabens ISTO 1 36 C***1 1
m
a
¦"Ijil
:f|»J
ifitl
Cancel |
5:071 SI5 5 Mix Parabens ISTD 1 36 "
" I ,
-
1 A" 1
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9.7.4. Go to display and select Mass
r™1
I S M. i m JJCSJ l*—
j -J- """¦ -
500 p-f^uL p
| A -ft ,fL © CV Of QJ» „
XEVO-TOOaQGAM
M Tta
Ciyft«o*4 .
V M
•*r« T* LMI
MMT»P«rrt
hi.' "n Dr^l La^ GH
0* Ai>o 201 & 1*6:21 :B3
9.7.5. Select the Methyl paraben 13C6 - Note to he used as the internal standard.
Double click on Channels 2.
Mass Chromatogram
File; 071615_5_Min_Pafabens_IST D_1_36
Description (chart):
OK
Cancel
File.
Function:
1; MRM of 2 Channels E S • Methyl paraben *
1 ¦ MRM of 2 Channels ES* Methyl paraben
Select All
Channeb:M.TJ;lggil»tt«ig-,iW.!.l*flSP.!fflB!-'?-'.,->-AK»H.
3; M RM of 2 Channels £S- Etfiyl paraben •'* Add trace
4: MRM of 1 Channel ES- 24eV Propyl paraben
5: MRM of 2 Channete ES - Guiylparaben Replace Uace
6: MRM of 2 Channete ES - n-Sutyl parafcien 13C8 r
7: MS2 (80.500] ES-CeV
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9.7.6. Click Select All. Select Add trace. Click OK.
Mass Chromatogrsm
FSe 071615_S_MtK_Pa»6ert_lST D_1_3S
OewaipSwi fchan)
[Chi ,Oi2
Fundionc 12: MRN ol 2 Channels £$- Methyl parabenl; |
Channels:
OK.
Cancel
Fie
1 157 036 > 9? 913 |Me%t parabenl 3C6J
2:157.036 > 141.974 |Me
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Chromatogram Display View
Normalize Data To:
f* Largest Peak
C Intensity (5
I- Normalise to Summed Trace
Baseline at Zero
Baseline abs [SO
'* Baseline % [o
Lowest Point
r Link Vertical Axes
Axis Label
Horizontal Axis
| Time ~^1
Style
I- Overlay Graphs
r Fill Trace
V Fill Detected Peaks
P Peak List
1
Split Axis
Overlay Step {%) [q
Grid
Off
OK.
W Graph Header
17 Process Description
17 Component T able
"3
Cancel
Header..
9.7.8. Click on the peak chromatogram window and color square appears across from
the % sign to select. Click on process and select smooth.
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Q Owc**atC9»»m - C07H&JS_5_Mcs_Pw«w Ml 974 (Mefliyt para&wl3C6)
1.57 6 23&3
120
"¦f"
1 70
1 60 1 90
? MRM <* 2 Ownnflj £S-
7 036 > 97 913 (Methyl paW&WH3C6)
1 3Se4
ri ¦ 11 ¦¦ 11 ¦¦¦¦!¦¦¦>,¦¦¦¦
rJIML JJ8L ,UI rL2Xl
SSITOTOHII RS I Fii^l
9.7.9. Enter 3 for Window size (scan) /-
9.7.10. Enter 2 for Numb er of Smooth s
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9.7.11. Select Mean for smoothing method. Click OK.
r
Smooth chromatogram
Window size (scans) ± OK
Number of smooths B Cancel
Smoothing method
(* Mean
f Savitzky Golay
9.7.12. Click on unsmoothed peaks and press the delete key.
s Ch*c*nito9.»m - 0371«15_5_M»_PwbmjJSID_l_3*3
& a is ¦§ sb ^ e ix a Li & a *5 o ' or or or ™ ~ ~ w- jfl te u <3
500 pg/uL parabens
071615_5_Mu_Parabe*i5jSTD_l_36 Sm 07 013 {Methyl para&enT3Cefr
1 17CJ
¦ ¦ ¦ ¦ 1 ". 11 I
1 60 1 70 180 100
2 mam or 2 Cn«mnef5 ES-
157 036 > 141 074 iMethyl parat*n13C6>
4 87e3
r,»
000 100
1 10 1 20
"T—»1
1.40 150
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-------
SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 21 of 31
9.7.13. On the sample list page Click on TargertLynx. Click on Edit Method.
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-------
SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 22 of 31
9.7.14. Go to file and select Open.
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-------
SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 23 of 31
9.7.16. Go to file click on save as Select Project
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-------
SOP # D-EMMD-PHCB-SOP-2327-O
Effective Date: 01/29/2018
Page 24 of 31
9.7.18. Click on Update. Check Quantitation Ion. Check Compound name.
9.7.19. Arrange the Method window and the Chromatogram windows side by side by
holding the left mouse button on the Method page and dragging to left. Click
on compound A. Note: Compound will be used as the internal standard i.e.
13C6 Methylparaben.
9.7.20. Click on First Icon "User Defined Properties"
9.7.21. Click on Compound A
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SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 25 of 31
a. Select user define properties
b. Right click on Peak 156.036>97 in Chromatogram window and drag a
bracket across the peak.
9.7.22. Enter the following:
a. Response Uses - Area
b. Response Type - External (absolute- no internal standard)
m
9.7.23. Click on Integration Properties
9.7.24. Click "Yes" on Smoothing Enabled
a. Enter 3 Smoothing Iterations
b. Enter 2 for Smoothing Width
-------
SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 26 of 31
9.7.25. Click on Target Ion Properties
9.7.26. Right click on Peak 156.036> 141.974 in Chromatogram window and drag a
bracket across the peak.
hi
9.7.27. Click on the save button.
9.7.28. Return to the Sample List.
9.7.29. Highlight Row 2 -11 by dragging Mouse from row 2 -10.
-------
SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 27 of 31
9.7.30. Click on Process samples.
9.7.31. Check the following:
a. Intergrate Sample
b. Calibrate Standards
c. Quantify Sample
d. Click OK
B
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-------
SOP # D-EMMD-PHCB-SOP-2327-O
Effective Date: 01/29/2018
Page 28 of 31
9.7.32. Click on Line 3-10 pg/|il parabens. Note: All retention times show be with +/-
% set in Method.
j a • " c y^3 i o» •!V< * • 5( r~r~ ' an b li • # =[T •» *
-------
SOP # D-EMMD-PHCB SOP-2327-O
Effective Date: 01/29/2018
Page 29 of 31
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-------
SOP # D-EMMD-PHCB-SOP-2327-O
Effective Date: 01/29/2018
Page 30 of 31
10. Data and Records Management
10.1. Raw data (including electronic data on individual PC hard drives and group shared
drives) should be backed up, maintained and made available for review.
10.2. A consistent file naming convention should be documented and used for each specific
project and data type generated.
10.3. Upon completion, data should be stored in accordance with EPA's record
management policy.
10.4. All instrument data should be backed up to network drives on a regular basis and
should be archived along with other supporting data and relative correspondence at
the completion of the study.
10.5. Printed data should be referenced, signed and dated in accordance with the Office of
Research & Development's Policies and Procedures Manual.
11. Quality Assurance/Quality Control
11.1. Analysis of standard solutions should result in a best fit regression coefficient of
determination (r2) of 0.99 or greater, using a minimum of six independent
concentrations that bracket the sample concentrations. Sample concentrations
resulting in peak area ratios that are lower or greater than the range of standards
should be reanalyzed with appropriate re- extraction or dilution of original water
sample, respectively.
11.2. A blank sample must be analyzed every 10 samples. The blank must be prepared for
50:50 Water: Acetonitrile (H20:ACN). When contaminations is noted analysts
should stop the analysis and investigate further to identify the source of
contamination before continuing.
11.3. A method blank must be analyzed prepared from mobile phase solvents A and B
between every 10 samples. If significant analyte levels (S/N > 5) are found in the
laboratory method blank, the source of contamination should be identified, corrected,
and verified as being eliminated before additional analyses of unknown samples
proceed.
11.4. For quality control check samples of deionized water fortified at one concentrations
that bracket the six-point curve. A QC standard should be analyzed between every 10
samples. Data is considered acceptable if the calculated recoveries are within 70% of
the expected values.
11.5. Recovery % = (Actual/Known) * 100 where actual is result received from analysis
and known is the prepared results.
-------
SOP # D-EMMD-PHCB-SOP-2327-O
Effective Date: 01/29/2018
Page 31 of 31
12. References
Determination of Dicyclohexylamine and Fumagillin in Honey by LC-MS/MSJohan P. van
den Heever & Thomas S. Thompson & Jonathan M. Curtis & Stephen F. Pernal Springer
Science+Business Media New York 2014
Simultaneous determination of benzotriazole and benzothiazole derivatives in aqueous
matrices by mixed-mode solid-phase extraction followed by liquid chromatography-tandem
mass spectrometry; I. Carpinteiro & B. Abuin & M. Ramil & I. Rodriguez &
R. Cela # Springer-Verlag 2012
Rapid and sensitive LC-MS-MS determination of 2-mercaptobenzothiazole, a rubber
additive, in human urine; Wolfgang Gries & Katja Kiipper & Gabriele Leng
# Springer-Verlag Berlin Heidelberg 2015
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[This page intentionally left blank.]
-------
U.S. Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Extraction and Analysis of SVOCs in Tire Crumb Rubber Samples
Number: D-EMMD-PHCB-033-SOP-01
Effective Date: 9/12/16
SOP was Developed
0 In-house
~ Extramural
SOP Steward
Name: M. Scott Clifb
Date:
pproval
Name: Myriam Medina-Vera
Title: Branch Chief, RHCB
Date: #
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 2 of 14
Extraction and Analysis of SVOCs in Tire Crumb Rubber Samples
Section
1.0 Scope and Application 3
2.0 Summary of Method 3
3.0 Definitions 4
4.0 Health and Safety Warnings 5
5.0 Materials and Equipment 5
6.0 Interferences 6
7.0 Personnel Qualifications 6
8.0 Method Calibration 6
9.0 Sample Collection, Preservation and Storage 6
10.0 Analytical Procedure 7
10.1 Sample Preparation, Extraction and Processing 7
10.2 Sample Analysis by GC/MS/MS 9
10.3 Sample Analysis by LC/TOF 9
12.0 Quality Control and Quality Assurance 9
Table 1 Stock Solution Preparation 10
Table 2 GC/MS/MS Parameters 11
Table 3 Compounds and Data Collection Parameters 12
-------
Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-033-SOP-01
September 12, 1016
Page 3 of 14
1.0 Scope and Application
Tire crumb rubber (TCR) is a material made from recycled tires that is used as
infill for synthetic turf athletic fields. In order to investigate the potential health
effects from human exposure to the tire crumb material, it is essential to be able to
measure the chemicals from the rubber itself. This method will be used for
extraction and analysis of semi-volatile organic compounds (SVOCs) from the
TCR.
2.0 Summary of Method
Samples of TCR are stored in a freezer at -20° C after receipt at the EPA lab. The
samples are allowed to warm to room temperature, then the sample is
homogenized inside of the collection jar by shaking in a manner to cycle the
content from the bottom to the top of the jar. Two separate lg aliquots will be
removed from each sample, shaking between each aliquot, with each being
transferred to a clean 50 mL polypropylene centrifuge tube. Internal Standard
solution is added to each tube along with a ceramic homogenizer. 10 mL of 1:1
acetone:hexane is then added to each sample tube. The tubes are capped and are
vortex mixed for 1 minute, allowed to sit for 2 minutes, then vortex mixed for an
additional minute. The tubes are then centrifuged at 4000 RPM for 5 minutes. The
solvent is removed and is transferred to a 15 mL vial. A 1 mL aliquot of the
extract is transferred to an autosampler vial for GC/MS/MS analysis. Another
aliquot is transferred to a vial where it is solvent exchanged to methanol for
LC/TOF analysis. Since there is no appropriate surrogate matrix for TCR, QAQC
samples will consist of a duplicate preparations, a reagent spike, reagent blank
and a TCR sample prepared from a TCR designated as a reference sample.
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 4 of 14
Definitions
3.1 Tire Crumb Rubber Samples - Samples of tire crumb collected at a
processing facility or from a synthetic turf field.
3.2 Spiking Solution - Solution containing stable isotope labeled chemicals
representative of target analytes. Aliquots of this solution are transferred
to blank media to prepare lab spikes.
3.3 Internal Standard Solution (IS) - Solution containing compounds used
to normalize instrument response. This solution is added to all standards,
spikes and blanks as indicated in the procedure.
3.4 Check Standard - A mid-level calibration standard that is analyzed
between ten sequential sample extracts to determine the continued
accuracy of the calibration curves.
3.5 Reagent Blank - A matrix free extract that is prepared and analyzed to
assess contamination and interferences from the materials and method.
3.6 Reagent Spike - A matrix-free extract that has been fortified and has been
through the extraction procedure to determine losses or interferences from
the method.
3.7 TCR Control - An extract prepared from a previously characterized TCR
sample that is used to evaluate performance of select chemicals that are
native to that sample.
3.8 TCR Reference Sample - A TCR sample that will have aliquots removed
and analyzed for each sample batch to determine the continuing
performance of the analytical method.
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 5 of 14
4.0 Health and Safety Warnings
4.1 Follow the procedures detailed in the Health and Safety Research Protocol
for your study or task.
4.2 Follow proper operating procedures for all equipment and instruments
used.
5.0 Materials and Equipment
5.1 50 mL polypropylene centrifuge tubes with caps, Falcon Tubes or
equivalent (Corning part No. 352098)
5.2 Spiking and Internal Standard (IS) Solutions, (See Tables 1 and 2).
5.3 TCR Reference S ampl e
5.4 Adjustable repeating pipette, Eppendorf Repeater, XStream or equivalent
5.5 Ceramic Homogenizers (Agilent part no. 5982-9313)
5.6 Acetone, Pesticide residue grade or equivalent
5.7 Hexane, Pesticide residue grade or equivalent
5.8 Methanol, HPLC grade or equivalent
5.9 Top loader pipettes, adjustable volume
5.10 Vortex mixer (Vortex Genie II, multi-tube vortex mixer or equivalent)
5.11 Centrifuge, capable of timed runs at 4000 RPM
5.12 15 mL amber vials w/PTFE-lined caps (Supelco part no. 27088-U or
equivalent)
5.13 Autosampler vials, 2 mL, caps with PTFE-lined septa
5.14 Gas Chromatograph with Triple Quadrupole mass spectrometer
(GC/MS/MS), Agilent 7890/7010 or equivalent
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 6 of 14
6.0 Interferences
Interferences are any component that interferes with the quantitative analysis of
the compounds used in this study. Interferences will be identified and evaluated as
part of this study's ongoing QA/QC plan.
7.0 Personnel Qualifications
This SOP is written to be used by personnel familiar with the equipment and
procedures that are used. Personnel should be adequately trained and display
proficiency with those techniques prior to using this SOP for sample analysis.
8.0 Method Calibration
The GC/MS/MS instrument should be calibrated for the analytes using the
parameters listed in Tables 3 through 6 prior to sample analysis. Calibrate the
GC/MS/MS system in a range from O.lng/mL to 500 ng/mL using the following
calibration levels (ng/mL): 0.1, 0.5, 1.0, 2.5, 5,10,25,50,100,250,500. The
calibration will be monitored by running a mid-level check standard between
every 10 samples. A check standard must be within ±25% of its prepared
concentration for the calibration to remain valid. If an analyte does not pass the
±25% criterion, but is not found in any of the relevant samples, the analysis may
continue unless the response has decreased to the point of compromising the
ability to detect that analyte.
If a check standard fails, investigate the problem and take corrective action.
Recalibrate the instrument and begin sample analysis from the point of the last
good calibration check.
9.0 Sample Collection, Preservation and Storage
Tire crumb rubber samples will be stored under freezer (-20° C) at the EPA
laboratory. Samples will be allowed to warm to room temperatures prior to
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 7 of 14
removing aliquots for analysis and will be returned to freezer storage immediately
following aliquot removal. Sample extracts will also be stored under freezer
conditions -20° C) in cases where analysis cannot be performed immediately.
Recap and store the autosampler vials after the analysis for later use, if needed.
Since PAHs are being analyzed, protect the extracts from light.
10.0 Analytical Procedure
10.1 Sample Preparation, Extraction and Processing
Remove the tire crumb rubber samples from the freezer and allow to warm
to room temperature (approximately 30 minutes). Mix the tire crumb
material well by shaking and rotating. For each sample, weigh three lg
aliquots into individual 50 mL polypropylene tubes, mixing well between
aliquots. Record the weights.
One sample batch will consist of triplicate aliquots from 24 tire crumb
rubber samples prepared in duplicate along with the following QAQC
samples.
1 Reagent Spike
1 Reagent Blank
1 Reference TCR Sample
10.1.1 Reagent Spike Preparation
1. Label a clean 50mL polypropylene tube as the Reagent Spike.
2. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
3. Fortify the solvent in the tube with 100 |iL of spiking solution and
100 |iL of Internal Standard solution.
4. Cap and process with TCR samples.
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 8 of 14
Reagent Blank Preparation
1. Label a clean 50mL polypropylene tube as the Reagent Blank.
2. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
3. Fortify the solvent in the tube with 100 |iL of Internal Standard
solution.
4. Cap and process with TCR samples.
TCR Reference Sample Preparation
1. Weigh a lg aliquot of the TCR material selected as the reference
sample into a clean 50 mL polypropylene tube and record the
weight.
2. Prepare along with other TCR samples using the steps in 10.1.4.
Samples
1. Transfer a 100 |iL aliquot Internal Standard solution to the surface
of the TCR in each sample.
2. Add a ceramic homogenizer and 10 mL or 1:1 acetone:hexane.
3. Vortex for 1 minute.
4. Allow to sit for 2 minutes.
5. Vortex for an additional minute.
6. Centrifuge at 4000 RPM for 5 minutes.
7. Transfer the solvent layer to a 15 mL amber tube with PTFE-lined
cap.
8. Transfer a 1 mL aliquot to an autosampler vial for GC/MS/MS
analysis.
9. Transfer a second 1 mL aliquot from each sample extract to a clean
anutosampler vial.
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 9 of 14
10.2 Sample Analysis by GC/MS/MS
Analyze samples by GC/MS/MS using the conditions specified in Tables 3 and 4.
10.3 Sample Analysis by LC/TOF
Analyze samples by LC/TOF using the conditions specified in D-EMMD-PHCB-
034-SOP-01 - Analytical method for non-targeted and suspect screening in
environmental and biological samples using Time of Flight Mass Spectrometry
(TOFMS).
12.0 Quality Control and Quality Assurance
Data will be reviewed by EMMD QA staff. The data quality objectives and
review procedures from the Quality Assurance Project Plan QAPP for the study
being conducted will dictate specific quality assurance practices. All QA practices
will be consistent with the NERL Quality Management Plan.
The Reagent Spike, Reagent Blank and Reference Sample will serve to measure
method performance for each sample. Target recovery for the reagent spike should
be ± 30% of the nominal concentration for each analyte. Any deviations will be
recorded and investigated. The measured concentrations in the Reference Sample
will be recorded and compared among batches to evaluate any potential issues
related to a specific batch as well as to evaluate long-term accuracy of the method as
a whole.
13.0 Records
Chain of custody records will be maintained to document the removal and
extraction of each TCR sample. Those records will be maintained by the study
coordinator upon completion of the analysis. Records of sample preparation and
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 10 of 14
analysis will be maintained in a 3 ring binder which will be transferred to the study
coordinator upon completion of sample analysis.
Table 1 Stock Solutions
Catalog Number Concentration
Spiking Solution
PAH Mix
S-70846-02a
10 |ig/mL
Phthalate Mix
S-70846-01a
10 |ig/mL
TCR Mix
S-70846-03a
10 |ig/mL
Internal Standard Solution
PAHs
Chrysene D12
ES-5164b
480 ng/mL
Phenanthrene D10
ES-5164
480 ng/mL
Acenaphthene D10
ES-5164
480 ng/mL
Benz [a] anthracene D12
ES-5164
480 ng/mL
Naphthalene Dx
ES-5164
480 ng/mL
Perylene D12
ES-5164
480 ng/mL
Fluoranthene D10
ES-5164
480 ng/mL
Benzo[b]fluoranthene D12
ES-5164
480 ng/mL
Benzo[a]pyrene D12
ES-5164
480 ng/mL
Benzo[g,h,i]perylene D12
ES-5164
480 ng/mL
Indeno[l,2,3-cd]pyrene D12
ES-5164
480 ng/mL
Dibenz[a,h]anthracene D14
ES-5164
480 ng/mL
Acenaphthalene Dx
ES-5164
480 ng/mL
Fluorene D10
ES-5164
480 ng/mL
Pyrene D10
ES-5164
480 ng/mL
Benzo[k]fluoranthene D12
ES-5164
480 ng/mL
Phthalates
Diethyl phthalate D4
DLM-1629-1.2b
480 ng/mL
Di-N-hexyl phthalate 1,2 13C2
CLM-4669-1.2b
480 ng/mL
Bis(2-ethylhexyl)phthalate D4
DLM-1368-1.2b
480 ng/mL
Benzyl butyl phthalate D4
DLM-1369-1.2b
480 ng/mL
Other
Dibenzothiophene Ds
DLM-2206-0.1b
1050 ng/mL
Suppliers:
a Accustandard
b Cambridge Isotope Labs
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Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-03 3 - SOP-01
September 12, 1016
Page 11 of 14
Table 2 GC/MS/MS Parameters
Parameter Value
GC System
Injector
Column
Temperature
Program
Detector
Agilent 7890 Gas chromatograph
Capillary injector in splitless mode
Pulsed splitless at 25 psi for 0.5 min, then split at 50 mL/min at 1 min.
Temperature: 250°C
Liner: Single gooseneck glass, deactivated
Injection volume: 1 |iL
Agilent VF-5ms, 30 M x 0.25 mm x 0.25 |im,
Column flow: 1.2 mL/min
50° C for 2 min to 325° C at 10° C/min, hold 5 min.
Agilent 7010 Triple Quadrupole
Mode: Electron Impact (EI) operating in MRM/Scan mode
Electron Multiplier Voltage by Gain Curve
Transfer Line: 300°
-------
1
1
1
2
2
3
3
4
4
4
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
7
7
8
8
8
8
8
9
Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-033-SOP-01
September 12, 1016
Page 12 of 14
Table 3
Compounds and Data Collection Parameters
Prodi
Prod2
Compound
Class
RT
Prel
Prod 1
CE
Pre2
Prod 2
CE
Cyclohexaneamine
TCR
4.471
69.8
43.1
15
99.8
56
10
Analine
TCR
6.521
92.7
66.1
15
65
39.1
15
n-Butylbenzene
TCR
7.858
90.5
65.1
20
134
91.2
25
Naphthalene d8
PAH
9.956
136
108.1
10
136
84.1
30
Naphthalene
PAH
10.003
127.9
102.1
20
127.9
78.1
20
Benzothiazole
TCR
10.62
135
82.1
30
135
108
20
Cyclohexylisothiocyanate
TCR
10.713
81.9
67
10
140.6
55.1
25
Resorcinol
TCR
11.241
109.8
82.1
15
109.8
69
20
2-Methylnaphthalene
PAH
11.638
142.3
141.2
20
142.3
115.1
45
1-Methylnaphthalene
PAH
11.863
142.3
141.2
20
142.3
115.1
45
Dicyclohexamine
TCR
13.229
137.5
56.1
10
137.5
83.1
15
Dimethyl phthalate
Phthalate
13.584
163
77
30
163
135
15
Acenaphthalene d8
PAH
13.712
159.9
158.1
20
159.9
132.1
20
Acenaphthalene
PAH
13.743
151.9
126.1
30
151.9
102.1
30
Phthalimide
TCR
13.889
146.8
103.1
10
146.8
76.1
35
Acenaphthene dlO
PAH
14.092
164.1
162.1
30
162.1
160.1
15
Acenaphthene
PAH
14.169
152.1
126.1
30
152.1
102.1
30
2,6-Di-tert-butyl-p-cresol
N,N-
Dicyclohexylmethylamine
TCR
14.241
144.5
105.1
15
144.5
129.1
20
TCR
14.33
151.5
70.1
10
151.5
55.1
25
Diethyl phthalate d4
Phthalate
15.252
153
69.1
50
153
97.1
30
Diethyl phthalate
Phthalate
15.278
149
65
30
149
93
20
n-Hexadecane
TCR
15.322
85.1
43.1
10
98.9
57.1
10
Fluorene dlO
PAH
15.33
176
174.2
20
175
172.1
50
Fluorene
PAH
15.401
166.1
165.1
15
165.1
164.1
15
4-tert-Octylphenol
TCR
15.453
106.8
77.1
20
134.3
107.1
15
2-
Bromomethylnaphthalene
PAH
16.29
140.6
115.1
20
219.8
141.1
10
2-Flydroxybenzothiazole
BT
16.396
150.7
96.1
25
150.7
123.1
20
Dibenzothiophene d8
BT
17.34
191.5
146.1
50
191.5
160.1
30
Dibenzothiophene
BT
17.385
183.4
139.1
25
183.4
152.1
50
Phenanthrene dlO
PAH
17.622
188.3
160.2
40
188.3
186.3
30
Phenanthrene
PAH
17.678
177.9
152.1
25
176.1
150.1
25
Anthracene
PAH
17.8
177.9
152.1
25
176.1
150.1
25
Diisobutyl phthalate
Phthalate
18.249
149
65
25
149
93
15
Pre3 Prod 3
Prod3
CE
114.7
114.7
89.1
89.1
20
20
-------
9
9
9
9
10
11
11
11
11
12
12
12
13
IB
13
13
13
13
13
13
14
15
15
15
15
15
15
15
15
15
16
16
16
16
Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-033-SOP-01
September 12, 1016
Page 13 of 14
Compound
Class
RT
Prel
Prod 1
Prodi
CE
Pre2
Prod 2
Prod2
CE
Pre3
Prod 3
Prod3
CE
3-Methylphenanthrene
PAH
18.843
192.2
191.2
20
188.7
163.1
40
192.2
165.1
45
2-Methylphenanthrene
PAH
18.906
188.7
163.1
40
192.2
191.2
20
192.2
165.1
45
1-Methyipherianthrene
PAH
19.153
188.7
163.1
40
192.2
191.2
20
192.2
165.1
45
Dibutyl phthalate
Phthalate
19.212
149
65
30
149
93
20
2-Mercaptobenzothiazole
TCR
19.45
166.5
123
10
166.5
109
30
Fluorantherie dlO
PAH
20.467
211.9
210.2
20
211.9
208.1
20
Fluoranthene
PAH
20.51
202.1
200.1
30
202.1
152.1
30
Pyrene dlO
PAH
20.994
211.9
210.2
20
211.9
208.1
20
Pyrene
Di-N-hexylphthalate
(2)13C2
PAH
Phthalate
21.036
22.647
201.1
153
200.1
66
15
25
200.1
153
174.1
95.1
30
20
Benzyl butyl phthalate d4
Phthalate
22.756
153
69.1
25
153
97.1
5
Benzyl butyl phthalate
Phthalate
22.77
149
65
25
91
65
15
bis(2-Ethylhexyl) adipate
Phthalate
23.017
147
55.1
25
111
55.1
15
Benz(a)anthracene dl2
PAH
23.858
240.2
236.2
50
118.1
116.1
15
Benz(a)anthracene
PAH
23.911
228.1
226.2
30
114
101.1
10
Chrysene dl2
PAH
23.929
240.2
236.2
50
118.1
116.1
15
Chrysene
Bis-2-ethylhexyl phthalate
d4
PAH
Phthalate
23.989
24.165
228.1
153
226.2
69.1
30
25
114
153
101.1
97.1
10
20
Bis-2-ethylhexyl phthalate
Phthalate
24.184
149
65
30
149
93
20
1-Hydroxypyrene
PAH
24.195
217.5
189.1
40
188.5
163.1
40
Di-n-octyl phthalate
Phthalate
25.65
149
65
30
149
93
20
Benzo(b)fluoranthene dl2
PAH
26.243
263.9
260.2
50
132.2
118.1
10
Benzo(b)fluoranthene
PAH
26.297
126.1
113.1
10
252.1
250.2
35
Benzo(k)fluoranthene dl2
PAH
26.311
263.9
260.2
50
132.2
118.1
10
Benzo(k)fluoranthene
PAH
26.355
252.1
250.2
35
126.1
113.1
10
Benzo(e)pyrene dl2
PAH
26.84
264
260.2
40
132.2
118.1
15
Benzo(e)pyrene
PAH
26.86
252
250.2
50
125
112
20
Benzo(a)pyrene dl2
PAH
26.907
264
260.2
40
132.2
118.1
15
Benzo(a)pyrene
PAH
26.959
252.1
250.1
35
125
124.2
10
Perylene dl2
PAH
27.08
264
260.1
40
130.1
116.1
15
Bis(2,2,6,6-tetramethyl-
4piperidyl) sebecate
lndeno[l,2,3-cd]pyrene
dl2
Dibenz(a,h)anthracene
dl4
TCR
PAH
PAH
28.153
28.988
29.022
123.6
288
288
107.1
284.2
284.2
10
50
50
97.6
288
288
42.1
286.2
286.2
20
40
40
lndeno(l,2,3-cd)pyrene
PAH
29.03
138.1
137.2
10
137
136.1
15
-------
Tire Crumb Rubber SVOC Analysis
D-EMMD-PHCB-033-SOP-01
September 12, 1016
Page 14 of 14
Time Prod
Segment
Compound
Class
RV
Prelb
lc
CEd
Pre2
Prod 2
CE
16
Dibenz(a,h)anthracene
PAH
29.075
138.1
137.2
10
125
124.2
10
16
Benzo(g,h,i)perylene dl2
PAH
29.43
288
284.2
50
288
286.2
20
16
Benzo(g,h,i)perylene
PAH
29.473
276.1
274.1
45
138
125.1
15
17
Coronene
PAH
32.449
299.4
298.1
30
299.4
298.1
30
Pre3 Prod 3 CE
a RT = Retention Time
b Prel = Precursor Ion 1
c Prodi = Product Ion 1
d CE = Collision Energy
-------
SOP # D-EMMD-PHCB-068-SOP-01
Effective Date:7/07/17
Page 1 of 14
? o \
w
PB01&
U.S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Exposure Methods and Measurements Division
Public Health Chemistry Branch
STANDARD OPERATING PROCEDURE
SOP Title: Standard Operating Procedure for Preparation of Synthetic Field Dust
Samples for SVOC Analysis
SOP ID: D-EMMD-PHCB-068-SOP-01
Effective Date: 07/07/2017
SOP was Developed: IE] In-house ~ Extramural: enter organization
SOP Discipline*: Organic Chemistry
Alternative Identification:
SOP Contact Signature
Name: M. Scott Clifton
Signature/Date:
Management Signature
Name: Myriam Medina-Vera
Title: Branch Chief, PHCB
Signature/Date:
QA Signature
Name: SaniaW. Tong Argao
Title: EMMD QA Manager
Signature/Date:
*See discipline descriptions on the NERL Scientific and Technical SOP intranet site.
-------
D-EMMD-PHCB-068-SOP-01
Standard Operating Procedure for Preparation of Synthetic Field Dust Samples for
SVOC Analysis
07/07/2017
Page 2 of 14
Table of Contents
I.0 Scope and Application 3
2.0 Summary of Method 3
3.0 Definitions 3
4.0 Health and Safety Warnings 4
5.0 Materials and Equipment 4
6.0 Interferences 5
7.0 Personnel Qualifications 5
8.0 Method Calibration 5
9.0 Analytical Procedure 6
9.1 Sample and QA/QC Sample Preparation and Extraction 6
9.1.1 Sample Preparation 6
9.1.2 Reagent Spike Preparation 6
9.1.3 Reagent Blank Preparation 6
9.1.4 Matrix Spike Preparation 6
9.1.5 Matrix Blank Preparation 7
9.1.6 Recovery Spike Preparation 7
9.1.7 Internal Standard Addition to the Samples 7
9.1.8 Dust and QA/QC Sample Extraction 7
9.2 Sample Analysis by GC/MS/MS 8
9.3 Sample Analysis by LC/TOF 8
10.0 Records 8
II.0 Quality Control and Quality Assurance 8
Table 1. Spiking and Internal Standard Solutions 9
Table 2. GC/MS/MS Parameters 10
Table 3. Compounds and Data Collection Parameters 11
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D-EMMD-PHCB-068-SOP-01
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Page 3 of 14
1.0 Scope and Application
This SOP details the extraction and work-up procedures for dust samples that are
collected from synthetic turf fields. This SOP is written for the extraction and preparation
of samples for analysis of semi-volatile organic chemicals (SVOCs).
2.0 Summary of Method
Dust samples are stored in a freezer at -20° C after receipt at the EPA lab. The
samples are allowed to warm to room temperature before weighing 100 mg of dust into a
50 mL polypropylene centrifuge tube. Internal Standard solution is added to each tube
along with a ceramic homogenizer. 10 mL of 1:1 acetone:hexane is then added to each
sample tube. The tubes are capped and are vortex mixed for 1 minute, allowed to sit for 2
minutes, then vortex mixed for an additional minute. The tubes are then centrifuged at
4000 RPM for 5 minutes. The solvent is removed and is transferred to a 15 mL vial. A 1
mL aliquot of the extract is transferred to an autosampler vial for GC/MS/MS analysis.
Another aliquot is transferred to a vial where it is solvent exchanged to methanol for
LC/TOF analysis. Quality assurance/quality control (QA/QC) samples will consist of a
duplicate preparation (if enough sample is available), a reagent spike, reagent blank,
method spike, method blank and a recovery spike.
3.0 Definitions
3.1. Synthetic Field Dust Samples - Samples of dust collected from a
synthetic turf field and processed to 150 |im during collection.
3.2. Spiking Solution - Solution containing stable isotope labeled chemicals
representative of target analytes. Aliquots of this solution are transferred
to blank media to prepare method spikes.
3.3. Internal Standard Solution (IS) - Solution containing compounds used
to normalize instrument response. This solution is added to all standards,
spikes and blanks as indicated in the procedure.
3.4. Check Standard - A mid-level calibration standard that is analyzed
between ten sequential sample extracts to determine the continued
accuracy of the calibration curves.
3.5. Reagent Blank - A matrix free extract that is prepared and analyzed to
assess contamination and interferences from the materials and method.
3.6. Reagent Spike - A matrix-free extract that has been fortified and has been
through the extraction procedure to determine losses or interferences from
the method.
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D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 4 of 14
3.7. Method Spike - An extract prepared from fortifying diatomaceous earth
with spiking solution prior to extraction to evaluate recovery from matrix.
3.8. Method Blank - An extract prepared using unfortified diatomaceous
earth to evaluate analyte contribution from the matrix.
3.9. Recovery Spike - An extract prepared using diatomaceous earth that is
extracted and then fortified to evaluate matrix effects and solution errors
assuming 100% recovery.
4.0 Health and Safety Warnings
4.1 Follow the procedures detailed in the Health and Safety Research Protocol
for your study or task.
4.2 Follow proper operating procedures for all equipment and instruments
used.
5.0 Materials and Equipment
5.1 50 mL polypropylene centrifuge tubes with caps, Falcon Tubes or
equivalent (Corning part No. 352098)
5.2 Spiking and Internal Standard (IS) Solutions, (See Tables 1.
5.3 Diatomaceous earth, pre-cleaned, muffled
5.4 Adjustable repeating pipette, Eppendorf Repeater XStream or equivalent
5.5 Ceramic Homogenizers (Agilent part no. 5982-9313)
5.6 Acetone, Pesticide residue grade or equivalent
5.7 Hexane, Pesticide residue grade or equivalent
5.8 Methanol, HPLC grade or equivalent
5.9 Top loader pipettes, adjustable volume
5.10 Vortex mixer (Vortex Genie II, multi-tube vortex mixer or equivalent)
5.11 Centrifuge, capable of timed runs at 4000 RPM
5.12 15 mL amber vials w/PTFE-lined caps (Supelco part no. 27088-U or
equivalent)
5.13 Autosampler vials, 2 mL, caps with PTFE-lined septa
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D-EMMD-PHCB-068-SOP-01
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Page 5 of 14
5.14 Gas Chromatograph with Triple Quadrupole mass spectrometer
(GC/MS/MS), Agilent 7890/7010 or equivalent
5.15 Stainless steel spatula
6.0 Interferences
Interferences are any component that interferes with the quantitative analysis.
Interferences should be evaluated prior to applying this method to study samples.
This method may be modified to deal with interferences if necessary as long as
modifications are documented and are acceptable within a study's QA Plan. If
interferences not identified during method evaluation are discovered with study
samples, they will be identified and evaluated as part of a study's ongoing QA/QC
plan.
7.0 Personnel Qualifications
This SOP is written to be used by personnel familiar with the equipment and
procedures that are used. Personnel should be adequately trained and display
proficiency with those techniques prior to using this SOP for sample analysis.
8.0 Method Calibration
The GC/MS/MS instrument should be calibrated for the analytes using the
parameters listed in Tables 2 and 3 prior to sample analysis. Calibrate the
GC/MS/MS system in a range from O.lng/mL to 500 ng/mL using the following
calibration levels (ng/mL): 0.1, 0.5, 1.0, 2.5, 5, 10, 25, 50, 100, 250, 500. The
calibration will be monitored by running a mid-level check standard between
every 10 samples. A check standard must be within ±25% of its prepared
concentration for the calibration to remain valid. If an analyte does not pass the
±25% criterion, but is not found in any of the relevant samples, the analysis may
continue unless the response has decreased to the point of compromising the
ability to detect that analyte.
If a check standard fails, investigate the problem and take corrective action.
Recalibrate the instrument and begin sample analysis from the point of the last
good calibration check.
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D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 6 of 14
Analytical Procedure
9.1 Sample and QA/QC Sample Preparation and Extraction
9.1.1 Sample Preparation
1. Remove the synthetic field dust samples from the freezer and allow to
warm to room temperature (approximately 30 minutes). Mix the dust
inside the collection vial well using a clean stainless steel spatula. For
each sample, weigh a 100 mg aliquot into a 50 mL polypropylene tube.
Record the weight.
2. One sample batch will consist of up to 24 tire synthetic field dust
samples along with the following QA/QC samples.
• 1 Reagent Spike
• 1 Reagent Blank
• 1 Method Spike
• 1 Method Blank
• 1 Recovery Spike
9.1.2 Reagent Spike Preparation
1. Label a clean 50mL polypropylene tube as the Reagent Spike.
2. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
3. Fortify the solvent in the tube by adding 100 |iL of spiking
solution and 100 |iL of Internal Standard solution.
4. Cap and process with dust samples as outlined in 10.1.7.
9.1.3 Reagent Blank Preparation
1. Label a clean 50mL polypropylene tube as the Reagent Blank.
2. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
3. Fortify the solvent in the tube with 100 |iL of Internal Standard
solution.
4. Cap and process with dust samples as outlined in 10.1.7.
9.1.4 Method Spike Preparation
1. Label a clean 50mL polypropylene tube as the Method Spike.
2. Weigh 100 mg of diatomaceous earth into the tube.
3. Fortify the diatomaceous earth with 100 |iL of spiking solution and
100 |iL of Internal Standard solution.
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D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 7 of 14
4. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
5. Cap and process with dust samples as outlined in 10.1.7.
9.1.5 Method Blank Preparation
1. Label a clean 50mL polypropylene tube as the Method Blank.
2. Weigh 100 mg of diatomaceous earth into the tube.
3. Fortify the diatomaceous earth with 100 |iL of Internal Standard
solution.
4. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
5. Cap and process with dust samples as outlined in 10.1.7.
9.1.6 Recovery Spike Preparation
1. Label a clean 50mL polypropylene tube as the Method Blank.
2. Weigh 100 mg of diatomaceous earth into the tube.
3. Add a ceramic homogenizer and 10 mL of 1:1 Acetone:Hexane to
the tube.
4. Cap and process with dust samples as outlined in 10.1.7.
5. After sample extraction, fortify the extract with 100 |iL of spiking
solution and 100 |iL of Internal Standard Solution.
9.1.7 Internal Standard Addition to the Samples
1. Transfer a 100 |iL aliquot Internal Standard solution to the surface
of the dust for each sample.
2. Add a ceramic homogenizer and 10 mL or 1:1 acetone:hexane.
3. Cap and process with QA/QC samples as outlined in 10.1.7.
9.1.8 Dust and QA/QC Sample Extraction
1. Vortex for 1 minute.
2. Allow to sit for 2 minutes.
3. Vortex for an additional minute.
4. Centrifuge at 4000 RPM for 5 minutes.
5. Transfer the solvent layer to a 15 mL amber tube with PTFE-lined
cap.
6. Transfer a 1 mL aliquot to an autosampler vial for GC/MS/MS
analysis.
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D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 8 of 14
7. Transfer a second 1 mL aliquot from each sample extract to a clean
anutosampler vial for solvent exchange to methanol for LC/TOF
analysis.
8. Store remaining extracts in a freezer at -20° C.
9.2 Sample Analysis by GC/MS/MS
Analyze samples by GC/MS/MS using the conditions specified in Tables
2 and 3.
9.3 Sample Analysis by LC/TOF
Analyze samples by LC/TOF using the conditions specified in D-EMMD-PHCB-
034-SOP-01 - Analytical method for non-targeted and suspect screening in
environmental and biological samples using Time of Flight Mass Spectrometry
(TOFMS).
10.0 Records
Chain of custody records will be maintained to document the removal and
extraction of each dust sample. Those records will be maintained by the study
coordinator upon completion of the analysis. Records of sample preparation and
analysis will be maintained in a NERL laboratory notebook.
11.0 Quality Control and Quality Assurance
Data will be reviewed by the analyst. The data quality objectives and review
procedures from the Quality Assurance Project Plan (QAPP) for the study being
conducted will dictate specific quality assurance practices. All QA practices will
be consistent with the NERL Quality Management Plan.
The Reagent Spike, Reagent Blank, Method Spike, Method Blank, and Recovery
Spike will serve to measure method performance for each sample. Target
recovery for the reagent spike, method spike, and recovery spike should be ± 30%
of the nominal concentration for each analyte. Any deviations will be recorded
and investigated. The measured concentrations in the Reference Sample will be
recorded and compared among batches to evaluate any potential issues related to a
specific batch as well as to evaluate long-term accuracy of the method as a whole.
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D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 9 of 14
Table 1. Spiking and Internal Standard Solutions
Catalog Number Concentration
Spiking Solution
PAH Mix S-70846-02a 10 |ig/mL
Phthalate Mix S-70846-01a 10 |ig/mL
TCR Mix S-70846-03a 10 |ig/mL
Internal Standard Solution
PAHs
Chrysene D12
Phenanthrene D10
Acenaphthene D10
Benz [a] anthracene D12
Naphthalene Dg
Perylene D12
Fluoranthene D10
Benzo[b]fluoranthene D12
Benzo[a]pyrene D12
Benzo[g,h,i]perylene D12
Indeno[l,2,3-cd]pyrene D12
Dibenz [a, h] anthracene D14
Acenaphthalene Dg
Fluorene D10
Pyrene D10
Benzo[k]fluoranthene D12
ES-5164b
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
Phthalates
Diethyl phthalate D4
Di-N-hexyl phthalate 1,2 13C2
Bis(2-ethylhexyl)phthalate D4
Benzyl butyl phthalate D4
DLM-1629-1.2b
CLM-4669-1.2b
DLM-1368-1.2b
DLM-1369-1.2b
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
Other
Dibenzothiophene Ds
DLM-2206-0.T
1050 ng/mL
Suppliers:
a Accustandard
b Cambridge Isotope Labs
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D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 10 of 14
Table 2. GC/MS/MS Parameters
Parameter Value
GC System
Injector
Column
Temperature
Program
Detector
Agilent 7890 Gas chromatograph
Capillary injector in splitless mode
Pulsed splitless at 25 psi for 0.5 min, then split at 50 mL/min at 1 min.
Temperature: 250°C
Liner: Single gooseneck glass, deactivated
Injection volume: 1 |iL
Agilent VF-5ms, 30 M x 0.25 mm x 0.25 |im,
Column flow: 1.2 mL/min
50° C for 2 min to 325° C at 10° C/min, hold 5 min.
Agilent 7010 Triple Quadrupole
Mode: Electron Impact (EI) operating in MRM/Scan mode
Electron Multiplier Voltage by Gain Curve
Transfer Line: 300°
-------
1
1
1
2
2
3
3
4
4
4
5
5
5
5
5
5
5
5
5
D-EMMD-PHCB-068-SOP-01
07/07/2017
Page 11 of 14
Compounds and Data Collection Parameters
Compound
Class
RTa
Prelb
Prod
r
CEd
Pre2
Prod 2
Prod2
CE
Cyclohexaneamine
TCR
4.471
69.8
43.1
15
99.8
56
10
Analine
TCR
6.521
92.7
66.1
15
65
39.1
15
n-Butylbenzene
TCR
7.858
90.5
65.1
20
134
91.2
25
Naphthalene d8
PAH
9.956
136
108.1
10
136
84.1
30
Naphthalene
PAH
10.003
127.9
102.1
20
127.9
78.1
20
Benzothiazole
TCR
10.62
135
82.1
30
135
108
20
Cyclohexylisothiocyanate
TCR
10.713
81.9
67
10
140.6
55.1
25
Resorcinol
TCR
11.241
109.8
82.1
15
109.8
69
20
2-Methylnaphthalene
PAH
11.638
142.3
141.2
20
142.3
115.1
45
1-Methylnaphthalene
PAH
11.863
142.3
141.2
20
142.3
115.1
45
Dicyclohexamine
TCR
13.229
137.5
56.1
10
137.5
83.1
15
Dimethyl phthalate
Phthalate
13.584
163
77
30
163
135
15
Acenaphthalene d8
PAH
13.712
159.9
158.1
20
159.9
132.1
20
Acenaphthalene
PAH
13.743
151.9
126.1
30
151.9
102.1
30
Phthalimide
TCR
13.889
146.8
103.1
10
146.8
76.1
35
Acenaphthene dlO
PAH
14.092
164.1
162.1
30
162.1
160.1
15
Acenaphthene
PAH
14.169
152.1
126.1
30
152.1
102.1
30
2,6-Di-tert-butyl-p-cresol
TCR
14.241
144.5
105.1
15
144.5
129.1
20
N,N-
Dicyclohexylmethylamine
TCR
14.33
151.5
70.1
10
151.5
55.1
25
Pre3 Prod 3
Prod3
CE
114.7
114.7
89.1
89.1
20
20
-------
Time
Segment
Compound
Class
RTa
Prelb
Prod
r
CEd
Pre2
Prod 2
D-EMMD-PHCB-068-SOP-01
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Page 12 of 14
Prod2 „ _ _ Prod3
CE Pre3 Prod 3 CE
-------
12
12
12
13
13
13
13
13
13
13
13
14
15
15
15
15
15
15
15
15
15
D-EMMD-PHCB-068-SOP-01
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Page 13 of 14
u Prod i Prod2 Prod3
Compound Class RF Prel> ^ CE< Pre2 Prod 2 CE Pre3 ProdS CE
Di-N-hexylphthalate
(2) 13C2
Phthalate
22.647
153
66
25
153
95.1
20
Benzyl butyl phthalate d4
Phthalate
22.756
153
69.1
25
153
97.1
5
Benzyl butyl phthalate
Phthalate
22.77
149
65
25
91
65
15
bis(2-Ethylhexyl) adipate
Phthalate
23.017
147
55.1
25
111
55.1
15
Benz(a)anthracene dl2
PAH
23.858
240.2
236.2
50
118.1
116.1
15
Benz(a)anthracene
PAH
23.911
228.1
226.2
30
114
101.1
10
Chrysene dl2
PAH
23.929
240.2
236.2
50
118.1
116.1
15
Chrysene
PAH
23.989
228.1
226.2
30
114
101.1
10
Bis-2-ethylhexyl phthalate
d4
Phthalate
24.165
153
69.1
25
153
97.1
20
Bis-2-ethylhexyl phthalate
Phthalate
24.184
149
65
30
149
93
20
1-Hydroxypyrene
PAH
24.195
217.5
189.1
40
188.5
163.1
40
Di-n-octyl phthalate
Phthalate
25.65
149
65
30
149
93
20
Benzo(b)fluoranthene dl2
PAH
26.243
263.9
260.2
50
132.2
118.1
10
Benzo(b)fluoranthene
PAH
26.297
126.1
113.1
10
252.1
250.2
35
Benzo(k)fluoranthene dl2
PAH
26.311
263.9
260.2
50
132.2
118.1
10
Benzo(k)fluoranthene
PAH
26.355
252.1
250.2
35
126.1
113.1
10
Benzo(e)pyrene dl2
PAH
26.84
264
260.2
40
132.2
118.1
15
Benzo(e)pyrene
PAH
26.86
252
250.2
50
125
112
20
Benzo(a)pyrene dl2
PAH
26.907
264
260.2
40
132.2
118.1
15
Benzo(a)pyrene
PAH
26.959
252.1
250.1
35
125
124.2
10
Perylene dl2
PAH
27.08
264
260.1
40
130.1
116.1
15
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Time
Segment
Compound
Class
RTa
Prelb
Prod
r
CEd
Pre2
Prod 2
Prod2 „ _ _ Prod3
CE Pre3 ProdS CE
16
Bis(2,2,6,6-tetramethyl-
4piperidyl) sebecate
TCR
28.153
123.6
107.1
10
97.6
42.1
20
16
lndeno[l,2,3-cd]pyrene
dl2
PAH
28.988
288
284.2
50
288
286.2
40
16
Dibenz(a,h)anthracene
dl4
PAH
29.022
288
284.2
50
288
286.2
40
16
lndeno(l,2,3-cd)pyrene
PAH
29.03
138.1
137.2
10
137
136.1
15
16
Dibenz(a,h)anthracene
PAH
29.075
138.1
137.2
10
125
124.2
10
16
Benzo(g,h,i)perylene dl2
PAH
29.43
288
284.2
50
288
286.2
20
16
Benzo(g,h,i)perylene
PAH
29.473
276.1
274.1
45
138
125.1
15
17
Coronene
PAH
32.449
299.4
298.1
30
299.4
298.1
30
a RT = Retention Time
b Prel = Precursor Ion 1
0 Prodi = Product Ion 1
d CE = Collision Energy
-------
SOP # D-EMMD-PHCB-067-SOP-01
Effective Date: 07/07/2017
Page 1 of 15
? o \
w
PB01&
U.S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Exposure Methods and Measurements Division
Public Health Chemistry Branch
STANDARD OPERATING PROCEDURE
SOP Title: Standard Operating Procedure for Preparation of Dermal and Surface
Wipe Samples for SVOC Analysis
SOP ID: D-EMMD-PHCB-067-SOP-01
Effective Date: 07/07/2017
SOP was Developed: IE] In-house ~ Extramural: enter organization
SOP Discipline*: Organic Chemistry
Alternative Identification:
SOP Contact Signature
Name: M. Scott Clifton
Signature/Date:
Management Signature
Name: Myriam Medina-Vera
Title: Branch Chief, PHCB
Signature/Date:
QA Signature
Name: SaniaW. Tong Argao
Title: EMMD QA Manager
Signature/Date:
*See discipline descriptions on the NERL Scientific and Technical SOP intranet site.
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Standard Operating Procedure for Preparation of Dermal and Surface Wipe
Samples for SVOC Analysis
Table of Contents
I.0 Scope and Application 3
2.0 Summary of Method 3
3.0 Definitions 3
4.0 Health and Safety Warnings 4
5.0 Materials and Equipment 4
6.0 Interferences 5
7.0 Personnel Qualifications 5
8.0 Method Calibration 5
9.0 Extraction Procedure for 4"x4" Wipe Samples 6
9.1 Wipe Preparation 6
9.2 Method Spike Preparation 6
9.3 Method blank Preparation 6
9.4 Recovery Spike Preparation 6
9.5 Internal Standard Addition 7
9.6 Sample Extraction (Spikes, Blanks and Wipe Samples) 7
9.7 Extract Processing 7
10.0 Extraction Procedure for 12"x 12" Wipe Samples 8
10.1 Wipe Preparation 8
10.2 Method Spike Preparation 8
10.3 Method blank Preparation 8
10.4 Recovery Spike Preparation 8
10.5 Internal Standard Addition 9
10.6 Sample Extraction (Spikes, Blanks and Wipe Samples) 9
10.7 Extract Processing 9
II.0 Records 10
12.0 Quality Control and Quality Assurance 10
Table 1. Spiking and Internal Standard Solutions 11
Table 2. GC/MS/MS Parameters 12
Table 3. Compounds and Data Collection Parameters 13
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1.0 Scope and Application
This SOP details the extraction and work-up procedures for wipe samples that are
collected for both dermal and surface measurements for measurement of semi-volatile
organic chemicals (SVOCs). This SOP is written to address specific conditions used for
samples collected for tire crumb rubber research, but the general procedure can be used
and modified as appropriate providing quality assurance/quality control (QA/QC) criteria
are met and any modifications are recorded in a laboratory notebook.
2.0 Summary of Method
Samples are first removed from freezer storage and are allowed to warm to room
temperature. The jars containing the samples are carefully opened and internal standard
solution is added to the surface of each wipe sample. Each jar containing a dermal or
4"x4" surface wipe is filled with 50 mL of 1:1 acetone:hexane and is then sealed with a
PTFE-lined cap. Jars containing the larger drag sled wipes are filled with 250 mL of 1:1
acetone:hexane. The jars are placed in an ultrasonic cleaner with water level well below
the level of the jar cap. The ultrasonic cleaner is then turned on for 15 minutes. Sample
jars are removed from the cleaner and the extracts are transferred through funnels
containing ~ lOg of anhydrous sodium sulfate into 250 mL narrow mouth bottles. The
funnels are rinsed with hexane from a wash bottle after the extracts are added. The
solvent addition, extraction, and transfer is repeated two more times. The extracts in the
bottles are then evaporated to 2-5 mL using a parallel evaporator. The concentrated
extracts are then transferred to a 15 mL graduated glass tube along with two 2 mL hexane
rinses of the bottle. The extracts are then concentrated to a final volume of 1 mL under
nitrogen. The extracts are then transferred through a 0.2 |im PTFE syringe filter into
autosampler vials for analysis.
3.0 Definitions
3.1 Dermal Wipe - Wipe sample collected from a participant's skin.
3.2 Surface wipe - Wipe collected from a field surface.
3.3 Drag Sled Wipe - Large wipe sample collected using a weighted drag
sled.
3.4 Internal Standard (IS) - Internal standard solution which is used in
quantification to establish response ratios.
3.5 Method Blank - Unfortified media that is extracted to
evaluateinterferences and possible contamination in the media or lab.
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3.6 Method Spike - Media that is fortified and extracted to evaluate analyte
recovery from the extraction process.
3.7 Recovery Spike - Unfortified media that is extracted and processed like
the Method Blank. The resulting extract is fortified after sample
preparation is complete. This is used to simulate 100% analyte recovery so
matrix effects that can influence the measured concentrations can be
evaluated.
4.0 Health and Safety Warnings
4.1 Follow the procedures detailed in applicable Health and Safety Research
Protocols.
4.2 Follow proper operating procedures for all equipment and instruments
used.
4.3 Exercise caution when using syringes and avoid inhalation or dermal
contact with all solvents and solutions used in this procedure.
4.4 The ultrasonic cleaner and the water bath inside can become very hot, so
exercise caution when removing containers from the bath and allow the
bath to cool or replace the water with cool water before continuing if the
heat is excessive.
5.0 Materials and Equipment
5.1 Clean wipe media, (Twillwipes MG Chemicals 4"x4" or Texwipe TX 100
12"xl2")
5.2 Stainless steel forceps
5.3 Spiking Solution, applicable to analytes being measured
5.4 Internal Standard Solution (IS), applicable to analytes being measured
5.5 Pipette or syringe capable of accurately delivering 100 |iL of solution
5.6 Hexane, pesticide grade or equivalent
5.7 Acetone, pesticide grade or equivalent
5.8 Amber glass jars (60 or 500 mL, I-Chem 300 series or equivalent)
5.9 Glass analytical funnels
5.10 Glass wool
5.11 Anhydrous Sodium Sulfate, 10-60 mesh
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5.12 250 mL glass bottles, narrow mouth
5.13 Parallel evaporator, Buchi Multivapor P6 or equivaleR-200 or equivalent
5.14 Boiling flasks, 500 mL
5.15 Rotary evaporator, Buchi
5.16 Glass serological or volumetric pipette capable of 5 mL
5.17 Pasteur pipettes - 9"
5.18 Graduated tubes, glass, 15 mL
5.19 Nitrogen evaporator with heated water bath (N-Evap or equivalent) or dry
block
5.20 Glass Lauer-tip syringes
5.21 Syringe filters, PTFE, 13 mm 0.2 |im
5.22 Autosampler vials, 2 mL, caps with PTFE-lined septa
6.0 Interferences
Interferences are any component that interferes with the quantitative analysis.
Interferences should be evaluated prior to applying this method to study samples.
This method may be modified to deal with interferences if necessary as long as
modifications are documented and are acceptable within a study's QA Plan. If
interferences not identified during method evaluation are discovered with study
samples, they will be identified and evaluated as part of a study's ongoing QA/QC
plan.
7.0 Personnel Qualifications
This SOP is written to be used by personnel familiar with the equipment and
procedures that will be used. Personnel should be adequately trained and display
proficiency with those techniques prior to using this SOP for sample analysis.
8.0 Method Calibration
The GC/MS/MS instrument should be calibrated for the analytes using the
parameters listed in Tables 2 and 3 prior to sample analysis. Calibrate the
GC/MS/MS system in a range from 0. Ing/mL to 500 ng/mL using the following
calibration levels (ng/mL): 0.1, 0.5, 1.0, 2.5, 5, 10, 25, 50, 100, 250, 500. The
calibration will be monitored by running a mid-level check standard between
every 10 samples. A check standard must be within ±25% of its prepared
concentration for the calibration to remain valid. If an analyte does not pass the
±25% criterion, but is not found in any of the relevant samples, the analysis may
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D-EMMD-PHCB-068-SOP-01
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Page 6 of 15
continue unless the response has decreased to the point of compromising the
ability to detect that analyte.
If a check standard fails, investigate the problem and take corrective action.
Recalibrate the instrument and begin sample analysis from the point of the last
good calibration check.
Extraction Procedure for 4"x4" Wipe Samples
9.1 Wipe Preparation
9.1.1 Remove 4"x4" wipe samples from the freezer and let warm to
room temperature.
One sample batch will consist of the following:
• Up to 24 wipe samples (from freezer)
• 1 Method spike
• 1 Method blank
• 1 Recovery spike
9.1.2 While the samples from the freezer are warming to room
temperature, the Method spike, Method blank and recovery spike
can be prepared for extraction.
9.2 Method Spike Preparation
9.2.1 Place one clean 4" x 4" wipe into a 60 mL wide mouth glass jar.
9.2.2 Transfer a 50 |iL aliquot of Spiking Solution to the wipe.
9.2.3 Transfer a 100 |iL aliquot of Internal Standard solution to the wipe.
9.2.4 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
9.3 Method blank Preparation
9.3.1 Place a clean 4" x 4" wipe into a 60 mL wide mouth glass jar.
9.3.2 Transfer a 100 |iL aliquot of Internal Standard solution to the wipe.
9.3.3 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
9.4 Recovery Spike Preparation
9.4.1 Place a clean 4" x 4" wipe into a 60 mL wide mouth glass jar.
9.4.2 Add 50 mL of 1:1 acetone:hexane to the jar and seal with a PTFE-
lined cap.
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9.4.3 After extraction and concentration, add 50 |iL of spiking solution
to the extract.
9.4.4 Add 100 |iL of internal standard solution, cap and vortex along
with the other samples processed in the sample batch.
Internal Standard Addition
9.5.1 After the sample has reached room temperature, write the sample
ID on the top of the cap and carefully remove the cap.
9.5.2 Fortify the wipe sample with 100 |iL of Internal Standard solution.
9.5.3 Add 50 mL of 1:1 acetone:hexane to the jar and seal with the
sample ID labeled PTFE-lined cap.
Sample Extraction (Spikes, Blanks and Wipe Samples)
9.6.1 Place samples into an Ultrasonic cleaner with the water level well
below the level of the jar's cap and start the cleaner.
9.6.2 Allow the cleaner to run for 15 minutes.
9.6.3 Carefully remove the samples from the ultrasonic cleaner, drying
the outside of each jar with a paper towel as it is removed.
9.6.4 Assemble an analytical funnel on a 250 mL glass Boston round
bottle and label one bottle for each sample extract.
9.6.5 Place a glass wool plug into each funnel and add ~ lOg of
anhydrous sodium sulfate into each funnel.
9.6.6 Carefully pour the solvent content of each sample jar into the
corresponding bottle through the funnel. Allow the jar to sit in the
funnel until solvent stops dripping. Carefully remove the jars.
9.6.7 Add another 50 mL of 1:1 acetone:hexane to each jar. Recap the
jars.
9.6.8 Rinse the inside of each funnel with hexane from a wash bottle and
collect the rinse into its bottle.
9.6.9 Repeat steps 9.6.1 to 9.6.3 and 9.6.6 to 9.6.8 two more times,
omitting step 9.6.7 after the third extraction.
Extract Processing
9.7.1 Concentrate the sample extracts inside of the bottles to a volume of
-2-5 mL on a parallel evaporator.
9.7.2 Transfer the concentrated extract to a 15 mL graduated tube. Rinse
the bottle twice with 2 mL aliquots of hexane. Transfer the rinsate
to the corresponding graduated tube.
9.7.3 Concentrate to a volume of 1 mL under nitrogen using the nitrogen
evaporator.
9.7.4 Transfer the sample solution to a syringe fitted with a 13mm 0.2
|im PTFE syringe filter and filter into a labeled autosampler vial.
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9.7.5 Cap the autosampler vial and analyze by GC/MS.
9.7.6 If the sample cannot be analyzed immediately, store in a freezer at
-20 °C until they can be analyzed.
10.0 Extraction Procedure for 12"x 12" Wipe Samples
10.1 Wipe Preparation
10.1.1 Remove 12"xl2" wipe samples from the freezer and let warm to
room temperature.
One sample batch will consist of the following:
• Up to 12 wipe samples (from freezer)
• 1 Method spike
• 1 Method blank
• 1 Recovery spike
10.1.2 While the samples from the freezer are warming to room
temperature, the method spike, method blank and recovery spike
can be prepared for extraction.
10.2 Method Spike Preparation
10.2.1 Place one clean 12" x 12" wipe into a 500 mL wide mouth glass
jar.
10.2.2 Transfer a 50 |iL aliquot of Spiking Solution to the wipe.
10.2.3 Transfer a 100 |iL aliquot of Internal Standard solution to the wipe.
10.2.4 Add 250 mL of 1:1 acetone:hexane to the jar and seal with a
PTFE-lined cap.
10.3 Method blank Preparation
10.3.1 Place a clean 12" x 12" wipe into a 500 mL wide mouth glass jar.
10.3.2 Transfer a 100 |iL aliquot of Internal Standard solution to the wipe.
10.3.3 Add 250 mL of 1:1 acetone:hexane to the jar and seal with a
PTFE-lined cap.
10.4 Recovery Spike Preparation
10.4.1 Place a clean 12" x 12" wipe into a 500 mL wide mouth glass jar.
10.4.2 Add 250 mL of 1:1 acetone:hexane to the jar and seal with a
PTFE-lined cap.
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10.4.3 After extraction and concentration, add 50 |iL of spiking solution
to the extract.
10.4.4 Add 100 |iL of internal standard solution, cap and vortex along
with the other samples processed in the sample batch.
10.5 Internal Standard Addition
10.5.1 After the sample has reached room temperature, write the sample
ID on the top of the cap and carefully remove the cap.
10.5.2 Fortify the wipe sample with 100 |iL of Internal Standard solution.
10.5.3 Add 250 mL of 1:1 acetone:hexane to the jar and seal with the
sample ID labeled PTFE-lined cap.
10.6 Sample Extraction (Spikes, Blanks and Wipe Samples)
10.6.1 Place samples into an Ultrasonic cleaner with the water level well
below the level of the jar's cap and start the cleaner.
10.6.2 Allow the cleaner to run for 15 minutes.
10.6.3 Carefully remove the samples from the ultrasonic cleaner, drying
the outside of each jar with a paper towel as it is removed.
10.6.4 Assemble an analytical funnel on a 500 mL boiling flask and label
one flask for each sample extract.
10.6.5 Place a glass wool plug into each funnel and add ~ lOg of
anhydrous sodium sulfate into each funnel.
10.6.6 Carefully pour the solvent content of each sample jar into the
corresponding flask through the funnel. Allow the jar to sit in the
funnel until solvent stops dripping. Carefully remove the jars.
10.6.7 Evaporate the content of each flask to a volume <10 mL using a
rotary evaporator.
10.6.8 Return each flask to its position under the corresponding funnel.
10.6.9 Add another 250 mL of 1:1 acetone:hexane. Recap the jars.
10.6.10Rinse the inside of each funnel with hexane from a wash bottle and
collect the rinse into its flask.
10.6.11Repeat steps 10.6.1 to 10.6.3, then 10.6.6 to 10.6.7, and finally step
10.6.10.
10.7 Extract Processing
10.7.1 Concentrate the sample extracts inside of the boiling flasks to a
volume of -2-5 mL on a rotary evaporator.
10.7.2 Transfer the concentrated extract to a 15 mL graduated tube. Rinse
the flask twice with 2 mL aliquots of hexane. Transfer the rinsate
to the corresponding graduated tube.
10.7.3 Concentrate to a volume of 1 mL under nitrogen using the nitrogen
evaporator.
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10.7.4 Transfer the sample solution to a syringe fitted with a 13mm 0.2
|im PTFE syringe filter and filter into a labeled autosampler vial.
10.7.5 Cap the autosampler vial and analyze by GC/MS.
10.7.6 If the sample cannot be analyzed immediately, store in a freezer at
-20 °C until they can be analyzed.
11.0 Records
Chain of custody records will be maintained to document the removal and
extraction of each wipe sample. Those records will be stored as indicated in the
applicable study's QA plan.
The performance of this procedure will be documented in a NERL research
notebook. This documentation will include details and observations for each
sample batch analyzed.
12.0 Quality Control and Quality Assurance
Data will be reviewed by the analyst. The data quality objectives and review
procedures from the QAPP for the study being conducted will dictate specific
quality assurance practices. All QA practices will be consistent with the NERL
Quality Management Plan.
The method blank, method spike and recovery spike will serve to measure method
performance for each batch of samples. Target recovery for the method spike, and
recovery spike should be ± 30% of the nominal concentration for each analyte.
Any deviations will be recorded and investigated.
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Table 1. Spiking and Internal Standard Solutions
Catalog Number Concentration
Spiking Solution
PAH Mix S-70846-02a 10 |ig/mL
Phthalate Mix S-70846-01a 10 |ig/mL
TCR Mix S-70846-03a 10 |ig/mL
Internal Standard Solution
PAHs
Chrysene D12
Phenanthrene D10
Acenaphthene D10
Benz [a] anthracene D12
Naphthalene Dg
Perylene D12
Fluoranthene D10
Benzo[b]fluoranthene D12
Benzo[a]pyrene D12
Benzo[g,h,i]perylene D12
Indeno[l,2,3-cd]pyrene D12
Dibenz [a, h] anthracene D14
Acenaphthalene Dg
Fluorene D10
Pyrene D10
Benzo[k]fluoranthene D12
ES-5164b
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
ES-5164
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
Phthalates
Diethyl phthalate D4
Di-N-hexyl phthalate 1,2 13C2
Bis(2-ethylhexyl)phthalate D4
Benzyl butyl phthalate D4
DLM-1629-1.2b
CLM-4669-1.2b
DLM-1368-1.2b
DLM-1369-1.2b
480 ng/mL
480 ng/mL
480 ng/mL
480 ng/mL
Other
Dibenzothiophene Ds
DLM-2206-0.T
1050 ng/mL
Suppliers:
a Accustandard
b Cambridge Isotope Labs
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Table 2. GC/MS/MS Parameters
Parameter Value
GC System
Injector
Column
Temperature
Program
Detector
Agilent 7890 Gas chromatograph
Capillary injector in splitless mode
Pulsed splitless at 25 psi for 0.5 min, then split at 50 mL/min at 1 min.
Temperature: 250°C
Liner: Single gooseneck glass, deactivated
Injection volume: 1 |iL
Agilent VF-5ms, 30 M x 0.25 mm x 0.25 |im,
Column flow: 1.2 mL/min
50° C for 2 min to 325° C at 10° C/min, hold 5 min.
Agilent 7010 Triple Quadrupole
Mode: Electron Impact (EI) operating in MRM/Scan mode
Electron Multiplier Voltage by Gain Curve
Transfer Line: 300°
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Table 3. Compounds and Data Collection Parameters
Time u Prod Prod2 Prod3
Compound Class RTa Prelb CEd Pre2 Prod 2 __ Pre3 Prod 3
Segment K lc CE CE
2,6-Di-tert-butyl-p-cresol
4-tert-Octylphenol
8 Phenanthrene dlO PAH 17.622 188.3 160.2 40 188.3 186.3 30
-------
8
8
9
9
9
9
9
10
11
11
11
11
12
12
12
13
13
13
13
13
13
13
13
14
15
15
15
15
15
15
15
15
15
D-EMMD-PHCB-067-SOP-01
07/07/2017
Page 14 of 15
Phenanthrene
PAH
17.678
177.9
152.1
25
176.1
150.1
25
Anthracene
PAH
17.8
177.9
152.1
25
176.1
150.1
25
Diisobutyl phthalate
Phthalate
18.249
149
65
25
149
93
15
3-Methylphenanthrene
PAH
18.843
192.2
191.2
20
188.7
163.1
40
192.2
165.1
45
2-Methylphenanthrene
PAH
18.906
188.7
163.1
40
192.2
191.2
20
192.2
165.1
45
1-Methylphenanthrene
PAH
19.153
188.7
163.1
40
192.2
191.2
20
192.2
165.1
45
Dibutyl phthalate
Phthalate
19.212
149
65
30
149
93
20
2-Mercaptobenzothiazole
TCR
19.45
166.5
123
10
166.5
109
30
Fluoranthene dlO
PAH
20.467
211.9
210.2
20
211.9
208.1
20
Fluoranthene
PAH
20.51
202.1
200.1
30
202.1
152.1
30
Pyrene dlO
PAH
20.994
211.9
210.2
20
211.9
208.1
20
Pyrene
PAH
21.036
201.1
200.1
15
200.1
174.1
30
Di-N-hexylphthalate
(2)13C2
Phthalate
22.647
153
66
25
153
95.1
20
Benzyl butyl phthalate d4
Phthalate
22.756
153
69.1
25
153
97.1
5
Benzyl butyl phthalate
Phthalate
22.77
149
65
25
91
65
15
bis(2-Ethylhexyl) adipate
Phthalate
23.017
147
55.1
25
111
55.1
15
Benz(a)anthracene dl2
PAH
23.858
240.2
236.2
50
118.1
116.1
15
Benz(a)anthracene
PAH
23.911
228.1
226.2
30
114
101.1
10
Chrysene dl2
PAH
23.929
240.2
236.2
50
118.1
116.1
15
Chrysene
PAH
23.989
228.1
226.2
30
114
101.1
10
Bis-2-ethylhexyl phthalate
d4
Phthalate
24.165
153
69.1
25
153
97.1
20
Bis-2-ethylhexyl phthalate
Phthalate
24.184
149
65
30
149
93
20
1-Hydroxypyrene
PAH
24.195
217.5
189.1
40
188.5
163.1
40
Di-n-octyl phthalate
Phthalate
25.65
149
65
30
149
93
20
Benzo(b)fluoranthene dl2
PAH
26.243
263.9
260.2
50
132.2
118.1
10
Benzo(b)fluoranthene
PAH
26.297
126.1
113.1
10
252.1
250.2
35
Benzo(k)fluoranthene dl2
PAH
26.311
263.9
260.2
50
132.2
118.1
10
Benzo(k)fluoranthene
PAH
26.355
252.1
250.2
35
126.1
113.1
10
Benzo(e)pyrene dl2
PAH
26.84
264
260.2
40
132.2
118.1
15
Benzo(e)pyrene
PAH
26.86
252
250.2
50
125
112
20
Benzo(a)pyrene dl2
PAH
26.907
264
260.2
40
132.2
118.1
15
Benzo(a)pyrene
PAH
26.959
252.1
250.1
35
125
124.2
10
Perylene dl2
PAH
27.08
264
260.1
40
130.1
116.1
15
-------
D-EMMD-PHCB-067-SOP-01
07/07/2017
Page 15 of 15
Time
Segment
Compound
Class
RTa
Prelb
Prod
r
CEd
Pre2
Prod 2
Prod2 „ „ „ , „ Prod3
Pre3 Prod 3
CE ri« nuuj CE
16
Bis(2,2,6,6-tetramethyl-
4piperidyl) sebecate
TCR
28.153
123.6
107.1
10
97.6
42.1
20
16
lndeno[l,2,3-cd]pyrene
dl2
PAH
28.988
288
284.2
50
288
286.2
40
16
Dibenz(a,h)anthracene
dl4
PAH
29.022
288
284.2
50
288
286.2
40
16
lndeno(l,2,3-cd)pyrene
PAH
29.03
138.1
137.2
10
137
136.1
15
16
Dibenz(a,h)anthracene
PAH
29.075
138.1
137.2
10
125
124.2
10
16
Benzo(g,h,i)perylene dl2
PAH
29.43
288
284.2
50
288
286.2
20
16
Benzo(g,h,i)perylene
PAH
29.473
276.1
274.1
45
138
125.1
15
17
Coronene
PAH
32.449
299.4
298.1
30
299.4
298.1
30
a RT = Retention Time
b Prel = Precursor Ion 1
0 Prodi = Product Ion 1
d CE = Collision Energy
-------
[This page intentionally left blank.]
-------
,,01^ WU.S Environmental Protection Agency
/ •. Office of Research and Development
w. National Exposure Research Laboratory
Exposure Methods and Measurement Division
Public Health Chemistry Branch
STANDARD OPERATING PROCEDURE
SOP Title: Extraction of Filter Media for Ion Chromatography and High
Resolution Inductively Coupled Plasma Mass Spectrometry
SOP ID: D-EMMD-PHCB-071 -SOP-01
Effective Date: November 1, 2017
SOP was Developed: IEI In-house ~ Extramural:
SOP Discipline*: Inorganic Chemistry
Alternative Identification:
SOP Contact Signature
Name: Kasey D. Kovalcik
Signature/Date: November 28, 2017
Management Signature
Name: Myriam Medina-Vera
Title: PHCB Chief MYRIAM SSMT"^
Signature/Date: i\ /i r— ni M A \ / A Date: 2017.11.29 07:04:08
MEDINA-VERA
-osw
QA Signature
Name: Margie Vazquez
iyyi_r *_ Digitally signed by Margie
Title: EMMD QA manager IVI a ly 16 Vazquez
Signature/Date: Vazquez SSSr2017'11"30 12:26:08
*See discipline descriptions on the NERL Scientific and Teclmical SOP intranet site
-------
Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 2 of 18
Version History
HR-ICPMS Analysis
Version
Date
Revisions/Changes
ECAB-114.0
1/1/11
Original Effective Date.
ECAB-114.0 Three-Stage Extraction of Filter Media for Ion
Chromatography and High Resolution Inductively Coupled
Plasma Mass Spectrometry
PHCB-071-01
11/01/17
Add Appendix 2 for Tire Crumb Rubber Study PM filter and
reference material single-stage hot acid extraction.
2
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 3 of 18
Extraction of Filter Media for Ion Chromatography and High Resolution Inductively
Coupled Plasma Mass Spectrometry
Table of Contents
Section Page
1. Scope and Applications 4
2. Summary of Method 4
3. Definitions/ Acronyms 4
4. Health and Safety Warnings 5
5. Cautions/Interferences 5
6. Personnel Qualifications and Responsibilities 6
7. Equipment and Supplies 6
8. Reagents and Standards 6
9. Procedures 7
9.1. Eutech Instruments pH Probe 7
9.2. Sample Tube Acid-Cleaning Procedure for ICPMS Analyses 8
9.3. Cleaning Procedure for Ion Chromatography (Dionex) Vials and Caps 9
9.4. Three-Stage Filter Extraction Procedure 9
10. Data and Records Management 14
11. QA/QC 16
12. References 16
Appendix 1: Two Stage Extraction Procedure for NEXUS and CMAPS Filter Samples 17
Appendix 2: Single Stage Extraction Procedure for Tire Crumb Rubber Study Samples 18
Table of Figures
Figure 1. Visual Representation of Extraction Procedure and Section Reference 10
Table of Tables
Table 1: Sample Spreadsheet for Extraction Mass Records and Calculations 11
Table 2: Sample Spreadsheet after Mass 3 and Acid Spiking 12
Table 3: Sample Spreadsheet After Mass 4 and Acid Spiking 14
3
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 4 of 18
1. Scope and Applications
Ion chromatography (IC) and high resolution inductively coupled plasma mass spectrometry
(HR-ICPMS) are solution phase analytical techniques for the analysis of stable inorganic
ions. This standard operating procedure details the extraction of aqueous and acid soluble
particulate matter from filter media for quantitative analysis to determine water soluble, weak
acid leachable, and total mass extracted from particulate matter (PM) collected on teflon
filters. For a particular inorganic species, by combining the resulting concentration results
with the volume(s) of a specific extraction step, mass per filter can be calculated for a host of
uses.
2. Summary of Method
Particulate matter from any sampling device collected on a variety of filter media is extracted
to estimate source solubility and total mass through various-stage extraction procedures. This
procedure can involve a 24-hour aqueous filter leach to determine water-soluble inorganic
species. Aliquots of this stage are analyzed for pH, for major cations and anions with IC, as
well as 51 elements with HR-ICPMS.
Following the 24-hour aqueous leach, the remaining filter and leachate are spiked with
hydrochloric and nitric acids to make an acid solution for determination of dilute acid-soluble
inorganic species. After 30 days under ambient conditions, an aliquot is collected for HR-
ICPMS analysis. The filter and remaining dilute acid solution is then spiked to 2% nitric and
1% hydrochloric acids and heated for 3 hours at 70 °C, for the last stage aliquot.
Any stage of this procedure can be performed independently, or as a series, dependent on the
study design.
3. Definitions/Acronyms
mL = milliliter
|iL = microliter
L = liter
cm = centimeter
NERL = National Exposure Research Laboratory
D456 = NERL ISO 5 Class 100 Clean Laboratory (Research Triangle Park, EPA)
RO = Reverse Osmosis water ("tap" or "faucet" water in D456)
MilliQ = Type I ultra clean water from the Millipore A10 Element (> 18.2 MQ-cm)
SHEM = Safety, Health, and Environmental Management
MSDS = Material Safety Data Sheets
HDPE = High Density Polyethylene
4
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 5 of 18
4. Health and Safety Warnings
4.1. All acid-cleaning procedures should be performed with the safety of the scientist as the
utmost importance. Lab coat, protective eye wear and particle-free clean room vinyl
gloves should be worn according to basic SHEM training guidelines.
4.2. Be extremely cautious with concentrated acids. MSDS' are located labeled 3-ring
binders in the clean room gowning area and in the D461A lab.
4.3. Perform all acid spiking and cleaning procedures in the exhausting laminar flow
hood in D456 Clean Room.
5. Cautions/Interferences
5.1 Cautions
5.1.1. Unless otherwise noted, all work is carried out in the NERL Class 100 Clean
Laboratory located in D456 of the Research Triangle Park, NC EPA campus.
5.1.2. A Class 100 Clean lab follows general Clean Lab Guidelines. You are required to
remove footwear (shoes) in the outmost room and wear a clean lab coat and clean
lab footwear (Crocs, or equivalent) in the middle room (gowning room). The
innermost room is the actual laboratory where HEPA-filtered air is continuously
circulated and the temperature and humidity are closely monitored (20 ± 2 °C and
55 ± 5 % Relative Humidity). A clean lab is considered "clean" because of the
filtered air and because it should be free of visible contamination. If there are any
questions or doubts concerning Clean Lab Practices, please see Kasey Kovalcik.
5.1.3. All filter handling procedures should focus on minimizing contamination.
Perform all filter work in the laminar flow hood. While handling filters in the
laminar hood, it is advisable to turn the HEPA filter fan off. This fan is forceful
enough to make filter handling with forceps difficult.
5.1.4. Wear vinyl clean room gloves at all times in the clean room.
5.1.5. Let the MilliQ water run for 30-60 seconds to flush the system, possibly longer
after extended shutdowns (i.e., Monday morning), to achieve 18.2 MQ-cm water.
5.1.6. Do not move analytical balances. The balances are certified for accuracy
(Precision Weighing, Cary, NC) at their present location and are placed to minimize
air flow, stability, and to stay level.
5.2. Interferences
5.2.1. In trace inorganic analyses, interferences (contamination) are caused by non-clean
lab practices. Refer back to Section 5.1, Cautions.
5
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 6 of 18
6. Personnel Qualifications and Responsibilities
Personnel are not allowed in the lab without proper SHEM training and appropriate badge-
access. After this status is achieved, Clean Lab Guidelines will be covered with Kasey
Kovalcik.
7. Equipment and Supplies
7.1. Clean Laboratory (see Section 5.1)
7.2. Eppendorf Research adjustable micro-pipette set and corresponding tips (D456)
7.3. If needed for large volume of samples:
7.3.1. Sartorius Analytical Balance connected to PC Laptop (D456)
7.3.2. WASP USB Barcode Scanner
7.4. Crest Liquid Sonicating Bath (D461B)
7.5. Fisher Isotemp laboratory convection oven capable of 70 °C (D461 A)
7.6. Eutech Instruments Hand-Held pH Probe (D456)
7.7. Ceramic Scissors (Kyocera Tycom Corp, or equivalent)
7.8. Dionex IC Vial and Cap Tool (Dionex 068925)
7.9. NIST-traceable thermometer/hygrometer for lab monitoring
7.10. 60 position large racks, Elemental Scientific, (LR-60-16)
7.11. 72 position racks, Thermo Scientific (14-809-22)
7.12. Barcode Labeler Software and PlazStyx Waterproof Labels (1/2" x 13/4", 15026)
7.13. Dionex 5.0mL Vials with Filter Caps (Dionex 038141)
7.14. 20 mil ziplockBags (18" x 12"; 8" x 5")
7.15. Acid Cleaned HDPE Forceps
7.16. Nalgene NUNC 15 mL Conical Centrifuge Tube PP w/HDPE Screw Cap (366036)
7.17. Fisher Scientific Easy Reader Centrifuge Tube, FisherBrand 50mL (06-443-20)
8. Reagents and Standards
8.1. TraceMetal Grade Nitric Acid, Fisher Scientific (A509SK 212)
8.2. Trace Grade Hydrochloric Acid, JT Baker (9530-33)
8.3. Ethyl Alcohol, 200 proof, ACS/USP Grade, Pharmco-AAPER (EPA store stock - all
plastic)
8.4. Optima Nitric Acid, Fisher Scientific (A46751)
8.5. Optima Hydrochloric Acid, Fisher Scientific (A466-1)
8.6. NIST Standard Reference Material 1648a, Urban Particulate Matter
8.7. pH 4.0 and 7.01 Buffer Solutions for pH meter calibration
6
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 7 of 18
9. Procedures
9.1. Eutech Instruments pH Probe
9.1.1. Calibration
9.1.1.1. Remove probe from electrode storage solution and rinse/shake a few times
with MilliQ water. Extra electrode storage solution is located under the
exhaust hood.
9.1.1.2. Turn meter on.
9.1.1.2.1. Rinse out 1 buffer container with pH 4.01 buffer solution and then fill
it with the same solution. Repeat this procedure with a second buffer
container for the pH 7.0 buffer solution.
9.1.1.2.2. Ensure calibration temperature matches room temperature using NIST
traceable thermometer, within ± 1°C.
9.1.1.2.3. Dip the electrode -2-3 cm into the pH 4.01 standard buffer solution.
9.1.1.2.4. Press the CAL button to enter calibration mode. The "CAL" indicator
will be shown.
9.1.1.2.5. Allow sufficient time (can be up to 2 minutes) for the reading to
stabilize. Check by moving the probe in the solution.
9.1.1.2.6. Once stabilized, press the HOLD/ENT button to confirm the first
calibration point.
9.1.1.2.7. Rinse with MilliQ water and repeat with pH 7.0 buffer solution
starting with step 9.1.1.2.2.
9.1.1.2.8. After calibration is complete, press the "CAL" button to exit
calibration mode. The calibration data is now stored.
Measurement
2.1. Pre-rinse the sample cup with 0.5 mL of the first sample. Shake off excess
sample.
2.2. In "MEAS" mode, dip the electrode -2-3 cm into the sample.
2.3. Let the signal stabilize, read to two decimal places and record the reading in
the dedicated laboratory notebook.
2.4. Rinse the electrode tip with MilliQ water, shake. Empty the sample cup into
an appropriate waste beaker.
2.5. After every 20 samples (with MilliQ water rinses in between each sample),
submerse the probe in pH 4.01 solution. If the reading is more than 10% off
(3.96-4.05), recalibrate using the steps in Section 9.1.1.
Helpful Hints
¦ Meter will go to standby mode after a few minutes of inactivity or simply after
a fixed amount of time. Just turn the unit back on and proceed with use.
¦ Sometimes it takes a few moments to stabilize the pH reading. Try moving
the meter and then let it settle.
¦ Rinse/shake pH probe glass tip with MilliQ water between measurements.
¦ Collected rinses can be disposed in the sink.
9.1.2.
9.1.
9.1.
9.1.
9.1.
9.1.
7
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 8 of 18
9.2. Sample Tube Acid-Cleaning Procedure for ICPMS Analyses
9.2.1. Obtain a desired amount of 15 mL and 50 mL tubes to be cleaned (for every 50
mL Fisherbrand tube used, three 15 mL Nalgene tubes are required). Remove the
plastic covers in the first entry-way of the D456 Clean Lab, ensuring that the
tubes and their Styrofoam trays are never placed on the floor. Be sure to wear
personal protective equipment (e.g. lab coat, gloves, safety glasses).
9.2.2. In the laminar exhausting hood located in the D456 Clean Lab, remove the tube
(15 mL or 50 mL) caps and place the caps in a plastic tub with reverse osmosis
(RO) water.
9.2.3. Leave the capless tubes in the Styrofoam tray, fill them with RO water and let
them sit in the hood for 1 hour.
9.2.4. After 1 hour, pour the contents of the tubes into the hood sink and empty the tub
from 9.2.2.
9.2.5. Loosen the cap slightly of the 20 L carboy of 4.0% nitric and 2.0% hydrochloric
acids (v/v)* to provide airflow. Carefully fill all tubes from the carboy spigot
with the acid solution and securely cap them.
¦ *This acid solution is made by mixing 800 mL Trace Grade nitric acid and
400 mL Trace Grade hydrochloric acid to a total volume of 20 L with MilliQ
water.
9.2.6. Once all desired tubes are filled with the acid cleaning solution, capped, and
placed back in their Styrofoam tray, carefully take them to D461 and place them
in the oven at 70 °C for 3 hours.
9.2.7. After 3 hours, carefully remove the tubes and let them cool in a hood before doing
any further work.
¦ CAUTION: mixed acids are considerably more aggressive when hot.
¦ With the oven turned off, these tubes can be left to sit overnight, or they can
be removed and let to sit in a hood to cool. Do not try to work with the tubes
while hot.
9.2.8. When cool, transport the tubes back to D456.
9.2.9. Within the laminar exhausting hood, remove the caps from the tubes and place
them in a plastic tub with MilliQ water and pour the acid back into the 20 L
carboy.
9.2.10. After a tray of tubes is empty, overfill them twice with MilliQ water and discard
rinses. Refill the tubes with MilliQ water and let the tubes sit in the laminar hood
for 1 hour.
9.2.11. After 1 hour, MilliQ rinse the clean tubes twice again and rinse the caps well.
9.2.12. Cap the MilliQ-full tubes, seal in ziplock bag (12" x 18"), and store them out of
the way in the D456 Clean Lab until needed.
8
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 9 of 18
9.3. Cleaning Procedure for Ion Chromatography (Dionex) Vials and Caps
9.3.1. Fill plastic 72-position racks with 5.0 mL Dionex vials.
9.3.2. Fill and empty twice with MilliQ water. Then fill and let them sit overnight in the
laminar flow hood.
9.3.3. Rinse two more times, shake any remaining droplets, and let dry in the laminar
flow hood.
9.3.4. Place the dried tubes in a ziplock bag for storage.
9.3.5. The caps can be soaked in MilliQ water overnight ziplock bag. Try to remove as
much air as possible from the bag to keep the caps submersed in the water.
9.3.6. The next day, discard the water and shake the caps to remove large droplets.
Place them on a lint-free task wiper and air dry overnight in the laminar hood.
9.3.7. Place the dry caps in a sealed ziplock bag (12" x 18").
9.4. Three-Stage Filter Extraction Procedure
The following section describes the three-stage, one-container extraction procedure for filters.
Figure 1 shows this process, with accompanying section references. Filters are subjected to a 24-
hour aqueous leach, and 30-day dilute acid leach, and an increased acid concentration under
heated conditions. During each leaching step, it is imperative to know the volume of the
extracting solution so that post analysis processing can calculate the mass of a desired analyte
from the concentration.
9
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 10 of 18
Figure 1. Visual Representation of Extraction Procedure and Section Reference
9.4.1-3
Massl
9.4.4-7
Mass2
9.4.8-9
24lir water leach
a
v7
(O.
9.4.13-14
Mass3
9.4.18 HAL
Mass4
9.4.15-16
30 Day
Leach
9.4.10
10 mL Water Soluble Leachate
ICPMS Collection
9.4.11
5 mL Water Soluble Leachate
IC Collection
9.4.12
-0.5 niL Water Soluble
pH measurement
9.4.17
10 mL Acid Soluble
ICPMS Collection
If the sample filter has a stamped ID number on the polypropylene ring, carefully cut it off
with acid cleaned ceramic scissors and discard.
9.4.1. Label an empty acid-cleaned 50 niL tube and cap (it does not need to be
completely dry) with appropriate bar code sample ID.
9.4.2. Using acid-cleaned HDPE forceps, carefully place a Teflon filter in the bottom of
the tube.
9.4.3. Weigh tube, cap, and filter (Massl) using the Sartorius Analytical Balance
(D456).
9.4.4. Carefully and evenly wet the filter with 200 ethanol using an Eppendorf
inicro-pipette. If the filter is polycarbonate, do not use ethanol. No additional
solvent is needed.
9.4.5. Prepare at least 3 water/tube blanks per full carboy with _WB#_ label.
¦ You must still add the 200 fiL ethanol per tube!
10
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
Page 11 of 18
9.4.6. Use the 20 L carboy and the tube graduations to deliver approximately 50 mL of
MilliQ water into the tube.
9.4.7. Weigh tube, cap, filter, and liquid contents (Mass2).
Example Calculation 1 - 1 DW f1 day water> Extraction Mass (see Table U
Mass (g) of 24 Hour Extraction Solution (1DW) = Mass2 - Massl
Assuming a density of 1 g/mL, mass (g) = volume (mL)
9.4.8. Sonicate tubes for 30 minutes at lab temperature D461B. Be careful not to
contaminate the underside of the caps with bath water.
9.4.9. Move the tubes back to the D45 Clean Lab and let the tubes sit for 24 hours.
Table 1: Sample Spreadsheet for Extraction Mass Records and Calculations
Sample ID
MASS 1
Tube, Cap, (filter)
(g)
MASS 2
Tube, Cap, 200uL EtOH,
50mL MilliQ, filter (g)
1DW Extraction
Mass (g)
PMC_WB1
13.61354
64.64846
51.03492
PMC_WB2
13.48995
64.74524
51.25529
PMC_WB3
13.76135
64.20034
50.43899
PMC_69B
13.84836
65.15102
51.30266
PMC_70B
13.65657
64.87368
51.21711
PMC_75A
13.79744
64.79582
50.99838
Water Soluble Extract Collection for ICPMS
9.4.10. Carefully pour 10 mL of the water-soluble leachate from the previous steps into a
labeled, acid cleaned 15 mL tube.
¦ Label is SampleName_lDW (one day water).
¦ This tube will get spiked with Ultra Pure nitric (HNO3) and Optima
hydrochloric acids (HC1) to make 0.2% and 0.1% (v/v), respectively.
Examnle Calculation 2 - Acid Sniking for Water Soluble 1DW Extract
If poured off solution from 9.4.10 is approximately 10 mL:
11
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Filter Extraction
D-EMMD-PHCB-071 -SOP-01
November 1, 2017
( ^ fl000 «L^ , Page 12 of 18
lOmLSol'n x O.lmLHCl V ^ =10//LHC1
^100 mL totalSol'lmL ^
( 0.2mL HNOs Vl000//L^
10 mLSol'n xhoomLtotaiSol'n 1 j = 2Q //L HNQ^
This is an essential step for ICPMS analysis for stability and calibration standard matrix
matching. It is also a very easy step to introduce contamination.
Water Soluble Extract Collection for IC and pH
9.4.11. Carefully pour 5 mL of the water-soluble leachate into a MilliQ cleaned IC vial
labeled with an appropriate bar code sample ID.
¦ Use the appropriate MilliQ rinsed vial tool to correctly position the cap.
¦ Samples can be stored at 4 °C until analysis.
9.4.12. Pour ~ 0.5 mL water soluble leachate for pH measurement (see section 9.1.2).
Dilute Acid Soluble Extract Collection for ICPMS
9.4.13. Obtain the mass (g) of the tube, cap, filter, and remaining water soluble leachate
after pour off from steps 9.4.11 and 9.4.12 (Mass3).
Table 2: Sample Spreadsheet after Mass 3 and Acid Spiking
4/23/09
4/23/09
4/23/09
4/24/09
Sample ID
MASS 1
Tube, Cap,
(filter)
(9)
MASS 2
Tube, Cap,
200uL
EtOH, 50mL
MilliQ, filter
(g)
1DW
Extraction
Mass (g)
MASS 3
after 1DW
pour off (g)
uL HN03
for 0.2%
(v/v)
uL HCI for
0.1% (v/v)
PMC_WB1
13.61354
64.64846
51.03492
35.53492
71
36
PMC_WB2
13.48995
64.74524
51.25529
35.75529
72
36
PMC_WB3
13.76135
64.20034
50.43899
34.93899
70
35
PMC_69B
13.84836
65.15102
51.30266
35.80266
72
36
PMC_70B
13.65657
64.87368
51.21711
35.71711
71
36
PMC_75A
13.79744
64.79582
50.99838
35.49838
71
36
12
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Examnle Calculation 3 - Mass Lost to IC and nH Pour Offs
Remaining Solution Mass (g) after 1DW pour off for 30 Day Acid Spiking =
[(Mass2 - Massl) - Mass3]
9.4.14. To the remaining ~ 34.5 mL of leachate and filter, spike with ultra high purity
nitric and hydrochloric acids to make 0.2% and 0.1% (v/v), respectively.
¦ See Table 2 and Example Calculation 4 below.
Examnle Calculation 4 - Acid Sniking for Acid Soluhle Extract
If remaining mass from SPREADSHEET = ~ 34.5 g,
34.5mLSorn/ O.lmLHCl V100° ML^ = 34.5 jjL HC1
^100 mL totalsol' ^ lmL ^
( 0.2mL HN03 Vl000 //L^
34.5 mLSol' n dlOOmLtotalSol'ii 1 J = 69 //L HNQ3
9.4.15. Sonicate 30 minutes at 80 °C.
9.4.16. Let sit in D456 (20 °C) for 30 days.
9.4.17. After 30 days, pour approximately 10 mL of the acid soluble leachate into a
labeled, acid cleaned 15 mL tube.
¦ Label is SampleName_30DA (30-day acid)
¦ This sample now has the matrix-matched acid concentrations needed for multi
element ICPMS analysis for D-EMMD-PHCB-042-SOP-03 Analysis,
Standard Operating Procedure for Operation and Maintenance of the Element
2 High-Resolution Inductively Coupled Plasma Mass Spectrometry
Instrument.
Concentrated Hot Acid Leach (HAL) for ICPMS Analysis
9.4.18. Record the mass of the remaining -25 mL of leachate and filter (Mass4), spike
with ultra high purity nitric and hydrochloric acids to make 2% and 1% (v/v),
respectively.
13
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Table 3: Sample Spreadsheet After Mass 4 and Acid Spiking
4/23/09
4/23/09
4/23/09
4/24/09
5/24/2009
Sample ID
MASS 1
Tube, Cap,
(filter)
(g)
MASS 2
Tube, Cap,
200uL
EtOH, 50m L
MilliQ, filter
(g)
1DW
Extraction
Mass (g)
MASS 3
after 1 DW
pour off (g)
uL HN03
for 0.2%
(v/v)
uL HCI for
0.1% (v/v)
Mass 4
after 30 DA
pour off (g)
uL HN03
for 2 %
(v/v) HAL
uL HCI for
1 % (v/v)
HAL
PMC_WB1
13.61354
64.64846
51.03492
35.53492
71
36
25.53492
511
255
PMC_WB2
13.48995
64.74524
51.25529
35.75529
72
36
25.75529
515
258
PMC_WB3
13.76135
64.20034
50.43899
34.93899
70
35
24.93899
499
24E
PMC_69B
13.84836
65.15102
51.30266
35.80266
72
36
25.80266
516
258
PMC_70B
13.65657
64.87368
51.21711
35.71711
71
36
25.71711
514
25;
PMC_75A
13.79744
64.79582
50.99838
35.49838
71
36
25.49838
510
255
Examnle Calculation 5 - HAL Acid Sniking
If poured off solution from 9.4.18 is approximately
25 mLSol' n x lmL HC1 V'000 //L ^
^100 mL totalSol' ^ lmL ^
( 2mL HNOs Vl000//L^
25 mLSol' n x|ioomLtotais0rn |x' lmL I
^ n J
Place the concentrated samples inside a convection lab oven at 70 °C for 3 hours
After 3 hours, carefully remove from the oven and let to cool at lab temperature.
Once cooled, pour a -10 mL aliquot into a labeled acid-cleaned 15 mL tube for
ICP-MS analysis, using HAL as the label suffix.
21.1. ICPMS calibration standards should be matrix-matched to 2% and 1%
nitric and hydrochloric acids, respectively.
25 mL:
= 250 juL HC1
= 500 juL HN03
9.4.19.
9.4.20.
9.4.21.
9.4.
ONCE ACIDIFIED, ALL TUBES FOR ICPMS CAN BE STORED AT ROOM TEMPERATURE.
10. Data and Records Management
Tubes with filters and any other samples for long-term storage are locked in the Filter
Storage Room (D458). Label the sample trays appropriately with Study Name, Analysis
14
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D-EMMD-PHCB-071 -SOP-01
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Date, and Analyst Initials. Bag the samples for storage before leaving the clean lab
environment (D456). See also section 11.2.
10.1. Sample Calculations for Final Results of Extractions
¦ All sample calculations below assume data has been flagged valid. Error
propagation has been omitted for simplicity.
1DW Extraction Mass (Mass2 - Massl (see 9.4.7 and Table 1)) = 51.30266 g
30DA Extraction Mass (Mass3 (see 9.4.13)) = 35.80266 g
Mass lost to IC and pH pour offs (1DW - 30DA) = 15.50000 g
ICPMS Sample Results for Fe57
PMC 69B1DW 1.12 |ig/L
PMC 69B 30DA 4.20 |ig/L
10.1.1. Single-stage extraction procedure. Also works for water soluble mass per filter
for ICPMS (same calculation for IC) or soluble mass after single-stage extraction
procedure
¦ First, calculate the single stage extraction mass (Appendix 2, Step 5) or the
1DW extraction mass (see 9.4.7), assuming density of solution is 1.0 g/mL.
Examnle Calculation 5 - Water Soluble Mass Per Filter
1.12 us, Fe t 1 L soln * ^ rn^so^n * si 30266 1 nnc7c t? f-u
ji.ju/oo g soln =0.0575 jug Fe per filter
L soln 1000 mL soln 1 g soln
10.1.2. Total mass per filter for ICPMS, combination of two extraction steps.
Examnle Calculation 6 - Total Mass Per Filter
1.12/^F e „ 1L soln— * l.OmLsoln # ^ 5 5000Qg §oln = 00176/lg Felost topour offs
L soln 1000mL soln 1 g soln
4 2°^Fe* soln .l.OmLsoln,3s 8Q266ggo|n=0 j50fl%Feafter30DA
L soln 1000mL soln 1 g soln
Total Mass = 0.0176 |ig + 0.150 |ig = 0.168 |ig Fe per filter
15
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D-EMMD-PHCB-071 -SOP-01
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11. QA/QC
11.1 Water or Tube Blanks collected during the filter extraction procedure (9.4.5) serve as
quality control samples to determine any water and tube contaminations. These
samples will be analyzed alongside filter samples and filter blanks and will be used in
the final interpretation of quantitative data.
11.2 Excel spreadsheets used for capturing pour-off mass data should be saved and archived
on the ICPMS computer (D456) that automatically archives to a removable hard drive.
These files can also be emailed to Kasey Kovalcik (kovalcik.kasey@epa.gov) for
duplicate archiving.
12. References
12.1. Graney, J.R.; Landis, M.S.; Norris, G.A; Concentrations and solubility of metals from
indoor and personal exposure PM2.5 samples. Atmospheric Environment, 2004, 237-
247.
12.2. Analytical Balance and Weight Certification performed annually by Precision
Weighing, Cary, NC.
12.3. D-EMMD-PHCB-042-SOP-03, Standard Operating Procedure for Operation and
Maintenance of the Element 2 High-Resolution Inductively Coupled Plasma Mass
Spectrometry Instrument, November 2017.
12.4. Oakes, M.M.; Burke, J.M.; Norris, G.A.; Kovalcik, K.D.; Pancras, J.P.; Landis, M.S:
Near-road enhancement and solubility of fine and coarse particulate matter trace
elements near a major interstate in Detroit, Michigan. Atmospheric Environment,
2016, 213-224.
16
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D-EMMD-PHCB-071 -SOP-01
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Appendix 1: Two Stage Extraction Procedure for NEXUS and CMAPS Filter
Samples.
1) Rinse the already acid-cleaned 50 mL sample tubes three times with MilliQ water, and air
dry the tubes in the Laminar Flow hood in D456 for 60 minutes.
2) Insert a filter sample into the dry 50 mL tube, add 100 |iL of ethanol to cover the filter
surface, cap the tube and label it appropriately. Weigh the tube (Wl).
3) Add approximately 40 mL of MilliQ water from the carboy and weigh again (W2).
a) Extraction Volume (mL) = W2 - Wl
4) Sonicate the samples at room temperature for 3 hours and let the filter leach in the aqueous
phase for 24 hours.
5) After 24 hours, pour 4 mL of the aqueous leachate into a 15-mL acid-cleaned tube that has
been rinsed three times with MilliQ water, and labeled. Then add 120 |iL of freshly prepared
(2+1) concentrated HNO3 and HC1 acid mix. Store for analysis.
a) Final concentrations are 2% HNO3 and 1% HC1 (v/v).
6) Weigh the remaining filter, leachate, and tube after the above pour-off (W3).
a) Volume Poured Off for Aqueous Extraction (mL) = W2 - W3
7) To the approximately remaining 36 mL of leachate and filter, add 1000 |iL of the (2+1)
concentrated acid mix to the tube and cap tightly.
a) Final concentrations are 2% HNO3 and 1% HC1 (v/v).
8) Set the ultrasonic water temperature to 70 °C and place the 50 mL sample tubes (24 tubes per
rack) in the bath. Once the set temperature is reached, Sonicate the samples for 3 hours.
a) To minimize potential contamination, ensure the ultrasonic bath water does not reach
the cap.
9) Set the 50 mL sample tubes aside for 9 days. Then pour off approximately 4 mL for ICP-MS
analysis.
17
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Appendix 2: Single Stage Extraction Procedure for Tire Crumb Rubber
Study Samples
1) Insert media to be extracted into a dry 50 mL acid-cleaned centrifuge tube.
2) Add 100 |iL of ethanol to cover the filter surface or to completely wet the reference material
cap the tube and label it appropriately. Weigh the tube (Wl).
i) Filter media is a teflon filter and teflon support ring with collected PM or
ii) NIST SRM 1648a. Refer to NIST insert for handling care. Typically, 100 mg of the
well-mixed material is used.
3) Add approximately 35 mL of a 2% HNO3 and 1% HC1 (v/v) solution using MilliQ water and
Optima acids.
a) The total volume added can vary depending on the size of the filter.
4) Weigh the filter, leachate, and tube after the above pour-off (W2).
a) Extraction Mass (g) = W2 - Wl
5) Set the ultrasonic water temperature to 70 °C and place the 50 mL sample tubes (24 tubes per
rack) in the bath. Once the set temperature is reached, sonicate the samples for 30 minutes
and leave the tubes in the water bath for 3 hours.
a) To minimize potential contamination, ensure the ultrasonic bath-water does not reach
the cap.
6) Set the 50 mL sample tubes aside for 9 days.
7) Into a cleaned 15 mL sample tube, pour approximately 10 mL for ICP-MS analysis, leaving
the original filter/sample submerged.
8) Calculations to determine the elemental mass per filter are shown in Section 10.1.1
18
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I
U. S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Total Nitric Acid Extractable Metals from Solid Samples by
Microwave Digestion
Number: sop#d-emmd-ecb-oo3-sop-oi
Effective Date: 11/01/16
SOP was Developed
~ In-house
~ Extramural
Alternative Identification:
SOP Steward
Name: Georges-Marie Momplaisir
Signature:
Approval
Name: Tammy Jones-Lepp
Title: ECB Chief
Signature:
Concurrence*
Name: Margie Vazquez
Title: EMMD QA mgr
Signature:
* Optional field
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SOP # D-EMMD-ECB-003-SOP-01
Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 2 of 21
STANDARD OPERATING PROCEDURE FOR TOTAL NITRIC ACID EXTRACTABLE
METALS FROM SOLID SAMPLES BY MICROWAVE DIGESTION
Prepared by
Georges-Marie Momplaisir
For
Environmental Chemistry Branch USEPA/ORD/NERL-EMMD
944 East Harmon Avenue
Las Vegas, Nevada 89119
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 3 of 21
Table of Contents
I.0 Definitions and Acronyms 4
2.0 Disclaimer 4
3.0 Purpose (Scope and Application) 5
4.0 Procedure Summary 5
5.0 Reagents/Chemicals 5
6.0 Equipment/Apparatus 6
7.0 Interferences 6
8.0 Health & Safety Precautions 7
10.0 Quality Assurance / Quality Control (QA/QC) 9
II.0 Calculations 10
12.0 Miscellaneous Notes 11
Appendix A: Microwave Extraction Programs 12
Appendix B: Quality Control Test for MARS-5 Vessels and Sensors 13
Appendix C: Procedure for Microwave Calibration 14
Appendix D: Procedure for Cleaning Vessels 15
Appendix E: Microwave Assisted Cleanup Programs 17
Appendix F: Bench Sheets for Sample Processing 18
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 4 of 21
1.0 Definitions and Acronyms
ECB Environmental Chemistry Branch
EMMD Environmental Measurement and Monitoring Division
ICPMS Inductively Coupled Plasma Mass Spectrometry
Dl Deionized
RO Reversed Osmosis
HN03 Nitric acid
HCI Hydrochloric acid
H202 Hydrogen peroxide
SHEMP Safety and Health Environmental Management Program
SOP Standard Operating Procedure
MARS Microwave Accelerated Reaction System
PPE Personal Protective Equipment
QA Quality assurance
QC Quality Control
2.0 Disclaimer
This standard operating procedure has been prepared for use of the Environmental
Measurement and Monitoring Division (EMMD) of the U.S. Environmental Protection Agency and
may not be specifically applicable to the activities of other organizations. It is a modified version
of ECB-012 SOP[Ref 111]. It uses the multi-element Nitric acid/ Hydrochloric acid-leach microwave-
assisted digestion procedure described in EPA Method 3051a[Ref 1121 which renders a sample
suitable for ICP-MS analysis. This procedure is limited to use by, or under direction of, chemists
and technicians who have demonstrated proficiency with the procedure. THIS IS NOT AN
OFFICIAL EPA APPROVED METHOD. This document has not been through the Agency's peer
review process or EMMD clearance process.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 5 of 21
3.0 Purpose (Scope and Application)
This document describes a procedure for the preparation of solid matrices such as tire crumb
rubber, soils, sediments or sludge and can be adapted for biological matrices and wipes, for
analysis by inductively coupled plasma mass spectrometry (ICP-MS). It uses a mixture of nitric
acid and hydrochloric acid to improve the extractability of metal analytes.
4.0 Procedure Summary
Organic material in the sample matrix is destroyed and metals that are extractable with a mixture
of nitric and hydrochloric acid are solubilized by microwave digestion in a sealed, pressurized
Teflon vessel. The sample is first allowed to pre-digest at room temperature, and then subjected
to a microwave heating program that increased the temperature of the mixture slowly to 200 °C
and kept it at this temperature for another 30 minutes. The MARS-5 microwave unit (CEM
Corporation, Matthews, NC) used is fitted with a fiber optic temperature sensor to monitor the
temperature of the reference vessel. The instrument has the ability to regulate the temperature
of the sample by adjusting the amount of applied power.
After cooling, the samples are diluted with deionized water and transferred to an acid cleaned
polyethylene or Teflon container that can be centrifuged if needed to separate solid particles.
5.0 Reagents/Chemicals
5.1 Deionized (Dl) water: in house 18.2 MQ Dl water.
5.2 Concentrated Nitric Acid Optima: high purity concentrated HN03 (65%-70% Fisher
Scientific, 1 liter bottle, catalog # A467-2).
5.3 Concentrated Hydrochloric Acid Optima: high purity concentrated HCI (Fisher Scientific,
500 mL bottle, A466-500) use if needed only.
5.4 Hydrogen Peroxide Optima: 30% H202 Trace-pure (Fisher Scientific, 500 mL bottle, P170).
5.5 Matrix Spike Standard: Multi-Element Custom Standard of 48 elements Ag, Al, As, Ba, Be,
Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Fe, Gd, Ge, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Pd, Pt,
Rb, Rh, S, Sb, Se, Si, Sm, Sn, Sr, Tb, Ti, Th, Tl, U, V, W, Y, and Zn in 15% HCL and 5% HN03,
(SCP Science, catalogue # AQ0-008-122).
5.6 Concentrated HN03: Trace-metal clean concentrated HN03 (65%, Fisher Scientific, catalog
# A509212) for washing labware.
5.7
10% Nitric Acid: Add 100 mL of concentrated nitric acid to 500 mL deionized water
and dilute to 1 L.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 6 of 21
6.0 Equipment/Apparatus
6.1 CEM Corporation Microwave Accelerated Reaction System, Model MARS-5 which includes
a microwave power system with selectable output of 0 - 1600 watts, a fluoropolymer-
coated microwave cavity and rotating turntable. The instrument is fitted with a pressure
sensor ESP-1500 Plus and fiber optic temperature sensor model RTP-300 Plus
(temperature range 40 to 250 °C) that can be used to monitor the XP-1500 Plus vessels.
Although both sensors are factory calibrated, it is strongly encourage to check the
instrument temperature reading against an external thermometer. A step by step
procedure for calibrating the temperature probe of the MARS-5 instrument is reported in
Appendix C. Please also refer to the MARS-5 Operation Manual [Ref 1131 for more
information on routine maintenance and cleaning.
6.2 MARS Digestion Vessels: CEM XP-1500 plus Control Vessel with a TFM liner
6.3 Centrifuge: Model IEC Centra MP4R International Equipment Company
6.4 Water Purification System: Water Pro Plus LABCONCO
6.5 Assorted micropipettes and appropriate tips Rainin E4™ XLS, Mettler Toledo
6.6 0.45 pirn PTFE filter membranes
6.7 Analytical balance: Mettler Toledo XP504, 4-decimal analytical balance, 520 gram
maximum capacity, and minimum sensitivity of 0.1 mg
6.8 Calibrated Class 1 NIST Certified Reference Weights
6.9 Sample bottles and tubes of varying sizes
7.0 Interferences
A clean laboratory environment and trace-clean reagents are required to conduct trace inorganic
analysis. Even when all of these are met, non-clean laboratory practices can lead to introduction
of contaminants into a sample matrix and/or extract that could interfere with instrumental
analysis. Attention to details and experience with clean lab practice procedures are necessary.
The analyst should demonstrate and implement clean laboratory practices. QC measures are put
in place to identify and reduce laboratory contaminants.
During microwave digestion, decomposition of organic rich materials may create high vessel
pressure. This may cause venting of the microwave vessel and result in either loss of analytes and
sample, which must be avoided. Digestion of such samples should be initially subjected to a
reduced initial mass. Gradual and incremental increase of sample size is necessary when the
digestion characteristics of a certain matrix are unknown. The concentration of reagents however
should remain the same.
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SOP # D-EMMD-ECB-003-SOP-01
Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 7 of 21
Health & Safety Precautions
8.0 Hydrochloric acid is a strong mineral acid that is highly corrosive. Nitric acid is a strong
oxidizing agent and a strong acid. Hydrogen peroxide is also a very strong oxidizer. All
these chemicals can cause skin irritation and burns, respiratory irritation, damage to eyes
and organs if not handled properly.
8.1 The analyst should review the Safety Data Sheets (SDS) for each chemical in this
procedure so that safe working procedure must be achieved. SDS are located in a properly
labeled 3-ring binder in CHL-43 Laboratory and are also available on-line.
8.2 All of the hazardous chemicals used in this procedure should be handled only while using
proper personal protective equipment (PPE) such as: gloves, lab coats, safety glasses and
appropriate close-toed shoes. Contact lenses may not be worn while working in the
laboratory. Fume hoods must be utilized whenever possible to avoid potential exposure.
Perform dilutions by adding acid to water.
8.3 The analyst should be familiar with the location and proper use of the fume hoods, eye
washes, safety showers, and fire extinguishers.
8.4 Waste disposal should follow the recommended EMMD procedures for waste disposal
whenever applicable. Contact the onsite EMMD's SHEMP Manager when the container is
full for disposal.
8.5 Rapid and/or explosive generation of gases can occur during the digestion of samples with
a high organic content such as oils, tissues and rubber based materials. The analyst should
follow the advice given in paragraph 2 of Section 7.0.
8.6 When working with samples of unknown composition, always perform a pre-digestion
step in an unsealed, open vessel, allowing a minimum of 15 minutes time for reaction of
volatile or easily oxidized compounds to subside before sealing the vessel and microwave
heating.
8.7 Never heat liquids in a sealed vessel that is not equipped with a pressure relief device.
8.8 Microwave digestion vessels can be highly pressurized and should be handled with care.
To minimize internal pressure, the microwave digestion vessels should be allowed to cool
to ambient temperature before opening. In addition the vessels should be vented in a
fume hood to release excess fumes.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
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8.9 Fumes from the microwave unit should be exhausted to a hood.
8.10 Organic solvents should not be subjected to microwave radiation as they may react
explosively. Organic solvent such as ethanol when mixed with concentrated acids like
nitric acid can react violently, even explosively, and this without applied heat.
8.11 All unused acids should be properly disposed in the acid waste collection container.
Microwave Extraction Protocol
All digestion and volumetric vessels must be acid washed and rinsed with deionized water before
use. Refer to Appendix C. for the step by step procedure for cleaning vessels.
9.1 Microwave Extraction of Tire Crumb Rubber Samples
Use the sets of 12 XP-1500 Plus microwave vessels which also include a control vessel. The
liner has a capacity of 100 mL and is made of Teflon® TFM, an advanced composite Teflon.
These vessels are adequate to handle the high temperature required to digest the rubber
material and can withstand a maximum pressure of 800 psi.
Bulk tire crumb rubber samples will be used without sieving or size reduction, to minimize
contamination.
9.1.0 Place the microwave vessel and cap on a tared balance and record the weight in the
digestion Notebook. Mix the sample thoroughly. Remove the cap and transfer 0.25 g
(within 0.02 g) of sample to the tared vessel. The sample must be placed in the
bottom of the liner. The side walls of the liner must be free of sample deposits.
9.1.1 Determine the weight of concentrated nitric acid and hydrochloric acid that will
make a slurry containing 9 mL HN03 and 3 mL HCI, taking their specific gravity into
consideration (Section 11, no. 11.1). According to the manufacturer SDS, the Optima
nitric acid has a specific gravity of 1.40 and the Optima HCI 1.18.
9.1.2 Tare the vessel, add concentrated nitric acid to the vessel and record the weight of
the acid. Zero the vessel one more time, add the hydrochloric acid and record the
weight. Make sure that the acid mixture covers the sample. Place a new rupture
membrane in the vessel cap and seal firmly by hand. Weigh the vessel and record
the weight before digestion.
9.1.3 Repeat the above procedure for a batch of up to 24 samples. Place a duplicate of
the sample most likely to be more reactive in the MARS-5 control vessel. Insert the
temperature probe in the control vessel sapphire well and secure the pressure line
to the cap. The control sample is not normally used for data since it may become
contaminated from the pressure monitoring line.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 9 of 21
9.1.4 MARS-5 System - The microwave unit can only process a set of 12 samples in XP-
1500 vessels at a time. Place the turntable into the microwave cavity. Place each
vessel into the turntable. Connect pressure and temperature lines to their
microwave ports.
9.1.5 Use program ECBTRC-1 1-4 vessels, ECBTRC-2 for 4-8 vessels and ECBTRC-3 for 9
- 12 vessels. These programs are described in Appendix A. Record the temperature
after ramp up and before the end of the digestion cycle.
NOTE: Due to the variable nature of the samples, some may be particularly reactive
and require a gentle pre-digestion to volatize potentially explosive compounds. For
example, samples with larger and more irregular particles may be targeted for this
extra step. Any change in the conditions used for digestion will be noted in the lab
notebook used to document sample preparation.
9.1.6 After digestion is complete, allow the vessels to cool until the temperature drops to
less than 30 °C. There is no need to open the microwave door to help cool the
vessels. Once the method run is complete, the MARS-5 system will go through an
automatic cooling cycle.
9.1.7 Vent the vessels in a fume hood and weigh to verify that no significant amount of
solution was lost.
9.1.8 Place the microwave vessels in the fume hood. Add 250 piL of hydrogen peroxide in
each vessel and allow enough time for the hydrogen peroxide to oxidize remaining
organic material. The extract should be quite clear at the end of the process.
9.1.9 Transfer the solution quantitatively to a 60 mL LDPE polyethylene sample bottle and
bring to a final weight of 50 g of solution using deionized water. Allow solids to
settle and if needed, centrifuge the sample. This sample will be further diluted and
analyzed by ICPMS. In addition, a filtration step can be included if judged necessary,
using a 0.45nm membrane filter.
9.1.10 Use the in-house developed Excel program to do all calculations and print digestion
log to be placed in the digestion log binder or paste in the project laboratory book.
The excel program will compute the Calculated Weight before Digestion, Percent
Difference, Recovery Percent and Dilution Factor.
10.0 Quality Assurance / Quality Control (QA/QC)
10.0 Blank: A preparation blank will accompany each digestion batch of 24 or fewer samples.
The mixture of acid reagents (Section 9.1.1) will be used. The blank is used to track
potential contamination during sample preparation and extraction. The blank is treated as
a regular sample. If a sample is filtered before analysis, than a blank will also need to be
filtered to assess if the filter is contributing any contamination.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 10 of 21
10.1 Laboratory Control Sample (LCS): Another reagent blank will be prepared and to this, will
be added 250 |al of the custom spike standard solution (Section 5.5) before digestion. The
LCS results will be used to determine if the laboratory can perform the analysis in a clean
matrix.
10.2 Laboratory Duplicate (Dup): One tire crumb sample will be digested in duplicate with
each batch of 24 or fewer samples to check the precision of the digestion method.
10.3 Matrix spike (MS): With each digestion batch of 24 or fewer samples, an additional
subsample taken from a randomly selected tire crumb container will be prepared. This will
be spiked with 250 |al of the standard mixture of analytes and digested. The MS is used to
document the effect of the sample matrix on analyte recovery.
10.4 Standard reference material: A standard reference sample (if available for the sample
matrix type to be analyzed) should be included with each batch of samples processed. As
of now there is no standard reference material available for tire crumb rubber.
10.5 Digestion Percent Difference: The percent difference between the weight after digestion
and the calculated weight before digestion should not exceed 10 %. If the percent
difference does exceed 10%, investigate the reason, correct, and re-digest the sample.
10.6 Pressure and Temperature Monitoring for the MARS-5 system: Examine the pressure and
temperature monitoring graph. If the pressure or temperature deviates from the set point
by 15 % or more after ramp up and before the end of the digestion, investigate the
problem, and consult the group leader to determine if re-digestion is necessary.
Determine if the sample in the monitoring vessel was the cause and if not, the microwave
may need recalibration (refer to Appendix B and C).
11.0 Calculations
11.1 Acid Weight = desired volume x density
Optima Nitric acid weight = 9 mLx 1.40 g/mL = 12.60 g
Optima Hydrochloric weight = 3 mLx 1.18 g/mL = 3.54 g
11.2 Calculated Weight before Digestion: The Excel program will add the vessel weight, the
sample weight and the acid weight to give the expected weight before digestion in grams.
11.3 Percent Difference: The Excel program will divide the weight after digestion by the
calculated weight before digestion and multiply by 100 to give a percent difference.
11.4 Dilution Factor: The Excel program will add the sample weight and the acid weight
adjusted for specific gravity, and divides the result by the sample weight to obtain the
dilution factor used in data calculations.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 11 of 21
12.0 Miscellaneous Notes
12.0 MARS-5 System: Monitor the pressure and temperature during the digestion process. If
the expected temperature or pressure is not maintained during the digestion, investigate
the cause, and consult the group leader to determine if re-digestion is necessary.
12.1 Follow instructions in Appendix B and the MARS-5 instruction manual if recalibration of
the pressure sensor or temperature sensor is required. The pressure sensor calibration
constant is 4315-4316-0621-0623-6637-2241.
12.2 The digestion data will be stored on the individual analyst computer and on a designated
EPA shared drive. Additionally, hard copies of the digestion data will be placed in the Tire
Crumb digestion binder located in CHL-43.
13.0 References
13.1 U.S.E.P.A. SW-846 Method 3015A. Microwave Assisted Acid Digestion of sediments,
sludges, soils and oils.
13.2 SOP-ECB-012.0 Total Nitric Acid Extractable Metals from Aqueous Samples by Microwave
Digestion, 2012.
13.3 Mars-5 Users Guide, CEM Corporation.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 12 of 21
Appendix A: Microwave Extraction Programs
Two microwave accelerated reaction systems MARS-5 are located in CHL-25 laboratory. The digestion
programs use a ramp to temperature approach and are available on both systems. Depending on the
number of vessels used, the analyst should choose the appropriate ECBTRC- method.
1. Program Name: ECBTRC-1
Max Power = 400W
% Power = 100%
Ramp = 20 minutes
Pressure = 0 psi
Temperature = 200 °C
Hold Time = 30 minutes
Number of Vessels = 1 to 4
2. Program Name: ECBTRC-2
Max Power = 800W
% Power = 100%
Ramp = 20 minutes
Pressure = 0 psi
Temperature = 200 °C
Hold = 30 minutes
Number of Vessels = 5 to 8
3. Program Name: ECBTRC-3
Max Power = 1600W
% Power = 100%
Ramp = 30 minutes
Pressure = 0 psi
Temperature = 200 °C
Hold = 20 minutes
Number of Vessels = 9 to 12
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 13 of 21
Appendix B: Quality Control Test for MARS-5 Vessels and Sensors
This quality control test should be performed only if deemed necessary.
1. Place 50 mL Dl water in the control vessel (XP1500+, or HP500+), and assemble as you normally
do with the temperature and pressure sensors attached.
2. Place the control vessel in the turntable and connect the sensors. (No other vessels are run
during this test.)
3. Go into the CEM Directory and load the preprogrammed "QC ESP/EST" method.
4. Allow the method to run, observing the temperature and pressure readings. When you get to
stage 5, record the temperature once the pressure has begun controlling at 200psi. The
temperature should be 200°C +/- 10C at 200psi. If it is not, either the temperature or pressure
sensor is out of calibration.
5. Allow the vessel to cool to < 50°C. Measure the volume of water remaining in the vessel. If you
put 50mL in, you should get 50mL back out. If the volume is < 50mL, then there is a leak.
Note that a vessel can be leaking and still pass the QC test (200psi = 200°C). Look for volume loss
instead.
6. If the QC test fails (i.e., you do not get 200°C +/-10C at 200psi), then recalibrate the temperature
probe and repeat the QC test.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 14 of 21
Appendix C: Procedure for Microwave Calibration
Prepared by Jason Sylva
Pressure Calibration
1. From the home screen on the instrument, press "Setup" then follow the outlined procedure.
2. Use the "select" button to select the option of choice. "Select Sensor" -> "Pressure Sensor" ->
3. "ESP-1500" -> "Yes" -> "Zero Sensor" then press back and select "Display Calibration Constant".
4. If the calibration constant read "0000-0000-0000-0000-0000-0000" refer to operation manual pg
60-66 or contact manufacturer for proper calibration constant for your model. The calibration
number used for our model is: 4315-4316-0523-6637-2241
Temperature Calibration
1. From the home screen of instrument, press "Setup" then follow the outlined procedure.
2. Use the "select" button to select the option of choice. "Select Sensor" -> "Temperature" -> "RTP-
300 plus" -> "GF number (GF number is located on thermometer) -> "Calibrate RTP-300 Plus".
3. Place microwave thermometer into the reference top of microwave cell, then insert into a beaker
of water. A second external thermometer is placed into the same bath and this is taken as the
actual temperature and entered into system.
4.
Refer to operation manual pg 67-68 for further details.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 15 of 21
Appendix D: Procedure for Cleaning Vessels
This cleaning sequence has been determined to be adequate to minimize contamination in glass,
polyethylene, polypropylene or PTFE vessels.
1. Prepare cleaning solution by adding a small amount (approximately 5 mL) of concentrated
Citranox (Alconox Inc.) liquid soap to a tub of reverse osmosis (RO) water (~6 L). Remove all
markings and residue from vessels using a designated lab brush or methanol if necessary.
Submerge vessels in soap solution and allow to soak for a few minutes.
2. Clean the vessels with a lab brush. Rinse three times with reversed osmosis water and one
last time with deionized water.
3. Place the vessels in an acid bath containing 10% (v/v) Trace-metal clean concentrated HN03
in Dl water, and let them soak overnight (and up to 48 hours).
4. Remove vessels, rinse three times with deionized water.
5. Allow vessels and lids to air dry (open end down) on a clean surface.
6. This step applied only to the XP-1500 microwave digestion vessels that already went
through the above cleaning steps.
Use the Optima grade acid to prepare 1 liter of 10% Nitric acid.
- Fill the vessels approximately half way with acid (~50 mL) and secure the lids. Don't forget
to place a safety membrane in the vent cap.
- Place the vessels in the carousel and microwave the solution using extraction program
ECBCM-1, -2 or -3 (Appendix E) depending on the number of vessels.
7. After cooling to room temperature, pour the nitric acid solution back into the Teflon
cleaning solution container. Rinse vessels and caps three times with deionized water, and
allow to air dry.
8. All sample bottles and microwave vessels should be capped and stored in sealable plastic
bags or plastic containers to prevent contamination.
9. Label bag or container with the cleanup date and batch number.
When cleaning polyethylene conical tubes with external graduation, soaking in an acid bath is not
recommended as the material used to graduate the tubes can be removed upon contact with acid
and therefore can become a source of contamination.
- Remove the caps and let the tubes stand in the Styrofoam base.
- Pour Dl water into each tube and secure the caps. Let the sealed tubes soak for a few
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SOP # D-EMMD-ECB-003-SOP-01
Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 16 of 21
minutes, shake well and discard the water. Repeat this step two more times.
- Fill each tube with 10% nitric acid and let sit overnight or at least twelve hours at room
temperature in the Styrofoam container with their lids on.
- The next morning, the sealed tubes are reversed to give the cap a chance to get in contact
with the acidic solution. Leave the tubes in that position for at least four hours.
- Pour the acid content into an acid cleaning bottle.
- Rinse tubes and lids several times with deionized water and allowed to air dry.
- Cap the tubes, place them back in their Styrofoam base and keep them seal until usage.
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 17 of 21
Appendix E: Microwave Assisted Cleanup Programs
1. Program Name: ECBCM-1
Max Power = 400W
% Power = 100%
Ramp = 10 minutes
Pressure = 100 psi
Temperature = 170 °C
Hold = 30 minutes
Number of Vessels = 1 to 4
Average Sample Volume = 50 mL
2. Program Name: ECBCM-2
Max Power = 800W
% Power = 100%
Ramp = 10 minutes
Pressure = 100 psi
Temperature = 170 °C
Hold = 30 minutes
Number of Vessels = 5 to 8
Average Sample Volume = 50 mL
3. Program Name: ECBCM-3
Max Power = 1600W
% Power = 100%
Ramp = 10 minutes
Pressure = 100 psi
Temperature = 170 °C
Hold = 30 minutes
Number of Vessels = 9 to 12
Average Sample Volume = 50 mL
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Microwave Assisted Digestion of Solid Matrices
November 1, 2016
Page 18 of 21
Appendix F: Bench Sheets for Sample Processing
See the following pages for bench sheets used to help track sample processing, including reagent and
standard lot numbers.
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ECB Microwave Digesion Sheet S
Date:
Sample Matrix:
Batch 1 D:
No. of Samples:
Analyst (s):
Reagents and Standards:
Manufacturer:
Cat. No.:
Lot No.:
Exp. Date:
Nitric Acid
Hydrochloric
Hydrogen Peroxide
Deionized Water 18.2 MQ
Water PRO PS
Spike Standard Solution
Microwave System:
Microwave Program:
Start Time:
End Time:
Table 1: Microwave Assisted Extraction of Metals ir
1
ECB-EMMD
Sample ID
Vessel
No.
Vessel Wt (g)
Sample Wt (g)
Nitric Acid
Wt (g)
Hydrochlori
c Acid Wt (g)
Wt of*
spi ke
Std. (g)
Wt Before
Digestion (g)
Wt After
Digestion (g)
Vol. of**
H202 (uL)
Wt of Dil.
Digestate (g)
Wt of Dil.
Digestate sent
to RTP (g)
Reference
1
2
3
4
5
6
7
8
9
10
11
12
¦ dup: duplicate sample, ¦ spk: spiked sample,
¦ BLK: procedure bl a nk, ¦ LCS: 1 a bora to ry control sample,
¦ Std: sta nda rd, ¦ Dil: dil uted, -Wt:weight, ¦ H202: H^
¦ Weight of Nitric acid needed:
¦ Weight of Hydrochloric acid needed:
[wt( g) = V(mL) X density (g/mL) ]
*Volume of spike standard solution:
¦ Reference sa mple ID:
** Hydrogen peroxide was added after digestion.
Use this digestionsheet if number of samples in a batch is <12
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ECB Microwave Digesion Sheet 1 of 2
Date:
Sample Matrix:
Batch ID:
No. of Samples:
No. of Sets
2
Analyst (s):
Reagents and Standards:
Manufacturer:
Cat. No.:
Lot No.:
Exp. Date:
Nitric Acid
Hydrochloric
Hydrogen Peroxide
Deionized Water 18.2 MQ
Water PRO PS
Spike Standard Solution
Microwave System:
Microwave Program:
Start Time:
End Time:
Table 1: Microwave Assisted Extraction of Metals in
ECB-EMMD
Sample ID
Vessel
No.
Vessel Wt (g)
Sample Wt (g)
Nitric Acid
Wt (g)
Hydrochloric
Acid Wt (g)
Wt of*
spike
Std.(g)
Wt Before
Digestion (g)
Wt After
Digestion (g)
Vol. of**
H202 (uL)
Wt of Dil.
Digestate (g)
Wt of Dil.
Digestate sent
to RTP (g)
Reference
1A
2A
3A
4A
5A
6A
7A
8A
9A
10A
11A
12A
¦ dup: duplicate sample, ¦ spk: spiked sample, "BLK: procedure blank, "LCS: laboratory control sample, "Std: standard, -Di 1: diluted, "Wt: weight, "H202: Hydrogen Peroxide
¦ Weight of Nitric acid needed: g ¦ Weight of Hydrochloric acid needed: g [wt( g) =V(mL) X density (g/mL) ]
* Volume of spike standard solution: piL ¦ Reference sample ID: ** Hydrogen peroxide was added after digestion.
Use digestion sheets 1 and 2 if the number of samples in a batch is > 12 and < 24
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ECB Microwave Digesion Sheet 2 of 2
Date:
Sample Matrix:
Batch ID:
No. of Samples:
No. of Sets
2
Analyst (s):
Reagents and Standards:
Manufacturer:
Cat. No.:
Lot No.:
Exp. Date:
Nitric Acid
Hydrochloric
Hydrogen Peroxide
Deionized Water 18.2 MQ
Water PRO PS
Spike Standard Solution
Microwave System:
Microwave Program:
Start Time:
End Time:
Table 1: Microwave Assisted Extraction of Metals in
ECB-EMMD
Sample ID
Vessel
No.
Vessel Wt (g)
Sample Wt (g)
Nitric Acid
Wt (g)
Hydrochloric
Acid Wt (g)
Wt of*
spike
Std.(g)
Wt Before
Digestion (g)
Wt After
Digestion (g)
Vol. of**
H202 (uL)
Wt of Dil.
Digestate (g)
Wt of Dil.
Digestate sent
to RTP (g)
Reference
IB
2B
3B
4B
5B
6B
7B
8B
9B
10B
11B
12B
¦ dup: duplicate sample, ¦ spk: spiked sample, "BLK: procedure blank, "LCS: laboratory control sample, "Std: standard, -Di 1: diluted, "Wt: weight, "H202: Hydrogen Peroxide
¦ Weight of Nitric acid needed: g ¦ Weight of Hydrochloric acid needed: g [wt( g) =V(mL) X density (g/mL) ]
* Volume of spike standard solution: piL ¦ Reference sample ID: ** Hydrogen peroxide was added after digestion.
Use digestion sheets 1 and 2 if the number of samples in a batch is > 12 and < 24
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[This page intentionally left blank.]
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U. S Environmental Protection Agency
D J
S •. Office of Research and Development
National Exposure Research Laboratory
Exposure Methods and Measurement Division
Environmental Chemistry Branch
STANDARD OPERATING PROCEDURE
SOP Title: total nitric acid extractable metals from wipe samples by microwave
DIGESTION
SOP ID: D-EMMD-ECB-013-SOP-01
Effective Date: 11/13/2017
SOP was Developed: IE! In-house ~ Extramural:
SOP Discipline*: Inorganic Chemistry
Alternative Identification: QA Track ID
SOP Contact Signature
Name: Georges-Marie Momplaisir, author
Signature/Date:
Management Signature
Name: Brian Schumacher
Title: Acting ECB Chief
NERL Associate Director for Science
Signature/Date:
QA Signature
Name: Margie Vazquez
Title: EMMD QA manager
Signature/Date:
*See discipline descriptions on the NERL Scientific and Technical SOP intranet site.
-------
Version History
Version
No.
Name
Date of
Revision
Description of Change(s)
1
Georges-Marie
Momplaisir
11/13/2017
Modification of ECB-003- SOP-01 for
wipe samples.
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SOP # D-EMMD-ECB-013-SOP-01
Effective Date: 11/13/17
Page 3 of 17
TABLE OF CONTENTS
1. Scope and Applicability 4
2. Summary of Method 4
3. Definitions/Acronyms 4
4. Health and Safety Warnings 5
5. Cautions/Interferences 6
6. Personnel Qualifications/Responsibilities 6
7. Equipment and Supplies 6
8. Reagents and Standards 7
9. Procedures (Microwave Extraction Protocol) 7
10. Data and Records Management 9
11. Quality Assurance/Quality Control 10
12. References 11
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SOP # D-EMMD-ECB-013-SOP-01
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SOP Title: total nitric acid extractable metals from wipe samples by microwave
DIGESTION
Scope and Applicability
This document describes a procedure for the preparation of wipe samples, for elemental analysis by
inductively coupled plasma mass spectrometry (ICP-MS). It uses a mixture of nitric acid and
hydrochloric acid to improve the extractability of metal analytes.
This standard operating procedure has been prepared for use of the Environmental Measurement
and Monitoring Division (EMMD) of the U.S. Environmental Protection Agency and may not be
specifically applicable to the activities of other organizations. It is a modified version of ECB-003- SOP-
01 [Ref. 13.1]. It uses the multi-element nitric acid/ hydrochloric acid-leach microwave-assisted
digestion procedure described in EPA Method 3051a [Ref. 13.2] which renders a sample suitable for
ICP-MS analysis. This procedure is limited to use by, or under direction of, chemists and technicians
who have demonstrated proficiency with the procedure. This document has not been through the
Agency's peer review process nor the EMMD clearance/publication process. THIS IS NOT AN OFFICIAL
EPA APPROVED Method.
Summary of Method
Organic material in the sample matrix is destroyed and metals that are extractable with a mixture of
nitric and hydrochloric acid are solubilized by microwave digestion in a sealed, pressurized Teflon
vessel. The sample is first allowed to pre-digest at room temperature, and then subjected to a
microwave heating program that increased the temperature of the mixture slowly to 200 °C and kept
it at this temperature for another 15 minutes. The MARS-5 microwave unit (CEM Corporation,
Matthews, NC) used is fitted with a fiber optic temperature sensor to monitor the temperature of the
reference vessel. The instrument has the ability to regulate the temperature of the sample by
adjusting the amount of applied power.
After cooling, the samples are diluted with deionized water and transferred to an acid cleaned
polyethylene or Teflon container that can be centrifuged if needed to separate solid particles.
Definitions/Acronyms
HN03
HCI
H202
SHEMP
SOP
ECB
EMMD
ICPMS
Dl
RO
Environmental Chemistry Branch
Environmental Measurement and Monitoring Division
Inductively Coupled Plasma Mass Spectrometry
Deionized
Reversed Osmosis
Nitric acid
Hydrochloric acid
Hydrogen peroxide
Safety and Health Environmental Management Program
Standard Operating Procedure
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SOP # D-EMMD-ECB-013-SOP-01
Effective Date: 11/13/17
Page 5 of 17
MARS
Microwave Accelerated Reaction System
PPE
Personal Protective Equipment
OA
Quality assurance
QC
Quality Control
FCS
Field Control Sample
LCS
Laboratory Control Sample
LBLK
Laboratory Blank
FBLK
Field Blank
RBLK
Reagent Blank
Health and Safety Warnings
4.0 Hydrochloric acid is a strong mineral acid that is highly corrosive. Nitric acid is a strong
oxidizing agent and a strong acid. Hydrogen peroxide is also a very strong oxidizer. All these
chemicals can cause skin irritation and burns, respiratory irritation, damage to eyes and
organs if not handled properly.
4.1 The analyst should review the Safety Data Sheets (SDS) for each chemical in this procedure so
that safe working procedure must be achieved. SDS are located in a properly labeled 3-ring
binder in CHL-43 Laboratory and are also available on-line.
4.2 All of the hazardous chemicals used in this procedure should be handled only while using
proper personal protective equipment (PPE) such as: gloves, lab coats, safety glasses and
appropriate close-toed shoes. Contact lenses may not be worn while working in the
laboratory. Fume hoods must be utilized whenever possible to avoid potential exposure.
Perform dilutions by adding acid to water.
4.3 The analyst should be familiar with the location and proper use of the fume hoods, eye
washes, safety showers, and fire extinguishers.
4.4 Waste disposal should follow the recommended EMMD procedures for waste disposal
whenever applicable. Contact the onsite EMMD's SHEMP Manager when the container is full
for disposal.
4.5 Rapid and/or explosive generation of gases can occur during the digestion of samples with a
high organic content such as oils, tissues and rubber based materials. The analyst should
follow the advice given in paragraph 2 of Section 5.0.
4.6 When working with samples of unknown composition, always perform a pre-digestion step in
an unsealed, open vessel, allowing a minimum of 15 minutes of time for reaction of volatile
or easily oxidized compounds to subside before sealing the vessel and microwave heating.
4.7 Never heat liquids in a sealed vessel that is not equipped with a pressure relief device.
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SOP # D-EMMD-ECB-013-SOP-01
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4.8 Microwave digestion vessels can be highly pressurized and should be handled with care. To
minimize internal pressure, the microwave digestion vessels should be allowed to cool to
ambient temperature before opening. In addition, the vessels should be vented in a fume
hood to release excess fumes.
4.9 Fumes from the microwave unit should be exhausted to a hood.
4.10 Organic solvents should not be subjected to microwave radiation as they may react
explosively. Organic solvent such as ethanol when mixed with concentrated acids like nitric
acid can react violently, even explosively, and this without applied heat.
4.11 All unused acids should be properly disposed in the acid waste collection container.
Cautions/Interferences
A clean laboratory environment and trace-clean reagents are required to conduct trace inorganic
analysis. Even when all of these are met, non-clean laboratory practices can lead to introduction of
contaminants into a sample matrix and/or extract that could interfere with instrumental analysis.
Attention to details and experience with clean lab practice procedures are necessary. The analyst
should demonstrate and implement clean laboratory practices. QC measures are put in place to
identify and reduce laboratory contaminants.
During microwave digestion, decomposition of organic rich materials may create high vessel
pressure. This may cause venting of the microwave vessel and result in either loss of analytes and
sample, which must be avoided. Digestion of such samples should be initially subjected to a reduced
initial mass. Gradual and incremental increase of sample size is necessary when the digestion
characteristics of a certain matrix are unknown. The concentration of reagents however should
remain the same.
Personnel Qualifications/Responsibilities
The procedures detailed in this SOP are to be conducted only by staff trained by the SOP contact
listed on the cover page or the contact's designee. Training will be documented and the trainee will
be allowed to conduct the procedures after demonstrating proficiency at the discretion of the trainer.
Equipment and Supplies
7.1 CEM Corporation Microwave Accelerated Reaction System, Model MARS-5 which includes a
microwave power system with selectable output of 0 - 1600 watts, a fluoropolymer-coated
microwave cavity and rotating turntable. The instrument is fitted with a pressure sensor ESP-
1500 Plus and fiber optic temperature sensor model RTP-300 Plus (temperature range 40 to
250 °C) that can be used to monitor the XP-1500 Plus vessels. Although both sensors are
factory calibrated, it is strongly encouraged to check the instrument temperature reading
against an external thermometer. A step by step procedure for calibrating the temperature
probe of the MARS-5 instrument is reported in Appendix C. Please also refer to the MARS-5
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SOP # D-EMMD-ECB-013-SOP-01
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Page 7 of 17
Operation Manual [Refl3 3l for more information on routine maintenance and cleaning.
7.2 MARS Digestion Vessels: CEM XP-1500 plus Control Vessel with a TFM liner
7.3 Centrifuge: Model IEC Centra MP4R International Equipment Company
7.4 Water Purification System: Water Pro Plus LABCONCO
7.5 Assorted micropipettes and appropriate tips Rainin E4™ XLS, Mettler Toledo
7.6 0.45 pirn PTFE filter membranes
7.7 Analytical balance: Mettler Toledo XP504, 4-decimal analytical balance, 520-gram maximum
capacity, and minimum sensitivity of 0.1 mg
7.8 Calibrated Class 1 NIST Certified Reference Weights
7.9 Sample bottles and tubes of varying sizes
Reagents and Standards
8.1 Deionized (Dl) water: in house 18.2 MQ Dl water.
8.2 Concentrated Nitric Acid Optima: high purity concentrated HN03 (65%-70% Fisher
Scientific, 1-liter bottle, catalog # A467-2).
8.3 Concentrated Hydrochloric Acid Optima: high purity concentrated HCI (Fisher Scientific, 500
mL bottle, A466-500) use if needed only.
8.4 Hydrogen Peroxide Optima: 30% H202 Trace-pure (Fisher Scientific, 500 mL bottle, P170).
8.5 Matrix Spike Standard: Multi-Element Custom Standard of 48 elements Ag, Al, As, Ba, Be, Bi,
Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Fe, Gd, Ge, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Pd, Pt, Rb,
Rh, S, Sb, Se, Si, Sm, Sn, Sr, Tb, Ti, Th, Tl, U, V, W, Y, and Zn in 15% HCL and 5% HN03, (SCP
Science, catalogue # AQ0-008-122).
8.6 Concentrated HN03: Trace-metal clean concentrated HN03 (65%, Fisher Scientific, catalog #
A509212) for washing labware.
8.7 10% Nitric Acid: Add 100 mL of concentrated nitric acid to 500 mL deionized water and
dilute to 1 L.
Procedures (Microwave Extraction Protocol)
All digestion and volumetric vessels must be acid washed and rinsed with deionized water before
use. Refer to Appendix C. for the step by step procedure for cleaning vessels.
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SOP # D-EMMD-ECB-013-SOP-01
Effective Date: 11/13/17
Page 8 of 17
Microwave Extraction of Wipe Samples
Use the sets of 12 XP-1500 Plus microwave vessels which also include a control vessel. The
liner has a capacity of 100 mL and is made of Teflon® TFM, an advanced composite Teflon.
These vessels are adequate to handle the high temperature required to digest the wipe
material and can withstand a maximum pressure of 800 psi. Whole wipe samples will be used.
9.1.0 Place the microwave vessel and lid on the analytical balance and record the weight in
the digestion Table. Using acid cleaned forceps (made of teflon or acid resistant
plastic), transfer 1 wipe sample (approximately 4.5 - 5.0 g) into the tared vessel. Record
the weight of the wipe. Tare the sample vessel. Place it in the fume hood and add 9 mL
of concentrated nitric acid and 3 mL of hydrochloric acid. Make sure that the entire
wipe is covered with reagent. Wait approximately 20 minutes before closing the vessel.
Caution: The reaction between wipe and acid is rapid. It produces brown fumes and is
quite exothermic (the experimentalist should exert extreme caution when performing
this task).
9.1.1 Place a safety membrane in the vessel cap and seal firmly by hand. Weigh the vessel
and record the weight before digestion.
9.1.2 Repeat the above procedure for a batch of up to 24 samples. Insert the temperature
probe in the control vessel sapphire well and secure the pressure line to the cap. The
control sample is not normally used for data since it may become contaminated from
the pressure monitoring line.
9.1.3 MARS-5 System - The microwave unit can only process a set of 12 samples in XP-1500
vessels at a time. Place the turntable into the microwave cavity. Place each vessel into
the turntable. Connect pressure and temperature lines to their microwave ports.
9.1.4 Use program ECBTRCW-11-4 vessels, ECBTRCW-2 for 4 - 8 vessels and ECBTRWC-3
for 9-12 vessels. These programs are described in Appendix A. Record the
temperature after ramp up and before the end of the digestion cycle.
9.1.5 After digestion is complete, allow the vessels to cool until the temperature drops to
less than 30 °C. There is no need to open the microwave door to help cool the vessels.
Once the method run is complete, the MARS-5 system will go through an automatic
cooling cycle.
9.1.6 Vent the vessels in a fume hood and weigh to verify that no significant amount of
solution was lost.
9.1.7 Place the microwave vessels in the fume hood. Add 250 piL of hydrogen peroxide in
each vessel and allow enough time for the hydrogen peroxide to oxidize remaining
organic material. The extract should be quite clear at the end of the process.
9.1.8 Transfer the solution quantitatively to a 60 mL LDPE polyethylene sample bottle and
bring to a final weight of 50 g of solution using deionized water. Allow solids to settle
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Page 9 of 17
and if needed, centrifuge the sample. This sample will be further diluted and analyzed
by ICPMS. In addition, a filtration step can be included if judged necessary, using a 0.45
pirn membrane filter.
9.1.9 Use the in-house developed Excel program to do all calculations and print digestion log
to be placed in the digestion log binder or paste in the project laboratory book. The
excel program will compute the Calculated Weight before Digestion, Percent
Difference, Recovery Percent and Dilution Factor.
9.2 Troubleshooting
9.2.1 MARS-5 System: Monitor the pressure and temperature during the digestion process.
If the expected temperature or pressure is not maintained during the digestion,
investigate the cause, and consult the group leader to determine if re-digestion is
necessary.
9.2.2 Follow instructions in Appendix B or the MARS-5 instruction manual if recalibration of
the pressure sensor or temperature sensor is required. The pressure sensor calibration
constant is 4315-4316-0621-0623-6637-2241.
10. Data and Records Management
Calculations
10.1 Acid Weight = desired volume x density
Optima Nitric acid weight = 9 mLx 1.40 g/mL = 12.60 g
Optima Hydrochloric weight = 3 mLx 1.18 g/mL = 3.54 g
10.2 Calculated Weight before Digestion: The Excel program will add the vessel weight, the
sample weight and the acid weight to give the expected weight before digestion in grams.
10.3 Percent Difference: The Excel program will divide the weight after digestion by the calculated
weight before digestion and multiply by 100 to give a percent difference.
10.4 Dilution Factor: The Excel program will add the sample weight and the acid weight adjusted
for specific gravity, and divides the result by the sample weight to obtain the dilution factor
used in data calculations.
Records Management
10.5 The digestion data will be stored on the individual analyst computer and on a designated EPA
shared drive. Additionally, hard copies of the digestion data bench sheets will be placed in
the Tire Crumb digestion binder located in CHL-43. Sample preparation and digestion notes
not included on the digestion bench sheets will be taken in a research notebook maintained
as per ORD requirements in ORD PPM 13.2
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11. Quality Assurance/Quality Control
11.0 Reagent Blank (RBLK): A reagent blank will accompany each digestion batch of 24 or fewer
samples. The mixture of acid reagents (Section 9.1.0) will be used. The reagent blank is used
to track potential contamination during sample preparation and extraction. The reagent
blank is treated as a regular sample. If a sample is filtered before analysis, then a blank will
also need to be filtered to assess if the filter is contributing any contamination.
11.1 Laboratory and Field Blank (LBLK and FBLK):Two matrix blanks will be prepared prior to
field-sampling, but the Laboratory Blank will remain in the lab and will not travel to the
sampling site, while the Field Blank will travel to the field sampling site. In an ISO 5 Class 100
Clean Lab, acid-cleaned plastic forceps will be used to place a wipe sample into an acid-
cleaned 50mL flat-bottom polypropylene sample tube.
11.2 Laboratory Control Sample (LCS): Another matrix blank will be prepared and to this, will be
added 250 |al of the custom spike standard solution (Section 8.5) before digestion. The LCS
results will be used to determine if the laboratory can perform the analysis in a clean matrix.
Acceptable recovery range of this sample is 65-125%.
11.3 Field Control Sample (FCS): This sample is similar to the LCS sample in 11.2, but it travels to
the field. A 250 |al aliquot of the custom spike standard is added to the ghost wipe.
11.4 Standard Reference Material: A standard reference sample (if available for the sample matrix
type to be analyzed) should be included with each batch of samples processed. As of now
there is no standard reference material available for wipes.
11.5 Digestion Percent Difference: The percent difference between the weight after digestion and
the calculated weight before digestion should not exceed 10 %. If the percent difference does
exceed 10%, investigate the reason, correct, and re-digest the sample.
11.6 Pressure and Temperature Monitoring for the MARS-5 system: Examine the pressure and
temperature monitoring graph. If the pressure or temperature deviates from the set point by
15 % or more after ramp up and before the end of the digestion, investigate the problem,
and consult the group leader to determine if re-digestion is necessary. Determine if the
sample in the monitoring vessel was the cause and if not, the microwave may need
recalibration (refer to Appendix B and C).
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12. References
12.0 U.S.E.P.A. SW-846 Method 3051A. Microwave Assisted Acid Digestion of sediments, sludges,
soils and oils.
12.1 SOP # D-EMMD-ECB-003-SOP-01. Microwave Assisted Digestion of Solid Matrices Rev #0.0
12.2 Mars-5 Users Guide, CEM Corporation.
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Appendix A
Microwave Extraction Programs
Two microwave accelerated reaction systems MARS-5 are located in CHL-25 laboratory. The digestion
programs use a ramp to temperature approach and are available on both systems. Depending on the
number of vessels used, the analyst should choose the appropriate ECBTRC- method.
1. Program Name: ECBTRCW-1
Max Power = 400W
% Power = 100%
Ramp = 15 minutes
Pressure = 0 psi
Temperature = 200 °C
Hold Time = 15 minutes
Number of Vessels = 1 to 4
2. Program Name: ECBTRC-2
Max Power = 800W
% Power = 100%
Ramp = 15 minutes
Pressure = 0 psi
Temperature = 200 °C
Hold = 15 minutes
Number of Vessels = 5 to 8
3. Program Name: ECBTRC-3
Max Power = 1600W
% Power = 100%
Ramp = 15 minutes
Pressure = 0 psi
Temperature = 200 °C
Hold = 15 minutes
Number of Vessels = 9 to 12
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Appendix B
Quality Control Test for MARS-5 Vessels and Sensors
This quality control test should be performed only if deemed necessary.
1. Place 50 mL Dl water in the control vessel (XP1500+, or HP500+), and assemble as you normally do
with the temperature and pressure sensors attached.
2. Place the control vessel in the turntable and connect the sensors. (No other vessels are run during
this test.)
3. Go into the CEM Directory and load the preprogrammed "QC ESP/EST" method.
4. Allow the method to run, observing the temperature and pressure readings. When you get to stage
5, record the temperature once the pressure has begun controlling at 200psi. The temperature
should be 200°C +/- 10C at 200psi. If it is not, either the temperature or pressure sensor is out of
calibration.
5. Allow the vessel to cool to < 50°C. Measure the volume of water remaining in the vessel. If you put
50mL in, you should get 50mL back out. If the volume is < 50mL, then there is a leak.
Note that a vessel can be leaking and still pass the QC test (200psi = 200°C). Look for volume loss
instead.
6. If the QC test fails (i.e., you do not get 200°C +/-10C at 200psi), then recalibrate the temperature
probe and repeat the QC test.
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Appendix C
Procedure for Microwave Calibration
Prepared by Jason Sylva
Pressure Calibration
1. From the home screen on the instrument, press "Setup" then follow the outlined procedure.
2. Use the "select" button to select the option of choice. "Select Sensor" -> "Pressure Sensor" ->
3. "ESP-1500" -> "Yes" -> "Zero Sensor" then press back and select "Display Calibration Constant".
4. If the calibration constant read "0000-0000-0000-0000-0000-0000" refer to operation manual pg
60-66 or contact manufacturer for proper calibration constant for your model. The calibration
number used for our model is: 4315-4316-0621-0623-6637-2241
Temperature Calibration
1. From the home screen of instrument, press "Setup" then follow the outlined procedure.
2. Use the "select" button to select the option of choice. "Select Sensor" -> "Temperature" -> "RTP-
300 plus" -> "GF number (GF number is located on thermometer) -> "Calibrate RTP-300 Plus".
3. Place microwave thermometer into the reference top of microwave cell, then insert into a beaker
of water. A second external thermometer is placed into the same bath and this is taken as the
actual temperature and entered into system.
4. Refer to operation manual pg 67-68 for further details.
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Appendix D
Procedure for Cleaning Vessels
This cleaning sequence has been determined to be adequate to minimize contamination in glass,
polyethylene, polypropylene or PTFE vessels.
1. Prepare cleaning solution by adding a small amount (approximately 5 mL) of concentrated
Citranox (Alconox Inc.) liquid soap to a tub of reverse osmosis (RO) water (~6 L). Remove all
markings and residue from vessels using a designated lab brush or methanol if necessary.
Submerge vessels in soap solution and allow to soak for a few minutes.
2. Clean the vessels with a lab brush. Rinse three times with reversed osmosis water and one
last time with deionized water.
3. Place the vessels in an acid bath containing 10% (v/v) Trace-metal clean concentrated HN03
in Dl water, and let them soak overnight (and up to 48 hours).
4. Remove vessels, rinse three times with deionized water.
5. Allow vessels and lids to air dry (open end down) on a clean surface.
6. This step applied only to the XP-1500 microwave digestion vessels that already went through
the above cleaning steps.
Use the Optima grade acid to prepare 1 liter of 10% Nitric acid.
- Fill the vessels approximately half way with acid (~50 mL) and secure the lids. Don't forget
to place a safety membrane in the vent cap.
- Place the vessels in the carousel and microwave the solution using extraction program
ECBCM-1, -2 or -3 (Appendix E) depending on the number of vessels.
7. After cooling to room temperature, pour the nitric acid solution back into the Teflon cleaning
solution container. Rinse vessels and caps three times with deionized water, and allow to air
dry.
8. All sample bottles and microwave vessels should be capped and stored in sealable plastic
bags or plastic containers to prevent contamination.
9. Label bag or container with the cleanup date and batch number.
When cleaning polyethylene conical tubes with external graduation, soaking in an acid bath is not
recommended as the material used to graduate the tubes can be removed upon contact with acid
and therefore can become a source of contamination.
- Remove the caps and let the tubes stand in the Styrofoam base.
- Pour Dl water into each tube and secure the caps. Let the sealed tubes soak for a few
minutes, shake well and discard the water. Repeat this step two more times.
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- Fill each tube with 10% nitric acid and let sit overnight or at least twelve hours at room
temperature in the Styrofoam container with their lids on.
- The next morning, the sealed tubes are reversed to give the cap a chance to get in contact
with the acidic solution. Leave the tubes in that position for at least four hours.
- Pour the acid content into an acid cleaning bottle.
- Rinse tubes and lids several times with deionized water and allowed to air dry.
- Cap the tubes, place them back in their Styrofoam base and keep them seal until usage.
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Appendix E
Microwave Assisted Cleanup Programs
1. Program Name: ECBCM-1
Max Power = 400W
% Power = 100%
Ramp = 10 minutes
Pressure = 100 psi
Temperature = 170 °C
Hold = 30 minutes
Number of Vessels = 1 to 4
Average Sample Volume = 50 mL
2. Program Name: ECBCM-2
Max Power = 800W
% Power = 100%
Ramp = 10 minutes
Pressure = 100 psi
Temperature = 170 °C
Hold = 30 minutes
Number of Vessels = 5 to 8
Average Sample Volume = 50 mL
3. Program Name: ECBCM-3
Max Power = 1600W
% Power = 100%
Ramp = 10 minutes
Pressure = 100 psi
Temperature = 170 °C
Hold = 30 minutes
Number of Vessels = 9 to 12
Average Sample Volume = 50 mL
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U. S Environmental Protection Agency
Office of Research and Development
National Exposure Research Laboratory
National Center for Computational Toxicology
Research Triangle Park, North Carolina, Headquarters
Athens, Georgia
Cincinnati, Ohio
Las Vegas, Nevada
STANDARD OPERATING PROCEDURE
Title: Standard Operating Procedure for Operation and Maintenance of the Element
2 High-Resolution Inductively Coupled Plasma Mass Spectrometry Instrument
Number: d-emmd-phcb-042-sop-03
Effective Date: February 2014
SOP was Developed
\E1 In-House
~ Extramural
Alternative Identification:
SOP Steward
Name: Kasey D. Kovalcik
Signature:
Date:
Approval
Name:
Title:
Signature:
Date:
Concurrence*
Name:
Title:
Signature:
Date:
For Use by QA Staff Only:
SOP Entered into QATS:
Initials
Date
* Optional Field
NERL-SOP.2 (11/2005)
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Revision Changes from Previous Version
HR-ICPMS Analvsis
Version
Date
Revisions/Changes
98.0
Original Effective Date.
(previously titled SOP-WDE-08-08)
98.1
1/12/11
Update Reagent Blank Concentration
Update Calibration Preparation and Concentrations
Update Instrument Analytical Method
98.2
2/1/14
Update QA/QC Guidelines
042-SOP-
03
9/1/16
Update to name due to new division/branch identification
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Standard Operating Procedure for
Operation and Maintenance of the Element 2
High-Resolution Inductively Coupled Plasma
Mass Spectrometry Instrument
Table of Contents
Section Page
I.0 Scope and Application 5
2.0 Summary of Method 5
3.0 Definitions 6
4.0 General Safety Considerations 7
5.0 Interferences 7
Table 1. Interferences and Resolving Power Required 7
6.0 Personnel Qualifications 8
7.0 Equipment and Supplies 8
8.0 Analytical Standards and QA/QC Solutions 8
Table 2. Preparation of Tune Solution 10
Table 3. Preparation of Stock Solutions 10
Table 4. Working Multi-element Standards for HR-ICPMS Calibration 11
9.0 Instrument and Software 12
Figure 1. Components of the Element 2 instrument 12
Figure 2. Task window folder 13
Table 5. Summary of Tasks for Each Application 14
10.0 Basic E2 Instrument Operations (Startup, Standby, and Shutdown) 14
Figure 3. Front and back views of E2 15
II.0 Autosampler Control 16
Figure 4. ASX-510 autosampler (source: Cetac web site) 16
Figure 5. GUI of ASX-510 sample trays with position numbers 17
12.0 Routine Operational Sequence of E2 18
Figure 6. Status display panel when E2 is in standby 19
Figure 7. Instrument task window 20
Figure 8. Spreadsheet view 22
Figure 9. GUI view 22
Figure 10. Run task window 23
Table 6. Tune Performance Criteria for NERL's E2 23
Table 7. Sequence Editor Definitions 25
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Figure 11. Sequence Editor with QC samples 26
13.0 Need-Based Procedures 27
Figure 12. Mass Calibration task window 27
Figure 13. Typical LR 2nd deriv diagnostic curve 29
Figure 14. Diagnostic curve for MR 30
Figure 15. Diagnostic curve for HR 30
Figure 16. Calibration Mass dialog box 31
14.0 Troubleshooting 34
15.0 Preventive Care 34
16.0 W aste Management 35
17.0 Documentation and Document Control 35
18.0 Quality Control 35
Appendix 1: Element 2 HR-ICPMS Method Settings 38
Appendix 2: Concentrations of Individual Elements in Working Calibration Standards 39
Appendix 3: Laboratory Forms and Log Sheets 41
Appendix 4: ICPMS Data Flagger 46
Appendix 5: Alternate Calibration Standard Preparation from Custom Multi-Element Certified Stock Solutions
(High Purity Standards, Charleston, SC, USA) 49
Table 8: Working Standard (WS) Preparation 49
Appendix 6: Hydraulic Fracturing Analysis Update 50
Table 9: Working Standard Calibration Preparation 50
Table 10: Working Standard Calibration Concentrations 51
Table 11: QA/QC Guidelines 52
Instrument Analytical Method Error! Bookmark not defined.
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1.0 Scope and Application
Inductively coupled plasma mass spectrometry (ICPMS) is a widely accepted analytical tool for trace and ultra-
trace elemental analysis. It has been the technique of choice for accurate and precise measurements needed for
today's demanding applications.
In ICPMS, an inductively coupled plasma (a gas consisting of ions, electrons, and neutral particles) is formed
from argon gas under an intense electromagnetic field. The plasma is used to atomize and ionize the sample
matrix. The resulting ions are then passed through a series of apertures into the high-vacuum mass analyzer.
Isotopes of the elements are identified by their mass-to-charge ratio (m/z), and the intensity of a specific peak in
the mass spectrum is proportional to the amount of that isotope (element) in the original sample.
Because of the enormous number of possible interferences, the ability to isolate analytes from interfering species
is critical to any analytical ICPMS instrument. Double-focusing magnetic sector field ICPMS, often called high-
resolution ICPMS (HR-ICPMS), provides a straightforward solution to most of the polyatomic and isobaric
interferences by separating the analyte of interest from its interfering species. EPA's National Exposure Research
Laboratory (NERL) purchased an HR-ICPMS instrument, the Element 2 (E2), from Thermo Finnigan (now
Thermo Fisher Scientific, Waltham, MA). This instrument has been installed in NERL's Class 100 clean lab.
This standard operating procedure (SOP) is intended to provide the following information:
• Descriptions of various components of E2 and its control software (v3.0)
• The basic operational settings of the E2
• Autosampler control procedures
• Procedures to prepare reagents and calibration standards
• Procedures for verifying performance measures of the E2 on a daily basis
• Instructions for preparing various logs
• Instructions for setting up a sequence for automated use of the instrument with QC checks
• Need-based instrument conditioning and maintenance procedures such as changing recirculating fluid, establishing
mass calibration, and changing the entrance slit assembly
• Instructions for flagging sequence results using the "ICPMS Data Flagger" application
2.0 Summary of Method
2.1 This SOP is intended for either (1) analysis of SEAS slurry samples after preparing samples according to
SOP-WDE-08-01 Standard Operating Procedure for Preparation of SEAS Samples for HR-ICP-MS
Analysis, or (2) analysis of ambient air particles collected on Teflon filter media after aqueous or dilute
acid-phase extraction (SOP# ECAB-114.0 "Standard Operating Procedure for the Three-Stage Extraction
of Filter Media for Ion Chromatography and High Resolution Inductively Coupled Plasma Mass
Spectrometry") and (3) ECAB 149.0 "Processing Hydraulic Fracturing Field Samples for Trace Metal
Analysis".
2.2 An internal standard is added on-line at the time of analysis using a second channel of the peristaltic
pump and a low dead-volume mixing manifold.
2.3 Data acquisition and evaluation parameters for this method have already been established in the clean lab.
Appendix 1 lists all parameters for the multi-elemental method used in this SOP.
2.4 This method employs the ASX-510 autosampler (CETAC Technologies, Omaha, NE) for analysis.
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Definitions
ALM Auto Lock Mass
cps counts per second
DI deionized water from ion-exchange resin cartridges, plastic tap water
E2 Element 2, the second-generation Element HR-ICPMS instrument
HEPA high-efficiency particulate air filter
HR high resolution (Am = 10,000)
ICPMS inductively coupled plasma mass spectrometry
IDL instrument detection limit
LR low resolution (Am = 300)
mL milliliter
mm millimeter
MR medium resolution (Am = 4000)
MSDS Material Safety Data Sheet
NIST National Institute of Standards and Technology
plasma mixture of ionized gases and free electrons
ppb parts per billion ((.ig/L)
ppm parts per million (mg/L)
QA quality assurance
QC quality control
reagent water sterilized (UV treated) DI water with a resistivity of 18.2 MQ-cm (at 25 °C)
or greater (DI water produced by Millipore or Barnstead system)
RF radio frequency
RO reverse osmosis (water used for tube-cleaning purposes)
RPD relative percent difference
RSD relative standard deviation
SD standard deviation
SEM secondary electron multiplier
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4.0 General Safety Considerations
4.1 To avoid personal injury or damage to the instrument, do not perform any servicing other than that
contained in the E2 hardware manual unless you are qualified to do so.
4.2 High voltages capable of causing personal injury are used in the instrument. Some maintenance
procedures require that the mass spectrometer be shut down and disconnected from the power before
service is performed.
4.3 Do not operate the mass spectrometer with the top or side covers off. Do not remove protective covers
from printed circuit boards. Safety labels are used on the instrument to show potential safety risks. Read
the labels carefully.
4.4 Ensure that you read and understand the hazards of the chemicals used.
4.5 Refer to MSDSs for information on the hazards and toxicity of specific chemical compounds and for the
proper handling of compounds, first aid for accidental exposure, and procedures for remedying spills or
leaks.
5.0 Interferences
E2 can be operated to achieve mass resolutions, R (Am/m), of up to 10,000 by means of entrance and exit slit
assemblies. By varying resolution settings, it is possible to tailor an analysis in such a way that each isotope is
analyzed at a resolution that will enable it to be fully resolved from any interference with minimal compromise of
its sensitivity.
Table 1 lists common interferences on the most abundant isotopes that require resolution settings (provided list is
not complete). If the needed R value is between 300 and 4000, the MR setting is used for data acquisition. If R is
in the 4000 to 10,000 range, the HR setting is recommended. If the calculated R value is over 10,000, that
interference cannot be resolved by E2. Under such circumstances, an alternative isotope and/or interference
correction equation, or combination of both, must be applied.
Table 1. Interferences and Resolving Power Required
Measurement
Alternate Isotope and
Analyte
Interference
R = m/1 Am |
Mode
Required Mode
Correction
40Ca
40 Ar
190,476
($)
39Ca in MR
40 K
40Ca
28,369
39K in HR
iisin
,,5Sn
212,963
($)
,,5Sn
87Sr
87Rb
300,000
88Sr in LR (*)
,,2Cd
,,2Sn
54,369
($)
1,1 Cd
95Mo,60
32,362
($)
1,1 MoO (*)
56pe
40 Ar160
2,506
56Fe in MR
51 v
35C|160
2,576
51V in MR
52Cr
,2C40Ar
2,378
52Cr in MR
75As
40Ar35CI
9,500
75As in HR
80Se
80 Kr, 40Ar40Ar
>10,000
77Se in HR
74Ge
56Fe180,74Se
>10,000
72Ge in HR
(*) Correction will not be required if the sample does not have a significant amount of the interferent.
($) Interference unavoidable at all resolution settings.
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6.0 Personnel Qualifications
The operator/analyst must have the following qualifications:
• High level experience using an ICPMS instrument
• A thorough understanding of the fundamentals of inorganic analytical chemistry
• User-level knowledge of the Windows XP operating system
7.0 Equipment and Supplies
7.1 Equipment
Equipment
Model No. and Manufacturer
Located in
Usage
Element 2
E2, Thermo Fisher Scientific
D456
Elemental analysis
Autosampler
ASX-510, Cetac Technologies
D456
Sample introduction system
Ultrasonic bath
1875HTA, Crest
D461-B
Sample preparation
Convection oven
737V, Fisher Scientific
D461-A
Sample tube cleaning
Weighing
balance
1)SP202, Scout Pro
2) ME235SD, Sartorius Genius
D456
Making reagents,
gravimetrically
7.2 Supplies and Ordering Information
Classification
Items
Vendor
Part No.
E2 usage-dependent
1. Entrance slit assembly
Thermo
1047360
2. Torch
ESI
ES-1002
3. RF load coil
Thermo
1139230
4. SEM ICP2 plug-in
Thermo
1114170
5. Platinum skimmer cone
ESI
ES-3000-1809
6. Platinum sampler cone
ESI
ES-3000-1807
7. Platinum guard electrode
ESI
ES-1001-0004
E2 annual maintenance
1 .Skimmer valve rebuild kit
Thermo
1120650
2. F5 oil, 1 L
Pfeiffer
PF001 852-T
3. P3 oil, 1 L
Pfeiffer
PK 001 106-T
4. Turbopump wicks
Thermo
E2 sample intro.
1. 100-(iL Teflon neb
ESI
ES-2040-27
2. Orange-green 2-stop PP
Cetac
020-030-004
3. Gray-gray
Cetac
020-030-011
Sample containers
1. 15-mL PP vials
Nalgene
366036
2. 50-mL PP vials
FisherBrand
06-443-20
8.0 Analytical Standards and QA/QC Solutions
8.1 General Guidelines
8.1.1 Always use reagent water for making analytical standards and for sample preparation.
8.1.2 Any acid concentration must be less than 4% for ICPMS analysis to minimize damage to the
interface and to minimize isobaric molecular interferences.
8.1.3 The concentrations of dissolved solids in analysis solutions should be less than 2% to protect the
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sample interface on the instrument. Higher concentrations may plug the sample cone orifice.
8.1.4 Know your sample. Protect the SEM from high chemical concentrations (high ion currents).
SEM suffers from fatigue after being exposed to high ion currents. This fatigue can last from
several seconds to hours depending on the extent of exposure. During this period, response
factors are constantly changing, which causes instrument instability that invalidates the
calibration curve, thereby invalidating all associated sample results. For instance, sodium
bicarbonate (NaHCCh) sample matrix is known to cause this problem.
8.1.5 Use acid-cleaned sampling tubes and containers for standards and samples using the following
procedure:
1. Rinse in reverse osmosis (RO) water, and then fill with RO water.
2. Let sample containers/tubes leach in RO water for 1 hour.
3. Empty tubes and fill with 4% HNO3 (v/v) + 2% HC1 (v/v) solution.
4. Place filled tubes in a convection oven at 90 °C for 3 hours.
5. Let tubes and contents cool, and then pour out the acid solution (save and reuse this acid
solution mix).
6. Fill tubes with reagent water for 1 hour.
7. Pour out the rinse solution, and triple rinse with ultra-clean reagent water. Store tubes
completely full with reagent water until use.
8. Tubes do not need to be completely dry before use.
8.2 Chemicals and Reagents
Concentrated analytical-grade Baseline nitric and hydrochloric acids (SeaStar Chemicals Inc., Sidney,
BC, Canada)
High Purity primary standard solutions
Reagent water (> 18.2 MQ-cm) for making calibration standards
Liquid argon, high-purity grade (99.99%)
8.3 Preparation of Reagents and Analytical Standards
8.3.1 Reagent Blank
Prepare 0.2% (v/v) nitric acid and 0.1% (v/v) hydrochloric acid solution by adding 4 mL of conc.
nitric acid and 2 mL of conc. hydrochloric acid to a 2-L Teflon bottle and make up the volume
with reagent water.
8.3.2 Tune Solution
The tune solution contains elements representing all of the mass regions of interest, thereby
allowing verification that the resolution and mass calibration of the instrument are within the
required specifications. The solution is also used to verify that the instrument has reached thermal
stability. Use individual primary standards from High Purity Standards (Charleston, SC, USA) to
make a stock tune solution according to procedures in Table 2, and then dilute it 100 times in 1%
HNO3 to create a working tune solution of 1 ppb.
8.3.3 Autosampler Rinse Solution
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Prepare 0.4% (v/v) nitric acid and 0.2% (v/v) hydrochloric acid solution by adding 4 mL of conc.
nitric acid and 2 mL of conc. hydrochloric acid to a 1-L Teflon water bottle and making up the
volume to 1000 mL with reagent water.
8.3.4 Stock Solutions
Depending on availability, Stock Solutions A, B, and S are made from certified primary standard
solutions procured from High Purity Standards. Use acid-washed, wide-mouth Teflon bottles to
make stock solutions. Table 3 summarizes the procedure to make all stock solutions. Appendix 5
shows an alternate method based on Custom Mulit-Element Mixed Stock Solutions.
Table 2. Preparation of Tune Solution
Conc.b
Volume Needed
Final Conc.
Element PSSa
(ppm)
(mL)
(ppb)
Matrix
Na
10
1
100
Mg
10
1
100
K
10
1
100
Ca
10
1
100
Al
10
1
100
Fe
10
1
100
Si
10
1
100
Zn
10
1
100
Ba
10
1
100
Reagent waterc
90
HNOs 100% (v/v)
1
1.18% HNOs
aPSS: certified primary standard solution. High Purity Standards (Charleston, SC, USA).
bPSS made in 2% nitric acid matrix.
cMakeup for reagent water, gravimetrically. (Procedure: After all individual elements are
pipetted into a wide-mouth labeled Teflon bottle, place bottle carefully on weighing scale. Tare
weight and add reagent water from a narrow-tip fit, squeeze-type reagent water bottle until
weight measurement reaches volume shown in table.)
Table 3. Preparation of Stock Solutions
Stock A
Conc.b
Volume Needed
Final Conc.
Element PSSa
(ppm)
(mL)
(ppb)
Matrix
Na
10
10
1000
Mg
10
10
1000
K
10
10
1000
Ca
10
10
1000
Al
10
3
300
Fe
10
3
300
Si
10
10
1000
Zn
10
3
300
Ba
10
3
300
Water0
38
HNOs 100% (v/v)
1.2% HNOs
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Table 3. Preparation of Stock Solutions (continued)
Stock B
Conc.b
Volume Needed
Individual Element PSSa
(ppm)
(mL)
Final Cone.
Matrix
Ag, As, Be, Bi
10
1 mL from every PSS
100 ppb each element
Cd, Ce, Co, Cr, Cs, Cu
Dy, Gd, Ge, La, Li
Mn, Mo, Nd, Ni
P, Pb, Pd, Pt, Rb, Rh
Sc, Sb, Se, Sm, Sn, Sr
Tb, Ti, Th, Tl, U, V, W, Y
Water0
60.3
HCI 100% (v/v)
0.50
0.5 % HCI
HNOs 100% (v/v)
0.22
1.0% HNOs
Stock S
Conc.d
Volume Needed
Final Cone.
Element PSSa
(ppm)
(mL)
(ppm)
Matrix
S
1000
1.0
10
Water0
99.0
aPSS: certified primary standard solution. High Purity Standards (Charleston, SC, USA).
bPSS made in 2% nitric acid matrix.
cMakeup for reagent water, gravimetrically.
dSulfur PSS is made in just reagent water (no acid in it).
8.3.5 Standard Reference Materials
National Institute of Standards and Technology (NIST) traceable materials SRM1640e and
SRM1643 should be diluted to 10 and 50 times, respectively, with reagent water.
8.3.6 Working Standards for HR-ICPMS Calibration
Use the guidelines in Table 4 to make working standard (WS) solutions to establish HR-ICPMS
analytical calibrations. Appendix 2 shows concentrations at which each species is present in every
working standard.
Table 4. Working Multi-element Standards for HR-ICPMS Calibration
Stock solution
wso
WS1
WS2
WS3
WS4
WS5
WS6
Stock S
40 |JL
400 |JL
1.0 mL
2.0 mL
3.0 mL
10.0 mL
Stock A
40 |JL
400 |JL
1.0 mL
2.0 mL
3.0 mL
10.0 mL
Stock B
20 |JL
200 |JL
0.5 mL
1.0 mL
1.5 mL
5.0 mL
Reagent blank0
100 mL
99.9 mL
99 mL
97.5 mL
95 mL
92.5 mL
75 mL
cAdd reagent blank gravimetrically.
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Instrument and Software
9.1 E2 Instrument
The various components of the E2 are shown in Figure 1. The E2 users are strongly urged to familiarize
and follow nomenclatures given in this figure. The design principle of E2 is a double-focusing sector field
analyzer based on a reverse Nier-Johnson geometry in which the magnetic sector is located in front of the
electrostatic sector. Details of components and operating principles can be found in the E2 hardware
manual.
9.2 Overview of E2 Software
Version 3.0 of the E2 software is currently in use. A program group is provided on the desktop for quick
access by clicking the "Thermo ELEMENT"' icon (see Figure 2). The applications can also be started by
selecting the program in C:\Program Files \Thermo\Element. The program group has 14 different
application task windows. Table 5 summarizes the applications for each task. Three of the 14 tasks—
Diagnostic, PCL, and MakePex—are not shown here because they are not to be explored at the user level.
Status display panel
Eh
(SEREN ant
Sample inlet
system
computer cabinet
Interface pump
Figure 1. Components of the Element 2 instrument.
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Table 5. Summary of Tasks for Each Application
Icons
Task Window
Application
e2
Element Tour and Interferences
Gives access to the interference workshop and other useful
information.
Network Processor
Responsible for the network connection between the PC and the
instrument (LAN connection).
1
Executive
Gives access to general instrument settings and is used to configure
the autosampler, default directories, etc.
0
Instrument
Used to acquire basic spectra and test methods.
1
Tune
Display and optimize mass spectrometer parameters (plasma
settings, lens voltages, etc.).
W
Method Editor
Define the elements to be measured (e.g., what data to acquire,
duration of the analysis and how it should be evaluated).
c
S
(q|*
Standard Editor
Generate standard concentration files for E2 analytical calibration.
Sequence Editor
Used to setup a series of analyses. Enables the user to run a number
of sample analyses, evaluate and quantify the data, and report the
results. The Sequence application is the key application of the
software.
I
Show
Display and process the acquired spectra or time-resolved data.
H
Result Display
Display information concerning the results from analyses already
performed. The report styles are also controlled here.
"4
Mass Calibration
Check, create, update or modify mass calibrations.
10.0 Basic E2 Instrument Operations (Startup, Standby, and Shutdown)
The procedure for starting an analysis is detailed below in sections 10.1 and 10.2. At the end of analysis, E2
should be taken to standby (section 10.3). Standby means the status of all components is known and the
components are okay. When E2 is in Standby, only the plasma is switched off. The shutdown procedure (section
10.4) should be performed only after consulting the laboratory manager. Shutdown status implies the E2 system is
vented and the power for all components, including the front-end computer, is switched off.
10.1 Bringing the E2 Instrument from Shutdown to Standby
1. Switch on the main power for the instrument (switch S1 on back of unit in Figure 3).
2. Turn on the argon gas so the overall head pressure >110 psi. Turn on the recirculating chiller unit
(the chiller should remain on unless performing maintenance that specifies otherwise - see section
12.1).
3. Turn the key-operated switch (status panel) to ON position to start the high vacuum (HV) for the
backing pump and the four turbo pumps.
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4. Switch on the power for the electronics and front-end computer (switch S2 on front of unit in Figure
3).
Note: It is recommended that the front-end PC be rebooted using the RESET button on the status display
panel. The instrument is in standby position when the high vacuum reaches 10 7 mbar. This will take
approximately 24 h.
Front Back
Figure 3. Front and back views of E2,
10.2 Bringing E2 from Standby to "Ready to Measure"
1. Open and fill in the Daily Startup Log (see Appendix 3 .1, and refer to section 12 for the complete
procedure). Once checks are passed, proceed to the next step.
2. Connect the drain line of the cyclone spray chamber to the peristaltic pump head. Connect sample
lines if needed.
3. Open the instrument task window, and switch on the plasma by activating the PLASMA ON button.
4. When the status box signals "Ready," switch on the high voltage by clicking the HV button in the
tool bar of the instrument task window.
After 2 hours of thermal equilibration, the instrument is now ready fortuning.
10.3 Bringing E2 from "Ready to Measure" to Standby
1. When measurements are finished, rinse the sample inlet for 5 min by inserting the sample inlet in a
0.2% acid rinse solution.
2. Go to the instrument task window and switch off the plasma by clicking the PLASMA OFF button.
Wait until the stop sequence is completed.
3. If the peristaltic pump was not stopped, stop it manually by clicking "Peri.pump on/off." Open the
brackets at the peristaltic pump and release the tubing.
4. Switch off the high voltage by clicking the HV button in the instrument tool bar. If the instrument is
in continuous daily usage, it is better not to switch off HV.
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10.4 Bringing E2 from Standby to Shutdown
This operation should be done only when a power shutdown is announced. Always consult the laboratory
manager before shutting down the instrument.
1. Turn the key switch of the status panel counterclockwise. This turns off the pumps.
2. Turn off switch S2 (front).
3. Turn off switch SI (back).
4. Turn off the recirculating chiller and argon gas lines.
11.0 Autosampler Control
An ASX-510 autosampler is connected to the host computer and controlled through the E2 software. The ASX-
510 is equipped with one built-in sample tray (Rack 00) capable of holding ten 50-mL polypropylene sample vials
and four removable trays (Racks 01-04) that are each capable of holding up to sixty 15-mL polypropylene sample
tubes (see Figure 4). This SOP covers only the required procedures for operation of the ASX-510. Refer to the
autosampler operator's manual for detailed procedures for installation, usage, maintenance, and troubleshooting.
Rack 04
-* Autosampler probe
Figure 4. ASX-510 autosampler (source: Cetac web site).
Check the following before you operate the autosampler via the host computer:
1. Ensure the autosampler power is on. The green LED indicator (above the flow-through rinse station) stays lit
while the power is on. Also make sure the RS-232 cable is securely connected at both ends.
2. Ensure the rinse station is properly connected. No air bubbles should be visible in the rinse uptake tubing
before you run samples. The rinse solution container should be filled with rinse solution, and the drain line of
the autosampler should be connected to the rinse collection tank.
11.1 Manual Operation
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The bottom left portion of the instrument task window displays the ASX-510 autosampler graphical user
interface (GUI), as shown in Figure 5. The RR/PPP format, where RR refers to the rack number and PPP
refers to position numbers, is used for moving the autosampler probe to a specific location. Selecting a
spot with the mouse creates a red square around the sample. Next the GO TO button at the top of the GUI
is pressed, which moves the sampler probe to the selected location and starts sampling. At this point, the
box turns green.
The HOME button at the top of the GUI returns the autosampler probe to the home position (does not
sample). Pressing the WASH button pumps rinse solution into the flow-through rinse cell. The sampler
probe is dipped into the rinse cell so it gets washed externally while rinse solution is sampled as well.
Home , '* Go To ^ Wash
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Figure 5. GUI of ASX-510 sample trays with position numbers.
11.2 Automated Operation
Vial positions have to be used in connection with the Sequence Editor to operate the ASX-510 in a fully
automated fashion (section 12 covers this in greater detail). Adhere to the following vial positions while
building an analytical sequence so that available sequence templates can be manipulated easily for new
sequence setups.
Rack 00:
Position 1 (00/001): Rinse solution
Position 2 (00/002): Tune solution
Positions 3-8 (00/003-00/008): Calibration standard solutions
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Position 9 (00/009): Check sample
Rack 01: Positions 48 and 49 are used for placing SRM samples. Other positions are generally left
unused.
Racks 02-04: Any number of these positions can be used depending on the number of samples. For
convenient sequence building, the last two positions of every row are left empty (see section 12.6). Once
sample vials are loaded, make sure the arrangement is correctly defined in the Sequence Editor.
12.0 Routine Operational Sequence of E2
The following sequences of steps assume that the instrument is in standby mode. If not, follow the steps in section
10 for bringing the instrument from shutdown to standby.
12.1 Getting Ready
1. Open the Daily Startup Log (Appendix 3.1). Fill in the form as you go through the following steps.
2. Check two argon gas tanks (located in the XRF laboratory in room D455-A). Check the liquid argon
level indicators and output pressure in the gas cylinders. At least one cylinder should have greater
than 50% Ar and approximately 200 psi output pressure. The secondary control (mounted on the
wall) is set to output 115-140 psi to the instrument.
Special note: In case of a limited argon gas supply, the slit assembly and skimmer valve assemblies can
be controlled by an additional gas line such as nitrogen. (Refer to p. 4-11 of the E2 hardware manual for
configuration). We do not recommend this setup unless the situation is unavoidable.
3. Check the recirculating chiller unit located next to the gas tanks. Write down the display temperature
(should be ~ 18 °C) and water level.
4. Make sure the backup power supply unit, located in the service corridor, is operational. No warning
messages should be displayed. Write down the percentage of backup power (usually 80%).
5. Check the system status panel of the E2 (top left). Make sure you see green LEDs as shown in Figure
6 on the following: TORCH IN POS, ARGON PRESSURE, INTERFACE COOL, HV
ELECTRONICS, INTERLOCK HOOD, BOARD CHECK, HV, FV, TP A, TP B, TP C, TP D, and
FORE PUMP. If not, go to section 15 for troubleshooting references.
6. Start the host computer and log on as "SEAS". Currently, the SEAS user group is set up for executing
multi-elemental analysis of fine PM samples in a 0.2% nitric acid and 0.1% hydrochloric acid (v/v)
matrix. Leave the password space empty and click LOGIN.
7. Open the folder labeled Thermo ELEMENT on the desktop.
8. Double click Network Processor, which will establish communication
between E2's front-end computer and the host computer. This will
automatically open and activate the EXECUTIVE task window.
9. Select EXECUTIVE task window, if not selected already, and click the
CUSTOMIZE menu.
10.
In AUTOSAMPLER settings, the ASX-510 should be selected and COM2 enabled.
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G-# SYSTEM READY
PUMP SYSTEM Y - STAND BY
TORCH IN POS.
ARGON PRESSURE
HV < 10"4 mbar
FV < 10"1 mbar
* COOL GAS FLOW | TP A >50%
I COIL COOLING | TP B >50%
I INTERFACE COOL. | TP C>50%
| HV ELECTRONICS fl TPD>50%
IINTEHLOCK HOOD | INTERFACE I
BOARD CHECK fl FORE PUMP
INTERFACE PUMP
FORE PUMP (TP)
SKIMMER VALVE
FORWARD POWER
REFLECTED POWER
mmm
OFF/ON
FRONT END PC
i RESET
Figure 6. Status display panel when E2 is in standby.
11. In INSTRUMENT settings, you should see the following:
DEADTIME: ACTIVE FIELD REGULATOR TYPE: FAST
COOL GAS: 18 LPM SEM TYPE: TYPE 2
ADDITIONAL GAS 1 AND 2: 1 LPM SCAN OPTIMIZATION: MASS ACCURACY
RF GENERATOR: SEREN NO OF PRE SCANS: 0
MATCHBOX: SEREN PELTIER COOLING: UNSELECT
If any settings differ, notify the laboratory manager and correct it.
12. Connect sample (autosampler end) and internal standard (IS) line outlets to E2's first and second
peristaltic pump channels using orange-green peristaltic tubings. Combine the outlet of tubings using
a T-joint. Connect the perpendicular end of the T-joint to the nebulizer with green-coded (100 uL)
capillary.
13. Connect the cyclone spray chamber drain to the peristaltic pump using gray-gray polypropylene
tubing, and connect its outlet to the ICPMS rinse collector underneath the E2"s sample tray.
14. Set the autosampler and IS sample inlet lines to draw reagent blank (0.2% HNOa and 0.1% HC1
solution).
12.2 Igniting Plasma
1. Select the Thermo ELEMENT folder on the desktop and click the INSTRUMENT icon. The
instrument task window is shown in Figure 7.
2. Start high voltage (HV) if not already on (see top left red circle in Figure7).
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W Instrument - Thermo ELEMENT
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LED
|S~HV
O Cooling System
O High VScuum
© tufagnetic Field Reg.
0 Temp. Field Reg.
DAC
Cool Gas [L/rnin]
Auxiliary Gas [L/min]
Sample Gas [L/min]
Argon Max [bar]
Argon Middle [bar]
Fore Vacuum [mbar]
High Vacuum [mbar]
o
o
LAN connection OK
Figure 7. Instrument task window.
3. Under the Instrument dropdown menu, select "peristaltic pump turn c.w.," and then "peristaltic
pump" on. E2"s peristaltic pump should then rotate clockwise. Adjust tension knobs in the pump such
that solutions from sample and IS lines flow smoothly. Also ensure that the cyclone continuously
drains.
4. Start Plasma by clicking the ON button in the plasma schematic (top right quadrant in the instrument
task window (top middle red circle in Figure 7). Plasma will start after approximately 5 mill. The
following sequence should be observed during the ignition process: interface pump starts, RF
generator starts, plasma appears, and sample gas slowly ramps up to set value.
Caution: Once the RF generator starts and "Forward Power" is displayed on the front status panel of the
E2, plasma should have been lit. Otherwise, a condition called "Cold Plasma" has developed which can
harm the torch. Under this circumstance, press the RF ON/OFF button on the status display panel to turn
off RF power, and terminate the startup sequence by pressing the STOP button in the plasma schematic
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(see Figure 7).
5. Record the High Vacuum pressure prior to plasma ignition.
6. After plasma ignition, fill in the fore and high vacuum readings in the Daily Startup Log (Appendix
3.1). Note: Typically, fore vac is on the order of 10"4 mbar and high vac is ~ 1.7 x 10"4 mbar. If the
vacuum readings differ significantly, contact the laboratory manager.
At this point, the Daily Startup Log should be completed and the E2 successfully started. Next follow the
instructions below fortuning the instrument.
12.3 Tuning the Instrument
1. Open the Tune task window. The most recent tune file (with extension .tpf) automatically loads.
Otherwise, find an earlier day's file and load it (older tune files are stored in folder
"C:\Element\user\SEAS\Tune ParametersV').
Note: If there have been hardware changes such as new cones, torch, or slit assembly, an extensive tuning
will be required. Detailed tune operations can be found in chapter 2 of E2 manual version 3.
2. Press to open the Scan List menu (alternatively, click the yellow spectrum in the tool fT
bar), and load THERMOLRTUNE.SCL. Press START SCAN (green button in the tool
bar). You should now see Li, In, and U panes active. Make sure you are still
sampling reagent blank through both channels.
3. Let the instrument warm up for approximately 30-60 min.
4. By default, tune parameters are locked for all resolutions. Make sure that "All Parameters Resolution
Dependent" under the Tune menu is not enabled.
5. Set the autosampler probe (sample line) to the tune solution (refer to section 11), normally placed at
position 00/002 of the ASX-510 autosampler. Select position 00/002 in the autosampler GUI
(instrument task window) and click GO TO. The IS sample line should still sample reagent blank.
The take-up time of tune solution by the ASX-510 setup is approximately 4 min.
6. Stop the scan and restart the LR tune for intensity and stability.
7. Check signal stability and intensity for Li, In, and U. The instrument specification (spec) for In is one
million cps. If the performance is not satisfactory, check and adjust the sample gas (by opening slider
controls with a right mouse click on the gas-flow box) and torch Z positions (in torch position box). If
the performance is satisfactory, click Stop Scan (red square). Click the Save As button in the tool bar
and create today's tune file. A suggested format is yourlastname_ddmonthyyyy (e.g.,
pancras_ 12 April2008).
8. Next perform MR tune for optimum peak shape and resolution. Open the scan list again and select
Thermo_MR_Tune_Fe_ArO_Resolution.scl. Start the scan. Lower the y scale so the 56Fe peak can be
seen. The current resolution for MR is displayed at the top left of the intensity box. You may need to
slightly adjust the Focus Quad 1 (FQ1) of the MR lens to achieve optimum resolution. For MR, the
spec is 4000.
9. Save the tune parameters and proceed to HR tune.
10. Open the scan list and select Thermo_HR_Tune_K_ArH_Resolution.scl. Tune for high-resolution
lenses.
11. If the mass separation between K39 and ArH38 is not satisfactory, adjust FQ1 of the HR lens such
that an R value of 10,000 is achieved.
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12. Once tuned, save the tune parameters under today's tune file name.
At this point, E2 is ready for performance evaluation.
4 Performance Evaluation
1. Open the Sequence Editor task window. Make sure ALM on the Actions menu is enabled. A mass
calibration is deemed valid when mass drift values do not exceed 500 ppm. The E2 operator can see
current drift values by going to Executive/Log files/EDAC.
2. Use the Open button in the tool bar of the Sequence task window to open the sequence named "Daily
Performance". The sequence settings can be viewed in two ways: spreadsheet (Figure 8) and GUI
(Figure 9). The spreadsheet is recommended for setting up or editing and the GUI for verifying and
running a sequence.
i/j Sequence
- Thermo ELEMENT - [Slurry_offset.seq]
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offset insert
offset update
1
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I I I 2 I 3 I 4 I 5 I 6 I 7 I 8 I 9 I 10 I II I 12
Header Type SMP
0 Analysis ^ Details QC Quality Control
Analysis Parameters
Data File: | offsetjnsert
Method:
T une Parameters:
Blank:
Calibration:
Sampling:
M E_S E AS_Aug2007_rev3
pancras_31_ March2008
:or Help, press F1
Figure 8, Spreadsheet view.
jjj, Seq
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Type
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IS Name
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Repconf
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3 |
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I For Help, press F1
Figure ?. GUI view.
3. Switch to spreadsheet view, and replace the old tune file with the current file.
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Note: The autosampler probe still samples tune solution, and the IS line samples reagent blank.
4. Click the Start Flag icon in the top center of the GUI page. This will open the
Run task window (showing acquisition status) at the bottom of the Sequence
task window (see Figure 10). Enable the Acquire, Evaluate and ASCII Report
boxes and browse to find the Daily Seq Summary sequence, and then click the Run button. This run
takes 2.5 min to complete.
A
Acquisition Status
Running Sequence STE2006_MOI_s4
0 Acquire 0 Evaluate
1 I Autostart
Sample Sequence
I I Print Report ~ Print Report
~ ASCII Report ~ ASCII Report
I I Chrom. Data ~ Chrom. Data
V
Scan Optimization:
Mass Accuracy
Figure 10. Run task window.
5. Once this sequence is completed, select the analyzed sample in the
daily performance sequence, and then click View Results. This action
will open the Results task window. Open the Daily Settings and
Performance Log (Appendix 3.2), and fill in the available data from
the Results page.
6. Compare your values with the established performance criteria (refer to Table 6). If your results do
not meet these criteria, tune again until the set criteria are met.
©
i
View Results
Table 6. Tune Performance Criteria for NERL's E2
Parameter
Criteria
RSD
Resolution
Inl 15 LR
>1,000,000 cps
< 1-2%
>300
Inl 15 MR
~8-l 2% of LR
<2%
>4000
Inl 15 HR
~ 1-2% of LR
<4%
>10,000
Bal 37016/Bal 37 (LR)
< 0.5%
Bal37++/Bal37(LR)
<5%
U238016/U238(LR)
<20%
Once the performance criteria are met, the E2 is ready for analysis.
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12.5 Sequence Start—Mass Offset
Check mass offsets every time a new analysis sequence is started. Generally, mass offset values are
method specific. Set the autosampler probe (sample line) to rinse for a few minutes to clean the sample
lines, but use a mid-level calibration standard to check the offsets.
1. Open the Sequence Editor task window, and make sure ALM on the Actions menu is enabled. From
the File menu, open the file "slurry_offset.seq".
2. Go to spreadsheet view, and type or browse by double-clicking the cell for the analytical method for
which method offsets are to be computed (for SEAS sample analysis, the method is
"MultiElement_SEAS_Aug2008"). Type or browse for the current tune file.
3. Click the Start Flag icon in the top center of the GUI page. This action will open a Run task window
at the bottom of the Sequence task window. Enable the "Acquire" and "Evaluate" boxes if not already
enabled, then click Run. Click "Continue" on the pop-up menu.
4. After the first sample is analyzed, a pop-up screen will ask if you want to continue to the next sample.
Press the Stop sequence.
5. Select the sample that was just analyzed, and click the Results task window icon in the menu bar. The
Results task window will open and display the results for the run just completed. Under the File menu
in the Results window, click "Update the offset values from the results into the active method file"
and press "OK".
6. Close the Results task window, and start the sequence again. Now monitor peak positions of the
second sample in the Show Task window while the sample is being analyzed. This provides visual
proof that the centroid of a mass peak is now centered within the chosen mass range.
At this point, mass offsets are computed and inserted into the analytical method. Next an analytical
sequence is created from an existing sequence. This template is specific for the ASX-510 autosampler.
12.6 Sequence Start—Analysis
1. In the Sequence task window, open the sequence "Slurry_sample_Seq_Template" by choosing
File/Open as Template/.
2. Go to the spreadsheet view and change sample names and method files as needed. Follow Table 7 to
fill in the needed columns/cells. You can select and drag cells to fill all of the rows in a column.
3. Standard files are named WSO, WS1, WS2, WS3, WS5, and WS6. Corresponding standards
concentration tables are created and stored in C:\Element\user\SEAS\
Standards\folder.
4. This sequence has autosampler positions, so therefore the sequence automatically starts when the Run
button is pressed.
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Table 7. Sequence Editor Definitions
Column
Fill-in Instructions
Typical Entries
Rack/Vial
Data File
Method
Tune Parameter
Blank File
Calibration
Report File
Standard
Internal Standard
Int. Stand. Active
Dilution Factor
Take-up Time
Unit Take-up Time
Wash Time
Unit Wash
Quantification Type
Pump Speed
Is before bs
xx/yyy, where xx is rack number and yyy is position number
Sample name
Method name
Today's tune file
None
Today's date
Must use this custom designed file
Standard file names
Internal standard file name
Status
None
Time for sample transportation
Varies
Must use ext.calib
Optimized rpm
None
01/002
DBE00232
MultiElement_SEAS_Aug2008
pancras_l 8_ Aug2008
5Aug2008
Sample_Specific_Report
WS1
ln_lr_IS_2ppb_Aug2008
Yes
5
Min
30-60 s
Min
Quant. (EXT CALIB)
5
5. Figure 11 shows atypical sequence setting with QC samples. Wherever "_dp" or "Check_" exists in
the sample name, those samples are not to be replaced with a new sample. Those are the spots for
QA/QC checks. Carefully follow Figure 11 to properly select/label samples for duplicate analysis.
Check samples are placed at position 00/009 of the ASX-510 and are analyzed after every 11
samples, where the sixth sample is a duplicate sample.
6. Click the Start Flag icon to open a Run task window. Enable the "Acquire" and "Evaluate" boxes if
not already enabled. Make sure the appropriate sequence file is selected to store the sequence
summary of your analytical results. Presently the file "DailySequenceSummary" is in use.
7. Click "Run" to start the sequence.
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Fife Item Actions Customise Dockable Windows View Window Help
~ a; y m 0 a
~ 3
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EPA08344
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EPAO 8-402
EPA08405
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02/131
02/141
02/151
TT?7TTr|
02/171
02/011
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EPA0B410
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EPA0B419
EPA0B42II
EPA0B421
Calibration standards
Duplicate sample
Future control sample spot
SRM analysis
Initial calibration verification
Check 1000 ppl rl k\ 00/091
Figure 11. Sequence Editor with QC samples.
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13.0 Need-Based Procedures
13.1 Mass Calibration
Mass calibration leads to correct identification of mass numbers of the mass peaks of interest. The mass
calibration can be executed either manually from the Instrument task window or automatically from the
Sequence task window. Only the automatic method is outlined in this SOP.
The Mass Calibration task window (see Figure 12) is used to display the data acquired for the purpose of
mass calibration. There are three display panels: mass spectrum (upper), MDAC vs. mass calibration
curve (lower left), and second derivative diagnostic curve (lower right). The second derivative curve
should be viewed carefully as large spikes in the curve indicate poor calibration. A smooth "L" curve
shape with small spikes indicates a good calibration.
a Thermo_HR_Narrow.mdc - Mass Calibration - Thermo ELEMENT |- [fnjfx]
File Resolution Calibration Options Diagnostic View Window Help
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Perform the automatic mass calibration from the Sequence Editor after a good tune. Follow the steps
below to execute mass calibration. Tune solution should be aspirated during a mass calibration procedure.
This procedure assumes that the E2 instrument has not been shut down lately.
1. Open the Sequence Task Editor.
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2.
3.
4.
5.
6.
9.
Load the calibration sequence file Thermo Automasscal.seq (located by default in directory
C:\Element\SEAS\data\). This sequence contains six samples, each with a unique method to cover all
three resolutions with two different mass window settings (wide and narrow).
The six samples in this sequence are named LRWide, LR Narrow,
MRWide, MR Narrow, HR Wide, and HR Narrow and are designated as
MCAL samples. Click the Reset icon in the tool bar and select 'All" from the dialog box.
Choose the current tune file for all six analyses.
Click the Start icon in the tool bar to check and start the sequence. This action will open the >
acquisition window. Because no reports are required from the auto mass calibration sequence,
all output check boxes should be cleared. Make sure the boxes "Acquire" and "Evaluate" are
checked!
Click the Run button in the acquisition
window. After an automatic check, the
following message appears: "Following
sample has no autosampler position." Click
Continue in the pop-up screen. Note: The
check box "Do not show this box again" in
the pop-up window remains unchecked so
that an analysis can be verified for accuracy
once it is completed.
Sequence - Next Sample
The following sample has no autosampler position:
Thermo_LR_Wide
Please prepare it for acquisition and press [Continue] when ready.
O Do not show this box again
Continue
Stop
7.
After LR_Wide is completed, click Continue in the "Sequence - Next Sample" task window. Once
LR_Narrow (LR with narrow peak window) is completed, click Stop in the "Sequence - Next
Sample" task window.
Open the Mass Calibration task window. After verifying the information in
section 13.1.1 (diagnostics of LR calibration), press the Gears button, click
"yes" to "delete current calibration" and then Files>Save and return to the Sequence Editor.
Continue the sequence until MR Wide and Narrow samples are analyzed. Then click Stop and go to
the Mass Calibration task window. After verifying the information in section 13.1.1, save the file and
return to the Sequence Editor.
10. Continue HR Wide and Narrow. Save.
11. The mass calibration is now completed. Go to section 13.1.2.
13.1.1 Diagnostics of a Mass Calibration
1. In the tool bar of the Mass Calibration task window, click on the "Open Analysis" icon to
show the browsing dialog.
2. Open subdirectory Thermo Automasscal. Find the acquired file for the latest (just completed)
analyses.
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Diagnostic Curve forLR Calibration
Figure 13 shows a typical LR 2nd deriv. diagnostic curve. Notice the following features in the
figure:
• There are two spikes at low mass: the Li isotopes 6Li and 7Li seem to be overlapping in the
LR plot, which is normal.
• There is a large gap between m/z 23 and 45: this causes spiking for both isotopes, which is
normal and can be ignored.
• The large spike at m/z 45 is normal: this is caused by the inaccuracy at m/z 45 due to
polyatomic ions (for example 12C16C>2H or 14N216OH) at the same nominal mass as Sc.
If you see any incorrect identification of peaks go to section 13.1.2 to fix it.
4000-
¦¦
2000-
c 0 -
o
\
V
-2000
-4000-
1 i
50 100 150 200 250
Mass [u]
Figure 13. Typical LR 2nd deriv diagnostic curve.
Diagnostic Curve for MR Calibration
Figure 14 shows a typical MR diagnostic curve. The following should be noted from this figure:
• There are two spikes at low mass: the Li isotopes 6Li and 7Li seem to be overlapping in the
plot, which is normal.
• There are more points at lower masses: more calibration points are added in the low mass
range to ensure mass accuracy.
• The biggest spike is 238U160 at m/z 254: the counts for 238U160 are low in MR so its spectral
peak is not well defined. This leads to a higher deviation than for other masses, which is
normal.
If you see any incorrect identification of peaks go to section 13.1.2 to fix it.
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Figure 14. Diagnostic curve for MR.
Diagnostic Curve forHR Calibration
Figure 15 shows a typical HR diagnostic curve. In this figure, notice the following:
• There is a large spike at low mass: only 7Li is calibrated in HR as the 6Li count rate is low.
• The spike between 7Li and 1 IB is normal in HR.
• There is some spiking around m/z 80: to ensure an accurate calibration for As and Se, the Ar
dimer background interferences at m/z 76, 78, and 80 are used as mass calibration points in
HR. As these masses are closely spaced, some small spikes may be seen, which is normal.
If you see any incorrect identification of peaks go to section 13.1.2 to fix it.
Figure 15. Diagnostic curve for HR.
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13.1.2 Check All Masses
1. Click the Manual Calibration icon in the Mass Calibration task window. It will display jjsjra*
a list of calibrated masses.
2. Select the first entry in the list. Double click it to zoom to it in the spectrum field. The mass
range around the calibrated mass is displayed. The mass marker should be centered on the
peak. If the mass is correctly calibrated, move on to the next entry.
3. If the mass marker is not correctly assigned (not centered on the peak), delete this jjjjj
reference point by clicking on the Delete icon.
4. To assign a new reference point, center the mouse over the peak in the spectrum and double
click it. A Calibration Mass dialog appears as shown in Figure 16.
Calibration Mass
Calibration Mass / j
Cancel
Pointed M ass: 7.0160
Centroid M ass: 7.01 GO
MDAC: 20491.00
Calibration Mass / Isotope: | 7.0160 | j Help
Suggestions
Isotope i Interfer. Nom. Mass Exact Mass Abundance
Li7 [7] 7.0155 92.5 %
I I Display Interferences
Figure 16. Calibration Mass dialog box.
5. Select the correct isotope/interference from the Suggestions list. (Note: Only elemental peaks
are initially displayed. To display the interferences, the option box at the bottom of the dialog
must be activated.)
6. Click on Add to add the new reference point to the calibration, and click Save to save
the new calibration.
7. Check all masses in the list and remember to save the file at the end.
The most commonly miscalibrated masses are between 6 and 70 amu. Comparing isotope ratios
or widening the display task window will aid in the identification of problem isotopes such as the
following:
• 6Li/7Li: Use the natural abundance Li isotope pattern, 7.5/92.5, to identify the Li isotopes.
• 28Si: The 3sSi peak is to the left of the two interfering polyatomic species.
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• 16C>2: The count rate for 16C>2 at m/z 32 is high, often close to the detector maximum of
5.0* 109 cps.
• 45Sc: The 45Sc peak is to the left of the interfering polyatomic species.
• 69Ga: The 69Ga peak is to the left of the interfering Ba2++ species. A high Ba2++ signal
indicates non-optimum tuning.
Reinitialization of mass calibration may be required if E2 was shut down lately. This process
starts using a default mass calibration, saved in the host computer, and eventually builds a new
valid calibration. E2 users should consult the laboratory manager if such a need arises.
Perform the following steps to reestablish mass calibration:
1. Open the default masscal file, and run the LRWide analysis.
2. Delete the old calibration, and save the new one.
3. Re set MR and HR calibrations.
4. Start the MR samples.
5. Fix mass peaks as needed.
6. Save and proceed to HR.
7. When done with the masscal, save the HR_Narrow as your new default file.
13.2 Change Water in Recirculating Chiller
Note: Use RO water only; do not use DI water. It is recommended that you take RO water from D461-B
(acid clean lab). A kit with all needed tools is placed on top of the chiller unit.
1. Turn off the chiller.
2. Disconnect the top hose from the chiller with a screwdriver. Clamp the hose to the drain pan and cap
the valve on the back of the chiller.
3. Open the reservoir on top of the chiller, unscrew the cap, and place a funnel into the container.
4. Turn on the chiller.
• Chiller may get loud periodically.
5. Turn off the chiller.
6. Pour the drain pan contents into the sink.
7. Reconnect the recirculating hose.
8. Fill reservoir to fill line as shown.
9. Turn on the chiller and ensure there are no leaks.
• Should start to recirculate water to the pan.
• Start filling water through funnel to flush the
system.
Fill
line
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13.3 Change Entrance Slit Assembly
Locate the following tools and accessories before beginning the procedure:
• Torque wrench (comes with the E2 instrument)
• Half-cut 1-mL pipette tip to hold screw
• Flat-type long-stem screwdriver
• Lint-free paper towels
• Powder-free vinyl gloves
Follow step by step the document titled "Slit_exchange_info_from_E2_Maintenance_
Course.pdf," published by Thermo Fisher and found in the laboratory manual holder or in the host
computer in the My Documents folder. After completion, turn on the E2 and let it pump down overnight.
Make sure the high vacuum is in the order of 10"7 mbar before using the E2 or activating the High Voltage
on the magnet.
Special note: Perform a mass calibration after a new entrance slit assembly is in place.
13.4 Maintenance of Sample and Skimmer Cones
The sample and skimmer cones require cleaning and eventually replacement after prolonged usage. It is
important not to damage the tips of the cones during the cleaning process because the ion extraction will
be degraded. Follow the steps below to clean them:
1. To remove the sample cone, line up the cone removal tool with the cone locking ring and unscrew
one full turn. Insert the magnet into the tool and unscrew the locking ring completely (the magnet will
capture the sample cone).
2. To remove the skimmer cone, loosen each Allen screw only one turn. Carefully insert the magnet
such that it does not touch the tip of the cone, place it on the skimmer and rotate the skimmer until the
notches match the screw positions, and then withdraw the skimmer. The skimmer valve plate will be
visible in the skimmer mounting orifice.
3. After removing the cones, place them in two separate clean plastic beakers such that the orifices face
upwards. Cover the cones with ultrapure water and sonicate for -10 min. Rinse with ultrapure water.
4. Mount the cleaned skimmer cone onto the magnet tool, taking care that the magnet does not touch the
tip of the cone.
5. Insert the skimmer into the mount and turn it until the notches no longer line up with the Allen
screws. Retighten the Allen screws.
6. Before placing the sample cone, replace the graphite seal (o-ring).
7. Place the threaded locking ring on the sample cone and insert the magnet. Insert the sample cone into
the front plate. Use the tool to screw the locking ring into the front plate. When tight, remove the
magnet and hand tighten further.
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14.0 Troubleshooting
Observation
Cause
Fix
TP A, B, C, or D is red
One of the turbomolecular
pumps is not operational or is
malfunctioning
Rebuild or replace the pump.
Refer to hardware manual.
HR intensity of In is less than
0.7% of its LR intensity
The entrance slit assembly is
bad
Replace it. Refer to the tutorial
file in the host computer.
HV pressure changes while a
scan is in progress or when the
entrance slit switches between
MR to LR or MR to HR
Bad entrance or exit slit. Place
a hemostat or hold-down
clamp at the exit gas line. If HV
does not change when
switching from MR to LR, then it
is a bad exit slit.
Change exit slit assembly. Not
recommended at the user
level. Place a service call.
15.0 Preventive Care
15.1 Daily
The following maintenance procedures need to be addressed daily:
• Check the sample waste container level.
• Inspect the argon tank supply and its pressure to the instrument.
• Inspect the nebulizer for clogs.
• Inspect the torch and aerosol injector tubes.
• Inspect the sample capillary tubing to be sure it is clean and in good condition.
• Check the peristaltic pump tubing before operation.
• Check the spray chamber for large droplets, indicating the unit needs cleaned. Soak well in
10% (v/v) HNO3 for 2 hours, rinse well with reagent water.
15.2 Weekly (Refer to the Weekly Maintenance Log, Appendix 3.3)
Inspect the fore pump and interface pump oil levels and color weekly.
15.3 Monthly (Refer to the Monthly Check List, Appendix 3.4)
Perform the following on a monthly basis:
• Change the RO water in the chiller unit. Refer to section 13.2.
• Inspect the RF coil for pits or holes.
• Make sure the peristaltic pump rollers are clean, and remove and clean the pump head as necessary.
15.4 Annual (Refer to Yearly Check List, Appendix 3.5)
A preventive maintenance visit is due from Thermo on an annual basis as part of the service contract. The
following services will be performed
• Skimmer valve O-ring change and lubrication
• Fore pump and interface pump oil change
• Interface oil mist chamber cleanup and filter change
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All maintenance activities should be documented on the Yearly Check List.
15.5 Usage Dependent (Refer to the Usage Dependent Log, Appendix 3.6)
Experienced analysts can perform the following usage-dependent maintenance:
• Entrance slit assembly change
• Guard electrode change
• RF coil change
• Skimmer and sample cone change
• Torch and sample tube cleanup or maintenance
16.0 Waste Management
16.1 The analyst is responsible for ensuring the safe storage and disposal of all analytical standards and
reagents associated with this method.
16.2 The analyst is responsible for notifying the laboratory manager of disposal needs.
16.3 The analyst is responsible for preserving/storing analyzed samples for future verification.
17.0 Documentation and Document Control
17.1 All information concerning sample preparation, standard preparation, instrument conditions, etc., must be
written in the analyst's notebook. Any unusual problems or conditions must also be noted.
17.2 Record all maintenance performed on the instrument in the maintenance logbook for this particular
instrument.
17.3 Record all analyses including QC samples performed by the instrument in the logbook for this particular
instrument.
17.4 Back up analysis data on a weekly basis. Copy the following folders and files to a CDr: a) Sequence data
folder, b) Sequence file (*.seq), c) Method file (*.mth), and d) Standards files (.std). Place the CD in a
labeled jewel case or paper sleeve, and deliver the data to the laboratory manager. The CD label should
include the date, your name, and a very brief description of the data inside.
18.0 Quality Control
In accordance with EPA Method 6020, the multi-element determination of samples by ICPMS, the following
practices are undertaken to ensure the highest quality analytical data.
18.1 All QC data are stored permanently and are easily available for reference or inspection.
18.2 A standard traceability record book is kept with certificates of analysis of all primary standards in use.
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18.3 An Analytical Calibration Traceability Log (see Appendix 3.7) is kept with expiration dates of primary
analytical calibration standards and dates of preparation of stock solutions A, B, and S.
18.4 Instrument detection limits are calculated every three months and kept in the instrument logbook.
18.5 Analytical calibrations are deemed valid only when the regression coefficient (R2) value exceeds 0.999.
18.6 An initial calibration verification standard and a reagent blank sample are run right after a new
calibration.
18.7 Accuracy of analytical calibrations is verified by analyzing Standard Reference Materials such as
SRM1643 and SRM1640. If measurements exceed ±15% of the certified elements, current calibration is
invalidated. New calibration will be established after the cause for QC failure is identified and corrected.
18.8 To obtain data of known quality in all resolution settings, at least one isotope is analyzed in all resolution
settings, where applicable.
18.9 Validity of the existing calibration is verified at a frequency of every 10 analyses. The instrument check
standards must agree within ±15%.
18.11 Duplicate samples are analyzed: One in every 10 samples in an analytical sequence is reanalyzed as a new
sample. A relative percent of difference (RPD) of less than 20% is the tolerance criteria for reanalysis.
RPD is calculated as
IC -C I
( 11 21 )xl00,
(Q +C2)/2
where C\ is the first analysis concentration and C2 is the second analysis (duplicate sample) concentration.
18.12 Intensities of internal standards are monitored in every analysis. When the intensity of an IS in a sample
analysis fails to fall between 80% and 120% of its initial (or reference) value, those samples can either be
re-analyzed, or diluted and reanalyzed.
18.13 Dilution tests are carried out when an analyte lies outside the established calibration region.
The current version of the E2 software does not support all of the QC steps mentioned above on-line. Use the
stand-alone VBA application macro, called "ICPMS Data Flagger," to flag analytical results after a sequence is
completed and the sequence report is generated. Appendix 4 describes how to install and use the ICPMS Data
Flagger application.
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19.0 References
All referenced manuals are located in the blue file holder next to the host computer of E2.
Finnigan ELEMENT2 Operating Manual (p/n 1091281).
Finnigan ELEMENT2 hardware manual.
Finnigan Application Notes: Peak Search Algorithm, Equations Used in E2, and Sequence Reevaluation.
Interface and Turbo Pump Manuals
EPA Method 6020: Inductively Coupled Plasma - Mass Spectrometry, US EPA, Sept 1999, pi-18.
ASX-500 Model 510 Auto Sampler Operator's Manual, CETAC Technologies, Omaha, NE, Version 1.0, Rev. 4,
April, 2002.
Inductively Coupled Plasma Mass Spectrometry Handbook, Simon Nelms (Editor), Thermo Elemental, Cheshire,
UK, Blackwell; 1st edition (October 21, 2005)
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Appendix 1: Element 2 HR-
Instrument Settings:
RF power
Gas flow rates:
Cool
Auxiliary
Sample
Sample update rate
Sampler cone (Pt)
Skimmer cone (Pt)
Nebulizer
Spray chamber
Detector dead time
Internal standard solution
>MS Method Settings
1200-1260 W
16 Ipm
0.9-1.0 Ipm
0.96-1.20 Ipm
-100 (iL/min
1.1 -mm orifice diameter
0.8-mm orifice diameter
100-(iL Teflon microneb
Air-cooled cyclone
30 ns
2.0 ppb solution of Inl 15 and Irl 93
Isotopes
Low resolution (LR)
Medium resolution (MR)
High resolution (HR)
Li7, Be9, Rb85, Sr88, Y89, Mo95, Rhl03, Pdl05, Agl07, Cdl 11, Snl 18, Sbl21
Csl33, Bal37, Lai39, Cel40, Ndl46, Sml47, Gdl57, Dyl63, W182, Ptl95, TI205,Pb206,
Pb207, Pb208, Bi209, Th232, U238, (Inl 15, Irl 93)
Na23, Mg24, AI27, Si28, P31, S32, Ca44, Sc45, Ti47, V51, Cr52, Mn55, Fe57
Co59, Ni60, Cu63, Zn66, Snl 18, (Inl 15, Irl 93)
K39, Ge72, As75, Se77, Snl 18, (Inl 15, Irl93)
Acquisition Parameters
Resolution Low
Mass task window, % 100
Samples/peak 30
Sample time/ns 10
Scan type E Scan
Detector mode (analog/counting) Both
No. replicates (runs) 3
No. scans per replicate (pass) 2
Evaluation Parameters
Resolution
Search task window, %
Integration task window, %
Integration type
Calibration type
Internal standard (In/lr)
Low
100
40
Ave
Linear
Indium
Medium
125
20
20-50
E Scan
Both
3
2
High
150
15-20
100-500
E Scan
Both
3
2
Medium
100
60
Ave
Linear
Indium
High
80-100
60-70
Ave
Linear
Indium
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Appendix 2: Concentrations of Individual Elements in Working Calibration Standards
Element
wsO_ppt
ws1_ppb
ws2_ppb
ws3_ppb
CheckStd
ws5_ppb
ws6_ppb
No
0
0.400
4.000
10.000
20.000
30.000
100.000
Mg
0
0.400
4.000
10.000
20.000
30.000
100.000
K
0
0.400
4.000
10.000
20.000
30.000
100.000
Ca
0
0.400
4.000
10.000
20.000
30.000
100.000
Si
0
0.400
4.000
10.000
20.000
30.000
100.000
Al
0
0.120
1.200
3.000
6.000
9.000
30.000
Fe
0
0.120
1.200
3.000
6.000
9.000
30.000
Zn
0
0.120
1.200
3.000
6.000
9.000
30.000
Ba
0
0.120
1.200
3.000
6.000
9.000
30.000
Ag
0
0.020
0.200
0.500
1.000
1.500
5.000
As
0
0.020
0.200
0.500
1.000
1.500
5.000
Be
0
0.020
0.200
0.500
1.000
1.500
5.000
Bi
0
0.020
0.200
0.500
1.000
1.500
5.000
Cd
0
0.020
0.200
0.500
1.000
1.500
5.000
Ce
0
0.020
0.200
0.500
1.000
1.500
5.000
Co
0
0.020
0.200
0.500
1.000
1.500
5.000
Cr
0
0.020
0.200
0.500
1.000
1.500
5.000
Cs
0
0.020
0.200
0.500
1.000
1.500
5.000
Cu
0
0.020
0.200
0.500
1.000
1.500
5.000
Dy
0
0.020
0.200
0.500
1.000
1.500
5.000
Gd
0
0.020
0.200
0.500
1.000
1.500
5.000
Ge
0
0.020
0.200
0.500
1.000
1.500
5.000
La
0
0.020
0.200
0.500
1.000
1.500
5.000
Li
0
0.020
0.200
0.500
1.000
1.500
5.000
Mn
0
0.020
0.200
0.500
1.000
1.500
5.000
Mo
0
0.020
0.200
0.500
1.000
1.500
5.000
Nb
0
0.020
0.200
0.500
1.000
1.500
5.000
Ni
0
0.020
0.200
0.500
1.000
1.500
5.000
P
0
0.020
0.200
0.500
1.000
1.500
5.000
Pb
0
0.020
0.200
0.500
1.000
1.500
5.000
Pd
0
0.020
0.200
0.500
1.000
1.500
5.000
Pt
0
0.020
0.200
0.500
1.000
1.500
5.000
Rb
0
0.020
0.200
0.500
1.000
1.500
5.000
Rh
0
0.020
0.200
0.500
1.000
1.500
5.000
Sc
0
0.020
0.200
0.500
1.000
1.500
5.000
Sb
0
0.020
0.200
0.500
1.000
1.500
5.000
Se
0
0.020
0.200
0.500
1.000
1.500
5.000
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Element
ws0_ppt
ws1_ppb
ws2_ppb
ws3_ppb
CheckStd
ws5_ppb
ws6_ppb
Sm
0
0.020
0.200
0.500
1.000
1.500
5.000
Sn
0
0.020
0.200
0.500
1.000
1.500
5.000
Sr
0
0.020
0.200
0.500
1.000
1.500
5.000
Tb
0
0.020
0.200
0.500
1.000
1.500
5.000
Ti
0
0.020
0.200
0.500
1.000
1.500
5.000
Th
0
0.020
0.200
0.500
1.000
1.500
5.000
TI
0
0.020
0.200
0.500
1.000
1.500
5.000
U
0
0.020
0.200
0.500
1.000
1.500
5.000
V
0
0.020
0.200
0.500
1.000
1.500
5.000
W
0
0.020
0.200
0.500
1.000
1.500
5.000
Y
0
0.020
0.200
0.500
1.000
1.500
5.000
S
0
4.000
40.000
100.000
200.000
300.000
1000.000
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Appendix 3: Laboratory Forms and Log Sheets
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3.1 Daily Startup Log
Date/User
Backup
Power
Chiller
Temp
Ar Gas
Skimmer
Cones
Torchbox
Exhaust
PeriPump
Tubing
Condition
Plasma
Start Time
High Vacuum,
Skimmer
Valve Closed
after plasma on, valve
open and sample aspiring
Plasma End
Time
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3.2 Daily Setting and Performance Log
Date
Torch
X
y
z
Gas Flows
C
A
S
Power (watts)
Lenses (v)
E
F
x-D
y-D
Sh
LR Lenses
Q1R
Q2R
Q1F
MR Lenses
Q1R
Q2R
Q1F
HR Lenses
Q1R
Q2R
Q1F
LR Check
Li (cps)
In (cps)
U (cps)
Oxides Check
BaO (%)
Ba++ (%)
UO (%)
MR Check
Co (resolution)
In (resolution)
In (cps)
HR Check
Ar38 (resolution)
ArAr (resolution)
In (resolution)
In (cps)
SEM Voltage
Application
User
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3.3 Usage Dependent Log
Date Item Replaced Cause of Change Operator Initials
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3.7 Analytical Calibration Traceability Log
Stock A / Stock B:
Date prepared:
Prepared by:
Standard
Concentration
Lot No.
Exp. Date
Final Cone.
Comments
Li
Be
Na
Mg
Al
P
S
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Se
Rb
Sr
Mo
Ag
Cd
In
Sn
Sb
Cs
Ba
La
Ce
Nd
Sm
Gd
Dy
W
TI
Pb
Bi
Th
U
Si
Gg
Rh
Pd
Pt
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Appendix 4: ICPMS Data Flagger
To view the analytical results easily, the data in the sequence summary file created by the current
software version needs major rearrangement. In addition, the sequence output does not have data quality
indicators (flags) for the end user to evaluate an analytical result. Therefore, we developed a VBA
application macro that runs in MS-Excel for post-processing a sequence summary file. This application
does the following:
• Reads the sequence summary file from a drop-down menu
• Reads appropriate instrument detection limit (IDL) values file from a drop-down menu
• Formats species name and rearranges data such that each row contains one sample with all associated
analysis information in columns
• Evaluates and introduces flags for below instrument detection concentrations, check sample analysis,
SRM sample analysis, and duplicate sample analysis.
• Outputs analytical concentration data, intensity data, and QC sample data separately.
Installation
This application has already been installed in E2's host computer. To install it in
another computer, copy the "ICPMS Data Flagger.EXE" file from the E2 host
computer (C:\PancrasV.) onto removable media and transfer it to the new computer. icpmsData Fbgger.EXE
Double click the EXE icon to initiate installation, and follow on-screen instructions.
This installation creates folder C:\Flag_Program\ and copies the needed folders and files to run the
application. The following folders are typically installed:
C: \Flag_Program\In\
C :\Flag_Program\Out\
Installation also creates a shortcut icon on the desktop to run the application. It is the user's responsibility
to update IDL information in the lookup file, "LookUp_IDL.xls". in the C:\Flag_Program\Out\ folder.
Application
1. Find the .CSV sequence report file in the sample sequence folder. The sequence report file is created
and saved by its sequence name (but with a .CSV extension). Copy and move it to folder
C:\Flag_program\In\. {Note: This step may not be required in the future version of ICPMS Data
Flagger.)
2. Find the ICPMS_VBA application macro on the desktop or in the folder C:\flag_progam\ I
and double click. This action will open the ICPMS Data Flagger application (see
Figure 1). The tab "How to Execute" has step-by-step instructions for first-time users.
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ICPMS Data Flagger
Data Flagger | How to Execute |
m
Raw ICPMS
E
LookLIp Data
E
Check Standards
QC Check Std Labels:
Check_500_ppt_HH
Check_l000_ppt_HX
QC Criteria
Input O.Ol for 10°o
0,15
Default: 15%
SRM
QC SRM samples and labels:
10"% 5RM1640: SRM1640_010p_HH
l°,'o SRM1643 : SRM1643_001p_HH
QC Criteria | o. 15
Input 0.01 for 10°o
Default: 15%
Duplicate Samples
Qualifier
Eh: "Dp", "dup" | dp
QC Criteria
Input 0.01 For 10%
0.20
Default: 20%
Check Data Integrity
Clear All
Execute Data Processing
Examine Flagged Data
Close
Data Export Options
File Name for the Flagged
ICPMS data
File Name for Intensity
data
QA Report
1
Click |
1
Click 1
1
Click |
Figure 1. ICPMS Data Flagger application screen.
3. Select the sequence report file that you want to process from the "Raw ICPMS" drop-down menu.
4. Select the "LookUp Data" file the same way. The LookUp file has the IDL and necessary QC
reference data to evaluate and flag analytical results.
5. Set QC criteria. Default values are entered automatically. Change if needed.
6. Press "Execute Data Processing," and wait until it is done. Warning messages may pop up if the
flagger does not find duplicate samples. Follow on-screen instructions.
7. Enter file names in the data export options and press "Click" to export.
8. Click "Examine Flagged Data" to view the processed data. All data used for processing are present in
the Excel file that opens up. Sheets are named to reflect its contents. Click "Return to ICPMS Data
Flagger" button (top left) to return to the flagger application menu. Do not close the Excel file
directly.
9. Use "Clear All" to start the next raw data processing. Note: Save reports (from Data Export options)
before clearing all and starting new processing.
10. Use the "Close" button to exit the flagger application.
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Flags
The following flags are used to indicate analytical data quality:
Analysis flags:
V0: Determined concentration is above the IDL
V1: Determined concentration is at or below the IDL
M2: Missing or unavailable data
SEC: Estimated concentration for a species when the detector was saturated
Quality control flags :
Cp: Check standard pass
Cf: Check standard fail
Cu: Check standard unavailable
Rp: SRM sample pass
Rf: SRM sample fail
Ru: SRM sample unavailable
Dp: Duplicate sample pass
Df: Duplicate sample fail
Identification of QC samples (QCflag):
1: Check samples
2: Duplicate pairs
22: Repeat samples
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Appendix 5: Alternate Calibration Standard Preparation from Custom Multi-
Element Certified Stock Solutions (High Purity Standards, Charleston, SC, USA).
Stock Name
Stock S
Element
Stock A
Al, B, Fe, Zn
Ca, Mg, K, Si, Na
Stock B, Soln A
As, Be, Bi, Cd, Ce
Cs, Cr, Co, Cu, Dy
Ga, La, Pb, Li, Mn
Ne, Ni, P, Ru, Sa
Sc, Se, Sr, Tb, Tl,
Th, U, V, Y
Stock B, Soln B Sb, Ge, Mo, Ag
Sn, Ti, W
Stock B, Soln C Pd, Pt, Rh
Concentration
Matrix
10 ppm
Water
300 ppb
1000 ppb
2% Nitric Acid
100 ppb
2% Nitric Acid
100 ppb
2% Nitric Acid
+ Tr HF
100 ppb
2% HC1
Table 8: Working Standard (WS) Preparation. Stock solutions are added volumetrically (mL), final
STOCK
WSO
WS1
WS2
WS3
WS4
WS5
WS6
Stock S
0.04
0.40
1.00
2.00
3.00
10.00
Stock A
0.04
0.40
1.00
2.00
3.00
10.00
Stock B-A
0.02
0.20
0.50
1.00
1.50
5.00
Stock B-B
0.02
0.20
0.50
1.00
1.50
5.00
Stock B-C
0.02
0.20
0.50
1.00
1.50
5.00
Reagent
100.00
99.86
98.60
96.50
93.00
89.50
65.00
Blank"
Final Mass
100.00
100.00
100.00
100.00
100.00
100.00
100.00
Solution (g)
"Reagent Blank is 0.2% HNOs and 0.1% HC1
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Appendix 6: Hydraulic Fracturing Analysis Update. Calibration Tables, Analytical
Method, and QA Guidelines.
Note: All solutions prepared will have a final 2% HNO3 and 0.5% HCl (v/v) concentration to
match the sample matrix.
Multi-element calibration standards purchased from High Purity Standards (Charleston, SC).
Stock Name
Element
Concentration
Matrix
Stock S
S
10 ppm
Water
Stock A
Al, B, Fe, Zn
Ca, Mg, K, Si, Na
300 ppb
1000 ppb
2% Nitric Acid
Stock B, Soln A
As, Be, Bi, Cd, Ce
Cs, Cr, Co, Cu, Dy
Ga, La, Pb, Li, Mn
Ne, Ni, P, Ru, Sa
Sc, Se, Sr, Tb, Tl,
Th, U, V, Y
100 ppb
2% Nitric Acid
Stock B, Soln B
Sb, Ge, Mo, Ag
Sn, Ti, W
100 ppb
2% Nitric Acid
+ Tr HF
Stock B, Soln C
Pd, Pt, Rh
100 ppb
2% HCl
Table 9: Working Standard Calibration Preparation.
Stock A (mL)
Stock S (mL)
StockB-A (mL)
StockB-B (mL)
StockB-C (mL)
WSl
0.04
0.04
0.02
0.02
0.02
WS2
0.4
0.4
0.2
0.2
0.2
WS3
1
1
0.5
0.5
0.5
WS4
2
2
1
1
1
WS5
3
3
1.5
1.5
1.5
WS6
10
10
5
5
5
WS7
20
20
10
10
10
WS9
5*
WS10
10
WS11
10
WS12
10
WS1-WS7 made up to 100.00g final mass with Reagent Blank (2% HNO3, 0.5% HCl)
WS9 is made by 5 mL StockB-A + 5 mL reagent blank
WS10-12 are 10 mL pours of the stock solution
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Table 10: Working Standard Calibration Concentrations.
WSO
WS1
WS2
WS3
WS5
WS6
WS7
WS9
WS10
WS11
WS12
K
0
0.4
4
10
30
100
200
1000
Si
0
0.4
4
10
30
100
200
1000
Al
0
0.12
1.2
3
9
30
60
300
Fe
0
0.12
1.2
3
9
30
60
300
Zn
0
0.12
1.2
3
9
30
60
300
Ba
0
0.12
1.2
3
9
30
60
300
S
0
4
40
100
300
1000
10000
Ag
0
0.02
0.2
0.5
1.5
5
As
0
0.02
0.2
0.5
1.5
5
10
Be
0
0.02
0.2
0.5
1.5
5
Bi
0
0.02
0.2
0.5
1.5
5
Cd
0
0.02
0.2
0.5
1.5
5
Ce
0
0.02
0.2
0.5
1.5
5
10
Co
0
0.02
0.2
0.5
1.5
5
10
50
Cr
0
0.02
0.2
0.5
1.5
5
10
Cs
0
0.02
0.2
0.5
1.5
Cu
0
0.02
0.2
0.5
1.5
5
10
50
100
Dy
0
0.02
0.2
0.5
1.5
Gd
0
0.02
0.2
0.5
1.5
Ge
0
0.02
0.2
0.5
1.5
5
La
0
0.02
0.2
0.5
1.5
5
Li
0
0.02
0.2
0.5
1.5
5
50
Mn
0
0.02
0.2
0.5
1.5
5
10
50
100
Mo
0
0.02
0.2
0.5
1.5
Nd
0
0.02
0.2
0.5
1.5
Ni
0
0.02
0.2
0.5
1.5
5
10
50
100
P
0
0.2
0.5
1.5
5
10
50
100
Pb
0
0.02
0.2
0.5
1.5
5
Pd
0
0.02
0.2
0.5
1.5
Pt
0
0.02
0.2
0.5
1.5
Rb
0
0.02
0.2
0.5
1.5
5
10
50
Rh
0
0.02
0.2
0.5
1.5
Sb
0
0.02
0.2
0.5
1.5
5
Se
0
0.2
0.5
1.5
5
10
Sm
0
0.02
0.2
0.5
1.5
Sn
0
0.02
0.2
0.5
1.5
5
10
Sr
0
0.5
1.5
5
10
50
100
Tb
0
0.02
0.2
0.5
1.5
Ti
0
0.02
0.2
0.5
1.5
5
10
Th
0
0.02
0.2
0.5
1.5
TI
0
0.02
0.2
0.5
1.5
U
0
0.02
0.2
0.5
1.5
V
0
0.02
0.2
0.5
1.5
5
10
50
W
0
0.02
0.2
0.5
1.5
Y
0
0.02
0.2
0.5
1.5
5
10
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Table 11: QA/QC Guidelines
Item
Frequency
Criteria
Action
Calibration
Once per sequence
R2> 0.995
Examine fitting
parameters; rerun
standards; remake
standards
Initial Calibration
Verification
(Check xxxx_ppt rOO
After calibration
±15% of target value
Examine calibration;
rerun sample, remake
sample
IBC
(Initial Blank Check)
After calibration
< lowest reportable
limit
Examine calibration;
rerun sample, remake
sample
Check Sample (s)
Check 1000_ppt r##
Check 1500_ppt r##
Check 10_ppb r##
After every 10
unknown samples.
High level check (10
ppb) followed by low
level check (lOOOppt
or 1500ppt)
±15% of target value
Examine calibration;
rerun sample, remake
sample. Examine
sequence of
unknowns to
determine repeats.
Duplicate
<_dp)
Every 10 unknown
samples; half-way
between the Check
Sample.
±20%) Relative
Percent Difference
Remake sample.
Examine sequence of
unknowns to
determine repeats.
SRM
(NIST Standard
Reference Materials)
Once per sequence
(1643e and 1640a
each at 2 different
dilutions)
±15%o of target value
Examine calibration;
rerun sample, remake
sample. Observe
trends of multiple
sequences.
QCS
(Quality Control
Sample)
Analyst Suggestion to
verify calibration
accuracy
±15%o of target value
Examine calibration.
-------
Appendix D
Synthetic Turf Field Facility User
Questionnaires - Adult/Adolescent and
Youth/Child Versions
611
-------
Form Approved
OMB No. 0923-0054
Exp. Date 01/31/2017
Adult/Adolescent Field User Questionnaire
PID
Facility Name
Interview Date
Site ID Number
Facility Location
Interviewer ID
Interviewer: I would like to ask you some questions about activities that may affect your
exposures to, and contact with synthetic turf fields that contain crumb rubber materials.
Field Contact Frequency and Duration Questions
Interviewer: I have several questions about the time you spend on synthetic turf fields at this facility.
B1. How long have you been coming to this facility?
(years)
(months)
B2. Specifically on the synthetic fields at this facility, what sports, physical education classes, or other
activities have you actively participated in by season (specify) over the past year?
Season
Sport
Specify Other
ATSDR estimates the average public reporting burden for this collection of information as 30 minutes per response,
including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data
needed, and completing and reviewing the collection of information. An agency may not conduct or sponsor, and a
person is not required to respond to collection of information unless it displays a currently valid OMB control
number. Send comments regarding this burden estimate or any other aspect of this collection of information,
including suggestions for reducing this burden to CDC/ATSDR Reports Clearance Officer; 1600 Clifton Road, MS
D-74, Atlanta, GA 30333, ATTN: PRA (0923-0054).
612
-------
B3. Over the past year, how many days per week by season have you typically spent
on the synthetic fields at this facility?
Spring
Summer
Fall
Winter
(days per week)
(days per week)
(days per week)
(days per week)
B4. Over the past year, how many hours per day by season have you typically spent on the
synthetic fields at this facility?
Spring
Summer
Fall
Winter
(hours per day)
(hours per day)
(hours per day)
(hours per day)
B5. Over the past year, what was the longest period of time that you spent on the synthetic fields
at this facility during a single day?
(number of hours)
613
-------
Contact Types and Scenarios per Each Type of Field Use
Interviewer: I have several questions about the kinds of activities that you take part in specifically on
synthetic turf fields installed at this facility.
For the following question, please use one of the three responses (often, sometimes, and rarely/never).
"Often" means > 50% of the time and "sometimes" means < 50%.
B6. How frequently do you do the following activities while on synthetic fields at this facility each
season?
Dive on Fallon Sit on turf Eat snacks Drink
ground ground
Spring
Summer
Fall | | | | | | | | |
Winter
Inhalation Exposure-Related Questions
B7. When using synthetic fields at this facility.
What % of your time are you highly active, for example, running?
What % of your time are you moderately active, for example, jogging?
What % of the time do you have low activity, for example, walking?
What % of the time are you resting, for example, sitting or standing?
614
-------
Dermal and Non-dietary Ingestion Exposure-related Questions
For the following questions, please use one of the four responses (every time, often, sometimes, or
rarely/never):
B8. When using synthetic turf fields at this facility.
Every Time Often Some Rarely
times /Never
How often do you chew gum?
3
2
0
How often do you use a mouth guard?
3
2
0
How often do you eat?
3
2
0
How often do you drink?
3
2
0
How often do you play in the rain?
3
2
0
How often do you wipe your hands with a hand wipe before eating?
3
2
0
How often do you sweat heavily?
3
2
0
How often do you touch the turf with your hand?
3
2
0
How often do you touch the turf with your other body parts
excluding hands?
3
2
0
How often do you sit on the turf with bare skin wearing shorts?
3
2
0
How often are you barefooted on the turf?
3
2
0
How often do you play with the turf materials or rubber granules?
3
2
0
How often do you touch your mouth with your hands or fingers?
3
2
0
How often do you place non-food objects in your mouth like
toothpicks, or pens or use your mouth to hold an object?
3
2
0
If rarely/never, skip next.
What type of object do you most often place in your mouth while at
this facility?
How often to you get cuts or abrasions from contact with the turf? 3 2 10
If rarely/never, skip next.
What is the body part that usually has the most cuts or abrasions:
knee, elbow, hand, thigh, shin, or other?
615
-------
B9. What clothing do you typically wear in this facility during each season (check all
that apply)?
Spring
Summer
Fall
Winter
Shorts
~
~
~
~
Short-sleeve shirt
~
~
~
~
Long pants
~
~
~
~
Long-sleeve shirt
~
~
~
~
Gloves
~
~
~
~
Socks
~
~
~
~
Helmet
~
~
~
~
Hat
~
~
~
~
Pads
~
~
~
~
Tire Crumb Take-Home Questions
For the following questions, please use one of the four responses (every time, often, sometimes, or
rarely/never):
B10. After using this facility:
How often do you notice tire crumbs, dirt, or debris
on your body?
in your car?
in your home?
In your laundry room/mudroom?
In your living room?
In your bedroom?
In your bathroom(s)?
Every Time
3
3
3
3
3
3
3
Often
2
2
2
2
2
2
2
Some
imes Rarely/Never
0
0
0
0
0
0
0
Post-Use Hygiene Practices Questions
For the following questions, please use one of the four responses (every time, often,
sometimes, or rarely/never):
616
-------
B11. After using this facility:
Every Time Often Sometimes Rarely/Never
How often do you take shower and change clothes 3 2 1 0
immediately after engaging in activities on the
synthetic turf at this facility?
How often do you take actions to prevent tire 3 2 1 0
crumbs from getting into your car?
How often do you wipe or remove shoes/equipment 3 2 1 0
before entering your home?
For the following questions, please use one of the six responses (never, once a month, 2 to 3 times a
month, once a week, 2-3 times a week, or four or more times a week).
B12. At other locations:
Never
Once a
month
2 to 3
times a
month
Once a
week
2 to 3
times
a week
4 or
more
times a
week
How often have you played on any other
synthetic turf fields during the past year?
How often have you played on any
synthetic turf fields in the last five years?
How often have you played on any natural
grass fields during the past year?
How often have you played on any natural
grass turf fields in the last five years?
How often have you played on
playgrounds with rubber mulch, mats or
synthetic turf during the past year?
How often have you played on
playgrounds with rubber mulch, mats or
synthetic turf during in the last five years?
General Hygiene Questions
B13. How many times in general do you wash hands per day?_
B14. How many times in general do you bathe or shower per weel
617
-------
General Demographic Questions
D1. How old are you?
D2. Are you male or female? O Male O Female O Refused
D3. Do you consider yourself to be Hispanic or Latino? OYes O No O Refused
D4. Which of the following categories best describes your race? (select one or more)
o
Native American
Indian or Alaska
Native
O
Black or African
American
O
White
O
Don't know
o
Asian
o
Native Hawaiian or
Other Pacific
Islander
O
Refused
D5. How tall are you?
(ft)
(in)
D6. How much do you weigh?
(lbs)
D7. Are you still in school? ~ yes ~
If so, what is your current grade in school?
O 7th o 8th
o 10th o llth
(j Technical School Q College
Q Other q Refused
no
O 9th
O 12th
Graduate School
Specify Other Grade
618
-------
D8. If No, what is your highest education level?
Q 11th or less q High School Graduate/ GED
Q Some College Q College Graduate School
Q Post High School Training
Q Post-graduate
q Other
q Refused
D9. What is your occupation?
This concludes the survey. Thank you for your time, i know that your time is
valuable.
If you have any questions or concerns, please, refer to the contact sheet for
information on who to contact.
619
-------
Form Approved
OMB No. 0923-xxxx
Exp. Date xx/xx/201x
Youth/Child Field User Questionnaire
PID
Facility Name
Interview Date
Site ID Number
Facility Location
Interviewer ID
Interviewer: I would like to ask you some questions about activities that may affect
your child's exposures to, and contact with synthetic turf fields that contain crumb
rubber materials.
Field Contact Frequency and Duration Questions
Interviewer: I have several questions about the time your child spends on synthetic turf fields
at this facility
B1. How long has your child been coming to this facility?
(years)
(months)
B2. Specifically on the synthetic fields at this facility, what sports, physical education classes,
or other activities has your child actively participated in by season (specify) over the past year?
Season
Sport
Specify Other
ATSDR estimates the average public reporting burden for this collection of information as 30 minutes per response,
including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data
needed, and completing and reviewing the collection of information. An agency may not conduct or sponsor, and a
person is not required to respond to collection of information unless it displays a currently valid OMB control
number. Send comments regarding this burden estimate or any other aspect of this collection of information,
including suggestions for reducing this burden to CDC/ATSDR Reports Clearance Officer; 1600 Clifton Road, MS
D-74, Atlanta, GA 30333, ATTN: PRA (0923-XXXX).
620
-------
B3. Over the past year, how many days per week by season has your
child typically spent on synthetic fields at this facility?
(days per week)
Spring
Summer
Fall
Winter
(days per week)
(days per week)
(days per week)
B4. Over the past year, how many hours per day by season has your child typically spent
on the synthetic fields at this facility?
Spring
Summer
Fall
Winter
(hours per day)
(hours per day)
(hours per day)
(hours per day)
B5. Over the past year, what was the longest period of time that your child has spent
on the synthetic fields at this facility during a single day?
(number of hours)
621
-------
Contact Types and Scenarios per Each Type of Field Use
Interviewer: I have several questions about the kinds of activities that your child takes part in
specifically on synthetic turf fields installed at this facility.
For the following question, please use one of the three responses (often, sometimes, and
rarely/never). "Often" means > 50% of the time and "sometimes" means < 50%.
B6. How frequently does your child do the following activities on synthetic fields at this facility each
season?
Dive on Fallon Sit on turf Eat snacks Drink
ground ground
Spring
Summer
Fall | | | | | | | | |
Winter
Inhalation Exposure-Related Questions
B7. When using synthetic fields at this facility:
What
%
of
the
time
is your child highly active, for example, running?
What
%
of
the
time
is your child moderately active, for example, jogging?
What
%
of
the
time
does your child have low activity, for example, walking?
What
%
of
the
time
is your child resting, for example, sitting or standing?
622
-------
Dermal and Non-Dietary Ingestion Exposure-Related Questions
For the following questions, please use one of the four responses (every time,
often, sometimes, or rarely/never):
B8. When using synthetic turf fields at this facility:
Every Time Often
Some
times
How often does your child chew gum? 3
How often does your child use a mouth guard? 3
How often does your child eat? 3
How often does your child drink? 3
How often does your child play in the rain? 3
How often does your child wipe their hands with a hand wipe 3
before eating?
How often does your child sweat heavily? 3
How often does your child touch the turf (with their hand)? 3
How often does your child touch the turf with their body excluding 3
hands?
How often does your child sit on turf with bare skin wearing shorts? 3
How often is your child barefooted on the turf? 3
How often does your child play with the turf materials or rubber 3
granules?
How often does your child touch their mouth with their hands or 3
fingers?
How often does your child place non-food objects in their mouth 3
every time like toothpicks, or pens or use their mouth to hold an
object? If rarely/never, skip next.
Rarely /
Never
0
0
0
0
0
0
0
0
0
0
0
0
What type of object does your child most often places in their
mouth while at this facility?
How often does your child get cuts or abrasions from contact with ^ 2 10
the turf?
If rarely/never, skip next.
What is the body part that usually has the most cuts or abrasions:
knee, elbow, hand, thigh, shin, or other?
B9. What clothing does your child typically wear in this facility during each season (check all that
apply)?
623
-------
Spring
Summer
Fall
Winter
Shorts
~
~
~
~
Short-sleeve shirt
~
~
~
~
Long pants
~
~
~
~
Long-sleeve shirt
~
~
~
~
Gloves
~
~
~
~
Socks
~
~
~
~
Helmet
~
~
~
~
Hat
~
~
~
~
Pads
~
~
~
~
Tire Crumb Take-Home Questions
Some
For the following questions, please use one of the four responses (every time, often, sometimes, or
rarely/never):
B10. After using this facility:
How often do you notice tire crumbs, dirt, or debris
Every Time Often
on your child's body? 3 2
in your car? 3 2
in your home? 3 2
In your laundry room/mudroom? 3 2
in living room? 3 2
in your child's bedroom? 3 2
in your bathroom(s) your child uses? 3 2
imes Rarely/Never
0
0
0
0
0
0
0
Post-Use Hygiene Practices Questions
For the following questions, please use one of the four responses (every time,
often, sometimes, or rarely/never):
B11. After using this facility:
How often does your child shower and change
clothes immediately after engaging in activities on
the synthetic turf at this facility?
Every Time Often Sometimes Rarely/Never
3 2 1 0
624
-------
How often does your child's shoes/equipment get 3 2 1 0
wiped or removed before entering your home?
For the following questions, please use one of the six responses (never, once a month, 2 to 3 times a
month, once a week, 2-3 times a week, or four or more times a week).
B12. At other locations:
Never Once a 2 to 3 Once 2 to 3 4 or
month times a times more
a week a times a
month week week
How often has your child played on any other
synthetic turf fields during the past year?
How often has your child played on any synthetic turf
fields in the last five years?
How often has your child played on any natural grass
fields during the past year?
How often has your child played on any natural grass
turf fields in the last five years?
How often has your child played on playgrounds with 0 1 2 3 4 5
rubber mulch, mats or synthetic turf during the past
year?
How often has your child played on playgrounds with 0 1 2 3 4 5
rubber mulch, mats or synthetic turf during in the last
five years?
General Hygiene Questions
B13. How many times in general does your child wash their hands per day?
B14. How many times in general does your child bathe or shower per week?
General Demographic Questions
D1. How old is your child?
D2. Is your child male or female? O Male O Female O Refused
D3. Do you consider your child to be Hispanic or Latino? OYes O No O Refused
D4. Which of the following categories best describes your child's race? (select one or
more)
625
-------
q Native American
Indian or Alaska
Native
Q Asian
Black or African q White
American
Native Hawaiian or Q Refused
Other Pacific
Islander
pi Don't know
D5. How tall is your child? (ft) (in)
D6. How much does your child weigh?
D7. What is your child's current grade in school?
o
2nd
o
6th
o
Other
o
3 rd
0
7th
o
Refused
o
4th
o
8th
o
5th
c>
gth
Specify other grade
(lbs)
That concludes the survey. Thank you for your time. I know that your time is
valuable.
If you have any questions or concerns, please, refer to the contact sheet for information on who
to contact.
626
-------
Appendix E
Exposure Characterization Meta-Data
Collection Forms
627
-------
E.1 Meteorological Conditions
TCRS Exposure Characterization Study
Meteorological Conditions
Note: Complete this form for each day of monitored participant activities at each field.
Field ID Number
Date
Outdoor or Indoor Field
NearStart of
Near Middle of
Near End of
Metric/Information
Participant Activities
Participant Activities
Participant Activities
Time of Day (Military time format)
Field AirTemperature at 1 m (°C)
Field Surface Temperature (°C)
Wind 1-minute average speed (km/h)
Wind 1-minute maximum speed (km/h)
Wind direction (compass degrees,
where wind is coming from)
Dew on field (yes/no)
Field wet from rain or watering (yes/no)
Conditions (sunny, partly cloudy,
cloudy, drizzle, rain)
628
-------
E.2 General Activity Information
TCRS Exposure Characterization Study General Activity Information
Note: Complete this form for each day of monitored participant activities at each field.
Field ID Number
Date
At Start of
Near Middle of
At End of
Metric/Information
Participant Activities
Participant Activities
Participant Activities
Approx. Number People in Active Play
on Study Field
Approx. Number People as Bystanders
on Study Field
Sport Name on Study Field (soccer,
football, etc.)
Type of Active Play on Study Field (1)
Type of Active Play on Study Field (2)
Type of Active Play on Study Field (3)
Type of Active Play on Study Field (4)
Type of Active Play on Study Field (5)
Adjacent Synthetic Fields in Use
(yes/no)
Approx. Number People at Adjacent
Synthetic Fields
Adjacent Grass Fields in Use (yes/no)
Approx. Number People at Adjacent
Grass Fields
629
-------
E.3 Participant Activity Information
TCRS Exposure Characterization Study Participant Information
Note: Complete this form for each participant at each field.
Field ID Number
Date
Participant ID
(from 1 to 8)
At Sta rt of
Approx. 30 minutes Into
Approx. 60 minutes Into
Approx. 90 minutes Into
Approx 120 minutes Into
At End of
Metric/Information
Pa rtici pa nt Activiti es
Participant Activities
Parti ci pa nt Activities
Parti ci pa nt Activities
Pa rtici pa nt Activities
Parti ci pa nt Activities
Time of Day (military time format)
Activities
Sport Name (soccer, football, etc.)
Sport Position (goal keeper, soccer
field player, football receiver, etc)
Type of Activities on Study Field
Physical Activity Level (low,
medium, high)
Contacting Turf (yes/no)
Types of Turf Contact (hands,
arms, legs, face, body)
Frequency of Turf Contact (>
1/min; > l/5min; < l/5min)
Clothing/Equipment Types (record only once - not at each time period)
Shirt (yes/no; long/short)
Pants (long/short)
Socks (yes/no; high/mid/low)
Gloves (yes/no and type)
Head Gear (yes/no and type; hat,
helmet, other)
Mouth Guard (yes/no)
Pads (yes/no and type; shoulder,
hip, leg, other)
Wearing sunscreen
Wearing bug repellent
Other Information
630
-------
E.4 General Field Information
TCRS Exposure Characterization Study General Field Information/Observations
Use this form to record observations that may be relevant to the research study.
Examples include, but are not limited to, condition of field, field maintenance, construction on/nearfield,
adjacent high traffic on roads or parking areas, ventilation information for indoorfields, other relevant information.
Use a different row for each type of observation.
Field ID Number
Date
631
-------
E.5 Field Sampling Locations
632
-------
E.6 Field Environment Information
Field Environment Record Form
Field ID Number
Sketch and label features within approx.. 100 m of field
Include roads, parking areas, other fields, buffers, buildings
or other natural and built features
Record approximate off-field sampling station location
633
-------
634
-------
Appendix F
Blood Metals and Serum Metals Analysis
Protocols
635
-------
Division of Laboratory Sciences
Laboratory Protocol
Analytes: Cadmium, Lead, Manganese, Mercury, and Selenium
Matrix: whole blood
Method: blood multi-element analysis by ICP-DRC-MS
Method code: DLS 3016.8-05
Branch: Inorganic and Radiation Analytical Toxicology
Prepared By: Deanria M. Jones, PhD
author's name signature date
author's name signature date
Supervisor: Jeffery M Jarrett, MS
supervisor's name signature date
Branch Chief: Robert L Jones, PhD
Branch Chief signature date
Date current version of method first used in lab:
Date
Director's Signature Block:
Re vi ewed:
Signature Date
-------
Procedure Change Log
Procedure: Blood multi-element analysis by ICP-DRC-MS
DLS Method Code: 3016.8-05
Date
Changes Made
By
Rev'd
By
(Initials
)
Date
Rev'd
4/1/2011
1UB and 2UB for Mn changed from 15 to 25
ug/L and from 30 to 50 ug/L, respectively.
JHJ8
JHJ8
4/1/2011
4/1/2011
Limit Rep Delta for Mn changed from 1.0 to
2.0.
JHJ8
JHJ8
4/1/2011
7/28/2011
Clarified matrix of internal standard
intermediate from "dilute HN03" to "1% v/v
HNOs".
JHJ8
JHJ8
7/28/2011
8/9/2011
Changed BMN 1 UB (25 ug/L to 20 ug/L) and
2UB (50ug/L to 35 ug/L). Supporting
references added.
JHJ8
JHJ8
8/9/2011
10/7/2011
Added comment to CV standard tables
regarding use of gravimetric preparation.
JHJ8
JHJ8
10/7/2011
3/20/2012
Sample Diluent Preparation: Triton X-100
percentage correction (typo)
napl
JHJ8
3/20/2012
3/20/2012
DRC Stability Test Preparation: alternate
preparation procedure using the intermediate
working calibrators
napl
JHJ8
3/20/2012
3/20/2012
Preparation of Samples for Analysis: changed
the Blood Blank name from "BldBlkChk" to
"WB Blank" and WB Blank2"
napl
JHJ8
3/20/2012
3/20/2012
Contaminated Blanks: added clarification on
procedure to follow in the event of
contaminated blanks
napl
JHJ8
3/20/2012
3/20/2012
Linear Calibration Curves: clarification on
dropping points
napl
JHJ8
3/20/2012
3/20/2012
Appendix B, Table 1:
Added description for method file names
Method Parameters: updated sample flush
times and sample wash times
Autosampler Locations: Aq Blank location
napl
JHJ8
3/20/2012
3/20/2012
Appendix B, Table 3:
Clarification of stock standard preparation
napl
JHJ8
3/20/2012
3/20/2012
Appendix B, Table 10:
Typical sample/batch window: changed
autosampler location to reflect current
positions
napl
JHJ8
3/20/2012
3/20/2012
Updated screenshots in Appendix B, Figures
1 e, 1 f, and 2d
napl
JHJ8
3/20/2012
3/20/2012
Created Appendix C for "help sheets"
napl
JHJ8
3/20/2012
-------
3/20/2012
Method Procedures:
Types of Quality Control: Removed reference
to blind QC
napl
JHJ8
3/20/2012
5/03/2012
Sample Diluent Preparation: Changed
concentration of TMAH from 0.25% to 0.4%
napl
JHJ8
5/03/2012
5/10/2012
Added Appendix A, Experiment 6: Validated
extra dilutions up to 20x. Updated Reportable
Range and Table 6 (descriptions of sample
preparation).
EMU2
JHJ8
5/10/2012
9/10/2012
Sample Rinse Preparation: Changed
concentration of TMAH from 0.25% to 0.4%
napl
JHJ8
9/10/2012
1/22/2013
Extended calibration range S0-S8 adding a
third bench QC level. Changed to weighted
linear regression and dual detector mode.
JHJ8
KLC7
1/22/2013
1/22/2013
Clarified and updated handling elevated
concentrations, Tables 8-11, Sections 7 -
11 and references. Added Figures 1 and 4.
JHJ8
KLC7
1/22/2013
1/22/2013
Added description of solutions for DRC and
dual detector optimizations.
JHJ8
KLC7
1/22/2013
1/22/2013
Updated reference range Tables
JHJ8
KLC7
1/22/2013
1/22/2013
Added detail of potential M0O2 interference
on 130Te
JHJ8
KLC7
1/22/2013
1/22/2013
Updated action levels
JHJ8
KLC7
1/22/2013
3/20/2013
Updated evaluating calibration curves
language
napl
JHJ8
3/20/2013
4/16/2013
Updated help sheets re: calibration std prep
napl
JHJ8
4/16/2013
5/15/2013
Replaced references to urine with references
to blood in Table of Figures, Section 7.c.ii,
and Section 12. Updated reference from
"Section 10a" to "Section 11a" in Section 10a.
References to Tables 5, 10, and 11 updated.
JHJ8
Klc7
5/20/2013
9/15/2014
Clarified method details (esp. references to
urine methods and solutions preparations).
Bldblkchk to be made with SO instead of
water.
JHJ8
Klc7
9/15/2014
12/08/2015
Changed method name from Blood Metals
Panel 3 (BMP3) by ICP-DRC-MS to Blood
multi-element analysis by ICP-DRC-MS
JJ
KLC
12/9/2015
12/08/2015
Updated Title page to new DLS template
JJ
KLC
12/9/2015
12/08/2015
Updated Section 3 to specify not to freeze
blood in blood collection tubes (esp. glass)
JJ
KLC
12/9/2015
12/08/2015
Clarified comments, updated examples,
corrected typos: Increased use of active
voice (eliminated 'may' and 'shall'). Clarified
comments in Tables 8 and 9. Renamed
second "Figure 2g" to "Figure 2h". Correct
table references in Section 10.
JJ
KLC
12/9/2015
-------
12/08/2015
Minor equipment updates: References to
Digiflex pipette changed to Hamilton Microlab
625 benchtop automatic pipette and updated
Table 8 volumes. Updated regulator part
numbers for methane and oxygen
compressed gases.
JJ
KLC
12/9/2015
12/08/2015
Updated instructions related to very elevated
results. Set criteria to confirm proper washout
after an elevated sample to ± 3SD limits of
low bench QC wash check (Section 8.b.iv).
Set criteria to confirm samples potentially
affected by insufficient washout to ±10% or
±3SD of the low bench QC, whichever is
greater (Section 8.b.vii.2.a). Updated
extended wash details in Table 1. Added
highest validated washout concentrations to
Table 9. Updated Figure 4 (Flow Chart for
handling an elevated result).
JJ
KLC
12/9/2015
12/08/2015
Added 2011-2012 NHANES reference level
data to Table 10 and replaced statement
about blood lead >10 |jg/dL with statement
about 5 (jg/dL reference level.
JJ
KLC
12/9/2015
12/08/2015
Updated record retention in section Section
9.c to match DLS policy (3 years to 2 years).
JJ
KLC
12/9/2015
03/02/2016
Left justified text. Updated references.
Removed "(esp. glass)" regarding do not
freeze blood in blood tubes. Referenced
highest calibrator and max extra dilution
tables in reportable range section. Updated
description of disinfectant. Changed "working
calibration standard" to "working calibrator"
throughout. Updated references to high purity
water.
JJ
RLJ
03/02/2016
-------
Laboratory Procedure Manual
Analytes: Cadmium, Lead, Manganese,
Mercury, and Selenium
Matrix: Whole Blood
Method: blood multi-element analysis by ICP-DRC-MS
Method No: DLS 3016.8-05
As performed by: Inorganic and Radiation Analytical Toxicology Branch
Division of Laboratory Sciences
National Center for Environmental Health
Contact: Jeffery M. Jarrett, MS
Phone: 770-488-7906
Fax: 770-488-4097
Email: JJarrett@cdc.gov
James L. Pirkle, M.D., Ph.D.
Director, Division of Laboratory Sciences
Important Information for Users
The Centers for Disease Control and Prevention (CDC) periodically refines these
laboratory methods. It is the responsibility of the user to contact the person listed on the
title page of each write-up before using the analytical method to find out whether any
changes have been made and what revisions, if any, have been incorporated.
Environmental Health
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 1 of 94
Table of Contents
Cross reference to DLS CLIA and Policy and Procedures 3
Index of tables 4
Index of figures 5
1) Clinical relevance & summary of test principle
a. Clinical relevance 6
b. Test principle 10
2) Limitations of method; interfering substances and conditions
a. Interferences addressed by this method 12
b. Limitations of method (interferences remaining in method) 13
3) Procedures for collecting, storing, and handling specimens; criteria for
specimen rejection
a. Procedures for collecting, storing, and handling specimens 13
b. Criteria for specimen rejection 14
c. Transfer or referral of specimens; procedures for specimen accountability
and tracking 14
4) Safety precautions
a. General safety 14
b. Waste disposal 15
5) Instrument & material sources
a. Sources for ICP-MS instrumentation 16
b. Sources for ICP-MS parts and consumables 16
c. Sources for ICP-MS maintenance equipment and supplies 22
d. Sources for general laboratory equipment and consumables 23
e. Sources for chemicals, gases, and regulators 24
6) Preparation of reagents and materials
a. Internal standard intermediate mixture 26
b. Intermediate Triton X-100 solution 27
c. Sample diluent and carrier 27
d. ICP-MS rinse solution 28
e. Standards, calibrators, base blood and QC 29
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 2 of 94
f. Optimization solutions 34
7) Analytical instrumentation setup
a. Instrumentation and equipment setup 36
b. Instrument and method parameters (see Table 1) 38
8) The run: quality, execution, evaluation, and reporting
a. Bench QC, reference materials and calibration verification 38
b. Perform, evaluate and report a run 39
9) Routine equipment maintenance and data backups
a. Equipment maintenance 47
b. Parameter optimizations 47
c. Data backup 47
10) Reporting thresholds
a. Reportable range 48
b. Reference ranges (normal values) 48
c. Action levels 48
11) Method calculations
a. Method limit of detection (LOD) 48
b. Method limit of quantitation (LOQ) 48
c. QC limits 48
12) Alternate methods for performing test and storing
specimens if test system fails 49
Appendix A (ruggedness test results) 50
Appendix B (tables and figures) 58
Appendix C (help sheets) 86
References 90
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IRAT-DLS Method Code: 3016.8-05 Page 3 of 94
Cross reference to DLS CLIA and Policy and Procedures policy
1. Summary of Test Principle and Clinical Relevance
1) a. b.
2. Safety Precautions
4) a.b.c.
3. Computerization; Data System Management
8) b.vi vii ix
4. Specimen Collection, Storage, and Handling Procedures; Criteria for Specimen
Rejection
3) a.b.
5. Procedures for Microscopic Examinations; Criteria for Rejection of Inadequately
Prepared Slides
- As no microscope is used in this process there are no procedures for
microscopic examinations and therefore no slide rejection criteria.
6. Preparation of Reagents, Calibrators (Standards), Controls, and All Other
Materials; Equipment and Instrumentation
5) a. i ii iii b. 6) a. b. c. d. e. 7) a. b. c. d. 8) c. i ii
7. Calibration and Calibration Verification Procedures
8) ii
8. Procedure Operating Instructions; Calculations; Interpretation of Results
8) b. i ii iv v x
9. Reportable Range of Results
9) a.
10. Quality Control (QC) Procedures
8) a. i
11. Remedial Action If Calibration or QC Systems Fail to Meet Acceptable Criteria
8) ii 1, ii 2, e.
12. Limitations of Method; Interfering Substances and Conditions
2) a. b
13. Reference Ranges (Normal Values)
9) b.
14. Critical Call Results ("Panic Values")
9) c.
15. Specimen Storage and Handling During Testing
8) b. iii
16. Alternate Methods for Performing Test or Storing Specimens If Test System Fails
11)
17. Test Result Reporting System; Protocol for Reporting Critical Calls (If Applicable)
9) c.
18. Transfer or Referral of Specimens; Procedures for Specimen Accountability and
Tracking
3) c.
19. References
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 4 of 94
Index of tables
Table 1. Instrument and method parameters 58
Potential Emergency Response Modifications 61
Table 2. Suggested analyte concentrations for base blood 62
Table 3. Stock standard concentrations 62
Table 4. Preparation of intermediate stock standard 63
Table 5. Preparation of intermediate working standards 63
Table 6. Acceptable ways to perform two consecutive analytical runs, bracketing
with bench quality control samples 64
Table 7. A typical SAMPLE/BATCH window 65
Table 8. Preparation of samples, working calibrators, and QC materials for
analysis 66
Table 9. Boundary concentrations (1UB, 2UB, and Lim Rep Delta) 67
Table 10. Reference ranges for blood concentrations (from the Fourth National
Report on Exposure to Environmental Chemicals) 68
Table 11. References concentrations from published literature for
blood manganese and blood selenium 68
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 5 of 94
Index of figures
Figure 1. Configuration of tubing and devices for liquid handling
a. ESI SC4DX-FAST autosampler 69
Figure 2. ICP-MS method screen shots (3016, 5 elements)
a. Timing page 70
b. Processing page 71
c. Equations page 72
d. Calibration page 73
e. Sampling page (AqBlank method) 74
f. Sampling page (BldBlank method) 75
g. Report page 76
h. QC / sample page 77
Figure 3. ESI SC4 FAST autosampler screen shots
a. Main page 78
b. 5x12 rack setup 79
c. 50m L tube rack setup 80
d. Rinse station rack setup 81
e. Configure autosampler page 82
f. Communication page 83
g. FAST method control page 84
Figure 4. Flow Chart for handling an elevated result 85
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 6 of 94
1. Clinical relevance & summary of test principle
a. Clinical relevance:
Metals ions affect human health in various ways. Some metals (i.e. lead,
cadmium, and mercury) show only deleterious effects on human health. Some
(i.e. selenium and manganese) play an essential role in the human biological
system if within certain concentration ranges, while negative health implications
are observed when concentrations in biological systems are in deficit or excess.
Determination of a person's level of environmental exposure to chemicals
through direct measurement of the substances or their metabolites in human
specimens such as blood is called biomonitoring. Biomonitoring reduces the
uncertainty of determining levels of exposure over making these determinations
through calculations of estimated dose based on analysis of environmental
samples and assumptions about exposure pathways[1], Biomonitoring
measurements are the most health-relevant assessments of exposure because
they indicate the amount of the chemical that actually gets into people from all
environmental sources (e.g., air, soil, water, dust, or food) combined, rather than
the amount that gets into them. The laboratory method described here is a multi-
element technique for monitoring the concentrations of cadmium (Cd), lead (Pb),
manganese (Mn), mercury (Hg), and selenium (Se) in whole human blood for the
purpose of biomonitoring.
There is no known biological role of mercury in the human body. The main
sources of mercury intake in humans are fish, dental amalgams, and
occupational exposures[2]. The main organs affected by mercury are the brain
and the kidneys. Exposure of childbearing-aged women is of particular concern
because of the potential adverse neurologic effects of Hg in fetuses. The health
effects of mercury are diverse and depend on the form of mercury encountered
and the severity and length of exposure. The general population is be exposed
to three forms of mercury: elemental, inorganic, and organic (predominantly
methyl). However, this method tests only for the total amount of mercury in the
blood without regard to chemical form. In the general population, total blood
mercury is due mostly to the dietary intake of organic forms which are formed
through microbial action from inorganic mercury that has deposited in aquatic
environments and bioaccumulated through the food chain (especially into large
predatory fish)[3]. Exposure to inorganic or elemental mercury (e.g. dental
amalgams or occupational exposures) is particularly reflected in urine excretion
rather than blood. Psychic and emotional disturbances are the initial signs of
chronic intoxication by elemental mercury vapors or salts. Those exposed are at
increased risk for parasthesia, neuralgias, renal disease, digestive disturbances,
and ocular lesions [4], Massive exposure over a longer period of time results in
violent muscular spasms, hallucinations, delirium, and death[5]. Except for
methylmercury exposures, blood is considered useful if samples are taken within
a few days of exposure. This is because most forms of mercury in the blood
decrease by one-half every three days if exposure has been stopped. Thus,
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 7 of 94
mercury levels in the blood provide more useful information after recent
exposures than after long-term exposures. Several months after an exposure,
mercury levels in the blood and urine are much lower. Blood mercury reference
ranges for the U.S. population are listed in Table 10 in Appendix B.
There is no known biological role of lead in the human body. Lead, a naturally
occurring metal, has had many different commercial uses from which a person
can be exposed either in the occupational / manufacturing process or by the
manufactured products such as paint (paint chips, or dust and soil contaminated
from deteriorating paint), solder or pipes (only now in older homes), gasoline
(now outlawed for all but specialized applications), glazes on pottery, hobby uses
(e.g. stained glass), commercial products (e.g. batteries, lead-containing jewelry),
home remedy medicines containing lead compounds and non-Western
cosmetics. Soil contains lead naturally, or from man-made uses of lead such as
paint (near older homes), gasoline (near roadways), mining, manufacturing, and
disposal. The main target for lead toxicity is the nervous system, both in adults
and children. The developing biological systems of children are most sensitive to
the effects of Pb, where effects are being recognized even at blood lead levels
<5 ng/dL [6-10], Acute, elevated lead exposure is associated with anorexia,
dyspepsia, and constipation followed by diffuse paroxysmal abdominal pain.
When lead exposure is high, particularly in children, the person is at increased
risk for encephalopathy [11 ]. The alkyl lead species are highly toxic to the central
nervous system[12], The primary screening method for lead exposure is blood
lead, which primarily reflects recent exposures (excretory half-life in blood is
approximately 30 days)[13]. Lead in blood is primarily (99%) in the red blood
cells. Blood lead reference ranges for the U.S. population are listed in Table 10
in Appendix B. The CDC now uses a reference level of 5 pg/dL to identify
children with blood lead levels that are much higher than most children's levels.
This new level is based on the U.S. population of children ages 1 -5 years who
are in the highest 2.5% of children when tested for lead in their blood. This
reference value is based on the 97.5th percentile of the National Health and
Nutrition Examination Survey (NHANES)'s blood lead distribution in children.
CDC will update the reference value every four years using the two most recent
NHANES surveys [14],
There is no known biological role of cadmium in the human body. The
predominant commercial use of cadmium is in battery manufacturing. Other uses
include pigment production, coatings and plating, plastic stabilizers, and
nonferrous alloys. Since 2001, U.S. cadmium use has declined in response to
environmental concerns. In the United States, for nonsmokers the primary
source of cadmium exposure is from the food supply. People who regularly
consume shellfish and organ meats will have higher exposures. In general, leafy
vegetables such as lettuce and spinach, potatoes and grains, peanuts,
soybeans, and sunflower seeds contain high levels of cadmium due to
bioaccumulation from the soil. Tobacco leaves accumulate high levels of
cadmium from the soil, and smoking is the primary non-occupational source of
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 8 of 94
cadmium exposure for smokers. Generally, the critical organ for Cd is the
kidney. Kidney dysfunction is one of the most characteristic signs of exposure to
Cd. Workers in an environment with high exposure levels have developed
proteinuria, renal glucosuria, aminoaciduria, hypercalciuria, phosphaturia, and
polyuria. Chronic obstructive lung disease of varying degrees of severities is
frequently seen in Cd workers. Concentration of cadmium in blood of healthy
unexposed adults are in the range 0.1-4 ng/L[15]. Newborn babies are
practically free of Cd[16], Exposure to high concentration of fumes appearing
from heated cadmium metal or compounds has led to acute poisoning and in
some cases to the death of workers[11 ]. Principal symptoms reported were
respiratory distress due to chemical pneumonitis and edema. It has been
estimated that 8 hrs. exposure to 5 g Cd/m3 will be lethal[11], Ingestion of high
amounts of Cd puts a person at increased risk to a rapid onset with severe
nausea, vomiting, and abdominal pain. Cadmium levels in blood, urine, feces,
liver, kidney, hair, and other tissues have been used as biological indicators of
exposure to cadmium. Blood cadmium levels are principally indicative of recent
exposure(s) to cadmium rather than whole-body burdens [17-20], Urine
cadmium levels primarily reflect total body burden of cadmium, although urine
levels do respond somewhat to recent exposure[21]. Blood cadmium reference
ranges for the U.S. population are listed in Table 10 in Appendix B.
Manganese (Mn) is a trace element essential to humans and is associated with
the formation of connective and bony tissue, growth and reproductive functions
and with carbohydrate and lipid metabolism [22], Manganese is also a known
neurotoxin but little information exists about levels of manganese that cause
toxicity. Symptoms of manganese toxicity are similar to Parkinson's Disease and
can also include disorientation, memory impairment, anxiety and compulsive
behavior [23], There is much concern for the levels of manganese in humans
whom are occupationally exposed to it [24-30], Recently, there are growing
concerns over exposure due to contamination of drinking water with manganese
[31-33] and as a result of methylcyclopentadienyl mangangese tricarbonyl (MMT)
used as an anti-knocking additive in gasoline [34-40], Populations suffering from
iron deficiencies are at an increased risk to manganese toxicity because iron
deficiency can result in an accumulation of manganese in the central nervous
system [37], To fully understand the essentiality and toxicity of manganese,
further investigations are needed regarding the levels of manganese in biological
matrices. Group average levels in blood appear to be related to manganese body
burden, while average urinary excretion levels appear to be most indicative of
recent exposures [41], On an individual basis the correlation between the level
of workplace exposure and the levels in blood or urine has always been found to
be a reliable predictor of exposure [25, 41-43], Manganese in blood or urine are
useful in detecting groups with above-average current exposure, but
measurements of manganese in these body fluids in individuals are sometimes
be related to exposure dose after the exposure has ceased. In addition to
individual variability, another factor that limits the usefulness of measuring
manganese in blood, urine, or feces as a measure of excess manganese
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 9 of 94
exposure is the relatively rapid rate of manganese clearance from the body.
Excess manganese in blood is rapidly removed by the liver and excreted into the
bile, with very little excretion in urine [44, 45], Thus, levels of manganese in blood
or urine are not expected to be the most sensitive indicators of exposure [46],
Typical blood manganese concentrations in humans which have been reported in
the literature are listed in Table 11 of Appendix B.
Selenium is an essential element that is required to maintain good health but
both selenium deficiency and excessive levels of selenium are associated with
several disorders[47, 48], Selenium is a naturally occurring mineral element that
is distributed widely in nature in most rocks and soils. Most processed selenium
is used in the electronics industry, but it is also used: as a nutritional supplement;
in the glass industry; as a component of pigments in plastics, paints, enamels,
inks, and rubber; in the preparation of pharmaceuticals; as a nutritional feed
additive for poultry and livestock; in pesticide formulations; in rubber production;
as an ingredient in antidandruff shampoos; and as a constituent of fungicides.
Radioactive selenium is used in diagnostic medicine. In the body, selenium is
incorporated into proteins to make selenoproteins, which are important
antioxidant enzymes. The antioxidant properties of selenoproteins help prevent
cellular damage from free radicals. Free radicals are natural by-products of
oxygen metabolism that increase risk of chronic diseases such as cancer and
heart disease[48, 49], Other selenoproteins help regulate thyroid function and
play a role in the immune system [50-53], Human selenium deficiency is rare in
the U.S. but is seen in other countries where soil concentration of selenium is
low[54]. There is evidence that selenium deficiency increases the risk of a form of
heart disease, hypothyroidism, and a weakened immune system[55, 56], There is
also evidence that selenium deficiency does not usually cause illness by itself.
Rather, it can make the body more susceptible to illnesses caused by other
nutritional, biochemical or infectious stresses[57]. Symptoms of very high
exposure to selenium, a condition called selenosis, include gastrointestinal
upsets, hair loss, white blotchy nails, garlic breath odor, fatigue, irritability, and
mild nerve damage[47]. Selenium can be detected in the blood, feces, urine,
hair, and nails of exposed individuals, however, field studies have used primarily
blood or urine levels to indicate the degree of selenium exposure[47]. Typical
blood selenium concentrations in humans which have been reported in the
literature are listed in Table 11 of Appendix B.
The laboratory method presented here can be used to achieve rapid and
accurate quantification of five elements of toxicological and nutritional interest
including cadmium (Cd), lead (Pb), mercury (Hg), manganese (Mn) and selenium
(Se) in whole human blood. Use this method to screen blood when people are
suspected to be acutely exposed to these elements or to evaluate chronic
environmental or other non-occupational exposure.
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IRAT-DLS Method Code: 3016.8-05 Page 10 of 94
b. Test principle:
This method directly measures the Cd, Mn, Hg, Pb, and Se content of whole
blood specimens using mass spectrometry after a simple dilution sample
preparation step.
During the sample dilution step, a small volume of whole blood is extracted from
a larger whole blood patient specimen after the entire specimen is mixed
(vortexed) to create a uniform distribution of cellular components. This mixing
step is important because some metals (e.g. Pb) are known to be associated
mostly with the red blood cells in the specimen and a uniform distribution of this
cellular material must be produced before a small volume extracted from the
larger specimen will accurately reflect the average metal concentration of all
fractions of the larger specimen. Coagulation is the process in which blood forms
solid clots from its cellular components. If steps are not taken to prevent this
process from occurring, i.e. addition of anti-coagulant reagents such as EDTA in
the blood collection tube prior to blood collection, blood will immediately begin to
form clots once leaving the body and entering the tube. These clots prevent the
uniform distribution of cellular material in the blood specimen even after rigorous
mixing, making a representative sub-sample of the larger specimen unattainable.
It is important that prior to or during sample preparation the analyst identify any
sample having clots or micro-clots (small clots). Clotted samples are not
analyzed by this method due to the inhomogeneity concerns (i.e. all results for
the sample are processed as "not reportable").
Dilution of the blood in the sample preparation step prior to analysis is a simple
dilution of 1 part sample + 1 part water + 48 parts diluent. The effects of the
chemicals in the diluent are to release metals bound to red blood cells making
them available for ionization, reduce ionization suppression by the biological
matrix, prevent clogging of the sample introduction system pathways by
undissolved biological solids, and allow introduction of internal standards to be
utilized in the analysis step. Tetramethylammonium hydroxide (TMAH, 0.4% v/v)
and Triton X-100® (0.05%) in the sample diluent solubilizes blood components.
Triton X-100® also helps prevent biological deposits on internal surfaces of the
instrument's sample introduction system and reduce collection of air bubbles in
sample transport tubing. Ammonium pyrrolidine dithiocarbamate (APDC) in the
sample diluent (0.01%) aids in solubilizing metals released from the biological
matrix. Ethyl alcohol in the sample diluent (1 %) aids solubility of blood
components and aids in aerosol generation by reduction of the surface tension of
the solution. The internal standards, rhodium, iridium, and tellurium, are at a
constant concentration in all blanks, calibrators, QC, and samples. Monitoring
the instrument signal ratio of a metal to its internal standard allows correction for
instrument noise and drift, and sample-to-sample matrix differences.
Liquid samples are introduced into the mass spectrometer through the inductively
coupled plasma (ICP) ionization source. The liquid diluted blood sample is
forced through a nebulizer which converts the bulk liquid into small droplets in an
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 11 of 94
argon aerosol. The smaller droplets from the aerosol are selectively passed
through the spray chamber by a flowing argon stream into the ICP. By coupling
radio-frequency power into flowing argon, plasma is created in which the
predominant species are positive argon ions and electrons and has a
temperature of 6000-8000 K. The small aerosol droplets pass through a region
of the plasma and the thermal energy vaporizes the liquid droplets, atomizes the
molecules of the sample and then ionizes the atoms. The ions, along with the
argon, enter the mass spectrometer through an interface that separates the ICP
(at atmospheric pressure, ~760 torr) from the mass spectrometer (operating at a
pressure of 10-5 torr). The ions first pass through a focusing region, then the
dynamic reaction cell (DRC), the quadrupole mass filter, and finally are
selectively counted in rapid sequence at the detector allowing individual isotopes
of an element to be determined.
Generally, the DRC operates in one of two modes. In 'vented' (or 'standard')
mode the cell is not pressurized and ions pass through the cell to the quadrupole
mass filter unaffected. In 'DRC' mode, the cell is pressurized with a gas for the
purpose of causing collisions and/or reactions between the fill gas and the
incoming ions. In general, collisions or reactions with the incoming ions
selectively occur to either eliminate an interfering ion, change the ion of interest
to a new mass, which is free from interference, or collisions between ions in the
beam and the DRC gas can focus the ion beam to the middle of the cell and
increase the ion signal. In this method, the instrument is operated in DRC mode
when analyzing for manganese, mercury, and selenium. For selenium, the DRC
is pressurized with methane gas (ChM, 99.999%) which reduces the signal from
40Ar2+ while allowing the 80Se+ ions to pass relatively unaffected through the DRC
on toward the analytical quadrupole and detector. Manganese and mercury are
both measured when the DRC is pressurized with oxygen gas (O2, 99.999%).
They are analyzed at the same flow rate of oxygen to the DRC cell to avoid
lengthening analysis time due to pause delays that would be necessary if
different gas flows were used for the two analytes. The oxygen reduces the ion
signal from several interfering ions (37CI180+, 40Ar15N+, 38Ar1601H+, 54Fe1H+) while
allowing the Mn+ ion stream to pass relatively unaffected through the DRC on
toward the analytical quadrupole and detector. In the case of mercury, collisional
focusing of the mercury ions occurs, increasing the observed mercury signal at
the detector by approximately a factor of two (2x).
Once ions pass through the DRC cell and electrically selected for passage
through the analytical quadrupole, electrical signals resulting from the ions
striking the discrete dynode detector are processed into digital information that is
used to indicate the intensity of the ions. The intensity of ions detected while
aspirating an unknown sample is correlated to an elemental concentration
through comparison of the analyte: internal standard signal ratio with that
obtained when aspirating calibration standards. This method was originally
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 12 of 94
based on the method by Lutz et al [58], The DRC portions of the method are
based on work published by Tanner et al. [59, 60],
2) Limitations of Method; Interfering Substances and Conditions
a. Interferences addressed by this method
i. Reduction of argon dimer (40Ar2+) interference on selenium (80Se+) using ICP-
DRC-MS: 40Ar2+ is a polyatomic ion formed in the plasma as a result of a
reaction between the plasma gas (Ar) and itself. The dynamic reaction cell of
the ICP-MS is used to reduce ion signals from polyatomic ions via ion-
molecule reaction chemistry [60, 61], In the reaction cell, methane (ChM)
molecules react with 40Ar2+ ions through a charge transfer reaction. The
products of the reaction are 40Ar+ (ion at a different mass) and 40Ar (neutral).
The background ion signal at m/z 80 is reduced by six orders of magnitude
because of this reaction.
ii. Reduction of argon nitride (40Ar15N+), argon hydroxide (38Ar16Q1H+)
interference on manganese (55Mn) using ICP-DRC-MS: 40Ar15N+ and
38Ar1601H+ are polyatomic ions formed in the plasma as a result of reactions
between the plasma gas (Ar) and atmospheric gases (N2, O2) or the solvent
(H2O). The dynamic reaction cell of the ICP-MS is used to reduce ion signals
from polyatomic ions via ion-molecule reaction chemistry [60, 61], In the
reaction cell, oxygen molecules react with 40Ar15N+ and 38Ar1601H+ ions
through either charge transfer reactions or oxygen transfer reactions. The
products of the reactions are either neutral molecules and are not detected
(charge transfer), or a new ion with higher mass (oxygen transfer). In either
case, attenuation of the background ion signal at m/z 55 occurs.
iii. Reduction of37CI18Q+, 39K16Q+, 54Fe1H+ interferences on manganese (55Mn)
using ICP-DRC-MS: 37CI180+, 39K160+, 54Fe1H+ are polyatomic ions created in
the plasma as a result of reactions between elements present in the blood
matrix (CI, K, and Fe) and the solvent (H2O). Due to the high concentrations of
CI, K, and Fe in the blood matrix the resulting ion signals of 37CI180+, 39K160+,
and 54Fe1H+interfere with the measurement of 55Mn+ at m/z 55. The dynamic
reaction cell of the ICP-MS is used to reduce ion signals from polyatomic ions
via ion-molecule reaction chemistry [60, 61], In the reaction cell, oxygen
molecules react with 37CI180+, 39K160+, 54Fe1H+ ions through either charge
transfer reactions or oxygen transfer reactions. The products of the reactions
are either neutral molecules and are not detected (charge transfer), or a new
ions with higher mass (oxygen transfer). In either case, attenuation of the
background ion signal at m/z 55 occurs.
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 13 of 94
b. Limitations of method (interferences remaining in method)
i. M0O2 interference on 130Te: Molybdenum will combine with oxygen in the DRC
conditions used in this method for Hg analysis to form a polyatomic ion,
98Mo1602+, which interferes with the measurement of the internal standard
i3°Ie+ increased signal at m/z 130 (due to measuring both 130Te+ and
98Mo1602+) results in an erroneously low net intensity for Hg (net intensity =
measured intensity for analyte isotope / measured intensity for internal
standard isotope). If this interference occurs during the measurement of the
calibration standards (i.e. a multi-element calibration stock standard includes
high levels of Mo) it can result in a positive bias for observed mercury
concentrations as a consequence of a nonlinear calibration curve having an
artificially low slope. If this interference occurs during the measurement of an
unknown sample, the reduced net intensity observed can result in reporting an
erroneously low Hg result. This interference has been verified to be of concern
(>5% effect negative bias) at blood molybdenum concentrations greater than
15 ug/L. However, typical levels of molybdenum in whole blood (0.2 - 4.6 ug/L
[62, 63]) are below this. Also, levels of molybdenum in whole blood after acute
exposures have been observed to be <15 ug/L [62], Molybdenum
concentrations below 5 ng/mL in stock calibration standard solutions do not
produce an observable interference.
3) Procedures for collecting, storing, and handling specimens; criteria for
specimen rejection; specimen accountability and tracking
a. Procedures for collecting, storing, and handling specimens: Specimen handling
conditions, special requirements, and procedures for collection and transport are
discussed in the Division of Laboratory Science's (DLS) Policies and Procedures
Manual [64], In general,
i. No fasting or special diets are required before collection of blood
ii. Specimen type - whole blood
iii. Optimal amount of specimen is 1+ mL. Request a minimum volume of 0.25
mL. Volume for one analytical measurement is 0.05 mL.
iv. Verify sample collection devices and containers are free of significant
contamination ("pre-screened") before use.
v. Draw the blood through a stainless steel needle into a pre-screened
vacutainer.
vi. Do not freeze blood in blood collection tubes due to risk the tubes cracking.
Transfer to plastic, pre-screened cryovials before freezing.
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IRAT-DLS Method Code: 3016.8-05 Page 14 of 94
vii. Once received, store blood collection tubes at refrigerated temperatures (2-8
°C). Transfer to plastic, pre-screened cryovials before freezing. Specimen
stability has been demonstrated for over 1 year at < -20 °C.
b. Criteria for specimen rejection: The criteria for an unacceptable specimen
include:
i. Contamination: Improper collection procedures, collection devices, or sample
handling can contaminate the blood through contact with dust, dirt, etc.
Manganese is present in the general environment, found often in combination
with iron, and is present in many alloys (especially stainless steel).
ii. Low Volume: Request a minimum volume of 0.25 ml_. Volume for one
analytical measurement is 0.05 ml_.
In all cases, request a second blood specimen.
c. Transfer or referral of specimens: procedures for specimen accountability and
tracking: Location, status, and final disposition of the specimens will be tracked
at least by paper document in the "Study Folder" (created before analysts receive
the samples). Apart from this specimen tracking form, this folder will also contain
the paper print outs of results from analysis of the specimens. Maintain records
for a minimum of 3 years. Use only numerical identifiers for samples within the
laboratory (e.g., case ID numbers) in order to safeguard confidentiality. Access
to personal identifiers for samples will be limited to the medical supervisor or
project coordinator (e.g. non-CDC personnel).
4) Safety precautions
a. General safety
i. Observe all safety regulations as detailed in the Laboratory Safety Manual and
the Chemical Hygiene Plan. Participate in training regarding blood-borne
pathogens prior to performing this method.
ii. Observe Universal Precautions when working with blood.
iii. Wear appropriate gloves, lab coat, and safety glasses while handling all
solutions.
iv. Take special care when handling and dispensing bases and concentrated
acids. Use additional personal protective equipment which protects face, neck,
and front of body. If TMAH or concentrated hydrochloric acid comes in
contact with any part of the body, quickly wash with copious quantities
of water for at least 15 minutes.
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v. Use secondary containment for containers holding biological or corrosive
liquids.
vi. The use of the foot pedal on the benchtop automatic pipette is recommended
because it reduces analyst contact with work surfaces that have been in
contact with blood and also keeps the analyst's hands free to hold the
specimen cups and autosampler tubes and to wipe off the tip of benchtop
automatic pipette.
vii. There are many potential hazards on an operating ICP-MS instrument
including ultraviolet radiation, high voltages, radio-frequency radiation, and
high temperatures. This information is detailed in the ICP-MS System Safety
Manual.
viii. Transport and store compressed gas cylinders with proper securing
harnesses. For compressed oxygen gas, use regulators which are oil-free and
are equipped with a flash arrestor.
ix. Wipe down all work surfaces at the end of the day with disinfectant.
Disinfectant may be either daily remake of diluted bleach (1 part household
bleach containing 5.25% sodium hypochlorite + 9 parts water) or an equivalent
disinfectant
b. Waste disposal:
i. Autoclaving: All diluted biological specimens, original biological specimens
being disposed, or consumables which come into contact with biological
specimens (even diluted or aerosolized). Use sharps containers or special
autoclave pans for broken glass / quartz or items which puncture autoclave
bags (e.g. pipette tips).
ii. Other liquid waste
1. Waste discarded down sink: Only non-corrosive liquid waste (EPA defines
as pH >2 and pH<12.5, 40CFR §261.22) from the ICP-MS instrument can
be discarded at the sink. Flush the sink with copious amounts of water.
2. Waste to be picked up by CDC hazardous waste program: Submit request
for hazardous waste removal of all other liquid waste generated in the CDC
laboratory for this method.
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IRAT-DLS Method Code: 3016.8-05 Page 16 of 94
5) Instrument & material sources
a. Sources for ICP-MS instrumentation
i. ICP-MS: Inductively Coupled Plasma Mass Spectrometer with Dynamic
Reaction Cell Technology (ELAN® DRC II) (PerkinElmer Norwalk, CT,
www.perkinelmer.com).
ii. Recirculating chiller / heat exchanger for ICP-MS: Refrigerated chiller
(PolyScience 6105PE) or heat exchanger (PolyScience 3370) (PerkinElmer
Norwalk, CT, www.perkinelmer.com).
iii. Autosampler: ESI SC4-DX autosampler (Elemental Scientific Inc., Omaha, NE)
or equivalent.
iv. Computer: Computer controller provided or recommended by ICP-MS
manufacturer is recommended to ensure proper communication between
computer and ICP-MS. Recommend 1-2 Gb RAM and secondary internal hard
disk for nightly backups (if network backups are not possible).
v. FAST sample introduction system (optional): Standard peristaltic pump on
ICP-MS replaced by DXi-FAST micro-peristaltic pump / FAST actuator and
valve combination unit. Like part # DXI-54-P4-F6. If DXi-FAST upgrade on
ICP-MS is not used, a separate FAST actuator (built-in option on ESI SC4-DX
autosampler or stand-alone FAST actuator) will be necessary to complete the
FAST sample introduction system.
b. Sources for ICP-MS parts & consumables
NOTE: The minimum number of spares recommended before reordering (if
owning one instrument) are listed as "# Spares = X amount" in the descriptions
below.
i. Adapter, PEEK: Securely connects 1,6mm O.D. PFA tubing to 0.03" I.D.
peristaltic tubing. Composed of three PEEK parts.
1. Female nut for 1,6mm O.D. (1/16") tubing. Like part P-420 (Upchurch
Scientific, Oak Harbor, WA, www, u pch u rch. com).
2. PEEK ferrule. Like part P-260x (10pk SuperFlangeless ferrule, Upchurch
Scientific, Oak Harbor, WA, www, upchurch.com).
3. Conical Adapter Body. Like part P-692 (Upchurch Scientific, Oak Harbor,
WA, www, upchurch. com).
ii. Bottles (for rinse solution): Four liter screw-cap polypropylene container with
built-in luer connections (2) designed for use with FAST sample introduction
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IRAT-DLS Method Code: 3016.8-05 Page 17 of 94
system (like catalog# SC-0305-1, Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
iii. Carboy and cap assembly for waste collection: 10-15 L, polypropylene wide-
mouth carboy (100 mm neck size) with handles and no spigot (Like part #7BE-
25126, Lab Safety Supply, Janesville, Wl, www.lss.com) with cap assembly
like part# N0690271 (PerkinElmer, Norwalk, CT, www.perkinelmer.com) with
tubing connections built into the cap for addition of liquid waste.
iv. Coolant, for polvscience chiller or heat exchanger: Only PerkinElmer part #
WE01-6558 (PerkinElmer Norwalk, CT, www.perkinelmer.com) is approved for
use by PerkinElmer. # Spares = 6.
v. Cones: Platinum or Nickel cones have been used and tested to be
comparable in performance from either PerkinElmer or Spectron. Platinum
cones are more expensive, but will last longer, can be refurbished (often for
free by the manufacturer), and will frequently yield higher sensitivity.
1. Sampler (nickel/platinum): PerkinElmer part # WE021140 / WE027802
(PerkinElmer Norwalk, CT, www.perkinelmer.com). # Spares = 4.
2. Skimmer (nickel / platinum): PerkinElmer part # WE021137 / WE027803
(PerkinElmer Norwalk, CT, www.perkinelmer.com). # Spares = 4.
vi. Connector (for tubing): Use to connect 1/8" I.D. PVC tubing to 0.125" I.D
peristaltic pump tubing. Use part # 3140715 (PerkinElmer Norwalk, CT,
www.perkinelmer.com) or equivalent. # Spares = 4.
vii. Detector, electron multiplier: Like part# N8125001 (PerkinElmer Norwalk, CT,
www.perkinelmer.com). # Spares = 1.
viii. FAST accessories
1. Valve: CTFE High-flow valve head for SC-FAST (uses %-28 fittings). Like
part# SC-0599-1010 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
2. Stator: CTFE Stator for 6 port SC-FAST high flow valve (%-28 fittings).
Like part# SC-0599-1010-01 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
3. Rotor: Composite rotor for 6 port SC-FAST high flow valve (%-28 fittings).
Like part# SC-0599-1010-05 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
4. Sample Loop: 1 mL Teflon, white connector-nuts for high flow valve
head(%-28 fittings). Like part# SC-0315-10 (Elemental Scientific Inc.,
Omaha, NE., www.elementalscientific.com).
5. Probe, Autosampler: Teflon, carbon fiber support, 0.8mm i.d., blue marker,
1/4-28 fittings. Like part number SC-5037-3751 (Elemental Scientific Inc.,
Omaha, NE., www.elementalscientific.com). # Spares = 2.
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6. Probe, Carrier Solution: Teflon, carbon fiber support, 0.5mm i d., orange
marker, 1/4-28 fittings. Like part number SC-5037-3501 (Elemental
Scientific Inc., Omaha, NE., www.elementalscientific.com). # Spares = 2.
7. Tubing, FAST vacuum: Vacuum line for SC-FAST high flow valve,
connects to port #6, black nut for connection to valve head, natural brown
color nut on other end for connection to SC autosampler vacuum port. Like
part# SC-0321 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
8. Tubing, connects nebulizer to valve: See "Nebulizer, PolyPro-ST micro
flow"
ix. Hose, for connection to chiller: Push on hose. I.D. = O.D. = Use part
# PB-8 (per inch, Georgia Valve and Fitting, Atlanta, GA, www.swagelok.com)
or eguivalent. Do not normally need spare hose (unless moving instrument
into a new location).
x. Hose, for exhaust of ICP-MS: Available as part of ICP-MS installation kit from
Perkin Elmer (PerkinElmer Norwalk, CT, www.perkinelmer.com). Available
direct from manufacturer as part # S-LP-10 air connector (Thermaflex,
Abbeville, SC, www.thermaflex.net), or equivalent. # Spares = 10 feet of 4"
diameter and 10 feet of 6" diameter hose.
xi. Injector, guartz with ball joint: I.D. = 2.0 mm. PerkinElmer part # WE023948
(PerkinElmer Norwalk, CT, www.perkinelmer.com). Available direct from
manufacturer as part #400-30 (Precision Glass Blowing, Centennial, CO,
www.precisionglassblowing.com) or from various distributors. # Spares = 2.
xii. Ion lens: PerkinElmer part # WE018034 (PerkinElmer Norwalk, CT,
www.perkinelmer.com). # Spares = 3.
xiii. Nebulizer: PolyPro-ST micro flow polypropylene nebulizer with external 1/4-28
threaded connector for liquid delivery, low pressure version or equivalent. Like
part# ES-4040-7010 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com). # Spares = 1. Different nebulizers are
acceptable, however, the nebulizer gas flow rate, sample flush time, read delay
time, loop fill time, loop size, blood sample dilution preparation volume, and
sample-to-sample carry-over must be evaluated and optimized.
1. Gas connection:
a. Teflon tubing: 4mm o.d., 2.4mm i.d. Teflon tubing (like part # ES-
2502, Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com). # Spares = 1.
b. Adapter kit: Plastic adapters to connect Teflon tubing (2.4 mm i.d) to
%" male Swagelok (compression) port on ICP-DRC-MS. Parts can
be obtained as components in a "gas fittings kit for microflow
nebulizer", kit like part# ES-2501-1000 (Elemental Scientific Inc.,
Omaha, NE., www.elementalscientific.com). # Spares = 1.
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2. Liquid connection: Connects nebulizer to port #3 of high flow FAST valve
head with green, 1/4-28fitting. Like part# SC-0317-0250 (Elemental
Scientific Inc., Omaha, NE., www.elementalscientific.com). # Spares = 2.
xiv. Nut: (for flanged connections of 1.59mm (1/16") o.d. PFA tubing) Flanged, for
1/16" o.d. tubing, 1/4-28 threads. Use part # P-406x (pkg. of 10, Upchurch
Scientific, Oak Harbor, WA, www.upchurch.com) or equivalent. Use a Teflon-
coated Viton o-ring with this nut instead of the stainless steel washer that
comes with part # P-406xJ. # Spares = 10.
xv. Nut and ferrule set, 1/8" Swagelok: Such as part # SS-200-NFSET (stainless
steel) or part# B-200-NFSET (brass) (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. For part numbers listed here a quantity of
1 means 1 nut, 1 front ferrule, and 1 back ferrule. Spares = 20.
xvi. Nut and ferrule set, 1/4" Swagelok: Such as part # SS-400-NFSET (stainless
steel) or part# B-400-NFSET (brass) (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. For part numbers listed here a quantity of
1 means 1 nut, 1 front ferrule, and 1 back ferrule. Spares = 20.
xvii. Oil for roughing pumps:
1. Welch Directorr Gold: For roughing pumps. Available direct from
manufacturer as part # 8995G-15 (1 gallon, Welch Rietschle Thomas,
Skokie, IL, www.welchvacuum.com), or equivalent. # Spares = 4.
2. Fomblin Y14/5 fluid: PerkinElmer part # N8122265 (1 kg bottle,
PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent. # Spares
=1 per instrument.
xviii. O-ring: (for sampler cone) PerkinElmer part # N8120511 (pkg. of 5,
PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent. # Spares =
20 o-rings.
xix. O-ring: (for skimmer cone) PerkinElmer part# N8120512 (pkg. of 5,
PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent. # Spares =
20 o-rings.
xx. O-ring: (for flanged connections of 1.59mm (1/16") o.d. PFA tubing) Teflon-
coated Viton o-ring, i.d. = 1/16", thickness = 1/16", o.d. = 3/16". Such as part#
V75-003 (O-rings West, Seattle, WA, www.oringswest.com) or equivalent. #
Spares = 20.
xxi. O-ring: (for injector support).
1. Internal o-rings: ID = %", OD = 3/8", thickness = 1/16". Need 2 o-rings per
injector support setup. PerkinElmer part # N8122008 (PerkinElmer,
Shelton, CT, www.perkinelmer.com) or equivalent (such as part # V75-010,
O-rings West, Seattle, WA, www.oringswest.com). # Spares = 20.
2. External o-rings: ID = 3/8", OD = 1/2", thickness = 1/16". Need 2 o-rings
for each injector support setup. PerkinElmer part # N8122009
(PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent (such as
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IRAT-DLS Method Code: 3016.8-05 Page 20 of 94
part # V75-012, O-rings West, Seattle, WA, www.oringswest.com). #
Spares = 20.
xxii. 0-ring (for inside nebulizer port on standard PerkinElmer cyclonic quartz spray
chamber for the ELAN): Such as part# 120-56 (Precision Glass Blowing,
Centennial, CO, www.precisionglassblowing.com). Additional o-rings can
sometimes be obtained free of charge or at reduced price when acquired while
purchasing spray chambers. # Spares = 20.
xxiii. O-ring: (for inside of bayonet torch mount): Part # WE017284 (PerkinElmer,
Shelton, CT, www.perkinelmer.com). Do not substitute. The PerkinElmer o-
ring is specially metal impregnated to minimize RF leakage though the torch
mount. # Spares = 2.
xxiv. Photon stop: PerkinElmer part # WE018278 (PerkinElmer, Shelton, CT,
www.perkinelmer.com). # Spares = 1.
xxv. Plugs, guick change for roughing pump oil: These plugs will only work on the
Varian roughing pumps which come standard on ELAN DRC II ICPMS
instruments. These plugs will not fit the Leybold pumps which come standard
on the ELAN DRC Plus instruments. Part # W1011013 (PerkinElmer, Shelton,
CT, www.perkinelmer.com). No spares typically needed.
xxvi. Probes
1. for ESI autosampler: Teflon, carbon fiber support, 0.8 mm i.d., blue marker,
1/4-28 fittings. Like part number SC-5037-3751 (Elemental Scientific Inc.,
Omaha, NE., www.elementalscientific.com). # Spares = 2.
2. for carrier solution of FAST sample introduction system: Teflon, carbon
fiber support, 0.5mm i.d., orange marker, 1/4-28 fittings. Like part number
SC-5037-3501 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com). # Spares = 2.
xxvii. RF coil: PerkinElmer part # WE02-1816 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. # Spares = 2.
xxviii. Spray chamber, guartz concentric: PerkinElmer part # WE025221
(PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent. Available
direct from manufacturer as part # 400-20 (Precision Glass Blowing,
Centennial, CO, www.precisionglassblowing.com) or from various distributors.
# Spares = 2.
xxix. Torch, guartz: PerkinElmer part # N812-2006 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. # New Spares = 2.
xxx. Tubing and adapter, for SC autosampler rinse station drain: Tygon tubing and
adapter to attach to back of SC autosampler for draining rinse station waste
(like part# SC-0303-002, Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
xxxi. Tubing and adapters, for SC autosampler rinse station filling: Teflon tubing
and adapters (to attach to back of SC autosampler for filling rinse stations and
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IRAT-DLS Method Code: 3016.8-05 Page 21 of 94
to attach to rinse containers). Like part # SC-0302-0500, Elemental Scientific
Inc., Omaha, NE., www.elementalscientific.com).
xxxii. Tubing and nut, for FAST carrier solution: 0.5 mm i.d. Teflon tubing (orange
marker) with red %-28 male nut. Connects to high flow FAST valve head, port
#2. Like part # SC-0316-0500 (Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com).
xxxiii. Tubing, FAST vacuum: Vacuum line for SC-FAST high flow valve, connects to
port #6, black nut for connection to valve head, natural brown color nut on
other end for connection to SC autosampler vacuum port. Like part # SC-0321
(Elemental Scientific Inc., Omaha, NE., www.elementalscientific.com).
xxxiv. Tubing, main argon delivery to instrument: I.D. = 1/8", O.D. = %". Like part#
C-06500-02 (pkg. of 100ft, polypropylene, Fisher Scientific International,
Hampton, NH, www.fishersci.com) or equivalent. # Spares = 50 ft.
xxxv. Tubing, PFA: I.D. = 0.5 mm, O.D. = 1.59 mm (1/16"). Used to transfer
liquidbetween rinse solution jug and peristaltic pump tubing
The Perfluoroalkoxy (PFA) copolymer is a form of Teflon®. Like part # 1548
(20ft length, Upchurch Scientific, Oak Harbor, WA, www.upchurch.com) or
equivalent.# Spares = 20ft.
xxxvi. Tubing, peristaltic, 0.03" i.d. (carrier solution for ESI autosampler): use either
1. Standard PVC, 2-stop (black / black) peristaltic pump tubing, i.d. = 0.03".
PerkinElmer part # 09908587 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. # Spares = 6 packs of 12 tubes.
2. Standard PVC, 3-stop (black/ black/black) peristaltic pump tubing, i.d. 0.76
mm. Spectron part # SC0056 (Spectron, Ventura, CA,
www.spectronus.com) or equivalent. #Spares = 6 packs of 12 tubes. Use
this type of tubing with ESI DXi micro-peristaltic pump.
xxxvii. Tubing, peristaltic, 0.125" i.d. (spray chamber drain): use either
1. Standard PVC, 2-stop (black/ white) peristaltic pump tubing, i.d. = 0.125"
or equivalent. PerkinElmer part # N812-2012 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. # Spares = 6 packs of 12 tubes.
2. Standard Santoprene, 3-stop (grey/ grey/ grey) peristaltic pump tubing, i.d.
1.30 mm. Spectron part # SC0311 (Spectron, Ventura, CA,
www.spectronus.com) or equivalent. #Spares = 6 packs of 12 tubes. Use
this type of tubing with ESI DXi micro-peristaltic pump.
xxxviii. Tubing, PVC, i.d. = 1/8", o.d. = 3/16". Used to transfer liquid
1. between spray chamber waste port and peristaltic pump
2. between peristaltic pump and liquid waste jug
Like part # 14-169-7A (pkg. of 50 ft, Fisher Scientific International, Hampton,
NH, www.fishersci.com) or equivalent. # Spares = 20ft.
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xxxix. Tubing, Stainless Steel, o.d. = 1/8", wall thickness = 0.028": Used to connect
gas cylinders to NexlONUCT gas ports. Like part # SS-T2-S-028-20 (20ft,
Georgia Valve and Fitting, Atlanta, GA, www.swagelok.com) or equivalent.
Spares = 20 ft.
xl. Tubing, Teflon, corrugated, %" o.d.: Connects to the auxiliary and plasma gas
side-arms of the torch. Part # WE015903 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. # Spares = 2.
xli. Tubing, vinyl (argon delivery to nebulizer): Vinyl Tubing, 1/8" ID x 1/4" OD.
Like part# EW-06405-02 (Cole Parmer, Vernon Hills, Illinois,
www.coleparmer.com) or equivalent. # Spares = 10 ft.
xlii. Union elbow, PTFE %" Swagelok (ELAN bayonet mount): Connects argon
tubing to torch auxiliary gas sidearm on bayonet mount NEXION ICP-MS
instruments. Like part # T-400-9 (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. Spares = 2.
xliii. Union tee, PTFE, %" Swagelok (ELAN bayonet mount): Connects argon tubing
to torch plasma gas sidearm and holds igniter inside torch sidearm on bayonet
mount NEXION ICP-MS instruments. Like part # T-400-3 (Georgia Valve and
Fitting, Atlanta, GA, www.swagelok.com) or equivalent. Spares = 2.
c. \Sources for ICP-MS maintenance eguipment & supplies
i. Anemometer: Like digital wind-vane anemomefer (Model 840032, SPER
Scientific LTD., Scottsdale, AZ, www.sperscientific.com) or equivalent. Use to
verify adequate exhaust ventilation for ICP-MS (check with hoses fully
disconnected).
ii. Pan, for changing roughing pump oil: Like part # 53216 (United States Plastics
Corporation, Lima, OH, www.usplastic.com) or equivalent.
iii. Container, to hold acid baths for glassware: Polypropylene or polyethylene
containers with lids (must be large enough for torch, injector, or spray chamber
submersion). Available from laboratory or home kitchen supply companies.
iv. Cotton swabs: Any vendor. For cleaning of cones and glassware.
v. Cutter (for 1/8" o.d. metal tubing): Terry tool with 3 replacement wheels. Like
part # TT-1008 (Chrom Tech, Inc., Saint Paul, MN, www.chromtech.com) or
equivalent.
vi. Getter regeneration Kit: Part # WE023257 (PerkinElmer, Shelton, CT,
www.perkinelmer.com). Use this as needed (at least annually) to clean the
getter in the pathway of channel A DRC gas.
vii. Magnifying glass: Any 10x + pocket loupe for inspection of cones and other
ICP-MS parts. Plastic body is preferred for non-corrosion characteristics. Like
part # 5BC-42813 (Lab Safety Supply, Janesville, Wl, www.labsafetv.com).
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viii. Ultrasonic bath: Like ULTRAsonik™ Benchtop Cleaners (NEYTECH,
Bloomfield, CT, www.nevtech.com) or equivalent.
d. Sources for general laboratory equipment and consumables
i. Bar code scanner: Like Code Reader 2.0 (Code Corporation, Draper, UT,
www.codecorp.com) or equivalent. For scanning sample IDs during analysis
setup. Any bar code scanner capable of reading Code 128 encoding at a 3 mil
label density can be substituted.
ii. Carboy (for preparation of blood quality control pool and waste jug for ICPMS
sample introduction system): Polypropylene 10-L carboy (like catalog # 02-
960-20C, Fisher Scientific, Pittsburgh, PA, www.fischersci.com) or equivalent.
Carboys with spouts are not advised due to potential for leaking.
iii. Containers for diluent and rinse solution: Two liter Teflon™ containers (like
catalog# 02-923-30E, Fisher Scientific, Pittsburgh, PA., www.fishersci.com, or
equivalent) and 4L polypropylene jugs (like catalog# 02-960-1 OA, Fisher
Scientific, Pittsburgh, PA, www.fishersci.com, or equivalent) have both been
used. Acid rinse before use.
iv. Gloves: Powder-free, low particulate nitrile (like Best CleaN-DEX™ 100%
nitrile gloves, any vendor).
v. Paper towels: For general lab use, any low-lint paper wipes such as
KIMWIPES0EX-L Delicate Task Wipers or KAYDRY0EX-L Delicate Task
Wipers (Kimberly-Clark Professional, Atlanta, GA, www.kcprofessional.com).
For sensitive applications in cleanrooms, use a wipe designed for cleanrooms
such as the Econowipe or Wetwipe (Liberty, East Berlin, CT, www.libertv-
ind.com).
vi. Pipette, benchtop automatic (for preparation of blood dilutions to be analyzed):
Like the Microlab 625 advanced dual syringe diluter (Hamilton, Reno, NV,
http://www.hamilton.com/) equipped with a 5.0 mL left syringe, a 250 pL right
syringe, a 12 gauge Concorde CT probe dispense tip, the Microlab cable
management system and a foot pedal. Alternatives are acceptable, including
the Micromedic Digiflex™ (Titertek, Huntsville, AL, http://www.titertek.com/)
equipped with 10.0-mL dispensing syringe, 200 pL sampling syringe, 0.75-mm
tip, and foot pedal.
vii. Pipettes (for preparation of intermediate stock working standards & other
reagents): Like Brinkmann Research Pro Electronic pipettes (Brinkmann
Instruments, Inc., Westbury, NY, http://www.brinkmann.com/home/). 5-100 |j,L
(catalog #4860 000.070), 20-300 ^L (catalog #4860 000.089), 50-1000 ^L
(catalog #4860 000.097), 100-5000 |j,L (catalog #4860 000.100). Note: pipette
catalog numbers are without individual chargers. Can purchase individual
chargers (pipette catalog numbers will differ) or a charging stand that will hold
four pipettes (catalog #4860 000.860). When purchasing pipette tips (epTips),
purchase one or more boxes, then "reloads" for those boxes after that: 5-100
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|j,L (box catalog # 22 49 133-4, reload catalog # 22 49 153-9), 20-300 |j,L (box
catalog # 22 49 134-2, reload catalog # 22 49 154-7), 50-1000 |j,L (box catalog
# 22 49 135-1, reload catalog # 22 49 155-5), 100-5000 (box catalog # 22
49 138-5, reload catalog # 22 49 198-9, bulk bag catalog # 22 49 208-0).
Equivalent pipettes and tips can be substituted.
viii. Tubes for sample analysis (for autosampler): Like polypropylene 15-mL
conical tubes, BD Falcon model #352097 (Becton Dickinson Labware,
FranklinLakes, NJ, www.bd.com) or equivalent. Clear plastics tend to have
lowest trace metal contamination. Blue colored caps have also been used
successfully for this method.
ix. Tubes for storage of intermediate working stock standards: Like polypropylene
50-mL conical tubes, BD Falcon model #352098 (Becton Dickinson Labware,
FranklinLakes, NJ, www.bd.com) or equivalent. For use in storage of
intermediate working stock standards. Clear plastics tend to have lowest trace
metal contamination. Blue colored caps have also been used successfully for
this method.
x. Vortexer: Like MV-1 Mini Vortexer (VWR, West Chester, PA, www.vwr.com).
Used for vortexing blood specimens before removing an aliquot for analysis.
Equivalent item can be substituted.
e. Sources of chemicals, gases, and regulators
i. Acid, hydrochloric acid: Veritas™ double-distilled grade, 30-35% (GFS
Chemicals Inc. Columbus, OH, www.gfschemicals.com) or equivalent. This is
referred to as "concentrated" hydrochloric acid in this method write-up. For use
in preparation of intermediate working stock standards.
ii. Acid, nitric acid: Veritas™ double-distilled grade, 68-70% (GFS Chemicals Inc.
Columbus, OH, www.gfschemicals.com). For use in cleaning any bottles,
vials, tubes, and flasks. This is referred to as "concentrated" nitric acid in this
method write-up.
iii. Blood, whole (human or bovine): Bags of human blood can be purchased from
various sources such as American Red Cross (http://www.redcross.org) or
Tennessee Blood services (Memphis, TN,
http://tennesseebloodservices.com/). Request that human blood be screened
for infectious diseases such as Hepatitis B and HIV. Source for bovine blood
includes the Wisconsin State Laboratory of Hygiene (WSLH, Madison, Wl,
http://www.slh.wisc.edu).
iv. Ethanol (EtOH): USP dehydrated 200 proof (Pharmco Products, Inc.) or
equivalent.
v. Ammonium pyrrolidine dithiocarbamate, laboratory grade (Fisher Scientific,
Fairlawn, NJ) or equivalent.
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vi. Argon gas (for plasma & nebulizer) and regulator: High purity argon
(>99.999% purity, Specialty Gases Southeast, Atlanta, GA, www.sgsgas.com)
for torch and nebulizer. Minimum tank source is a dewar of liquid argon (180-
250 L). Bulk tank (1500+L is preferred).
1. Regulator for argon (at dewar): Stainless steel, single stage, specially
cleaned regulator with 3000 psig max inlet, 0-200 outlet pressure range,
CGA 580 cylinder connector, and needle valve shutoff on delivery side
terminating in a %" Swagelok connector. Part number
"KPRCGRF415A2/AG10-AR1" (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. # Spares = 1.
2. Regulator for argon (between bulk tank and PerkinElmer filter regulator):
Single Stage 316SS Regulator, with 0-300 psi Inlet Gauge, 0-200 psi
Outlet Gauge, Outlet Spring Range, 0-250 psi, %" Swagelok Inlet
Connection, % turn Shut off Valve on Outlet with %" Swagelok Connection
and Teflon Seals. Part number KPR1GRF412A20000-AR1 (Georgia Valve
and Fitting, Atlanta, GA, www.swagelok.com) or equivalent. # Spares = 1.
3. Regulator for argon (filter regulator on back of ICP-MS): Argon regulator
filter kit. Catalog number N812-0508 (PerkinElmer, Shelton, CT,
www.perkinelmer.com).
vii. Disinfectant, for work surfaces: Daily remake of diluted bleach (1 part
household bleach containing 5.25% sodium hypochlorite + 9 parts water), or
an equivalent disinfectant.
viii. Methane: Methane (Research Grade 5.0, 99.99% purity), for DRC channel A.
Typically purchased in cylinder size 200 (part # ME R200, Airgas South,
Atlanta, GA, www.airgas.com).
1. Regulator for methane: Stainless steel, two stage, specially cleaned
regulator with 3000 psig max inlet, 0-25 outlet pressure range, CGA 350
cylinder connector, and needle valve shutoff on delivery side terminating in
a %" Swagelok connector. Like part number KCYADPF412A2AD10
(Georgia Valve and Fitting, Atlanta, GA, www.swagelok.com), or
equivalent. # Spares = 1.
2. Flash Arrestor: Like part # 6104a (Matheson Tri Gas, Montgomeryville,
PA, www.mathesontrigas.com) or equivalent.
ix. Oxygen: Oxygen ("Research Grade Research Grade 5.0", 99.9999% purity)
for DRC channel B. Like part # OX R33A (Airgas South, Atlanta, GA,
www.airgas.com).
1. Regulator for oxygen: Stainless steel, two stage regulator for use with high
purity oxygen (cleaned to be free of all oils). Maximum inlet pressure
3600-5000 psi. Inlet gauge pressure 0-5000 psi (no oil in gauge).
Maximum delivery pressure 50-100 psi with a 0-30 psi outlet gauge (no oil
in gauge). CGA 540 cylinder connector on inlet side and an angle pattern
(90 degree) stainless steel needle valve on the delivery side terminating in
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a 1/8" stainless steel Swagelok connector. Like part #
GEORG/KCYCFR/ORS2/540 (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com), or equivalent.
2. Flash arrestor: Like part # 6104A (Matheson Tri Gas, Montgomeryville, PA,
www.mathesontrigas.com), or equivalent. # Spares = 1.
x. Standard, iridium: Like 1,000 pg/mL, item #CGIR1-1 (Inorganic Ventures,
Christiansburg, VA http://www.inorganicventures.com). Used as an internal
standard in diluent. Standard must be traceable to the National Institute for
Standards and Technology.
xi. Standard, multi-element stock calibration standard: Item number SM-2107-
042 (High Purity Standards, Charleston, SC, http://www.hps.net/). Standard
must be traceable to the National Institute for Standards and Technology.
xii. Standard, rhodium: Like 1,000 mg/L, item # PLRH3-2Y. (SPEX Industries,
Inc., Edison, NJ, www.spexcsp.com). Used as an internal standard in diluent.
Standard must be traceable to the National Institute for Standards and
Technology.
xiii. Standard, single element stock standards for preparation of calibrators and
blood gualitv control pools: National Institute of Standards and Technology
(NIST) Standard Reference Materials (SRMs): 3108 (Cd), 3132 (Mn), 3128
(Pb), 3133 (Hg), 3149 (Se). (Gaithersburg, MD, www.nist.gov). Standard
must be traceable to the National Institute for Standards and Technology.
xiv. Standard, tellurium: Like 1,000 mg/L, item #CGTE1-1 (Inorganic Ventures,
Christiansburg, VA http://www.inorganicventures.com).Used as an internal
standard in diluent. Standard must be traceable to the National Institute for
Standards and Technology.
xv. Tetramethvlammonium hydroxide, 25% w/w, or equivalent (AlfaAesar, 30 Bond
St., Ward Hill, MA 01835).
xvi. Triton X-100™ surfactant: Like "Baker Analyzed" TritonX-100™ (J.T. Baker
Chemical Co., www.itbaker.com).
6) Preparation of reagents and materials
a. Internal standard intermediate mixture:
i. Purpose: Preparation of single intermediate solution containing all internal
standards simplifies the addition of the internal standard(s) into the final diluent
solution. This solution can be purchased rather than prepared.
ii. Preparation: To prepare 50 mL of 20 mg/L Rh, Ir, Te in 1 % v/v HNO3:
1. If not previously dedicated to this purpose, acid wash a 50 mL volumetric
flask (PP, PMP, or Teflon™). For example, with 1% (v/v) HNCteand >18
Mohmcm water (at least 3 times each) and verify cleanliness through
analysis of rinsate.
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2. Partially fill the 50 mL volumetric flask with 1 % v/v HNO3 (approximately
25-40 mL).
3. Add 1 mL of 1,000 ng/mL Rh standard, 1 mL of 1,000 ng/mL Ir standard,
and 1 mL of 1,000 ng/mL Te standard. If initial Rh, Ir, or Te standard
concentration is different, adjust volume proportionally.
4. Fill to mark (50 mL) with 1% v/v HNCteand mix thoroughly.
5. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
b. Intermediate Triton X-100® solution:
i. Purpose: To ease daily preparation of the diluent and rinse solutions by first
preparing an intermediate Triton X-100® solution.
ii. Preparation: To prepare 1 L of 20% Triton x-100®
1. If not previously dedicated to this purpose, acid wash a 200 mL volumetric
flask (PP, PMP, or Teflon™). For example, with 1% (v/v) HNCteand >18
Mohm-cm water (at least 3 times each) and verify cleanliness through
analysis of rinsate.
2. Add 200 mL of Triton X-100® to the 1L container that is partially filled with
>18 Mohm-cm water.
3. Fill to 1 L with >18 Mohm-cm water and mix until the Triton X-100® has
completely dissolved into solution (overnight). A magnetic stirring plate
can be used to assist mixing by adding an acid-washed Teflon®coated
stirring bar to the bottle.
4. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
c. Sample diluent and carrier
i. Purpose: This solution will be used in the preparation of all samples and
calibrators during the dilution process prior to analysis. Make all samples,
standards, blanks, QC, etc. . . in a run from the same diluent solution so that
the concentration of the internal standards will be the same among all
calibrators and samples in the run. When using a flow-injection component in
the sample introduction system (i.e. the Elemental Scientific SC4-FAST
autosampler), use the same solution for the the 'carrier' and sample diluent.
The diluent is an aqueous solution of 5 ng/L internal standard mixture (Rh, Ir,
Te), in 0.4% v/v tetramethyl ammonia hydroxide (TMAH), 1% ethyl alcohol,
0.01% APDC, and 0.05% v/v Triton X-100®. Larger volumes of these solutions
can be prepared by adjusting component volumes proportionally.
ii. Preparation: To prepare 2L of 5 ng/L Rh, Ir and Te, 0.01% APDC in 0.4% v/v
TMAH, 1% ethanol, and 0.05% v/v Triton X-100:
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1. If not previously dedicated to this purpose, acid wash a 2L container (PP,
PMP, or Teflon™). For example, with 1% (v/v) HNCteand >18 Mohmcm
water (at least 3 times each) and verify cleanliness through analysis of
rinsate.
2. Partially fill the 2L container with >18 Mohm cm water.
3. Add 0.2 g of APDC , 8 ml_ of 25% v/v TMAH, 20 ml_ of ethanol, and 5 ml_
of 20% Triton X-100®.
4. Dilute to volume (2L) with >18 Mohm cm water.
5. Spike 500 |u.L of 20 mg/L Rh, Ir, Te to the final diluent.
6. Invert bottle a few times to insure thorough mixing. Allow to sit for several
hours or overnight before using.
7. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
d. ICP-MS rinse solution
i. Purpose: The rinse solution used in this method is an aqueous solution of
0.01% APDC in 0.4% v/v TMAH, 1% ethanol, and 0.05% v/v Triton X-100.
This solution will be pumped through the autosampler rinse station, probe, and
sample loop between sample analyses to prevent carry-over of analytes from
one sample measurement to the next.
ii. Preparation: To Prepare 4 L of 0.01 % APDC in 0.4% v/v TMAH, 1 % ethanol,
and 0.05% v/v Triton X-100:
1. If not previously dedicated to this purpose, acid wash a 4L container (PP,
PMP, or Teflon™). For example, with 1% v/v HNO3 and >18 Mohm cm
water (at least 3 times each) and verify cleanliness through analysis of
rinsate.
2. Partially fill the 4 L bottle with >18 Mohm cm water (approximately 2-3 L).
Use of volumetric flask is not required.
3. Add 0.4 g of APDC
4. Add 16 ml_ of TMAH
5. Add 40 ml_ of ethyl alcohol,
6. Add 10ml_ of 20% Triton X-100®, (See Section 6.b for details on
preparation)
7. Fill to 4 L using >18 Mohm cm water.
8. Store at room temperature and prepare as needed. To prepare volumes
other than specified here, add proportionally larger or smaller volumes of
the solution constituents.
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9. Invert bottle a few times to ensure thorough mixing. Allow to sit for several
hours or overnight before using.
10. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
e. Standards, calibrators, base blood and QC
i. Multi-element stock calibration standards
1. Purpose: This multi-element stock standard will be used to prepare the
intermediate working calibration standards.
2. Purchase & Storage:
a. Purchasing from vendors: Whether purchased or prepared in-house,
the starting materials must be NIST-traceable. Matrix and
concentrations of Pb, Cd, Hg, Mn and Se are listed in Table 3 of
Appendix B.
b. Storage: Store at room temperature and label appropriately.
Expiration is as defined by the manufacturer or 1 year from date of
opening, whichever comes first.
ii. Diluent for intermediate calibration standard preparations:
1. Purpose: This diluent is used to dilute stock and intermediate stock
calibration standards, not to prepare working calibrators or blood samples
for analysis.
2. Preparation: To prepare 2L of 3% v/v HCI:
a. If not previously dedicated to this purpose, acid wash a 2L container
(PP, PMP, or Teflon™). For example, with 3% HCI and >18 Mohm-cm
water (at least 3 times each) and verify cleanliness through analysis of
rinsate.
b. In the 2 L flask, add 1 -1,5L >18 Mohm-cm water.
c. Add 60 ml_ high purity concentrated HCI.
d. Fill to the mark and mix thoroughly.
e. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
iii. Multi-element intermediate stock calibration standard
1. Purpose: This multi-element intermediate stock standard will be used to
prepare the intermediate working calibration standards.
2. Preparation: To prepare 3% v/v HCI solutions containing Cd, Pb, Hg, Se,
and Mn with concentrations listed in Table 4 of Appendix B:
a. Acid-rinse one 100 ml_, PP (or PMP) volumetric flask. For example,
with 3% HCI and >18 Mohm-cm water (at least 3 times each) and verify
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cleanliness through analysis of rinsate. Mark flask according to
intended use. Dedicate to purpose.
b. Partially fill (50-75% full) the 100 mL flask with the 3% (v/v) HCI diluent
prepared in Section 6.e.ii.
c. Using the volume listed in Table 4 of Appendix B, pipette the
appropriate volume of the multi-element stock calibration standard
solution into the volumetric flask. Dilute to the volumetric mark with the
3% HCI (v/v) diluent using a pipette for the final drops. Mix each
solution thoroughly. Final concentrations are listed in Table 4 of
Appendix B.
d. Once mixed, transfer to acid-cleaned, labeled, 50 mL containers (PP,
PMP, or Teflon™) for storage.
e. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
iv. Intermediate working calibration standards
1. Purpose: Used each day of analysis to prepare the final working
calibrators that will be placed on the autosampler.
2. Preparation: To prepare 3% v/v HCI solutions containing Cd, Pb, Hg, Se,
and Mn with concentrations listed in Table 3 of Appendix B:
a. Acid-rinse eight 100 mL, PP (or PMP) volumetric flasks and one 2 L
PP (or PMP) volumetric flasks. For example, with 3% HCI and >18
Mohmcm water (at least 3 times each) and verify cleanliness through
analysis of rinsate. Mark each flask according to intended use.
Dedicate to purpose.
b. Fill each 100 mL flask 50-75% with the 3% (v/v) HCI diluent prepared
in Section 6.e.ii.
c. Using the volumes listed in Table 5 of Appendix B, pipette the
appropriate volume of the multi-element intermediate stock calibration
standard solutions into each of the volumetric flasks. Dilute each to
the volumetric mark with the 3% HCI diluent using a pipette for the final
drops. Mix each solution thoroughly. Final concentrations are listed in
Table 5 of Appendix B.
d. Once mixed, transfer to acid-cleaned, labeled, 50 mL containers (PP,
PMP, or Teflon™) for storage.
e. Store at room temperature and label appropriately. Expiration is 1 year
from date of preparation.
f. Pour aliquots of each standard into clean 15mL polypropylene tubes
and label for daily use.
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v. Working calibrators
1. Purpose: The working calibrators will be analyzed in each run to provide a
signal-to-concentration response curve for each analyte in the method.
The concentration of the analyte of interest in a patient blood sample
dilution is determined by comparing the observed signal ratio
(element/internal standard) from the dilution of the patient blood sample to
the signal ratio response curve from the working calibrators.
2. Content: Dilutions (1:50) of the corresponding eight intermediate working
calibration standards with base blood and sample diluent.
3. Preparation: Mix with base blood and diluent (Section 6.c) using a
benchtop automatic pipette to make 1:50 dilutions of the corresponding
eight intermediate working calibration standards immediately prior to
analysis (see Table 8 of Appendix B).
vi. Base blood
1. Purpose: This blood pool material will be mixed with the intermediate
working calibrators just prior to analysis to matrix-match the calibration
curve to the blood matrix of the unknown samples.
2. Preparation: To prepare a mixture of multiple blood sources collected from
anonymous donors to approximate an average blood matrix:
a. Purchase several bags of whole blood.
b. Screen each individual bag of blood for concentration of analytes of
interest. See Table 2 in Appendix B for minimum acceptable values
c. Once screened, mix the acceptable blood together in a larger container
(i.e. acid washed polypropylene (PP), polymethylpentene (PMP), or
Teflon™) and stir for 30+ minutes on a large stir plate (acid wash large
Teflon™ stir bar before use).
d. Store long-term as smaller portions for daily use (e.g. 2 ml_ cryovials)
according the same storing and handling criteria described in Section
3.
vii. Internal quality control materials ("bench" QC)
1. Purpose: Internal (or "bench") quality control (QC) materials are used to
evaluate the accuracy and precision of the analysis process, and to
determine if the analytical system is "in control" (is producing results that
are acceptably accurate and precise). They are included in the beginning
and at the end of each analytical run.
2. Preparation: To prepare pooled animal or human blood at low-normal and
high-normal concentrations:
Both purchased or in-house prepared quality control materials are suitable
for this purpose if volumes, concentrations meet method requirements and
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any spikes of elemental levels are traceable to the National Institute for
Standards and Technology (NIST).
3. Screening blood: Screen bags of blood for analyte of interest
concentration before mixing together to make 2 separate base blood pools
(for preparing the low and high bench QC materials). Samples can be
screened individually
a. Keep blood refrigerated whenever possible to minimize microbial
growth.
b. Because this is only a quick screen of the analyte of interest
concentration, the number of replicates in the blood method can be
reduced to one in order to reduce analysis time.
c. Select blood for the low bench QC pool which has analyte
concentrations in the low-normal population range. Select blood for
the high and elevated bench QC pools which has analyte
concentrations less than some pre-selected target concentration
values in the high normal population range. See Table 2 in Appendix
B for recommended concentration ranges.
4. Combining collected blood: The goal is for combining samples is to
approach an 'average' matrix for each pool.
a. Graduate four acid-washed 10 L carboys (PP or PMP) in 0.5 L
increments (two will be used for decanting into).
b. Combine collected blood samples into two separate acid-washed 10 L
carboys (PP or PMP), according to their concentrations, for the low
bench and high bench QC pools.
c. Mix each blood pool using carboy stirrers and large stir plates. Keep
blood refrigerated whenever possible.
5. Spiking of blood
a. Analyze three samples of each blood pool. Record these results for
future recovery calculations.
b. Use these results to determine target analyte concentrations possible
for the pools
c. Calculate the volume of single element standards needed to spike
each pool to the desired concentrations. See Table 2 in Appendix B
for recommended concentration ranges.
d. While stirring the pools on large stir plates, spike each pool with
calculated volumes of single element standards (all spiking standards
used must be traceable to NIST).
e. Continue to stir pools overnight after spiking, then reanalyze.
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f. Repeat steps 4 and 5 until all analytes reach target concentrations
keeping track of the total volume of spiking solution added to each
blood pool.
6. Dispensing and storage of blood
a. Container types: Dispense blood into lot screened containers (i.e. - 2
mL polypropylene tubes). If possible, prepare tubes of QC which have
only enough volume for one typical run + 1 repeat analysis. This
allows for one vial of QC to be used per day of analysis, reducing
chances of contamination of QC materials due to multi-day use.
b. Labels: Place labels on vials after dispensing and capping if the vials
are originally bagged separately from the caps. This minimizes the
chance for contamination during the process. Include at least the
name of QC pool (text and bar code), date of preparation, and a vial
number on the labels.
c. Dispensing: Dispensing can be accomplished most easily using a
benchtop automatic pipette in continuous cycling dispense mode.
Dispense the pools in a clean environment (i.e. a class 100 cleanroom
area or hood).
1. Allow blood to reach room temperature before dispensing (to
prevent temperature gradients possibly causing concentration
gradients across the large number of vials being dispensed
and to prevent condensation problems during labeling of
vials).
2. Replace the tubing attached to the dispensing syringe (left
when looking at front of the benchtop automatic pipette) with a
length of clean Teflon™ tubing long enough to reach into the
bottom of the 10 L carboy while it is sitting on the stir plate.
3. Check cleanliness of the benchtop automatic pipette before
use by analyzing 1-2% (v/v) HNO3 which has been flushed
through the benchtop automatic pipette with a portion of the
same solution which has not been through the benchtop
automatic pipette.
4. Approximately one hour before dispensing begins,
a. With the large stir plate close to the left side of the
benchtop automatic pipette, begin stirring the blood pool to
be dispensed.
b. Also during this time, flush the benchtop automatic pipette
with blood from the pool to be dispensed. Place the ends
of the tubing attached to both the sample and dispensing
syringes into the carboy of blood so that blood won't be
used up during this process. Be sure to secure both ends
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of tubing in the carboy with Parafilm so they will not come
out during the flushing process.
5. After dispensing the blood into the vials, cap the vials and
label them. Placing labels on vials after capping minimizes the
chance for contamination during the process.
d. Homogeneity test: Check homogeneity of analyte concentrations in
pool aliquots.
e. Storage: Store long-term as smaller portions for daily use (e.g. 2 ml_
cryovials) according the same storing and handling criteria described in
Section 3.
f. Optimization solutions
i. PRC optimization:
1. Purpose: For periodic testing of the DRC cell parameters. Procedure
requires at a minimum a blank (i), an analyte solution (ii), a blank with
interference (iii), and an analyte and interference containing solution (iv).
For Se, only the blank (i), an analyte solution (ii) are needed because the
interference on Se is plasma based.
2. Content:
Diluent in this section refers to sample diluent (5 ng/L internal standard
mixture (Rh, Ir, Te), 0.4% v/v tetramethyl ammonia hydroxide (TMAH),
1% ethyl alcohol, 0.01% APDC, and 0.05% v/v Triton X-100® as
described in Section 6c.
a. Solutions for testing elimination of 54Fe1H interference on 55Mn:
i. Base blood in diluent (1 + 49)
ii. Base blood in diluent (1 + 49) + 4.5 ng/L Mn
iii. Base blood in diluent (1 + 49) + 500 ng/L Fe
iv. Base blood in diluent (1 + 49) + 4.5 ng/L Mn + 500 ng/L Fe
b. Solutions for testing elimination of 40Ar2 interference on 80Se:
i. Base blood in diluent (1 + 49)
ii. Base blood in diluent (1 + 49) + 90 ng/L Se
3. Preparation & storage: Prepare different volumes, if needed, by adding
proportionally larger or smaller volumes of solution constituents.
Interference concentrations can be prepared higher as needed by
adjusting the volume of this spike. Keep interference spike volume small
(<0.3 ml_) using a high concentration stock solution (i.e. 1000 mg/mL).
Analyte concentrations can be made higher if needed for sensitivity
reasons by preparing a higher concentration calibrator.
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a. Solutions for testing elimination of 54Fe1H interference on 55Mn:
i. Base blood in diluent (1 + 49)
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 50 mL portion of working calibrator 0 as described in
Table 6 (multiply volumes by 5).
ii. Base blood in diluent (1 + 49) + 4.5 ng/L Mn
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 50 mL portion of working calibrator 2 as described in
Table 6 (multiply volumes by 5).
iii. Base blood in diluent (1 + 49) + 500 ng/L Fe
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 50 mL portion of working calibrator 0 as described in
Table 6 (multiply volumes by 5).
2. Add 0.025 mL of 1000 mg/mL Fe.
iv. Base blood in diluent (1 + 49) + 4.5 ng/L Mn + 500 ng/L Fe
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 50 mL portion of working calibrator 2 as described in
Table 6 (multiply volumes by 5).
2. Add 0.025 mL of 1000 mg/mL Fe.
Solutions for testing elimination of 40Ar2 interference on 80Se:
i. Base blood in diluent (1 + 49)
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 50 mL portion of working calibrator 0 as described in
Table 6 (multiply volumes by 5).
ii. Base blood in diluent (1 + 49) + 90 ng/L Se
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 50 mL portion of working calibrator 2 as described in
Table 6 (multiply volumes by 5).
Store at room temperature and prepare as needed.
Label appropriately (see Section 6.f.i.2), "Store at room temperature",
preparation date, expiration date one year from preparation date, and
preparer's initials.
ii. Dual detector calibration:
1. Purpose: Use as necessary to perform the dual detector calibration.
2. Content: Aqueous dilutions of single element stock standard solutions in
2% (v/v) nitric acid. Current solution in use contains: Pb with a final
concentration of 200 ug/L.
c.
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3. Preparation & storage: Prepare different volumes, if needed, by adding
proportionally larger or smaller volumes of solution constituents.
a. To prepare a total of 50 ml_: In a 50 ml_ lot screened polypropylene
tubes, spike in 0.01 ml_ of 1000 mg/mL single element stock solution
for each element desired in the final solution.
b. Dilute to the 50 ml_ mark with 2% (v/v) nitric acid.
c. Store at room temperature and prepare as needed.
d. Label appropriately, e.g. "200 ug/L Pb in 2% (v/v) HN03", "Store at
room temperature", preparation date, expiration date one year from
preparation date, and preparer's initials.
7) Analytical instrumentation setup
(see Section 5 for details on hardware used, including sources)
a. Instrumentation and equipment setup:
i. Configuration for liquid handling
1. FAST valve setup: See Appendix B, Figure 1 for diagram and Section 5.b
"FAST / ESI SC4-DX autosampler accessories" for source information,
sample loop (white nut).
0.5 mm ID probe (red nut) for carrier solution,
nebulizer line (green nut) for transfer of liquid to nebulizer,
sample loop (white nut).
0.8 mm ID probe (blue nut) for diluted samples,
vacuum line (black nut).
a.
Port 1
b.
Port 2
c.
Port 3
d.
Port 4
e.
Port 5
f.
Port 6
2. Carrier solution uptake: Use peristaltic pump to control uptake flow rate of
carrier solution to the SC-FAST valve. Use of a 'peristaltic to Teflon tubing
adapter' for prevents damage to small i.d. tubing when making connections
(see consumables descriptions in Section 5.b).
3. Spray chamber waste removal
Use of a 'peristaltic to Teflon tubing adapter' for prevents damage to small
i.d. tubing when making connections (see consumables descriptions in
Section 5.b).
a. Between spray chamber and peristaltic tubing:
i. Spray chambers with threaded connection: Use vendor-supplied
threaded connector on base of chamber, connecting tubing directly
to peristaltic pump tubing through a PEEK adapter or directly.
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ii. Spray chambers without threaded connection: Use of specialized
push-on connectors available from various vendors (like UFT-075
from Glass Expansion, Pocasset, MA) are preferred for safety
reasons to direct connection of PVC tubing (e.g. 1/8" i.d. x %" o.d.).
b. Between peristaltic pump tubing and waste container: Connect 1/8"
i.d. x %" o.d. PVC tubing to the white / black peristaltic pump tubing
using a tubing connector (PerkinElmer item # B3140715). Place the
free end of the PVC tubing through the lid of the waste jug (be sure it is
secure). Place waste container in a deep secondary containment tray
in case of overflow.
4. Rinse solution for autosampler:
a. Rinse solution jug: Leave one of the caps on the top of the rinse jug
loose to allow air venting into the jug as liquid is removed. Otherwise
the jug will collapse on itself as the liquid is removed and a vacuum is
created inside. Use secondary containment tray.
b. Rinse solution uptake to autosampler rinse station: Use tubing of
different lengths and inner diameters between the rinse solution
container and the autosampler rinse station to control uptake rate of
rinse solution. These can be obtained from the autosampler
manufacturer, their distributors, or custom built in the lab. Optimize
these factors along with fill time in the software so that waste of rinse
solution is minimized and rinse station does not go empty.
c. Autosampler rinse station waste removal: Gravity drain of waste to the
waste container is sufficient. Use minimum drain tubing to make this
connection. If this tube is too long, the rinse station will not drain
properly.
ii. Gas delivery and regulation
1. ICP-MS modifications:
a. Plastic tubing between mass flow controllers and dynamic reaction cell
have been replaced with stainless steel. Stainless steel tubing is
preferred between the reaction gas cylinder / regulator and the back of
the ICP-MS instrument.
b. A second mass flow controller will be needed (channel B) that does not
send the DRC gas through a 'getter'.
2. Argon gas: Used for various ICP-MS functions including plasma and
nebulizer.
a. Regulator for argon source (if a dewar): Set delivery pressure of this
regulator at least 10 psi higher than the delivery pressure of the step-
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down regulator to allow for pressure drop across tubing that stretches to
the instrument.
b. Step down regulator (if source of argon is a bulk tank): Place this single
stage regulator in the lab so that incoming argon pressure can be
monitored and adjusted. Set delivery pressure to 10 psig above the
delivery pressure of the filter regulator on the ICP-MS.
c. Filter regulator at ICP-MS: Single stage "argon regulator filter kit"
supplied with the ICP-DRC-MS. Set the delivery pressure depending
on the instrument setup:
i. ELAN with a 0-60psi gauge on the filter regulator: 52±1 psi when
plasma is running (need 0-150 psi regulator if using a PolyPro or
PFA nebulizer made by Elemental Scientific Inc).
ii. ELAN with a 0-150psi gauge on the filter regulator: 90-100 psi
when plasma is running.
3. Methane (99.99%) gas: Used for dynamic reaction cell interference
removal from selenium isotopes.
a. Connect to DRC channel A
b. Set the delivery pressure of regulator to 5-7 psig when gas is flowing.
See section 5.e for part numbers and details.
4. Oxygen (99.999+%) gas: Used for dynamic reaction cell interference
removal from manganese isotopes.
a. Connect to DRC channel B.
b. Set the delivery pressure of regulator to 5-7 psig when gas is flowing.
See Section 5.e for part numbers and details.
c. Use a brass flash arrestor on outlet side of regulator. See Section 5.e
for part numbers and details.
iii. Chiller / heat exchanger: If using refrigerated chiller, set temperature control to
approximately 18 °C.
b. Instrument and method parameters: See Tables and Figures in Appendix B for a
complete listing of the instrument and method parameters and software screen
shots.
8) The run: quality, execution, evaluation, and reporting
a. Bench QC, reference materials and calibration verification:
i. Bench "QC": Analysis of bench QC permits assessment of methodological
imprecision, determination of whether the analytical system is 'in control' during
the run, and assessment of time-associated trends. Before QC materials can
be used in the QC process, they must be characterized by at least twenty (20)
analytical runs to determine appropriate QC parameters.
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Bench QC pool analyte concentrations in this method span the analyte
concentration range of the calibrators including "low-normal" ('Low QC'), "high-
normal" ('High QC'), and "above-normal" ('Elevated QC') concentrations.
In each analytical run the analyst will test each of the three bench QC samples
two times, subjecting them to the complete analytical process. Bench QC pool
samples are analyzed first in the run after the calibration standards but before
any patient samples are analyzed. This permits making judgments on
calibration linearity and blank levels prior to analysis of patient samples. The
second analysis of the bench QC pools is done after analysis of all patient
samples in the run (typically 40-50 patient samples total when analyzing for all
elements in the method) to ensure analytical performance has not degraded
across the time of the run. If more patient samples are analyzed on the same
calibration curve after the second run of the bench QC, all bench QC must be
reanalyzed before and after the additional samples. For example, the schemes
shown in Table 6 in Appendix B are both acceptable ways to analyze multiple
consecutive "runs".
ii. Reference materials: Use standard reference materials (SRM) from the
National Institute of Standards and Technology (NIST) (i.e. SRM 955c Levels
1 -4) to verify method accuracy. Use previously characterized samples from
proficiency testing program or commercially-produced reference materials
when NIST SRMs are unavailable.
iii. Calibration verification: The test system is calibrated as part of each analytical
run with NIST-traceable calibration standards. These calibrators, along with
the QCs and blanks, are used to verify that the test system is performing
properly.
b. Perform, evaluate and report a run
/'. Starting the equipment for a run
1. Power on the computer, printer, and autosampler, and instrument
computer controller.
2. Peristaltic pump: Set proper tension on peristaltic pump tubing.
3. Software: Start software for the ICP-MS and autosampler control.
4. Daily pre-ignition maintenance checks: Perform and document daily
maintenance checks (e.g., Ar supply pressure, interface components
cleanliness and positioning, interface pump oil condition, vacuum pressure,
etc.).
5. Place probe in adequate volume of carrier or rinse solution: If using an ESI
FAST, manually place carrier probe into carrier solution. If not, send the
autosampler probe to a rinse solution (e.g. autosampler rinse station).
6. Start the plasma
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7. Start the peristaltic pump: Start the pump running slowly, making sure that
the rotational direction is correct for the way the tubing is set up.
8. Warm-up time: Allow warm-up time suggested by the manufacturer for the
ICP-MS (e.g. RF generator) after igniting the plasma. There will be
another warm-up time (or "stability time") for the DRC later in this
procedure.
9. Daily performance check: Perform and document a daily performance
check and any optimizations necessary.
Save new parameters to the "default.tun" and "default.dac" files.
10. DRC stability time: Best analyte-to-internal standard ratio stability is
typically observed after 1-1.5 hours of analysis of diluted blood samples
using the DRC mode method (~15 measurements of the 5 element panel
can be made in 1 hour). Prepare 50ml_+ of a calibration standard (e.g.
standard 2) to be analyzed repeatedly before the beginning of the run to
achieve a stable analyte-to-internal standard ratio. Time to reach stability
is instrument-specific and learned from performance of runs. See Table 7
in Appendix B for example of setup in the Samples / Batch window and
Table 8 in Appendix B for details of making a working standard.
11. Readying the instrument for quick-start analysis: Leave the plasma
running to eliminate the need for an initial instrument warm-up period and /
or a DRC stabilization period as long as appropriate planning is made for
sufficient solution supply and waste collection. Analysis of conditioning
samples (diluted blood matrix) can also be scheduled to occur at roughly a
predetermined time. Accomplish this by setting up multiple sample
analyses with extended rinse times (e.g. one 5 element analysis with a
1500s rinse time will take approximately 30 minutes to complete). Initial
samples would be non-matrix, while final samples would be diluted matrix
for conditioning. If running a DRC-only method during these scheduled
analyses, the ICP-MS will remain in DRC-mode for approximately 45
minutes without depressurizing the cell.
12. Software setup for analysis:
a. Workspace (files & folders): Verify & set up the correct files and data
directories for your analysis (See Table 1 in Appendix B for defaults).
b. Samples / batch window: Update the software to reflect the current
sample set. Use a bar code scanner to input data whenever possible.
See Table 1 in Appendix B for times and speeds.
1. Blood vs. aqueous method files:
a. The difference: There are two method files for this one
method (see Table 1 in Appendix B). It is necessary to use
both to accomplish each run because the current
PerkinElmer software will not allow for more than one blank
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per method file. The ONLY DIFFERENCE between these
two files is on the Sampling tab where one lists the
autosampler positions of the blood blank and blood-based
calibrators (the "bldblk" method file) and the other lists the
autosampler position of the aqueous blank (the "aqblk"
method file).
b. Use: The ONLY TIME when it matters which of these files
is used is when the measurement action includes "Run
blank" or "Run standards". When the measurement action
is only 'run sample', it does not matter whether the "bldblk"
or "aqblk" method file is used. Analysts typically follow the
pattern below, however, for the sake of consistency and as
a reminder of which blank must be used for which type of
sample. See Table 7 in Appendix B.
i. The "bldblk" method file: Use to analyze the initial
blood blank (blank for the calibration curve), the blood
calibrators, and the blood blank checks at the very
beginning of the run. The blood blank method defines
the autosampler location of the blood blank and the
blood calibration standards.
ii. The "aabllc" method file must be used to analyze all QC
materials and patient samples. The aqueous blank
method defines the aqueous blank in autosampler
location.
ii. Preparation of samples for analysis (See Table 6 in Appendix B)
1. Thaw blood samples; allow them to reach ambient temperature.
2. Prepare the following solutions into pre-labeled containers using the
benchtop automatic pipette or other volumetric sample transfer device.
See Table 8 in Appendix B for a summary.
a. Aqueous Blank. Prepare a minimum of two aqueous blanks. One will
be the actual aqueous blank and the other will be a backup ("Aqueous
Blank Check") in case the original aqueous blank is unusable.
b. Calibrators: Prepare the working calibrators (S0-S8). Prepare SO in
triplicate. One of these SO preparations will be the zero calibrator
(blood blank) for the calibrators; the other two will be analyzed twice
after the last calibrator to collect run blank data that can be used in
calculating method limit of detection (LOD).
c. Patient & QC Samples: Before taking an aliquot for analysis,
homogenize the sample thoroughly.
After preparation, mix and cover. Place prepared dilutions on the
autosampler of the ICP-MS in the order corresponding to the sequence
setup in the ICP-MS software.
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Room temperature is acceptable for the original samples for the work
day.
NOTE: Samples must be analyzed within 24 hours of preparation to
obtain valid results for selenium. The method has been validated to
produce valid results for other Pb, Cd, Hg, and Mn even 48 hrs after
sample preparation. See critical parameter test results in Appendix A for
details.
iii. Start the analysis using the ICP-MS software.
iv. Monitor the analysis in real-time as much as possible. If necessary, leave the
run to complete itself unattended as long as appropriate planning is made for
either overnight operation or Auto Stop (see below).
Monitor the analysis for the following:
1. Verify proper operation of the instrument (proper loop filling, sample
reaching nebulizer in correct timing, autosampler arm moving properly, etc
...).
2. Verify that background signal from instrument and reagents are low.
Helpful checks when diagnosing high background problems include:
a. Water to be used in Aq Blank Checks and dilutions.
b. Diluent before and after being flushed through the benchtop automatic
pipette.
If contamination is observed from the pipette, flush the pipette with
>500 ml_ of nitric acid solution (< 5% v/v HNO3) and retest.
c. Comparison with other instruments.
3. Verify analyte / internal standard ratio stability
The net intensity (analyte / internal standard ratio) of the measurements
made while stabilizing the DRC can be evaluated to determine the
readiness of the system to begin analysis. Continual trending in this ratio
indicates that unwanted instrument drift will occur within the run.
4. Verify calibration curves meet R2 requirements (minimum of 0.98, typically
0.99 to 1.000).
5. Verify bench QC results are within the acceptable limits.
If an analyte result for the beginning QC material(s) falls outside of the ±
3SD limits, then the following steps are recommended:
a. Evaluate the blank results.
b. Evaluate the reproducibility of the 3 replicates within the
measurements.
c. Evaluate the consistency of the internal standard across the
measurements (esp. the calibrators).
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d. Evaluate calibration curves. If a particular calibration standard is
obviously in error, it can be re-analyzed as a sample (old or new
dilution) and incorporated into the curve through data reprocessing as
a calibrator. As a last resort, a single calibration point per analyte
between or including S2 and S7 can be removed from the curve (Do
not drop SO, S1 or S8). Follow up problems with calibration standards
with appropriate corrective actions (e.g. re-preparation of intermediate
working standards or troubleshooting instrument parameters).
e. Prepare a fresh dilution of the failing QC material (same vial) and
reanalyze it to see if the QC dilution was not properly made.
f. Prepare a fresh dilution of the failing QC material (unused vial) and
analyze it to see if the QC vial had become compromised.
g. Prepare and analyze new working calibrators.
h. Test a different preparation of intermediate working calibration
standards.
If these steps do not result in correction of the out-of-control values for QC
materials, consult the supervisor for other appropriate corrective actions.
6. Verify good precision among replicates of each measurement.
7. Verify consistent measured intensities of the internal standards.
Some sample-to-sample variations are to be expected, however,
intensities drifting continuously in one direction resulting in failing results
for ending QC indicate the instrument needs additional pre-conditioning
before the run or environmental conditions are changing too much
around the instrument.
8. Verify elevated patient results.
Refer to Figure 4 in Appendix B for flowchart.
a. Confirming an elevated concentration: Repeat for confirmation any
sample having a concentration greater than the 1UB threshold. See
Table 9 in Appendix B.
b. Dilution of a sample to within the calibration range: Repeat in duplicate
with extra dilution any sample having a concentration greater than the
highest calibration standard to bring the observed result within the
concentration range of the calibrators. See Table 7 in Appendix B for
validated extra dilutions.
c. Confirming proper washout after an elevated sample: When monitoring
the analysis in real-time, if a sample concentration is greater than the
highest concentration validated for washout (see Table 9 of Appendix
B), do the following to verify that the run is still in control for low
concentration samples before proceeding with analysis.
i. Stop run following elevated sample
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ii. Verify that the run is still in control for lower concentration samples
before proceeding with analysis. Analyze 2 blood blank checks
followed by a low bench QC washout check. If the low bench QC
wash check is not in control (within ± 3SD limits), repeat these 3
check samples until washout is verified before proceeding with
analysis.
Example:
3016 BldBlkChk Washl
3016 BldBlkChk Wash2
LBXXXXX Wash
/'//. If the run is not verified in-control for low concentration samples
before the next samples are analyzed, see Section 8.b.vii.2. for
directions.
v. Overnight operation or using auto stop: The run may be left to complete itself
unattended as long as appropriate planning is made (e.g. sufficient solution
supply and waste collection). Turn on the AutoStop feature of the ICP-MS
software. Delay the shutdown at least 10 minutes (use peristaltic pump speed
approximately that of the method wash) to rinse the sample introduction
system of blood matrix before turning off the plasma. It will be necessary to
replace the sample peristaltic pump tubing the next day since it will have been
clamped shut overnight. Enable "Auto Start / Stop" is on the "AutoStop" tab of
the Instrument window.
vi. Records of results: Run results will be documented after each run in both
electronic and paper form.
1. Electronic records: Transfer data electronically to the laboratory
information system. When keyboard entry must be used, proofread
transcribed data after entry.
a. Export data from the ICP-MS software using "original conditions" or
files and folders used during the analysis. Use descriptive report
filenames (e.g. 2005-0714a_group55.txt). In the ICP-MS software
under "Report Format" (METHOD window, REPORT tab) choose the
"Use Separator" option, and under the "File Write" Section choose
"Append."
b. Move the generated .TXT data file to the appropriate subdirectory on
the network drive where exported data are stored prior to import to the
laboratory information management system.
c. Import the instrument file into the laboratory information system with
appropriate documentation (e.g. instrument ID, analyst, calibration
standards lot number, and run or sample specific comments).
2. Paper records: Printed run sheets must be documented with
i. Analyst initials
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ii. Instrument ID
iii. Date of analysis and run # for the day
vii. Analyst evaluation of run results:
1. Bench quality control: After completing a run, and importing the results into
the laboratory information system, evaluate the run bench QC according to
laboratory QC rules. The QC limits are based on the average and standard
deviation of the beginning and ending analyses of each of the bench QC
pools, so it will not be possible to know if the run is in control until
statistically reviewed.
a. Rules for bench quality control evaluation: The following are the CDC
DLS QC rules for three QC pools per run with two or more QC results
per pool.
i. If all three QC run means are within 2Sm limits and individual
results are within 2Si limits, then accept the run.
ii. If one of the three QC run means is outside a 2Sm limit - reject run
if:
1. Extreme Outlier - Run mean is beyond the characterization
mean ± 4Sm
2. 3S Rule - Run mean is outside a 3Sm limit
3. 2S Rule - Two or more of the run means are outside the same
2Sm limit
4. 10 X-bar Rule - Current and previous 9 run means are on
same side of the characterization mean
iii. If one of the QC individual results is outside a 2Si limit - reject run
if:
1. Extreme Outlier - One individual result is beyond the
characterization mean ± 4Sm
2. R 4S Rule - 2 or more of the within-run ranges in the same run
exceed 4Sw (i.e., 95% range limit)
Note: Since runs have multiple results per pool for 3 pools, the
R 4S rule is applied within runs only.
Abbreviations:
Si = Standard deviation of individual results.
Sm = Standard deviation of the run means.
Sw = Within-run standard deviation.
b. Implications of QC failures: If the DLS SAS program declares the run
"out of control" for any analyte, use the following to determine the
implications on usability of the data from the run.
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i. For 1 or 2 analvtes: ONLY the analytes which were "out of control"
are invalid for reporting from the run.
ii. For 3 or more analvtes: All results, regardless of analyte, are
invalid for reporting from the run.
2. Patient results:
a. Elevated concentrations: Refer to Figure 5 in Appendix B for flowchart.
i. Boundaries requiring confirmatory measurement:
1. Results greater than the first (1 UB) or second (2UB) upper
boundaries.
The concentrations assigned to 1 UB and 2UB for an element
is determined by study protocol but default concentrations are
in Table 9 in Appendix B.
a. Results greater than the first upper boundary (1 UB):
Confirm by repeat analysis of a new sample preparation
concentrations observed greater than the "first upper
boundary" (defined in the laboratory database as the
"1 UB"). Report the first analytically valid result, as long as
the confirmation is within 10%. Continue repeat analysis
until a concentration can be confirmed.
b. Analyst reporting of elevated results: Report any patient
results confirmed to be greater than the second upper
boundary (2UB) as an "elevated result".
2. Results greater than highest calibrator: Samples that exceed
the high calibrator must be prepared with minimum extra
dilution in duplicate to bring the observed result within the
calibration range (< S8). Report the first analytically valid
result (i.e. the first one within the calibration range), as long as
the confirmation is within 10%. Continue repeat analysis until
a concentration can be confirmed.
ii. Concentrations reguiring verification of washout: Following a result
greater than the highest concentrations validated for washout (see
Table 9 of Appendix B) do the following:
1. If the run was determined to be in-control for low concentration
samples before the next samples were analyzed, no further
action is required.
2. If the run was not determined to be in-control for low
concentration samples before the next samples were analyzed
confirm by re-analysis the results for the 2 samples
immediately following the elevated sample. Report the results
if they confirm the initial results within ±10% or ±3SD of the low
bench QC, whichever is greater.
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b. Unacceptable reproducibility: If the range of the three replicate
readings (maximum replicate concentration value - minimum replicate
concentration value) for a single sample analysis is greater than the
range maximum criteria listed in Table 9 in Appendix B and the range
of the three replicate readings is greater than 10% of the observed
concentration, do not use the measurement for reporting. Repeat the
analysis of the sample.
viii. Submitting final work for review: All analyses must undergo quality control and
quality assurance review. After appropriately documenting the run in the
laboratory information system (e.g. sample and run QC, and run and sample
comments), inform the first level reviewer of the completed work and submit
any printed documentation.
9) Routine equipment maintenance and data backups
Maintenance activities will be documented in the instrument logbook.
a. Equipment maintenance: Analysts are expected to regularly evaluate the need
for, and when necessary perform, cleaning, replacement, or re-positioning of
components in ICP-MS the sample introduction system, interface, ion optics
region, and equipment required resources (e.g. autosampler, exhaust,
compressed gases, and coolant). Frequency of equipment maintenance will be
dependent on instrument throughput.
b. Parameter optimizations: Analysts are expected to optimize instrument
parameters.
i. Dual detector calibration: Perform dual detector calibration regularly for any
element exceeding 1,000,000 cps for calibration standard 8. This is typically
only Pb. Dual detector calibration solution is described in Section 6.f.ii.
Frequency of dual detector calibration is typically monthly when throughput
requires multiple analytical runs per week, or as needed for optimized linearity.
ii. PRC optimizations: DRC conditions (cell gas flow rate and RPq value) can be
verified by analyzing the DRC optimization solutions (see Section 6.f.i) as
needed to ensure proper reduction of potential ICP-MS interferences.
c. Data backup: Data on the instrument computer will be backed up via two backup
routines. Files used and produced by the ICP-MS in analyzing samples will be
backed up and kept a minimum of two years after analysis.
i. Daily backups to secondary hard drive: Program automatic backups of the
relevant computer files to occur each night onto a secondary hard drive to
prevent loss of data from failure of primary hard drive.
ii. Weekly backup: Backup relevant computer files weekly either to secondary
hard drive which is remote to the laboratory or to removable media which will
be placed remote to the laboratory for retrieval in the case of catastrophic data
loss elsewhere.
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10)Reporting thresholds
a. Reportable range: Blood elemental concentrations are reportable in the range
between the method LOD and the highest calibrator (see 'calibrator
concentrations' in Table 1) times the maximum validated extra dilution (see Table
8). Above the highest concentration verified, extra dilutions are made of the
blood sample to bring it within the reportable range.
b. Reference ranges (normal values): In this method the 95% reference ranges
(see Appendix B, Table 10) for these elements in blood fall within the range of
the calibrators.
c. Action levels: Report concentrations observed greater than the "second upper
boundary" (defined in the laboratory database as the "2UB") to the QC reviewer
as an "elevated result". The concentration assigned to the 2UB for an element is
determined by study protocol but default concentrations are listed in Table 9 in
Appendix B. The protocol for supervisors reporting elevated results to medical
personnel is defined according to the study protocol. But typically,
i. Lead: Levels of lead in blood of children ages 1 -5 are considered elevated
above 5 ng/dL and chelation treatment is recommended at blood lead levels
>45 ng/dL[65]. The Occupational Safety and Health Administration regulations
use a blood lead level of 40 ng/dL as cause for written notification and a
medical exam, and a blood lead level of 60 ng/dL as cause for medical
removal from exposure[66],
ii. Cadmium: Levels of concern for cadmium in blood is >5 ng/L[67, 68],
iii. Mercury: The American Conference of Governmental Industrial Hygienists has
a biological exposure index (BEI) of 15 ng/L for inorganic mercury in blood
(end of shift at end of work week)[68],
iv. Manganese: Insufficient data to establish an action level.
v. Selenium: >500 ng/L [69, 70]
11) Method Calculations
a. Method limit of detection (LODs): The method detection limits for elements in
blood specimens are defined as 3 times so, where so is the estimate of the
standard deviation at zero analyte concentration. So is taken as the y-intercept of
a linear or 2nd order polynomial regression of standard deviation versus
concentration (4 concentration levels of the analytes in blood each measured 60
times across at least a 2-month timeframe). Method LODs are re-evaluated
periodically.
b. Method limit of Quantitation (LOQ): The Division of Laboratory Sciences does not
currently utilize limits of quantitation in regards to reporting limits [71],
c. QC Limits: Quality control limits are calculated based on concentration results
obtained in at least 20 separate runs. It is preferable to perform separate
analyses on separate days and using multiple calibrator lot numbers,
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 49 of 94
instruments, and analysts to best mimic real-life variability. The statistical
calculations are performed using the SAS program developed for the Division of
Laboratory Sciences (DLS_QC_compute_char_stats.sas).
12) Alternate methods for performing test and storing specimens if test system
fails:
If the analytical system fails, the analysis may be setup on other ICP-MS instruments
in the laboratory. If no other instrument is available, store the specimens at ~4 °C
until the analytical system can be restored to functionality. If interruption longer than
4 weeks in anticipated, then store blood specimens at < -20 °C.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 50 of 94
Appendix A: Critical parameter test results
Critical parameter test #1: Testing scenario of something preventing a set of prepared
samples from being analyzed immediately.
Test details:
Day 1: Prepared a set of dilutions (calibrators, blanks, reference material, fake samples)
for analysis in triplicate. Analyzed set 1 immediately (normal practice). Cap sets
2 and 3 and leave at room temperature for later analysis.
Day 2: Prepared run set 4 and analyzed it sequentially with run set 2
Day 3: Prepared run set 5 and analyzed it sequentially with run set 3
Table 1. Ruggedness testing results: Evaluating the significance of time from preparation to analysis
on sample stability. Test performed 12/6-8/10 by Deanna Jones. Results are the average of the
beginning and ending QC results for each analytical run.
ID
Time, prep to
analysis
Hg (|jg/L)
Pb (|jg /dL)
Cd (Mg /L)
Mn (|jg /L)
Se (Mg /L)
target mean
0.585
2.12
0.488
7.98
r-
and 3SD range
0.318-0.852
1.99-2.25
0.353 - 0.623
6.38-9.59
LB087I
_WB2
0 hr
0.418
2.03
0.399
6.09
24 hr (fresh)
0.504 (0.522)
1.99 (2.18)
0.419 (0.47)
7.06 (7.88)
48 hr
0.396 (0.418)
2.04 (2.03)
0.509 (0.40)
7.82 (6.09)
target mean
6.19
10.1
3.14
14.9
CO
o
and 3SD range
5.74-6.63
9.73-10.4
2.84-3.44
12.8-17.1
B087
WB2
0 hr
5.86
10.0
3.03
12.5
24 hr
5.46 (5.7)
9.5 (10.7)
2.85 (3.17)
13.6 (14.7)
X |
48 hr
2.64 (5.9)
9.2 (10.0)
2.79 (3.03)
13.5 (12.5)
c/)
< *
target mean
and 3SD range
228
206 - 251
o 2
LU V
0 hr
192
24 hr
202 (217)
G o
48 hr
56 (192)
c/)
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 51 of 94
Appendix A: Critical parameter test results (continued)
Critical parameter test #2: This test evaluated the significance of the RF Power setting
of the ICP when analyzing blood samples for whole blood metals.
Test details:
1. Prepare a set of dilutions (calibrators, blanks, reference material, dummy samples)
for analysis in triplicate (three separate sets of tubes).
2. Analyze them in three separate runs on the same day, same instrument.
3. Change the RF Power across the runs
4. Allow 15 minutes equilibration time between runs for RF Power to stabilize
Table
sampl
Resul
2. Ruggedness testing results: Evaluating the significance of F
e stability. Test performed on December 6 and December 10,
ts below are the average of the beginning and ending QC resul
\F Power setting on
2010 by Deanna Jones,
ts for each analytical run.
ID
RF power (W)
Hg (M9 /l)
Pb (Mg /dL)
Cd (jjg /L)
Mn (Mg /L)
Se (jjg /L)
LB08707 W
B2
target mean
and 2SD range
0.585
0.407-0.763
2.12
2.03-2.21
0.488
0.398-0.578
7.98
6.91 -9.05
1150 W
0.517
2.09
0.432
7.35
1450 W
(default)
0.512
2.03
0.369
6.76
1600 W
0.529
2.02
0.418
7.17
HB08708 W
B2
target mean
and 2SD range
6.19
5.89-6.48
10.1
9.84-10.3
3.14
2.94-3.34
14.9
13.5-16.4
1150 W
5.90
10.0
2.93
13.7
1450 W
(default)
6.23
10.2
2.90
12.8
1600 W
5.99
10.1
3.07
13.3
QMEQAS08
B-02*
target mean
and 2SD range
293
273-313
1150 W
269
1450 W
(default)
288
1600 W
314
QMEQAS08
B-08*
target mean
and 2SD range
165
154- 176
1150 W
179
1450 W
(default)
147
1600 W
146
*samples purchase from Le centre de toxicology du Q
uebec (Quebec, Canada)
Conclusion: Results are not compromised by changes in RF power within the range of
1150W to 1600W.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 52 of 94
Appendix A: Critical parameter test results (continued)
Critical parameter test #3: This test evaluated the significance of the dynamic reaction
cell gas flow rate of the reaction gas (oxygen and methane) while analyzing blood
samples for elements analyzed in DRC mode (Hg, Mn, and Se). The cell gas flow rate
for Mn and Hg is oxygen (62) and the per method setting is 1.2 mL/min. The cell gas
flow rate for Se is methane (ChM) and the per method setting is 0.84 mL/min.
Test details:
1. Prepare a set of dilutions (calibrators, blanks, reference material, dummy samples)
for analysis in triplicate (three separate sets of tubes).
2. Analyze them in three separate runs on the same day using the same instrument.
3. Change the cell gas flow rate.
Table 3. Ruggedness testing results: Evaluating the significance of dynamic reaction cell gas
flow rate on sample stability. Test performed on December 6, 2010 and January 4, 2010 by
Deanna Jones. Results below are the average of the beginning and ending QC results for
each analytical run.
ID
cell gas
flow rate
Hg (M9 /L)
Pb (Mg /dL)
Cd (jjg /L)
Mn (Mg /L)
Se (jjg /L)
LB08707_WB2
target mean
and 2SD range
0.585
0.407 - 0.763
2.12
2.03-2.21
0.488
0.398-0.578
7.98
6.91 -9.05
See
Table 4
0.96 mL/min O2;
0.7 mL/min CH4
0.457
2.10
0.471
8.49
1.2 mL/min O2;
0.84 mL/min CH4
0.479
2.10
0.438
8.15
1.44 mL/min O2;
1.0 mL/min CH4
0.555
2.11
0.457
8.12
HB08708_WB2
Target Mean
and 2SD Range
6.19
5.89-6.48
10.1
9.84-10.3
3.14
2.94-3.34
14.9
13.5-16.4
0.96 mL/min O2;
0.7 mL/min CH4
4.71
10.0
3.19
14.4
1.2 mL/min O2;
0.84 mL/min CH4
5.45
10.1
2.92
15.2
1.44 mL/min O2;
1.0 mL/min CH4
5.34
10.3
3.04
14.6
Conclusion: Accuracy of Mn and Hg results are not compromised by changes in cell
gas flow rate within the range tested (0.96 - 1.44 mL/min).
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 53 of 94
Appendix A: Critical Parameter Test Results (Continued)
Table 4. Ruggedness testing results: Evaluating the significance of dynamic reaction cell gas
flow rate on sample stability. Test performed on December 6, 2010 and January 4, 2010 by
Deanna Jones. Results below are the average of the beginning and ending QC results for
each analytical run.
ID
cell gas
flow rate
Hg (Mg /L) Pb (Mg /dL) Cd ftjg IL) Mn ftjg IL)
Se (|jg /L)
QMEQAS07B-09*
target mean
and 2SD range
See
Table 3, Appendix A
157
146- 168
0.96 mL/min O2;
0.7 mL/min CH4
187
1.2 mL/min O2;
0.84 mL/min CH4
186
1.44 mL/min O2;
1.0 mL/min ChM
191
QMEQAS08B-02*
target mean
and 2SD range
293
273-313
0.96 mL/min O2;
0.7 mL/min CH4
328
1.2 mL/min O2;
0.84 mL/min CH4
334
1.44 mL/min O2;
1.0 mL/min ChM
339
*samples purchase from Le centre de toxicology du Quebec (Quebec, Canada)
Conclusion: Accuracy of Se results are not compromised by changes in cell gas flow
rate within the range tested (0.7 - 1.0 mL/min).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 54 of 94
Appendix A: Critical parameter test results (continued)
Critical parameter test #4: This test evaluated the significance of the RPq value while
analyzing blood samples for Se, Mn and Hg. The RPq value setting per method for Mn
and Hg is 0.6, and for Se it is 0.65. The reduced and elevated RPq values for Mn and
Hg are 0.48 and 0.72, respectively. The reduced and elevated RPq values for Se are
0.52.and 0.78, respectively. The results are presented in Tables 5 and 6.
Test details:
1. Prepare a set of dilutions (calibrators, blanks, reference material, fake samples) for
analysis in triplicate (three separate sets of tubes).
2. Analyze them in three separate runs on the same day, using the same instrument.
3. Change the RPq value.
Table 5. Ruggedness testing results: Evaluating the significance of RPq value on sample
stability. Test performed on December 21, 2010 by Deanna Jones. Results below are the
average of the beginning and ending QC results for each analytical run.
ID
RPq
Hg (M9 /L)
Pb (Mg /dL)
Cd (jjg 11)
Mn (Mg /L)
Se (Mg /L)
LB08707_WB2
Target Mean
and 2SD Range
0.585
0.407 - 0.763
2.12
2.03-2.21
0.488
0.398-0.578
7.98
6.91 -9.05
See
Table 6
0.48 Mn and Hg;
0.52 Se
0.455
1.97
0.361
7.86
0.6 Mn and Hg;
0.7 Se
0.418
2.03
0.399
6.09
0.72 Mn and Hg;
0.78 Se
0.402
2.07
0.402
7.99
HB08708_WB2
Target Mean
and 2SD Range
6.19
5.89-6.48
10.1
9.84-10.3
3.14
2.94-3.34
14.9
13.5-16.4
0.48 Mn and Hg;
0.52 Se
5.54
9.4
2.79
14.4
0.6 Mn and Hg;
0.7 Se
5.86
10.0
3.03
12.5
0.72 Mn and Hg;
0.78 Se
5.53
9.7
2.88
14.9
Conclusion: Accuracy of Mn and Hg results are not compromised by changes in RPq
settings within the range tested (0.48 - 0.72).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 55 of 94
Appendix A: Critical Parameter Test Results (Continued)
Table 6. Ruggedness testing results: Evaluating the significance of RPq value on sample
stability. Test performed on December 21, 2010 by Deanna Jones. Results below are the
average of the beginning and ending QC results for each analytical run.
ID
RPq
Hg (Mg IL) Pb (Mg /dL) Cd ftjg IL) Mn ftjg IL)
Se (|jg /L)
QMEQAS07B-09*
target mean
and 2SD range
See
Table 5, Appendix A
293
273-313
0.48 Mn and Hg;
0.52 Se
262
0.6 Mn and Hg;
0.7 Se
250
0.72 Mn and Hg;
0.78 Se
277
QMEQAS08B-02*
target mean
and 2SD range
361
337 - 385
0.48 Mn and Hg;
0.52 Se
347
0.6 Mn and Hg;
0.7 Se
349
0.72 Mn and Hg;
0.78 Se
364
*samples purchase from Le centre de toxicology du Quebec (Quebec, Canada)
Conclusion: Accuracy of Se results are not compromised by changes in RPq settings
within the range tested (0.52 - 0.78 for Se).
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IRAT-DLS Method Code: 3016.8-05 Page 56 of 94
Appendix A: Critical parameter test results (continued)
Critical parameter test #5: This test evaluated the significance of the Axial Field Voltage
(AFT) while analyzing blood samples for whole blood metals. The Axial Field Voltage
may vary on each instrument. The Axial Field Voltage was increased and decreased by
20%. The results are presented in Table 7.
Test details:
1. Prepare a set of dilutions (calibrators, blanks, reference materials, fake samples) for
analysis in triplicate (three separate sets of tubes).
2. Analyze them in three separate runs on the same day, same instrument.
3. Change the AFV value +/-100 V.
Table 7. Ruggedness testing results: Evaluating the significance of Axial Field Voltage on sample
stability. Test performed on December 20, 2010 by Deanna Jones. Results below are the average of
the beginning and ending QC results for each analytical run.
ID
axial field voltage
Hg (|jg /L)
Pb (|jg /dL)
Cd (Mg /L)
Mn (|jg /L)
Se (Mg /L)
1
Target Mean
0.585
2.12
0.488
7.98
and 2SD Range
0.407-0.763
2.03-2.21
0.398-0.578
6.91 -9.05
LB087I
WB2
(optimized - 100V)
0.511
2.00
40.415
7.77
(optimized)
0.461
2.04
0.394
6.36
(optimized + 100V)
0.414
2.01
0.376
6.95
l
Target Mean
6.19
10.1
3.14
14.9
CO
o
and 2SD Range
5.89-6.48
9.84-10.3
2.94-3.34
13.5-16.4
HB087
WB2
(optimized - 100V)
5.50
9.8
2.91
14.3
(optimized)
5.62
9.8
2.84
12.0
(optimized + 100V)
5.75
10.1
2.99
12.8
c/)
< *
Target Mean
and 2SD Range
157
146-168
O §
LU V
(optimized - 100V)
139
(optimized)
147
G o
(optimized + 100V)
138
o
C/D
<
Target Mean
and 2SD Range
548
511 - 585
(optimized - 100V)
501
LU o
^ m
(optimized)
556
O o5
(optimized + 100V)
532
*samp
es purchase from Le centre de toxicology du Quebec (Quebec, Canad
a)
Conclusion: Accuracy of Mn, Hg and Se results are not compromised by changes in
AFV settings within the range tested (optimized setting +/- 100V).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 57 of 94
Appendix A: Critical parameter test results (continued)
Parameter test #6: Evaluate the impact on observed concentration if an extra dilution is
performed on the sample relative to the calibration standards.
Test details:
1. A large blood sample was spiked to elevated concentrations, and mixed well. The
spiked sample was then prepared for analysis at various extra dilution levels and the
observed results compared to results obtained with no extra dilution performed.
normalized concentration ± 1RSD
Dilution level
Mn
Hg
Se
Cd
Pb
No Extra (N=8)
1.00
1.00
1.00
1.00
1.00
2x dilution (N=8)
1.00 ±0.01
1.03 ±0.05
1.02 ±0.03
1.00 ±0.01
1.01 ±0.01
5x dilution (N=6)
1.01 ±0.01
1.06 ±0.06
1.01 ±0.02
1.01 ±0.01
1.02 ±0.01
10x dilution (N=8)
1.01 ±0.03
1.04 ±0.06
1.04 ±0.06
1.00 ±0.02
1.02 ±0.02
20x dilution (N=8)
1.02 ±0.04
1.09 ±0.05
1.06 ±0.08
1.01 ±0.03
1.02 ±0.02
Conclusion: Results show that all analytes of the method (Pb, Cd, Hg, Mn, and Se) can
be analyzed at up to a 20x extra dilution without significant effect (> ± 10% error) to the
observed concentration.
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 58 of 94
Appendix B
Table 1. Instrument and method parameters.
Instrument: PerkinElmer ELAN DRC II ICP-MS
ESI SC4 autosampler with (optional) PC3 Peltier cooled spray chamber
Optimization window parameters
RF power
1450 W
Plasma Gas Flow (Ar)
15 L/min
Auxiliary Gas Flow (Ar)
1.2 L/min
Nebulizer Gas Flow (Ar)
~0.90 - 1.0 L/min (optimized as needed for sensitivity)
Ion Lens Voltage(s)
AutoLens (optimized as needed for sensitivity)
AFV, QRO, CRO, CPV,
Discriminator Threshold
Optimized per instrument by service engineer, or advanced
user.
Parameters of x-y alignment, nebulizer gas flow, AutoLens voltages, mass calibration,
dual detector calibration and detector voltages are optimized regularly. Optimization file
name = default.dac.
Configurations window
parameters
cell gas changes
pause times
Pressurize Delay (From Standard to DRC mode) = 60
Exhaust Delay (From DRC to Standard mode) = 30
Flow Delay (Gas changes while in DRC mode) = 30
Channel Delay (Gas channel change in DRC mode) = 30
File names & directories
method file names
calibration curve (programmed for blood blank)
CDC_DLS3016_bldblk.mth
For QC & patient sample analysis
(programmed for aqueous blank)
CDC DLS3016 aqblk.mth
dataset
Create a new dataset subfolder each day. Name as "2011 -
0820" for all work done on August 20, 2011
sample file
Create for each day's work
report file name
For sample results printouts
cdc_quant comprehensive.rop
For calibration curve information
CDC_Quant Comprehensive (calib curve info).rop
tuning
Default.tun
optimization
Default.dac
calibration
N/A
polyatomic
elan.ply
report options template
(transferring results to
the database)
CDC_Database Output.rop
Report Format Options: select only "Use Separator"
File Write Option: Append
Report File name: make descriptive including date
(e.g. 2005-0311b_DRC2A_HM-0364.txt)
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IRAT-DLS Method Code: 3016.8-05 Page 59 of 94
Table 1. Instrument and method parameters.
Method Parameters
Method Parameters: Timing Page (see Figures 1a, 2a and 2d in Appendix B)
sweeps/reading
30
readings/replicate
1
replicates
3
enable qc checking
On
isotopes monitored
and internal standard
associations
(exact mass)
use 103Rh, 130Te, 193lras internal standards
103Rh (102.905): 55Mn (54.93805)
130Te(129.907): 202Hg (201.971), 80Se(79.9165)
193lr(192.963):208Pb(207.977), 114Cd(113.904)
dwell times
100 ms for 55Mn,202Hg, 80Se, 208Pb, and 114Cd
50 ms for 130Te,103Rh, and 193lr
scan mode
Peak Hopping for all isotopes (1 MCA channel)
DRC channel A
gas flow rate
99.999% methane (5-7 psig delivery pressure)
typically 0.84 L/min (0.7 - 1.0) *
*optimized per instrument, and periodically verified
DRC channel B
gas flow rate
99.99% oxygen (5-7 psig delivery pressure)
typically 1.2 L/min (0.96 - 1.44) *
*optimized per instrument, and periodically verified
RPa
0 for all isotopes
RPq
Typically*
0.6 (0.48 - 0.72) for 103Rh,55Mn,130Te, and 202Hg.
0.65 (0.52 - 0.78) for 130Te and 80Se.
0.25 for 193lr, 208Pb, and114Cd
Use the same RPQ for each analyte and its IS.
(* Optimize per instrument, and periodically verified)
Method parameters:
processing page (see Figures 1b in Appendix B)
detector mode
Dual
process spectral peak
N/A
autolens
On
isotope ratio mode
Off
enable short settling
time
Off
blank subtraction
After internal standard
measurement units
cps
process signal profile
N/A
Method parameters: equations page (see Figure 1c in Appendix B)
equations
+Hg 200
-0.027250 *Sn118
+Pb 206 +Pb 207
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IRAT-DLS Method Code: 3016.8-05 Page 60 of 94
Table 1. Instrument and method parameters.
Method parameters: calibration page (see Figures 1d in Appendix B)
calibration type
external std.
curve type
weighted linear
sample units
Vg/L" or "ppb"
calibrator concentrations
(ng/L)
Mn (|jg /L): 1.5, 4.5, 10.5, 15, 30, 75, 225, 600
Cd and Hg (pg /L): 0.5, 1.5, 3.5, 5, 10, 25, 75, 200
Pb (pg /dL): 1,3,7,10, 20, 50, 150, 400
Se (pg /L): 30, 90, 210, 300, 600, 1500, 4500, 12000
Method parameters: sampling page (see Figures 1e and 1f in Appendix B)
"peristaltic pump under
computer control"
On
autosampler
tray
port
sampling device
If using ESI autosampler
Autosampler Type: AS-93plus
Tray Name: esi.try
Sampling Device: None
If using other autosampler, refer to user guide.
sample flush
default is 4s at 1.5 rpm (-160 uL/min, ESI DXi peristaltic pump,
FAST sample introduction system)
Time can be optimized as needed to adequately fill the FAST
loop. Time and rpm can be optimized as needed to using a
different style peristaltic pump (maintaining approximate liquid
flow rate). As a matter of lab practice, set this time to equal the
loop fill time in the ESI FAST program. As long as the combined
time of sample flush + read delay is equal to the time required for
signal to reach stability, analytical measurement will be good.
read delay
60s at 1.5 rpm (-160 uL/min, ESI DXi peristaltic pump, FAST
sample introduction system)
Time can be optimized as needed to reach signal stability before
beginning analysis. Time and rpm can be optimized as needed to
using a different style peristaltic pump (maintaining approximate
liquid flow rate). As a matter of lab practice, set this time equal to
the total time required for the signal to reach stability minus the
loop fill time. As long as the combined time of sample flush +
read delay is equal to the time required for signal to reach
stability, analytical measurement will be good.
wash
30s at 1.5 rpm (-160 uL/min, ESI DXi peristaltic pump, FAST
sample introduction system)
Time can be optimized to allow for changes in FAST loop rinsing
(must be greater than total time of steps in FAST program after
the initial "on rinse" command). Time and rpm can be optimized
as needed to using a different style peristaltic pump (maintaining
approximate liquid flow rate).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 61 of 94
Table 1. Instrument and method parameters.
extra wash
(via ICP-MS software
QC checking)
For sample concentrations greater than these, setup the
ICP-MS software's 'QC checking' feature to "Wash for X and
continue"
Analyte Concentration Extra Rinse Time
Cd 200 ng/L 200s
Hg 200 ng/L 200s
Mn 600 ng/L 200s
Pb 400 ng/dL 200s
Se 1200 ng/L 200s
autosampler locations of
blanks and standards
For calibration curve (points to blood blank)
CDC_DLS3016_bldblk.mth
Calibration Stds 0 - 8 in autosampler positions 105 - 113 by
default, but can be customized.
For QC & patient sample analysis (points to aqueous blank)
CDC_DLS3016_aqblk.mth
Aqueous Blank in autosampler position 117 by default, but
can be customized.
FAST parameters: See
=igures 4a through 4h in Appendix B for details
configuration file
default.sc
(saved at C:\Program Files\ESI\ESI-SC\)
FAST program
cdc_dls3016_5element_loop1ml_scfast.txt
Potential Emergency Response Modifications:
mercury:
Analyze mercury in standard mode with tellurium as the internal
standard. Set dwell time to 100ms, DRC gas flow to 0, and RPq
to 0.25.
Non-FAST sample
introduction system:
If the FAST sample introduction system is not available on any
instruments, the method can still be implemented, but these
changes will need to be made in the ELAN (and ESI software if
present). Peristaltic pump speeds are for DXi pump; adjust
accordingly if another pump is installed.
• sample flush: Default is ~30s at-16 rpm. Set so that solution
reaches nebulizer.
• read delay: Default is 45s at -5 rpm. Set for best
reproducibility of replicate measured intensities.
• wash: Default is 60s at -11rpm. Set to prevent significant
carry-over from one sample to the next.
• If using ESI autosampler without FAST, disable FAST in the
ESI software before running analysis.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 62 of 94
Appendix B (continued)
Table 2. Suggested concentrations for base blood
analyte (units)
suggested concentration
Cd (ug/L)
<0.5
Hg (mq/l)
<0.5
Mn (pg/L)
< 8
Pb (pg/dL)
<2
Se (pg/L)
<200
Table 3. Stock calibration standard concentrations
Analyte
Stock calibration concentration (mg/L)
High Purity Standards Item # SM-2107-042
10% v/v HCI
Cd
50
Hg
50
Mn
150
Pb
1000
Se
3000
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 63 of 94
Appendix B (continued)
Table 4. Preparation of intermediate stock calibration standard
volume of flask (mL)
100
volume of spike of stock standard solution
2
concentrations ( mg /L)
Cd
1
Hg
1
Mn
3
Pb (mg/dL)
20
Se
60
Table 5. Preparation of intermediate working standards
Standard #
1
2
3
4
5
6
7
8
volume of
flask (mL)
100
100
100
100
100
100
100
100
volume spike
of stock std.
(mL)
0.05
0.15
0.4
volume spike
of int. stock
Std. (mL)
0.05
0.15
0.35
0.50
1.00
concentrations (jjg /L) *
Cd
0.5
1.5
3.5
5
10
25
75
200
Hg
0.5
1.5
3.5
5
10
25
75
200
Mn
1.5
4.5
10.5
15
30
75
225
600
Pb ( ug /dL)
1
3
7
10
20
50
150
400
Se
30
90
210
300
600
1500
4500
12000
* These same concentrations are entered in the ICP-MS software's calibration page to
describe the concentrations of the working calibrators (preparations analyzed during a
run). This eliminates the need to multiply ICP-MS observed results by a dilution factor
except for the case of extra dilutions (see Table 8).
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 64 of 94
Appendix B (continued)
Table 6. Acceptable ways to perform two consecutive analytical runs,
bracketing with bench quality control samples.
setup 1
setup 2
Run#1
Run#1
calibration standards
calibration standards
low bench QC
low bench QC
high bench QC
high bench QC
elevated bench QC
elevated bench QC
patient samples
patient samples
low bench QC
low bench QC
high bench QC
high bench QC
elevated bench QC
elevated bench QC
Run #2
Run #2
low bench QC
calibration standards
high bench QC
low bench QC
elevated bench QC
high bench QC
patient samples
elevated bench QC
low bench QC
patient samples
high bench QC
low bench QC
elevated bench QC
high bench QC
elevated bench QC
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 65 of 94
Appendix B (continued)
Table 7. A
typical SAMPLE/BATCH window.
AS
Location*
Sample ID
Measurements Action
Method
233
DRCstabilityl
Run sample
...DLS3016 bldblk.mth
233
DRCstability2
Run sample
...DLS3016 bldblk.mth
233
DRCstability3
Run sample
...DLS3016 bldblk.mth
233
DRCstability4
Run sample
...DLS3016 bldblk.mth
Continue DRC stability samples . . .
233
DRCstability9
Run sample
...DLS3016 bldblk.mth
233
DRCstabilityl 0
Run sample
...DLS3016 bldblk.mth
114
3016 BldBlkChkl
Run blank, standards, and
sample **
...DLS3016 bldblk.mth
115
3016 BldBlkChk2
Run sample
..DLS3016 bldblk.mth
116
3016 AQBLK
Run blank and sample ¥
..DLS3016 aqblk.mth
125
L Bench QC
Run sample
..DLS3016 aqblk.mth
126
H Bench QC
Run sample
..DLS3016 aqblk.mth
127
E Bench QC
Run sample
..DLS3016 aqblk.mth
137
Sample 1
Run sample
..DLS3016 aqblk.mth
138
Sample 2
Run sample
..DLS3016 aqblk.mth
125
L Bench QC
Run sample
..DLS3016 aqblk.mth
126
H Bench QC
Run sample
..DLS3016 aqblk.mth
127
E Bench QC
Run sample
..DLS3016 aqblk.mth
* The exact autosampler positions of QCs and patient samples do not have to be those
shown above. QC samples do not have to be run in the order of low, then high, then
elevated.
** When executing this row, the ELAN will first analyze the standard 0 (blood blank) at AS
position 105, then standards 1 -8 at autosampler positions 106-113, then the "3016
BldBlkChkl" sample at A/S position 114. The sampling information about AS positions 105-
113 are stored in the "bldblk" method file.
¥ When executing this row, the ELAN will first analyze the aqueous blank at AS position
117, then the "Aq blank" at AS position 103. The sampling information about AS positions
117 is stored in the "aqblk" method file.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 66 of 94
Appendix B (continued)
Table 8. Preparation of samples, working calibrators, and QC materials for
analysis *
If a different total volume is prepared, adjust the volumes for each component proportionally.
* These directions are written with the expectation of a 5,000 jj.L syringe on the left side and a 250
jj.L syringe on the right side of the benchtop automatic pipette.
Description
Water
(HL)
Base
Blood
(HL)
AQ
Intermediate
Working
Standard (|j.L)
Patient or
QC blood
sample
(nL)
Diluent
(M-L)**
Working Calibrators (S0-S8)
and Bldblkchk (SO)
-
50 x 1
50 x 1
-
2,400
(1,200 x 2)
AQ Blank
100x1
-
-
-
2,400
(1,200 x 2)
Patient blood or Blood-Based QC
50 x 1
-
-
50 x 1
2,400
(1,200 x 2)
Patient Blood 2x Extra Dilution H
150x1
-
-
50 x 1
4,800
(2,400 x 2)
Patient Blood 5x Extra Dilution H
450
(225 x 2)
50 x 1
12,000
(4,000 x 3)
Patient Blood 10x Extra Dilution H
950
(190x5)
50 x 1
24,000
(4,000 x 6)
Patient Blood 20x Extra Dilution H
1950
(195x10)
50 x 1
48,000
(4,000 x 12)
** By splitting the dispense step of diluent into two or more portions, liquids pulled up into the right
pipette tip are flushed out more completely. For example, when preparing a working calibrator, do
the preparation in two steps: in step 1, dispense 2400 jj.L diluent + 50 jj.L; in step 2, dispense 2400
M.L diluent + 50 m.L base blood to prepare a 2.5 mL total volume dilution.
H Extra dilution is performed on urine samples whose concentration is greater than the highest
calibrator listed in the 'calibrator concentrations' section of Table 1 in the Appendix B.
Maximum extra dilution (see Appendix A, ruggedness test #6 for details)
20xforCd, Hg, Mn, Pb, and Se
Any extra level of dilution up to 20x (see Appendix A, Experiment 6) can be prepared as long as the
4.8:5 ratio of diluent to total dilution volume is maintained. Use of the lowest possible dilution level
is preferred to minimize differences between the calibrators and the samples (i.e. 2x dilution is
preferred over 10x if 2x is sufficient to dilute analyte into the documented linearity range).
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 67 of 94
Appendix B (continued)
Table 9. Boundary concentrations for whole blood concentrations
analyte
(units)
1st upper
boundary
("1UB") *
2nd upper
boundary
("2UB") **
range
maximum
("Lim Rep Delta") t
Highest
Concentration
Validated for
Washout
Mn (ug/L)
20
35
2.0
600
Pb (ng/dL)
5.0
5.0
1.0
400
Cd (ug/L)
5.0
5.0
1.0
200
Hg (ug/L)
10.0
10.0
1.0
200
Se (ug/L)
400
400
20
12,000
* Typically, the 1 st upper boundary (1UB) is
concentration results from the NHANES 199"
significant to public health, or a concentratior
1 UB concentrations are listed in this table.
he 99th percentile of non-weighted
3-2000 subset groups, a concentration
i defined by study protocol. The default
** The 2nd upper boundary (2UB) may be 2x the 1 UB, a concentration significant to
public health, or defined by study protocol.
t Range maximum (Lim Rep Delta) is the allowed limit to the range of the three
replicate readings for a single sample analysis.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 68 of 94
Appendix B (continued)
Table 10. Reference ranges for blood concentrations [72].
analyte
(units)
survey
years
geometric
mean
50th
75th
90th
95th
N
Cd (ng/L)
07-08
0.315
0.270
0.500
1.00
1.52
8266
09-10
0.302
0.260
0.480
0.960
1.40
8793
11-12
0.279
0.250
0.460
0.960
1.50
7920
Hg (ng/L)
07-08
0.769
0.740
1.48
2.95
4.64
8266
09-10
0.863
0.790
1.68
3.43
5.13
8793
11-12
0.703
0.640
1.38
2.87
4.40
7920
Pb (ng/dL)
07-08
1.27
1.22
1.90
2.80
3.70
8266
09-10
1.12
1.07
1.70
2.58
3.34
8793
11-12
0.973
0.930
1.52
2.38
3.16
7920
Mn (ng/L)
11-12
9.35
9.22
11.5
14.4
16.7
7920
Se (ng/L)
11-12
190
190
206
223
236
7920
Table 11. Reference concentrations from published literature for blood Mn and
Se.
analyte
(units)
published concentrations
Se (ug/L)
157-265 ug/L [731
Mn ( |jg /L)f
Non-exposed 4 — 14 (|jg /L) [46]
Exposed workers (adults) 3.2 - 101 pg /L [28]
Children receiving long term parenteral nutrition 33.8 - 101 pg /L [74]
Ohio adults (N=49) residing near a refinery (possible Mn emission):
Mean (range) 9.4 (4.2-21.7) pg/L [30]
Mexican infants
Age 1, mean (SD) = 24.3 (4.5) pg/L, median = 23.7 pg/L, N=270
Age 2, mean (SD) = 21.1 (6.2) pg/L, median = 20.3 pg/L, N=430 [75]
Japanese women (N = 1420)
GM 13.2 pg/L overall,
Range of median (max) across 8 regions 12.0-14.3 (25.0-33.4) pg/L [76]
South African children, ages 8-10 years old (n = 49)
Mean (SD) 8.48 (2.45) pg/L, range 4.58-18.20 pg/L. [341
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 69 of 94
Appendix B (continued)
Figure 1. Configuration of tubing and devices for liquid handling using FAST
sample introduction.
Below shows the correct connections to the 6-port FAST valve. The two diagrams show
the differences in liquid flow directions when the valve changes from "Load" to "Inject"
This change is internal to the valve. The shift of the valve cannot be seen, but it can be
heard, and felt (with hand on the valve). The light indicators on the actuator body also
indicate the valve position.
LOAD SAMPLE
To Waste
Teflon vacuum pump loads sample into loop
while carrier solution is nebulized
RINSE/ INJECT
To Waste
SC Aulosampler
with FAST
Carrier
Solution]
Carrier solution pushes sample into nebulizer
at the same time sample line is rinsed
The connections to the valve are color-coded (see Section 7.a.i).
Enable the FAST program in the ESI software before running the method, but
optimizations can be done in either FAST or non-FAST mode.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 70 of 94
Appendix B (continued)
Figure 2a. ELAN ICP-MS method screen shots (timing page).
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-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 71 of 94
Appendix B (continued)
Figure 2b. ELAN ICP-MS method screen shots (processing page).
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-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 72 of 94
Appendix B (continued)
Figure 2c. ELAN ICP-MS method screen shots (equation page).
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Isotope
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Has s
54.9381
Abundance
100.000000
Interferences
ArH, HC10, C10
Int
Std
Analyte
(*)
Mass
(amu)
Corrections
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Mn
54.9381
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2
3
4
5
6
7
8
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m
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r
L
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Hg
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Te-1
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Pb
102.905
129.907
201.971
79.9165
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+ Hg 200
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-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 73 of 94
Appendix B (continued)
Figure 2d. ELAN ICP-MS method screen shots (calibration page).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 74 of 94
Appendix B (continued)
Figure 2e. ELAN ICP-MS method screen shots (sampling page, AqBlank method).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 75 of 94
Appendix B (continued)
Figure 2f. ELAN ICP-MS method screen shots (sampling page, BldBlank method).
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-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 76 of 94
Appendix B (continued)
Figure 2g. ELAN ICP-MS method screen shots (report page).
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 77 of 94
Appendix B (continued)
Figure 2h. ELAN ICP-MS method screen shots (QC / Sample page).
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Mass
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QC Action
Priority
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Sample Upper
(Cone.)
Sample
Core SD
Sample
Cone RSD
D
y
Mn
Hg
Se
Cd
Pb
54,9381
201,971
79,9165
113,904
600
200
12000
200
207.977
400
Measurement
Action 1
(*)
Action 1 Action 2
Data (*)
Action 2
Data
1
Mn 55 Lower
Continue
Continue
2
Mn 55 Upper, S, EEE
Wash far X and Continue
200 seconds Continue
3
Mn 55 Std Dev
Continue
Continue
4
Mn 55 RSD
Continue
Continue
5
Hg 202 Lower
Continue
Continue
6
Hg 202 Upper, S, EEE
Wash for X and Continue
200 seconds Continue
7
Hg 202 Std Dev
Continue
Continue
8
Hg 202 RSD
Continue
Continue
9
Se 80 Lower
Continue
Continue
10
Se 80 Upper, S, EEE
Wash for X and Continue
200 seconds Continue
11
Se 80 Std Dev
Continue
Continue
12
Se 80 RSD
Continue
Continue
13
Cd 114 Lower
Continue
Continue
14
Cd 114 Upper, S, EEE
Wash for X and Continue
200 seconds Continue
15
Cd 114 Std Dev
Continue
Continue
16
Cd 114 RSD
Continue
Continue
17
Pb 208 Lower
Continue
Continue
18
Pb 208 Upper, S, EEE
Pb 208 Std Dev
Wash for X arid Continue
200 seconds Continue
19
Continue
Continue
20
Pb 208 RSD
Continue
Continue
\Calibration ^QC Stds. ^QC Measurement Frequency ^QC Std. Int. Stds. ^Calibration Stds. ^Sample Int Stds ^Sample
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 78 of 94
Appendix B (continued)
Figure 3a. ESI SC4 autosampler screen shots (main page). Additional flush times
and "Max Rinse Time" are approximate. Optimize these for best reduction of elemental
carry-over between samples. Tray types can be changed to allow for different volumes
of diluted sample digests. 'FAST control' must be enabled before start of method, but
does not need to be used in instrument optimization (pre-analysis) steps. Rinse and
additional flush times for eliminating carry-over from one sample to the next while using
the minimum amount of rinse solution.
A rinse time of -1 causes the rinse station to be skipped.
A rinse time of 0 causes the probe to only dip into the station, but spends no time there.
Additional flush times can be optimized to keep the rinse station full while not using too
much rinse solution. The inner diameter size of the tubing providing the rinse solution to
the rinse station determines how quickly the station will fill. Various sizes are available
for purchase or can be made in the laboratory.
M ESI SC Autosampler
B0B
File Calibrate Manual Configure Diagnosis Communication FAST About
Rinse Settings (sec)
PI FAST Control Enabled
FAST Method File: Blood Metals Par.el2 DLS3016_SC4 F
Initialize Autosampler
Rinse Time
Additional Rinse
Flush Time Count Down
Rinse 1:
Rinse 2:
0
20
Rinse/Wash
PI "Max Rinse Time" Enabled
300
5x 12
aaaa
5x 12
aaaa
Select Tray
2x2
5x 12
5x 12
Configuration File: default.sc Instrument: Perk in Elmer ELAN Autosampler Model: SC-4 DX SC Co mm Port: COM2
Autosampler Initialized - Instrument Comm Port Opened - » » Autosampler Position Rack 1 Vial: 44 - Syringe »
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 79 of 94
Appendix B (continued)
Figure 3b. ESI SC4 autosampler screen shots (5x12 rack setup window). Settings
are approximate. To be sure the loop is filled, set the probe to go close to the bottom of
the cup, but not touch. Optimize retraction speed for least droplet splatter.
II Rack Setup
Select Array
LR21 (3x7)
LR24 (3x8)
LR40 (4x10
LR90 (6x15)
MR 21 (3x7)
MR4nr4xim
MR 60 (5x121
MR90 (6x15)
M icro 24
Micro 48
Micro 96
MT24G
Probe Settings
Down Height(rnm) ^6
Retraction Speed(1-5)
1500
Save
Cancel
3
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 80 of 94
Appendix B (continued)
Figure 3c. ESI SC4 autosampler screen shots (50mL tube rack setup window).
Settings are approximate. To be sure the loop is filled, set the probe to go close to the
bottom of the cup, but riot touch. Optimize retraction speed for least droplet splatter.
M Rack Setup
Select Array
ST10CP
ST12
Probe Settings
Down Height(mm)
Retraction Speed(1 -5)
145
Save
Cancel
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 81 of 94
Appendix B (continued)
Figure 3d. ESI SC4 autosampler screen shots (rinse station rack setup window).
Settings are approximate. Optimize down height for best probe cleaning, and retraction
speed for least droplet splatter.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 82 of 94
Appendix B (continued)
Figure 3e. ESI SC4 autosampler screen shots ("Configure" page). "High Speed"
option is to only be used for 'High Speed' models of the SC4 (look for "HS" in serial
number). Speeds and accel / decel values can be optimized per analyst preference and
to minimize droplet splatter off of probe.
M ConfigureAutosampler
Horizontal
400
5000
Start Speed
Max Speed
Accel/Decel
0 High Speed (HS)
Rotational
Start Speed
Max Speed
Accel/Decel
0-5
1-5
1-5
Configuration File
Configuration File Name
default, sc
~ pen File
Save File
Cancel
30
350
0-5
1-5
[^1 Auto Initialize
Autosampler Model
Autosampler Model
SC-4/E4
] |]T 1-5
~ Enable FlTU 0
Vertical
Start Speed
Max Speed
Accel/Decel
Rail Height
500
2
3000
2
6
3
16 inches v
0-5
1-5
1-5
Instrument/Autosampler Emulation
Instrument Type
Perkin Elmer ELhN
Autosampler Type
AS 93
0 High Speed (HS)
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 83 of 94
Appendix B (continued)
Figure 3f. ESI SC4 autosampler screen shots ("Communication" page).
Communication ports will differ depending on available ports on instrument control
computer.
|}| ConfigureCommunication
SC Autosampler Communication Port:
Instrument Communication Port:
Instrument Communication
® GPIB or Physical COM Port
O Virtual COM Port
COM4
V
C0M1
V
AutoConfigure
OK
Cancel
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 84 of 94
Appendix B (continued)
Figure 3g. ESI SC4 autosampler screen shots ("FAST" page). Timer A can be
optimized to achieve proper filling of loop with diluted sample digestate. Timers B, C, D.
E, and F control rinsing the loop after analysis and can be optimized for eliminating
carry-over from one sample to the next while using the minimum amount of rinse
solution. Save the file with the name "DLS 3016.8 FAST parameters.txt". It can be
found in the directory C:\Program Files\ESI\ESI-SC\.
Manually clicking the "Load" button prior to starting analysis will ensure the position of
the actuator is always the same at the beginning of the analysis.
Manually clicking the "Vacuum On" button prior to starting the analysis will help initial
sample uptake to be consistent (the vacuum pump may be slow to start for the first
sample if this is not done, possibly resulting in loop filling inconsistencies)
|i| FAST Method Control
File Sub-Method
Event
Action
Parameters
Parameter
Units
Event
Parameter
~
On Probe Down
Vacuuml On
On Probe Down
Loadl
Probe In Sample
Timer A
4
seconds
Timer A Expires
Injectl
Timer A Expires
Move Rinse
Rinse Completed
Probe Up
On Rinse
Loadl
On Rinse
Probe Down
On Rinse
A2 On
On Rinse
Timer B
2
seconds
Timer B Expires
Probe Up
Timer B Expires
Timer C
2
seconds
Timer C Expires
Probe Down
Timer C Expires
Timer D
2
seconds
Timer D Expires
Probe Up
Timer D Expires
Timer E
2
seconds
Timer E Expires
Probe Down
Timer E Expires
Timer F
2
seconds
Timer F Expires
Probe Up
Timer F Expires
A2 Off
Timer F Expires
Move Next
*
Events
Probe In Sample
Rinse Completed
Move Into Next Co
On Probe Down
On Probe Up
On Rinse
On Rinse Type2
On RRW
On TTL Signal#
Timer A Expires
Timer B Expires
Timer C Expires
Timer D Expires
Timer E Expires
Timer F Expires
Timer G Expires
Timer H Expires
Timer I Expires
Timer J Expires
Actions
Vacuum On
Vacuum Off
Load
Inject
Trigger Instrument
Move Rinse
Move Next
Probe Up
Probe Down
Move To(rrvv)
Move Into Next
Move Into(rrvv)
T oggle Valve
Timer A
Timer B
Timer C
Timer D
Timer E
Timer F
Timer G
Timer H
Timer I
Timer J
Send Position Text
AuxOutX
AuxOutY
AuxOutZ
Sub-Method
Stop FAST
FAST Control
I | Enable FAST Control
Method File Name:
Blood Metals Panel2_DLS3016_
I | Enable Virtual Samples
RinseTime (s)
Rinsel
Rinse2 1^
Max Vacuum Time (s)
[300
FAST Syringe Peripump oneFAST GDP Flow Co
0ut1 On
0ut2 On
Injectl
Vacuuml On
0ut1 Off
0ut2 Off
Load2
Inject2
Vacuum2 On
Vacuum2 Off
T rigger
Actions
Vacuuml On
Vacuuml Off
Vacuum2 On
Vacuum2 Off
Loadl
Injectl
Load2
Inject2
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05
Page 85 of 94
Appendix B (continued)
Figure 4. chart for handling an elevated result
no
no
no
no
no
repeat elevated result for
confirmation by dilution in
duplicate, and report the first
analytically valid result as >2UB
Report the first analytically
valid result.
Repeat elevated result for
confirmation, and report the
first analytically valid result.
Repeat elevated result for
confirmation, and report the
first analytically valid result
as >2UB.
Repeat elevated result for
confirmation by dilution in
duplicate, and report the first
analytically valid result as >2UB.
Repeat elevated result for confirmation
by dilution in duplicate, and report the
first analytically valid result as >2UB.
Confirm by re-analysis the results for the
2 samples immediately following the
elevated sample. Report first analytically
valid result when it is confirmed within
±10% or ±3SD of the low bench QC,
whichever is larger.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 86 of 94
Appendix C: Help Sheets
Reagent Preparation (page 1 of 3)
NOTE:
mg/L = ppm
ug/L = ppb
ug/mL = ppm
Rinse solution
(0.4% TMAH. 0.05% Triton X-100. 1% ethyl alcohol. 0.01% APDC)
1. Partially fill a 4 liter bottle with >18 Mohmcm water.
2. Add 0.4 grams of APDC.
3. Add 16 mL of TMAH (Tetramethylammonium hydroxide, 25% w/w ((CH3)4NOH).
4. Add 40 mL of ethyl alcohol (C2H50H, 200 proof)
5. Add 200 mL of 1 % Triton X-100 (OR add 10mL of 20%Triton X-100).
6. Add enough >18 Mohm cm water to bring to 4 liter mark.
7. Mix well by gently inverting several times.
Sample diluent
(0.4% TMAH. 0.01% APDC. 0.05% Triton X-100. 1% Ethanol. 5ppb Te. Rh. Ir)
1. Partially fill a 2 liter bottle with >18 Mohm cm water.
2. Add 0.2 gram of APDC.
3. Add 8 mL of TMAH.
4. Add 20 mL of ethyl alcohol.
5. Add 500 uL of a 20 mg/L stock solution of Te, Rh, and Ir.
8. Add 100 mL of 1% Triton X-100 (OR, if using a 20% Triton X-100 solution, add 5mL)
9. Add enough >18 Mohm cm water to bring to 2 liter mark.
10. Mix well by gently inverting several times.
0.5. HNQ3
(Carrier solution for optimization)
1. Partially fill a 2 liter bottle with >18 Mohm cm water.
2. Add 10 mL of conc. HNO3.
3. Add enough >18 Mohm cm water to bring to 2 liter mark.
4. Mix well by gently inverting several times.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 87 of 94
Appendix C: Help Sheets (continued)
Reagent Preparation (page 2 of 3)
1% v/v HNOs
1. Partially fill a 10 liter bottle with >18 Mohmcm water.
2. Add 100 mL of conc. HNO3.
3. Add enough >18 Mohm cm water to bring to 10 liter mark.
4. Mix well by gently swirling several times.
5% v/v HNOs
1. Partially fill a 2 liter bottle with >18 Mohm cm water.
2. Add 100 mL of conc. HNO3.
3. Add enough >18 Mohm cm water to bring to 2 liter mark.
4. Mix well by gently inverting several times.
20% Triton X-100
1. Partially fill a 1 liter bottle with >18 Mohm cm water.
2. Add 200 mL of Triton X-100.
3. Add enough >18 Mohm cm water to bring to 1 liter mark.
4. Allow to dissolve overnight (or add a Teflon magnetic stirring bar and stir on stirrer
until dissolved).
5. Mix well by gently inverting several times.
1% Triton X-100
1. Partially fill a 1 liter bottle with >18 Mohm cm water.
2. Add 10 mL of Triton X-100.
3. Add enough >18 Mohm cm water to bring to 1 liter mark.
4. Allow to dissolve overnight (or add a Teflon magnetic stirring bar and stir on stirrer
until dissolved).
5. Mix well by gently inverting several times.
20 ppm Rh. Te and Ir internal standard solution
1. Partially fill an acid rinsed, 50 mL flask with 1 % v/v HNO3.
2. Add 1mL of Rh from 1000ppm stock standard.
3. Add 1mL of Te from 1000ppm stock standard.
4. Add 1mL of Irfrom 1000ppm stock standard.
5. Add enough 1 % v/v HNO3 to fill to 50mL mark.
6. Mix well by gently inverting several times.
7. Pour the standard solution over into an appropriately labeled 50mL polypropylene
tube.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 88 of 94
Appendix C: Help Sheets (continued)
Reagent Preparation (page 3 of 3)
Daily solution (1ppb) in 2% v/v HNO3
1. Partially fill a 1 liter volumetric flask with >18 Mohmcm water.
2. Add 1mLof High Purity Standard: SM-2107-018 (or current lot #)
3. Add 20mL of concentrated HNO3
4. Add enough >18 Mohm cm water to bring to 1 liter mark.
5. Mix well by gently inverting several times.
Stability test solution (1 liter bulk prep)
1. Use a 1 liter bottle dedicated to stability test solution preparation
2. Add 960 ml_ of Sample Diluent
3. Add 20 ml_ of "junk" whole blood
4. Add 20 ml_ of Intermediate Working Calibration Standard (may use S1 or S2)
OR add 1.5ml_ of Intermediate Stock Calibration Standard.
5. Mix well by gently inverting several times.
6. Store in the refrigerator (when not using).
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 89 of 94
Appendix C: Help Sheets (continued)
Standard Preparation (page 1 of 1)
(from single element stock standards)
Prepare 3% HCI v/v solution:
1. Partially fill a clean 2 liter bottle with >18 Mohmcm water.
2. Using a clean 50 mL polypropylene tube to measure, add 60 mL of high purity
concentrated HCI.
3. Add enough >18 Mohm cm water to bring to 2 liter mark.
4. Gently invert to mix.
Prepare intermediate stock standard (see Table 4 in Appendix B):
1. Partially fill a 100 mL volumetric flask with 3% v/v HCI solution.
2. Label as: "HgPbCdMnSe Intermediate Stock Std"
3. Add 2 mL of HgPbCdMnSe multi-element stock solution.
4. Add enough 3% v/v HCI to bring to 100 mL mark.
5. Mix well by gently inverting several times.
Prepare intermediate working standards (see Table 5 in Appendix B):
1. Partially fill each of eight, 100 mL volumetric flasks with 3% v/v HCI solution.
2. Label as: Intermediate Working Std "S1", "S2", "S3" and "S4", "S5", "S6", "S7"
and "S8".
3. For"S1 Intermediate Working Std"
4. For "S2 Intermediate Working Std"
5. For "S3 Intermediate Working Std"
6. For "S4 Intermediate Working Std"
7. For "S5 Intermediate Working Std"
8. For "S6 Intermediate Working Std"
9. For "S7 Intermediate Working Std"
10. For "S8 Intermediate Working Std"
11. Add enough 3% v/v HCI solution to bring to 100 mL mark.
12. Mix well by gently inverting several times.
13.These intermediate working standards may be poured over into clean 15 mL
Falcon tubes for daily use (NOTE: "SO Intermediate Working Std" is 3% HCI
only).
add 50 uL of the Intermediate Stock Std.
add 150 uL of the Intermediate Stock Std.
add 350 uL of the Intermediate Stock Std.
add 500 uL of the Intermediate Stock Std.
add 1mL of the Intermediate Stock Std.
add 50 uL of the Multi-Element Stock Std.
add 150 uL of the Multi-Element Stock Std.
add 400 uL of the Multi-Element Stock Std.
-------
blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 90 of 94
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blood multi-element analysis by ICP-DRC-MS
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60. Tanner, S.D., V.I. Baranov, and D.R. Bandura, Reaction cells and collision cells
for ICP-MS: a tutorial review. Spectrochimica Acta Part B-Atomic Spectroscopy,
2002. 57(9): p. 1361-1452.
61. Tanner, S.D. and V.I. Baranov, Theory, design, and operation of a dynamic
reaction cell for ICP-MS. Atomic Spectroscopy, 1999. 20(2): p. 45-52.
62. Burguera, J.L., et al., Electrothermal atomic absorption spectrometry
determination of molybdenum in whole blood. Spectrochimica Acta Part B-Atomic
Spectroscopy, 2002. 57(3): p. 561-569.
63. Jarrett, J.M., et al., Eliminating molybdenum oxide interference in urine cadmium
biomonitoring using ICP-DRC-MS. Journal of Analytical Atomic Spectrometry,
2008. 23(7): p. 962-967.
64. Division of Laboratory Sciences, Division of Laboratory Sciences Policies and
Procedures Manual. 2015, Centers for Disease Control and Prevention: Atlanta,
GA.
65. Centers for Disease Control and Prevention, CDC Response to Advisory
Committee on Childhood Lead Poisoning Prevention Recommendations in "Low
Level Lead Exposure Harms Children: A Renewed Call of Primary Prevention"",
Department of Health and Human Services, Editor. 2012: Atlanta, GA.
66. Occupational Safety and Health Administration, Occupational Safety and Health
Standards, in 29 CFR part 1910, Subpart Z, Standard number 1910.1025,
"Lead",. 1989.
67. Occupational Safety and Health Administration, Cadmium (OSHA 3136-06R
2004). 2004.
68. American Conference of Governmental Industrial Hygienists, Tlvs and Beis 2007:
Based on the Documentation for Chemical Substances and Physical Agents &
Biological Exposure Indices. 2007: American Conference of Governmental
Industrial Hygienists.
69. Baselt, R.C., Disposition of Toxic Drugs and Chemicals in Man,. 2011, Seal
Beach, CA: Biomedical Publications.
70. Nuttall, K., Evaluating selenium poisoning. Annals of clinical & laboratory
science, 2006. 36(4): p. 409-420.
71. Office of Health and Safety in the Division of Laboratory Sciences, Policies and
Procedures Manual. 2002, Division of Laboratory Sciences (DLS), National
Center for Environmental Health, Centers for Disease Control and Prevention,
Public Health Service, Department of Health and Human ServicesCenters for
Disease Control and Prevention, .
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blood multi-element analysis by ICP-DRC-MS
IRAT-DLS Method Code: 3016.8-05 Page 94 of 94
72. Centers for Disease Control and Prevention, Fourth National Report on Human
Exposure to Environmental Chemicals, February 2015 Update. 2015, CDC:
Atlanta, GA.
73. Carson, B.L., H.V.E. Ill, and J.L. McCann, Selenium, in Toxicology and biological
monitoring of metals in humans., B.L. Carson, H.V.E. Ill, and J.L. McCann,
Editors. 1986, Lewis Publishers, Inc.: Chelsea, Michigan, p. 213-218.
74. Fell, J.M.E., et al., Manganese toxicity in children receiving long-term parenteral
nutrition. Lancet, 1996. 347(9010): p. 1218-1221.
75. Henn, B.C., et al., Early Postnatal Blood Manganese Levels and Children's
Neurodevelopment. Epidemiology, 2010. 21(4): p. 433-439.
76. Ikeda, M., et al., Cadmium, chromium, lead, manganese and nickel
concentrations in blood of women in non-polluted areas in Japan, as determined
by inductively coupled plasma-sector field-mass spectrometry. International
Archives of Occupational and Environmental Health, 2011. 84(2): p. 139-150.
-------
Division of Laboratory Sciences
Laboratory Protocol
Analytes: Copper, Selenium, and Zinc
Matrix: Serum
Method: Multi-Elements in Serum by ICP-DRC-MS
Method code: DLS 3006.8-03
Branch: inorganic and Radiation Analytical Toxicology
Prepared By: Jeffery M. JarrelLMS W
Author's name
{7// /Signature
Date
Author's name
Signature
Date
Kathleen L. Caldwell PhD
Supervisor's name
Signature
Date
Robert L. Jones PhD ~
Branch Chiefs name
' ' Siartafure
- ?M/> ?
Date
Date current version of method first used in lab:
Date
Director's Signature Block:
Reviewed: Sr
\ iX'AI z/aobf
Signature Date
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This page is intentionally blank
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Procedure Change Log
Procedure: Multi-Elements in Serum by ICP-DRC-MS DLS Method Code: 3006.8-03
Date
Changes Made
By
Rev'd
By
(Initials)
Date
Rev'd
11/25/2011
Use of concentrated nitric acid during
preparation of calibrators and calibration
verification standards documented.
GM
JJ
11/25/2011
3/8/2012
Removed requirement for blind QC in each run
GM
JJ
3/8/12
7/26/2012
Revised maximum suggested concentrations of
analytes in base serum, Table 2 of Appendix C.
KW
JJ
7/27/12
7/27/2012
Updated page number references for normal
population ranges
KW
JJ
7/27/12
7/27/2012
Updated Appendix C Figure 2e. Method
screenshot Sampling page
KW
JJ
7/27/12
8/8/2012
Updated Table 1: Instrument and Method
Parameters (expanded typical nebulizer gas
flow range and updated pump speeds and delay
times for flush, read, and wash)
KW
JJ
8/8/12
12/18/2014
Defined top end of reportable range as S5 times
the maximum validated extra dilution factor
rather than by highest calibration verification
check analyzed. Updated Tables 1 and 4.
Added ruggedness testing for extra dilutions
(parameter #6).
KW
JJ
12/18/2014
12/18/2014
Updated Table 7. Changed to preparing serum
blank (and checks) with SO rather than water.
Clarified splitting volumes in use of Digifiex.
KW
JJ
12/18/2014
12/18/2014
Corrected volumes of Triton X-100 in
intermediate Triton solution and revised default
volume prep of diluent to 2L.
KW
JJ
12/18/2014
12/18/2014
Added description of solutions for DRC and
dual detector optimizations.
KW
JJ
12/18/2014
12/18/2014
Added reference to SOP DLS3500 for handling
corrosive liquid waste to the instrument waste
disposal guidelines.
KW
JJ
12/18/2014
12/18/2014
Updated instrumentation and equipment
sources for vendor names and part numbers.
KW
JJ
12/18/2014
12/18/2014
Added clarifying instruction of running water for
-30min between consecutive runs.
KW
JJ
12/18/2014
12/18/2014
Clarified and updated table of contents, section
headings, table numbers and naming, and
figure numbering and naming. Updated
instrument software screen shots.
KW
JJ
12/18/2014
12/18/2014
Updated 1 LB and 2LB for copper from
10 ug/dL to 50 ug/dL.
KW
JJ
12/18/2014
12/18/2014
Updated sections 8, 9, 10, 11 for clarity and to
match other laboratory methods.
KW
JJ
12/18/2014
4/6/2015
Added Appendix D "Help sheets"
ZF
JJ
4/7/2015
4/6/2015
Updated the minimum R2 of calibration curves to
0.98 to match DLS Policy and Procedures
JJ
JJ
4/7/2015
4/7/2015
Updated cover page per DLS Office of Director
JJ
JJ
4/7/2015
-------
Date
Changes Made
By
Rev'd
By
(Initials)
Date
Rev'd
12/08/2015
Updated Title page to new DLS
ZF
JJ
12/08/2015
template.
12/08/2015
Clarified comments, updated
examples, corrected typos: Removed
passive language (e.g. may, shall,
should) throughout. Clarified instruction
of standards preparation in Section 6.e.
Removed dual detector solution prep
instructions (Section 6.f,). Updated
Section 8.b.ii.2 to use junk serum
during DRC stability time rather than
standard 2. Clarified data backup
instructions in Section 9,b. Clarified
comments in Table 7 (prep of samples)
and 8 (boundary conditions).
ZF
JJ
12/08/2015
12/08/2015
Minor equipment updates: References
to Digiflex pipette changed to Hamilton
Microlab 625 benchtop automatic
pipette.
ZF
JJ
12/08/2015
12/08/2015
Updated expiration dates of
optimization solutions and base serum
in Section 6.e.
JJ
KLC
12/9/2015
12/08/2015
Added recommendation for baseline
checks before run in Section 8.b.iv.
ZF
JJ
12/08/2015
12/08/2015
Updated instructions related to very
elevated results. Set criteria to confirm
proper washout after an elevated
sample to ± 3SD limits of low bench
QC wash check (Section 8.b.iv). Set
criteria to confirm samples potentially
affected by insufficient washout to
±10% or ±3SD of the low bench QC,
whichever is greater (Section
8.b.vii.2.a). Added highest validated
washout concentrations to Table 9 in
Appendix C. Added extended wash
details for As in Table 1. Added Figure
2g (Method Screen Shot, QC / Sample
page) and Figure 4 (Flow Chart for
handling an elevated result)
JJ
KLC
12/9/2015
12/08/2015
Updated record retention in section
Section 9,c to match DLS policy (3
years to 2 years).
JJ
KLC
12/9/2015
12/08/2015
Updated Appendix D: Help sheets
ZF
JJ
12/08/2015
-------
Date
Changes Made
By
Rev'd
By
(Initials)
Date
Rev'd
4/20/2016
(3006.8-03)
Updated instructions on disposal of
carboy waste with the addition of
Clorox bleach or equivalent prior to
disposal and changed pH requirements
to Dekalb County limits pH>5 pH<11.5.
DS
JJ
3/7/2018
3/7/2018
(3006.8-03)
Clarified section 10.a on the reportable
range of the method and in section
8.b.iv.8.b on diluting a sample to within
the calibration range. Added Table 8
(Reportable range concentrations),
changing "Boundary concentrations"
from Table 8 to Table 9, and
"Reference ranges" from Table 9 to
Table 10. Clarified references to
Tables 8-10 throughout document.
KW
JJ
3/7/2018
3/7/2018
(3006.8-03)
Clarified how to homogenize the
sample dilution in Section S.b.ii. Added
"(e.g. vortex for 3-5 seconds, or invert
5-10 times)."
KW
JJ
3/7/2018
3/7/2018
(3006.8-03)
Changed figures in Appendix C from
2a-2g numbering to figures 2-8.
Changed figures 3a-3e numbering to
figures 9-13.
KW
JJ
3/7/2018
3/7/2018
(3006,8-03)
Updated source information for cones,
handheld pipettes, barcode scanner,
and added part information for
Hamilton diluter PEEK valves and
volumetric flasks.
KW
JJ
3/7/2018
3/7/2018
(3006.8-03)
Added an index of tables for the
rugged ness tables.
KW
JJ
3/7/2018
3/7/2018
(3006.8-03)
Updated references including:
formatting, new (v6.0) DLS Policies
and Procedures manual, and New (Jan
2017) Report on Human Exposure to
Environmental Chemicals. Updated
reference ranges to include NHANES
11-14.
KW
JJ
3/7/2018
3/7/2018
(3006.8-03)
Added Section 13 (Method
performance documentation) and
supporting data in Appendix A.
Previous Appendix A (Ruggedness
testing) became Appendix B. Previous
Appendix B (Method tables and
figures) became Appendix C. Previous
Appendix C (Help sheets) became
Appendix D. Updated references
throughout document.
KW
JJ
3/7/2018
-------
Date
Changes Made
By
Rev'd
By
(Initials)
Date
Rev'd
3/7/2018
Added Microsoft Word captions to all
KW
JJ
3/7/2018
(3006.8-03)
Tables and Figures. Added Title" in
Microsoft Word 'Alt Text' for every
Table and Figure. Added an Index of
Tables for Ruggedness Tables.
Updated the numbering of all figures,
eliminating letter designations for
straight numbering.
3/7/2018
(3006.8-03)
Updated Cross reference to DLS CLIA
and Policy and Procedure
KW
JJ
3/7/2018
3/7/2018
(3006.8-03)
Updated specimen stability statement
in section 3.a and section 6.e.vi to
match stability data in Appendix A.
JJ
RLJ
3/8/2018
3/7/2018
(3006.8-03)
Added a total volume column to Table
7 in Appendix C.
JJ
RLJ
3/8/2018
3/9/2018
(3006.8-03)
Clarified prescreening of acceptable
containers and acceptable container
materials (from 'polyethylene' to 'like
polyethylene and polypropylene') in
Section 3.a.vi.
JJ
RLJ
3/8/2018
3/9/2018
(3006.8-03)
Changed 2 L to 1 L, and reduced 40
mL to 20 mL regarding making of 2%
v/v nitric acid in Section 6.e.ii.2 to
match with Help Sheets in Appendix D
JJ
RLJ
3/8/2018
3/9/2018
(3006.8-03)
Changed "room temperature" to
"ambient temperature" throughout.
JJ
RLJ
3/8/2018
3/9/2018
(3006.8-03)
Added reference to Figure 7 and
Figure 8 in Table 1 of Appendix C.
JJ
RLJ
3/8/2018
-------
wm
wmBm
Environmental Health
Laboratory Procedure Manual
Analytes: Zinc, Copper and Selenium
Matrix: Sei*Um
Method: Serum Multi-Element ICP-DRC-MS
Method No: DLS 3006.8-03
Revised: 3/9/2018
As performed by: Inorganic Radiation Analytical Toxicology
Division of Laboratory Sciences
National Center for Environmental Health
Contact: Dr. Kathleen L. Caldwell
Phone: 770-488-7990
Fax: 770-488-4097
Email: KCaldwell@cdc.gov
Dr. James L. Pirkle, M.D., PhD
Director, Division of Laboratory Sciences
Important Information for Users
The Centers for Disease Control and Prevention (CDC) periodically refines these
laboratory methods. It is the responsibility of the user to contact the person
listed on the title page of each write-up before using the analytical method to find
out whether any changes have been made and what revisions, if any, have been
incorporated.
-------
Serum Multi-Element ICP-DRC-MS
Table of Contents
Cross reference to DLS CLIA and Policy and Procedures policy 4
Index of Ruggedness Tables 5
Index of Tables 5
Index of Figures 6
1) Clinical relevance and summary of test principle 7
a. Clinical Relevance: 7
b. Test Principle: 7
2) Limitations of method; interfering substances and conditions 8
a. Interferences addressed by this method 8
b. Limitations of method 8
3) Procedures for collecting, storing, and handling specimens; criteria for
specimen rejection; specimen accountability and tracking 9
a. Procedures for collecting, storing, and handling specimens: 9
b. Criteria for specimen rejection: 9
c. Transfer or referral of specimens; procedures for specimen accountability and
tracking: 10
4) Safety precautions 10
a. General safety 10
b. Waste disposal: 10
5) Instrument and material sources 11
a. Sources for ICP-MS instrumentation 11
b. Sources for ICP-MS parts and consumables 11
c. Sources for ICP-MS maintenance equipment and supplies 17
d. Sources for general laboratory consumable supplies 17
e. Sources of chemicals, gases, and regulators 19
6) Preparation of reagents and materials 21
a. Intermediate Ga internal standard solution: 21
b. Intermediate Triton X-100 solution 21
c. Diluent 21
d. ICP-DRC-MS rinse solution 22
e. Standards, calibrators, and QC 23
f. Optimization solutions 27
7) Analytical instrumentation and parameters 30
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 2 of 86
a. Instrumentation and equipment setup: 30
b. Parameters for instrument and method: 32
8) The run: quality, execution, evaluation, and reporting 32
a. Bench QC, reference materials, and calibration verification: 32
b. Perform, evaluate, and report a run 32
9) Routine equipment maintenance and data backups 41
a. Equipment maintenance: 41
b. Parameter optimizations: 41
c. Data backup: 41
10) Reporting thresholds 41
a. Reportable range: 41
b. Reference ranges (normal values): 41
c. Action levels: 42
11) Method calculations 42
a. Method limit of detection (LOD): 42
b. Method limit of quantitation (LOQ): 42
c. QC limits: 42
12) Alternate methods for performing test and storing specimens if test system
fails 42
13) Method performance documentation 42
Appendix A. Method performance documentation 43
a. Accuracy 43
b. Precision 45
c. Stability 48
d. Analytical Sensitivity and Specificity 51
Appendix B. Ruggedness testing results 52
a. Ruggedness parameter test #1 52
b. Ruggedness parameter test #2 53
c. Ruggedness parameter test #3 54
d. Ruggedness parameter test #4 55
e. Ruggedness parameter test #5 56
f. Ruggedness parameter test #6 58
Appendix C. Tables and figures 60
Appendix D. Help sheets 81
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 3 of 86
References
86
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 4 of 86
Cross reference to DLS CLIA and Policy and Procedures policy
1. Summary of test principle and clinical relevance
1
2. Safety precautions
4
3. Computerization; data system management
5.a, 8.b, 9.c
4. Specimen collection, storage, and handling procedures; criteria for specimen
rejection
3
5. Procedures for microscopic examinations; criteria for rejection of inadequately
prepared slides
- As no microscope used in this process there are no procedures for
microscopic examinations; and as no slides are prepared for this analysis
there is no criteria for rejection of inadequately prepared slides
6. Preparation of reagents, calibrators (standards), controls, and all other materials;
equipment and instrumentation
5, 6, 7, 8
7. Calibration and calibration verification procedures
8.a.iii, 8.b.ii
8. Procedure operating instructions; calculations; interpretation of results
8, 9, 10, 11
9. Reportable range of results
10.a
10. Quality control (qc) procedures
8.a.i, 8.b.vii, 8.b.viii, 11.c
11. Remedial action if calibration or qc systems fail to meet acceptable criteria
8.b.vii
12. Limitations of method; interfering substances and conditions
2
13. Reference ranges (normal values)
10.b
14. Critical call results ("panic values")
10.c
15. Specimen storage and handling during testing
8.b.ii
16. Alternate methods for performing test or storing specimens if test system fails
12
17. Test result reporting system; protocol for reporting critical calls (if applicable)
8.b.vi, 8.b.vii, 10.c.
18. Transfer or referral of specimens; procedures for specimen accountability and
tracking
3.c
19. Method performance documentation
13
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Serum Multi-Element ICP-DRC-MS
Index of Ruggedness Tables
Ruggedness Table 1. Impact of changing RF power on observed analyte
concentrations 52
Ruggedness Table 2. Impact of changing DRC mode cell gas flow rate on observed
analyte concentrations 53
Ruggedness Table 3. Impact of changing RPq value on observed analyte
concentrations 54
Ruggedness Table 4. Impact of changing axial field voltage (AFV) on observed analyte
concentrations 55
Ruggedness Table 5. Stability of sample preparations part 1 (24-hour increments) 57
Ruggedness Table 6. Stability of sample preparations part 2 (within 24 hours) 57
Ruggedness Table 7. Impact of extra dilutions on observed concentrations of serum
copper (SCU) in pg/dL 59
Ruggedness Table 8. Impact of extra dilutions on observed concentrations of serum
selenium (SSE) in pg/L 59
Ruggedness Table 9. Impact of extra dilutions on observed concentrations of serum
zinc (SZN) in pg/dL 59
Index of Tables
Table 1. Instrument and method parameters 60
Table 2. Suggested maximum analyte concentrations for base serum 63
Table 3. Stock calibration standard concentrations 63
Table 4. Preparation of multi-element intermediate working calibration standards 63
Table 5. Acceptable ways to perform two consecutive analytical runs, bracketing with
bench quality control samples 64
Table 6. A typical SAMPLE/BATCH window 65
Table 7. Preparation of samples, working calibrators, and QC materials for analysis... 66
Table 8. Reportable range concentrations 67
Table 9. Boundary concentrations and replicate range maximums for serum 67
Table 10. Reference ranges for concentrations of zinc, copper, and selenium in serum
[6] 68
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Serum Multi-Element ICP-DRC-MS
Index of Figures
Figure 1. Example configuration of tubing and devices for liquid handling 69
Figure 2. ELAN ICP-DRC-MS method screen shots (timing page) 70
Figure 3. ELAN ICP-DRC-MS method screen shots (processing page) 71
Figure 4. ELAN ICP-DRC-MS method screen shots (equation page) 72
Figure 5. ELAN ICP-DRC-MS method screen shots (calibration page) 73
Figure 6. ELAN ICP-DRC-MS method screen shots (sampling page) 74
Figure 7. ELAN ICP-DRC-MS method screen shots (report page) 75
Figure 8. ELAN ICP-MS method screen shots (QC/Sample page) 76
Figure 9. ESI SC4 autosampler screen shots used (main page) 77
Figure 10. ESI SC4 autosampler screen shots used (configuration page) 78
Figure 11. ESI SC4 autosampler screen shots used (communication page) 78
Figure 12. ESI SC4 autosampler screen shots (5x12 rack setup window) 79
Figure 13. ESI SC4 autosampler screen shots (50mL tube rack setup window) 79
Figure 14. Flow chart for handling an elevated result 80
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 7 of 86
1) Clinical relevance and summary of test principle
a. Clinical Relevance:
This method is used to achieve rapid and accurate quantification of three
elements of toxicological and nutritional interest including Zinc (Zn), Copper (Cu)
and Selenium (Se). The method is useful to screen serum when people are
suspected to be acutely exposed to these elements or to evaluate chronic
environmental or other non-occupational exposure.
b. Test Principle:
Inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-
MS) is a multi-element analytical technique capable of trace level elemental
analysis [1-4], This ICP-DRC-MS method is used to measure the entire panel of
3 elements, or any subgroup. Liquid samples are introduced into the ICP through
a nebulizer and spray chamber carried by a flowing argon stream. By coupling
radio-frequency power into flowing argon, a plasma is created in which the
predominant species are positive argon ions and electrons and has a
temperature of 6,000-8,000 K. The sample passes through a region of the
plasma and the thermal energy atomizes the sample and then ionizes the atoms.
The ions, along with the argon, enter the mass spectrometer through an interface
that separates the ICP (at atmospheric pressure, ~760 torr) from the mass
spectrometer (operating at a pressure of 10"5 torr). The ions pass through a
focusing region, the dynamic reaction cell (DRC), the quadrupole mass filter, and
finally are counted in rapid sequence at the detector allowing individual isotopes
of an element to be determined.
Generally, the DRC operates in one of two modes. In 'vented' (or 'standard')
mode the cell is not pressurized and ions pass through the cell to the quadrupole
mass filter unaffected. In 'DRC' mode, the cell is pressurized with a molecular
gas for the purpose of causing collisions and/or reactions between the molecular
gas and the incoming ions. In general, collisions or reactions with the incoming
ions selectively occur to eliminate an interfering ion by changing the ion of
interest to a new mass which is free from interference, or causing collisions
between ions in the beam and the DRC gas which can focus the ion beam to the
middle of the cell thus increasing the ion signal. In this method, the instrument is
operated in 'DRC' mode when measuring Zn, Cu and Se, and the cell is
pressurized with 99.99+% ammonia gas which collides or reacts with the
incoming ions to eliminate interfering ions and leave the ion of interest to be
detected.
After leaving the DRC cell, the ions are focused with ion optics into a quadrupole
mass analyzer with a nominal mass resolution of 0.7 amu. The quadrupole is
sequentially scanned to specific mass to charge ratio of each analyte and
intensity is detected with a pulse detector. Electrical signals resulting from the
detection of ions are processed into digital information that is used to indicate
first the intensity of the ions and then the concentration of the element. This
method was originally based on the methods by Piraner and Walters [5-8] and
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 8 of 86
the DRC portions of the method are based on work published by Tanner et al. [2,
3], The isotopes measured by this method are zinc (m/z 64), copper (m/z 65) and
selenium (m/z 78) and the internal standard, gallium (m/z 71). Serum samples
are diluted 1:1:28 with >18 MQ-cm water and diluent containing gallium (Ga) for
multi-internal standardization.
2) Limitations of method; interfering substances and conditions
a. Interferences addressed by this method
i. Correction and elimination of interferences (64Ni, 36Ar14N2) on zinc (64Zn).
1. Mathematical correction for nickel (64Ni) interference:
The correction equation (-0.035297* 60Ni) is used in the "Equations" tab of
the method to correct the counts observed as m/z 64 to exclude counts
due to 64Ni.
2. Elimination of 36Ar14N2interference using DRC: The dynamic reaction cell
of the ELAN ICP-DRC-MS is used in this method to eliminate interference
from 36Ar14N2 onto zinc at m/z 64. See Section 1 .b for an explanation of
this process.
ii. Elimination of interferences (40Ar25Mg, 36Ar14N21H) on copper (65Cu) using DRC.
The dynamic reaction cell of the ELAN ICP-DRC-MS is used in this method to
eliminate the interference 40Ar25Mg, 36Ar14N21H on copper at m/z 65. See Section
1 .b for an explanation of this process.
iii. Correction and elimination of interferences (78Kr, 38Ar40Ar, ^Ar^Ca) on selenium
(78Se).
1. Mathematical correction for krypton (78Kr) interference:
The correction equation (-0.030461 *83Kr) is used in the "Equations" tab of
the method to correct the counts observed as m/z 78 to exclude counts
due to 78Kr.
2. Elimination of 38Ar40Ar, 38Ar40Ca interference using DRC: The dynamic
reaction cell of the ELAN ICP-DRC-MS is used in this method to eliminate
interference from ^Ar^Ar, 38Ar40Ca onto selenium at m/z 78. See Section
1 .b for an explanation of this process.
b. Limitations of method
i. 48Ca16Q1H interference on copper (65Cu):
It has been determined that a small interference remains at m/z 65 when the
serum matrix contains very high calcium levels. Even at extreme calcium
levels, this interference has not been found to be significant (< 1%).
ii. Time between dilution of serum materials and analysis:
Selenium is not stable in the diluted sample for more than 7 hours. Diluted
serum must be analyzed within 7 hours of preparation (see Appendix B, test 5
for details).
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 9 of 86
3) Procedures for collecting, storing, and handling specimens; criteria for
specimen rejection; specimen accountability and tracking
a. Procedures for collecting, storing, and handling specimens:
Specimen handling conditions, special requirements, and procedures for
collection and transport are discussed in the Division of Laboratory Science's
(DLS) Policies and Procedures Manual [5], In general, if more than one
vacutainer of blood is to be drawn from an individual, collect the trace metals
tube second or later. Draw the blood through a stainless steel needle into a pre-
screened 7-mL vacutainer. Allow the blood in the stoppered vacutainer clot for
30-40 minutes, but not longer than 60 minutes. Without opening the vacutainer,
centrifuge it for 10 minutes at 2400 rpm. Use a pre-screened serum separator to
remove the serum from the clot. Under a laminar flow hood, pour the serum in
the serum separator into pre-screened polyethylene vials.
i. No fasting or special diets are required.
ii. Use sterile, lot screened collectors for specimen acquisition.
iii. Transport serum specimens at < 4°C.
iv. Once received, store at < -20°C until time for analysis. Re-freeze remaining
portions < -20°C after analytical aliquots are withdrawn. Thawing and refreezing
samples has not been found to compromise sample results.
v. Specimen stability for at 3 years has been demonstrated at < -70°C storage
conditions.
vi. Acceptable containers for analytical aliquots include vials (like polyethylene and
polypropylene) and 7-mL vacutainers determined by pre-screening to be free of
significant contamination of the metals tested in this method. A 3-mL vacutainer
size will not produce the optimal volume of serum for this test. Externally
threaded containers are preferred because they are less prone to contamination
of the specimen and to leaks (internally threaded containers can develop leaks
when biological material dries within the threads, compromising resealing).
b. Criteria for specimen rejection:
Specimen characteristics that compromise test results are indicated above.
Reasons for rejection of a sample for analysis include
i. Low volume: Optimal amount of serum is 1 mL, minimum is 0.8 mL. The volume
of serum used for one analysis is 0.15 mL.
ii. Contamination: Improper collection procedures or collection devices can
contaminate the serum by contact with dust, dirt, etc.
In all cases, request a second serum specimen.
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c. Transfer or referral of specimens; procedures for specimen accountability and
tracking:
Location, status, and final disposition of the specimens will be tracked and
records are maintained according to the DLS Policies and Procedures Manual
[5], Use only numerical identifiers for samples within the laboratory (e.g., case ID
numbers) in order to safeguard confidentiality. Only the medical supervisor (MS)
or project coordinator (PC) (i.e. non CDC personnel) will have access to the
personal identifiers.
4) Safety precautions
a. General safety
i. Observe all safety regulations as detailed in the Division (DLS) Safety Manual.
Additional information can be found in your lab's chemical hygiene plan.
ii. Observe Universal Precautions when working with serum.
iii. Wear appropriate gloves, lab coat, and safety glasses while handling all
solutions.
iv. Exercise special care when handling and dispensing concentrated nitric acid.
Add acid to water. Nitric acid is a caustic chemical that is capable of causing
severe eye and skin damage. If nitric acid comes in contact with any part of
the body, quickly wash the affected area with copious quantities of water
for at least 15 minutes.
v. Use secondary containment for containers holding biological or corrosive liquids.
vi. The use of the foot pedal on the benchtop automatic pipette is recommended
because it reduces analyst contact with work surfaces that have been in contact
with serum and also keeps the analyst's hands free to hold the specimen cups
and autosampler tubes and to wipe off the dispensing tip.
vii. Training will be given before operating the ICP-DRC-MS, as there are many
possible hazards including ultraviolet radiation, high voltages, radio-frequency
radiation, and high temperatures. This information is also detailed in the
PerkinElmer ELAN® ICP-DRC-MS System Safety Manual.
viii. Place ammonia gas cylinders (either in use or in storage) in a cabinet which is
well ventilated to the house exhaust. Do not place ammonia cylinders on their
side while in use as the cylinder valve can become "frozen" in place as a result
of the cooling capacity of expanding ammonia gas.
ix. Wipe down all work surfaces at the end of the day with disinfectant. Disinfectant
may be either daily remake of diluted bleach (1 part household bleach containing
5.25% sodium hypochlorite + 9 parts water) or an equivalent disinfectant.
b. Waste disposal:
i. Autoclaving: All diluted biological specimens, original biological specimens being
disposed, or consumables which come into contact with biological specimens
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(even diluted or aerosolized). Use sharps containers or special autoclave pans
for broken glass / quartz or items which are puncture hazards (e.g. pipette tips),
(see the "Autoclaving" section of the CDC safety policies and practices manual
located in the laboratory).
ii. Other liquid waste
1. Waste discarded down sink: Do not discard solutions at the sink having a
pH lower than 5.0 or higher than 11.5 (limits defined by Dekalb County,
GA). Inactivate biological compounds and cellular constituents in mixed
chemical and biological waste, such as the waste carboy of the ICP-MS, by
adding an approved disinfectant (e.g. household bleach at a 1:100 dilution
or equivalent) prior to drain disposal. Flush the sink with copious amounts
of water. Waste from the spray chamber and autosampler rinse station
drain into the same carboy and are handled according to DLS 3500
standard operating procedure for handling corrosive liquid laboratory
waste.
2. Waste to be picked up by hazardous waste program: Submit request for
hazardous waste removal of all other liquid waste generated in the CDC
laboratory for this method.
5) Instrument and material sources
a. Sources for ICP-MS instrumentation
i. ICP-MS: Inductively Coupled Plasma Dynamic Reaction Cell Mass
Spectrometer (ELAN® 6100 DRCP|US or ELAN® DRC II) (PerkinElmer Norwalk,
CT, www.perkinelmer.com).
ii. Recirculating chiller / heat exchanger for ICP-MS: Refrigerated chiller
(PolyScience 6105PE for ELAN® 6100 DRCP|US instruments) or heat exchanger
(PolyScience 3370 for ELAN® DRC II instruments) (PerkinElmer Norwalk, CT,
www, perkinelmer. com).
iii. Autosampler: ESI SC-4 autosampler (Elemental Scientific Inc., Omaha, NE) or
equivalent.
b. Sources for ICP-MS parts and consumables
NOTE: The minimum number of spares recommended before reordering (if
owning one instrument) are listed as "# Spares =" in the descriptions below.
i. Adapter, plastic: 1/4-28 female threads on one side, 1,8mm barb adapter on the
other. Connects %-28 nut at flanged tubing connection to 0.045" i.d. peristaltic
pump tubing. Use part # B019-3342 ("Type A" adapter, PerkinElmer Norwalk,
CT, www.perkinelmer.com) or equivalent. # Spares = 4.
ii. Adapter, PEEK: Securely connects 1,6mm O.D. PFA tubing to 0.03" I.D.
peristaltic tubing. Composed of three PEEK parts.
1. Female nut for 1,6mm O.D. (1/16") tubing. Like part P-420 (Upchurch
Scientific, Oak Harbor, WA, www.upchurch.com).
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2. PEEK ferrule. Like part P-260x (10pk SuperFlangeless ferrule, Upchurch
Scientific, Oak Harbor, WA, www.upchurch.com).
3. Conical Adapter Body. Like part P-692 (Upchurch Scientific, Oak Harbor,
WA, www.upchurch.com).
iii. Coolant, for Polvscience chiller or heat exchanger: Only PerkinElmer part #
WE01-6558 (PerkinElmer Norwalk, CT, www.perkinelmer.com) is approved for
use by PerkinElmer. # Spares = 6.
iv. Cones: Platinum or Nickel cones have been used. Platinum cones are more
expensive, but will last longer, can be refurbished, and will frequently yield
higher sensitivity.
1. Sampler (nickel/platinum): PerkinElmer part # WE021140/WE027802
(PerkinElmer Norwalk, CT, www.perkinelmer.com) or cross-referenced part
number manufactured by Spectron Inc. (Ventura, CA,
www.spectronus.com) or Glass Expansion (Pocasset, MA,
www.geicp.com). # Spares = 4.
2. Skimmer (nickel/platinum): PerkinElmer part # WE021137/WE027803
(PerkinElmer Norwalk, CT, www.perkinelmer.com) or cross-referenced part
number manufactured by Spectron Inc. (Ventura, CA,
www.spectronus.com) or Glass Expansion (Pocasset, MA,
www.geicp.com). # Spares = 4.
v. Connector (for tubing): Use to connect 1/8" I.D. PVC tubing to 0.125" I.D
peristaltic pump tubing. Use part # 3140715 (PerkinElmer Norwalk, CT,
www.perkinelmer.com) or equivalent. # Spares = 4.
vi. Detector, electron multiplier: Like part # N8125001 (PerkinElmer Norwalk, CT,
www, perkinelmer. com). Available direct from manufacturer (part# 14210, SGE
Incorporated, Austin, Texas, http://www.etpsci.com) or various distributors. #
Spares = 1.
vii. Hose, for connection to chiller: Push on hose. I.D. = O.D. = Use part #
PB-8 (per inch, Georgia Valve and Fitting, Atlanta, GA, www.swagelok.com) or
equivalent. Do not normally need spare hose (unless moving instrument into a
new location).
viii. Hose, for exhaust of ELAN: Available as part of ELAN installation kit from
Perkin Elmer (PerkinElmer Norwalk, CT, www.perkinelmer.com). Available
direct from manufacturer as part # S-LP-10 air connector (Thermaflex, Abbeville,
SC, www.thermaflex.net). Equivalent part is acceptable. # Spares = 10 feet of
4" diameter and 10 feet of 6" diameter hose.
ix. Injector, guartzwith ball joint: I.D. = 2.0 mm. PerkinElmer part # WE023948
(PerkinElmer Norwalk, CT, www.perkinelmer.com). Available direct from
manufacturer as part # 400-30 (Precision Glass Blowing, Centennial, CO,
www.precisionglassblowing.com) or from various distributors. # Spares = 2.
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x. Injector support (for pass-through injector): PerkinElmer part # WE023951
(PerkinElmer Norwalk, CT, www.perkinelmer.com). Available direct from
manufacturer as part # 400-37 (Precision Glass Blowing, Centennial, CO,
www.precisionglassblowing.com) or from various distributors. # Spares = 2.
xi. Ion Lens: PerkinElmer part # WE018034 (PerkinElmer Norwalk, CT,
www.perkinelmer.com). # Spares = 3.
xii. Nebulizer, guartz concentric: Type C, 1 mL/min nebulizer with quick disconnects
for liquid and gas ports such as part # 500-70QQDAC (Precision Glass Blowing,
Centennial, CO, www.precisionglassblowing.com). This nebulizer is designed to
use quick disconnects part # 500-QD (liquid) and # 500-AC (argon).
xiii. Nebulizer connections (gas): (for nebulizer argon side-arm).
1. If not using guick disconnection fitting, insert nebulizer argon side-arm into
the 1/8" i.d. vinyl tubing and secure the connection with a hose clamp for
%" o.d tubing (like part # EW-06832-01, Cole Palmer Instrument Company,
Vernon Hills, Illinois, www.colepalmer.com). # Spares = 2.
2. Quick disconnection fitting: Like part # 500-AC (Precision Glass Blowing,
Centennial, CO, www.precisionglassblowing.com). # Spares = 2.
xiv. Nebulizer connections (liguid): (for nebulizer 4mm o.d. liquid sample backend).
Can use quick disconnect orflangeless nut and ferrule assembly.
1. Quick disconnect: Like Part # 500-QD (Precision Glass Blowing,
Centennial, CO, www.precisionglassblowing.com). # Spares = 2.
2. Flangeless nut and ferrule assembly: An assembly such as part # FIT KIT
3 (Meinhard Glass Products, Golden, CO, www.meinhard.com) or
equivalent. Individual pieces of FIT KIT #3 can be purchased as follows.
a. Nut, flangeless, 1/16", %-28, Delrin® (Acetal), red. Part# P202x (1 Opk,
Upchurch Scientific, Oak Harbor, WA, www.upchurch.com). # Spares
= 10.
b. Ferrule, flangeless, 1/16", Tefzel® (ETFE), blue. Part # P-200x (10pk,
Upchurch Scientific, Oak Harbor, WA, www.upchurch.com). # Spares
= 10.
c. Adapter, 1/4-28 internal to 5/16-24 internal, PEEK™. Part# P-135
(Upchurch Scientific, Oak Harbor, WA, www.upchurch.com). # Spares
= 2.
d. Nut, 4mm ID PEEK. Part of fit kit 3 for concentric nebulizers. Part # S-
1050 (Meinhard Glass Products, Golden, CO, www.meinhard.com). #
Spares = 2.
e. Ferrule, 4mm ID green Delrin. Part of fit kit 3 for concentric nebulizers.
Part# S-1121 (Meinhard Glass Products, Golden, CO,
www.meinhard.com). # Spares = 2.
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xv. Nut: (for flanged connections of 1.59mm (1/16") o.d. PFA tubing) Flanged, for
1/16" o.d. tubing, 1/4-28 threads. Use part# P-406x (pkg. of 10, Upchurch
Scientific, Oak Harbor, WA, www.upchurch.com) or equivalent. Use a Teflon-
coated Viton o-ring with this nut instead of the stainless steel washer that comes
with part # P-406xJ. # Spares = 10.
xvi. Nut: (for bottom port of autosampler rinse station) 10-32 UMC threads for 1/16"
tubing. Such as part # M653x (Upchurch Scientific, Oak Harbor, WA,
www.upchurch.com) or equivalent. # Spares = 2.
xvii. Nut and ferrule set, 1/8" Swagelok: Such as part # SS-200-NFSET (stainless
steel) or part # B-200-NFSET (brass) (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. For part numbers listed here a quantity of 1
means 1 nut, 1 front ferrule, and 1 back ferrule. Spares = 20.
xviii. Nut and ferrule set, 1/4" Swagelok: Such as part # SS-400-NFSET (stainless
steel) or part # B-400-NFSET (brass) (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. For part numbers listed here a quantity of 1
means 1 nut, 1 front ferrule, and 1 back ferrule. Spares = 20.
xix. Oil for roughing pumps:
1. Oil, Welch Directorr Gold: For roughing pumps. Available direct from
manufacturer as part # 8995G-15 (1 gallon, Welch Rietschle Thomas,
Skokie, IL, www.welchvacuum.com) or from various distributors.
Equivalent oil is acceptable. # Spares = 4.
2. Fomblin Y14/5 fluid: PerkinElmer part # N8122265 (1 kg bottle,
PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent. # Spares
=1 per instrument.
xx. O-ring: (for sampler cone) PerkinElmer part # N8120511 (pkg. of 5, PerkinElmer,
Shelton, CT, www.perkinelmer.com) or equivalent. # Spares = 20 o-rings.
xxi. O-ring: (for skimmer cone) PerkinElmer part # N8120512 (pkg. of 5,
PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent. # Spares = 20
o-rings.
xxii. O-ring: (for flanged connections of 1.59mm (1/16") o.d. PFA tubing) Teflon-
coated Viton o-ring, i.d. = 1/16", thickness = 1/16", o.d. = 3/16". Such as part #
V75-003 (O-rings West, Seattle, WA, www.oringswest.com) or equivalent. #
Spares = 20.
xxiii. O-ring: (for injector support).
1. Internal o-rings: ID = %", OD = 3/8", thickness = 1/16". Need 2 o-rings per
injector support to setup. PerkinElmer part # N8122008 (PerkinElmer,
Shelton, CT, www.perkinelmer.com) or equivalent (such as part # V75-010,
O-rings West, Seattle, WA, www.oringswest.com). # Spares = 20.
2. External o-rings: ID = 3/8", OD = 1/2", thickness = 1/16". Need 2 o-rings
for each injector support setup. PerkinElmer part # N8122009
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(PerkinElmer, Shelton, CT, www.perkinelmer.com) or equivalent (such as
part # V75-012, O-rings West, Seattle, WA, www.oringswest.com). #
Spares = 20.
xxiv. 0-ring: (for inside spray chamber at nebulizer port) Such as part # 120-56
(Precision Glass Blowing, Centennial, CO, www.precisionglassblowing.com).
Additional o-rings can sometimes be obtained free of charge or at reduced price
when acquired while purchasing spray chambers. # Spares = 20.
xxv. 0-ring: (for inside of torch mount): Part # WE017284 (PerkinElmer, Shelton,
CT, www.perkinelmer.com). Do not substitute. The PerkinElmer o-ring is
special metal impregnated to minimize RF leakage though the torch mount. #
Spares = 2.
xxvi. Photon stop: PerkinElmer part # WE018278 (PerkinElmer, Shelton, CT,
www.perkinelmer.com). Alternate "snap in" lens assembly requires PerkinElmer
part # W1013361 (PerkinElmer Norwalk, CT, www.perkinelmer.com). # Spares
= 1.
xxvii. Plugs, guick change for roughing pump oil: These plugs will only work on the
Varian roughing pumps which come standard on ELAN DRC II ICPMS
instruments. These plugs will not fit the Leybold pumps which come standard on
the ELAN DRC Plus instruments. Part # W1011013 (PerkinElmer, Shelton, CT,
www.perkinelmer.com). No spares typically needed.
xxviii. Probes: (for ESI autosampler) Teflon, carbon fiber support, 0.8mm i.d., blue
marker, 1/4-28fittings. Like part number SC-5037-3751 (Elemental Scientific Inc.,
Omaha, NE., www.elementalscientific.com). # Spares = 2.
xxix. RF coil. PerkinElmer part # WE02-1816 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. # Spares = 2.
xxx. Screw, for torch mount: PerkinElmer part # WE011870. (PerkinElmer, Shelton,
CT, www.perkinelmer.com) or equivalent. # Spares = 3.
xxxi. Spray chamber, guartz concentric: PerkinElmer part # WE025221 (PerkinElmer,
Shelton, CT, www.perkinelmer.com) or equivalent. Available direct from
manufacturer as part # 400-20 (Precision Glass Blowing, Centennial, CO,
www.precisionglassblowing.com) or from various distributors. # Spares = 2.
xxxii. Torch, guartz: PerkinElmer part # N812-2006 (PerkinElmer, Shelton, CT,
www.perkinelmer.com) or equivalent. Available direct from manufacturer as part
#400-10 (Precision Glass Blowing, Centennial, CO,
www.precisionglassblowing.com) or various distributors. Damaged torches can
often be repaired for substantially lower cost than purchasing a new one by
companies such as Wilmad LabGlass (Buena, NJ, www.wilmad-labglass.com)
or Precision Glass Blowing (Centennial, CO, www.precisionglassblowing.com).
# New Spares = 2.
xxxiii. Tubing and adapter, for SC autosampler rinse station drain: Tygon tubing and
adapter to attach to back of SC autosampler for draining rinse station waste (like
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part # SC-0303-002, Elemental Scientific Inc., Omaha, NE.,
www.elementalscientific.com)
xxxiv. Tubing and adapters, for SC autosampler rinse station filling: Teflon tubing and
adapters (to attach to back of SC autosampler for filling rinse stations and to
attach to rinse containers). Like part # SC-0302-0500, Elemental Scientific Inc.,
Omaha, NE., www.elementalscientific.com).
xxxv. Tubing, argon delivery to instrument: I.D. = 1/8", O.D. = %". Such as part # C-
06500-02 (pkg. of 100ft, polypropylene, Fisher Scientific International, Hampton,
NH, www.fishersci.com) or equivalent. # Spares = 50ft.
xxxvi. Tubing, peristaltic, 0.76 mm i.d. (sampling): Standard PVC, 2-stop (black/black)
peristaltic pump tubing, i.d. = 0.76 mm. ESI part # MPP-076-F-PVC (Elemental
Scientific Inc., Omaha, NE., www.elementalscientific.com) or equivalent. #
Spares = 6 packs of 12 tubes.
xxxvii. Tubing, peristaltic, 1.3 mm i.d. (spray chamber drain): Santoprene, 2-stop
(gray/gray) peristaltic pump tubing, i.d. = 1,3mm. ESI Part # MPP-130-PHR
(Elemental Scientific Inc., Omaha, NE., www.elementalscientific.com) or
equivalent. # Spares = 6 packs of 12 tubes.
xxxviii. Tubing, PFA: I.D. = 0.5mm, O.D. = 1,59mm (1/16"). Used to transfer liquid
1. possibly used between nebulizer and peristaltic pump tubing (if quick
connection is not used for liquid sample delivery)
The Perfluoroalkoxy (PFA) copolymer is a form of Teflon®. Such as part #
1548 (20ft length, Upchurch Scientific, Oak Harbor, WA, www.upchurch.com)
or equivalent. # Spares = 20ft.
xxxix. Tubing, PVC, i.d. = 1/8", o.d. = 3/16". Used to transfer liquid
1. between spray chamber waste port and peristaltic pump
Like part # 14-169-7A (pkg. of 50ft, Fisher Scientific International, Hampton,
NH, www.f ishersci. com) or equivalent. # Spares = 20ft.
xl. Tubing, stainless steel, o.d. = 1/8", wall thickness = 0.028": Used to connect
DRC gas cylinders to ELAN DRC gas ports. Also used to replace plastic tubing
in the DRC gas path within the ELAN. Like part # SS-T2-S-028-20 (20ft,
Georgia Valve and Fitting, Atlanta, GA, www.swagelok.com) or equivalent.
Spares = 20ft.
xli. Tubing, Teflon, corrugated, %" o.d.: Connects to the auxiliary and plasma gas
side-arms of the torch. Part # WE015903 (PerkinElmer, Shelton, CT,
www, perkinelmer.com). # Spares = 2.
xlii. Tubing, Tygon, i.d. = 3/16", o.d. = 5/16": Used to transfer liquid between rinse
station drain port and liquid waste jug. Like part # EW-06409-15 (50 ft, Cole
Parmer, Vernon Hills, Illinois, www.coleparmer.com) or equivalent. # Spares =
20ft.
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xliii. Tubing, vinyl (argon delivery to nebulizer): Vinyl Tubing, 1/8" ID x 1/4" OD. Like
part# EW-06405-02 (Cole Parmer, Vernon Hills, Illinois, www.coleparmer.com)
or equivalent. Equivalent tubing material is acceptable. # Spares = 10ft.
xliv. Union elbow, PTFE %" Swagelok: Connects argon tubing to torch auxiliary gas
sidearm. Like part # T-400-9 (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com) or equivalent. Spares = 2.
xlv. Union tee, PTFE, %" Swagelok: Connects argon tubing to torch plasma gas
sidearm and holds igniter inside torch sidearm. Like part # T-400-3 (Georgia
Valve and Fitting, Atlanta, GA, www.swagelok.com) or equivalent. Spares = 2.
c. Sources for ICP-MS maintenance eguipment and supplies
i. Anemometer: Like digital wind-vane anemometer (Model 840032, SPER
Scientific LTD., Scottsdale, AZ, www.sperscientific.com) or equivalent. Use to
verify adequate exhaust ventilation for ICP-MS (check with hoses fully
disconnected).
ii. Pan, for changing roughing pump oil: Like part # 53216 (United States Plastics
Corporation, Lima, OH, www.usplastic.com) or equivalent. # On hand = 1.
iii. Container, to hold acid baths for glassware: Polypropylene or polyethylene
containers with lids (must be large enough for torch, injector, or spray chamber
submersion). Available from laboratory or home kitchen supply companies. #
On hand = 4.
iv. Cotton swabs: Any vendor. For cleaning of cones and glassware.
v. Cutter (for 1/8" o.d. metal tubing): Terry tool with 3 replacement wheels. Like
part #TT-1008 (Chrom Tech, Inc., Saint Paul, MN, www.chromtech.com) or
equivalent.
vi. Getter regeneration kit: Part # WE023257 (PerkinElmer, Shelton, CT,
www.perkinelmer.com). Use this as needed (at least annually) to clean the
getter in the pathway of channel A DRC gas.
vii. Magnifying glass: Any 10x + pocket loupe for inspection of cones and other
ICP-MS parts. Plastic body is preferred for non-corrosion characteristics. Like
part # 5BC-42813 (Lab Safety Supply, Janesville, Wl, www.labsafetv.com).
viii. Screw driver, for ion lens removal: Screw driver with long, flexible shaft, and
2mm ball-Allen end for removal of ion lens screws, part # W1010620. Extra
2mm bits, part # W1010598 (PerkinElmer, Shelton, CT, www.perkinelmer.com).
ix. Toothbrush: Any vendor. For cleaning ion lens and glassware.
x. Ultrasonic bath: Like ULTRAsonik™ Benchtop Cleaners (NEYTECH, Bloomfield,
CT, www.nevtech.com) or equivalent.
d. Sources for general laboratory consumable supplies
i. Bar code scanner: Like Xenon 1902 cordless area-imaging scanner (Honeywell
International Inc., Morristown, NJ, www.honeywellaidc.com). For scanning
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sample IDs during analysis setup. Any bar code scanner capable of reading
Code 128 encoding at a 3 mil label density and 2D bar codes can be substituted
ii. Carboy (for preparation of serum quality control pool and waste jug for ICPMS
sample introduction system): Polypropylene 10-L carboy (like catalog # 02-960-
20C, Fisher Scientific, Pittsburgh, PA, www.fischersci.com) or equivalent.
Carboys with spouts are not advised due to potential for leaking.
iii. Containers for diluent and rinse solution: Two liter Teflon™ containers (like
catalog# 02-923-30E, Fisher Scientific, Pittsburgh, PA., www.fishersci.com) and
4L polypropylene jugs (like catalog# 02-960-1 OA, Fisher Scientific, Pittsburgh,
PA, www.fishersci.com) have both been used. Acid rinse before use. Equivalent
containers are acceptable.
iv. Flask, volumetric:
1. Four 10OmL volumetric flasks (like catalog # 40000100, Thermo Scientific,
Fisher Scientific, Pittsburgh, PA., www.fishersci.com). Plastic or glass is
acceptable.
2. One 200ml_ volumetric flask (like catalog # 40000200, Thermo Scientific,
Fisher Scientific, Pittsburgh, PA., www.fishersci.com). Plastic or glass is
acceptable.
3. One 500ml_ volumetric flask (like catalog # 40000500, Thermo Scientific,
Fisher Scientific, Pittsburgh, PA., www.fishersci.com). Plastic or glass is
acceptable.
4. One 1L volumetric flask (like catalog # 40001000, Thermo Scientific, Fisher
Scientific, Pittsburgh, PA., www.fishersci.com). Plastic or glass is
acceptable.
v. Gloves: Powder-free, low particulate nitrile (like Best CleaN-DEX™ 100% nitrile
gloves, any vendor). Equivalent nitrile or latex gloves are acceptable.
vi. Paper towels: For general lab use, any low lint paper wipes such as
KIMWIPES0EX-L Delicate Task Wipers or KAYDRY0EX-L Delicate Task
Wipers (Kimberly-Clark Professional, Atlanta, GA, www.kcprofessional.com).
For sensitive applications in cleanrooms, wipes designed for cleanroom use are
available such as the Econowipe or Wetwipe (Liberty, East Berlin, CT,
www.libertv-ind.com).
vii. Pipette, benchtop automatic (for preparation of serum dilutions to be analyzed):
Like the Microlab 625 advanced dual syringe diluter (Hamilton, Reno, NV,
http://www.hamilton.com/) equipped with a 5.0 mL left syringe, a 2.5 mL right
syringe, a 12 gauge Concorde CT probe dispense tip, the Microlab cable
management system and a foot pedal. PEEK valves like part # 60676-01 (left)
and part # 60675-01 (right) may reduce metal background in prepared samples.
viii. Pipettes (for preparation of intermediate working standards and other reagents):
Like Picus® NxT electronic, single-channel pipettes (Sartorius AG, Gottingen,
Germany, www.sartorius.com). 5-120 pL (catalog # LH-745041), 10-300 pL
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(catalog #LH-745061), 50-1000 |jL (catalog #LH-745081), 100-5000 |jL (catalog
#LH-745101). Equivalent pipettes and tips can be substituted.
ix. Tubes for sample analysis (for autosampler): Like polypropylene 15-mL conical
tubes, BD Falcon model #352097 (Becton Dickinson Labware, Franklin Lakes,
NJ, www.bd.com). Equivalent tubes are acceptable which are shown by lot
screening to be free of trace metal contamination. Clear plastics tend to have
lowest trace metal contamination. Blue colored caps have also been used
successfully for this method.
x. Tubes for storage of intermediate working stock standards: Like polypropylene
50-mL centrifuge tubes, Corning Incorporated #430290 (Corning, NJ, 14831.
www.scienceproduct.corning.com). For use in storage of intermediate working
stock standards. Equivalent tubes are acceptable which are shown by lot
screening to be free of trace metal contamination. Clear plastics tend to have
lowest trace metal contamination. Orange colored caps have also been used
successfully for this method.
xi. Vortexer: Like MV-1 Mini Vortexer (VWR, West Chester, PA, www.vwr.com).
Used for vortexing serum specimens before removing an aliquot for analysis.
Equivalent item can be substituted.
xii. Water purification system: Like NANOpure Diamond Ultrapure Water System
(Barnstead International, Dubuque, Iowa, www.barnstead.com), or equivalent.
For ultra-pure >18 MQ-cm water used in reagent and dilution preparations.
e. Sources of chemicals, gases, and regulators
i. Acid, hydrochloric acid: Veritas™ environmental grade, 30-35% (GFS
Chemicals Inc. Columbus, OH, www.gfschemicals.com). This is referred to as
"concentrated" hydrochloric acid in this method write-up. It is approximately 12
molar in concentration. For use in preparation of intermediate working stock
standards. Equivalent products must meet or exceed the purity specifications of
this product for trace metals content.
ii. Acid, nitric acid: Veritas™ environmental grade, 68-70% (GFS Chemicals Inc.
Columbus, OH, www.gfschemicals.com). For use in diluent, rinse solution,
intermediate working stock standards, and QC pool preparations. This is
referred to as "concentrated" nitric acid in this method write-up. It is
approximately 16 molar in concentration. Equivalent nitric acid must meet or
exceed the purity specifications of this product for trace metals content.
iii. Ethyl alcohol (C2H5OH), USP dehydrated 200 proof (Pharmco Products, Inc.) or
equivalent.
iv. Triton X-100™ ("Baker Analyzed," J.T. Baker Chemical Co. [www.jtbaker.com],
or any source whose product is low in trace-metal contamination).
v. Argon gas (for plasma and nebulizer) and regulator: High purity argon
(99.999+% purity, Specialty Gases Southeast, Atlanta, GA, www.sgsgas.com)
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for torch and nebulizer. Minimum tank source is a dewar of liquid argon (180-
250L) but bulk tank for total building needs is preferred.
1. Regulator for argon (at dewar, if used): Stainless steel, single stage,
specially cleaned regulator with 3,000 psig max inlet, 0-100 outlet pressure
range, CGA 580 cylinder connector, and needle valve shutoff on delivery
side terminating in a %" Swagelok connector. Part number
KPRAFPF415A2AG10 (Georgia Valve and Fitting, Atlanta, GA,
www.swagelok.com), or equivalent. # Spares = 1.
2. Regulator for argon (between bulk tank and PerkinElmer filter regulator):
Single Stage 316SS Regulator, with 0-300 psi Inlet Gauge, 0-200 psi
Outlet Gauge, Outlet Spring Range, 0-250 psi, %" Swagelok Inlet
Connection, % turn Shut off Valve on Outlet with %" Swagelok Connection
and Teflon Seals. Part number KPR1GRF412A20000-AR1 (Georgia Valve
and Fitting, Atlanta, GA, www.swagelok.com), or equivalent. # Spares = 1.
3. Regulator for argon (PerkinElmer filter regulator on back of ELAN): Argon
regulator filter kit. Catalog number N812-0508 (PerkinElmer, Shelton, CT,
www.perkinelmer.com).
vi. Ammonia: Anhydrous ammonia (99.99+%) for DRC channel A is typically
purchased in cylinder size LB (2"x12") (Matheson Tri-Gas, Montgomeryville, PA,
18936. www.mathesontrigas.com).
1. Regulator for ammonia: Stainless steel, two stage, specially cleaned
regulator with 3,000 psig max inlet, 2-30 outlet pressure range, cylinder
connector CGA 180 or 660 (or designated by the vendor) or CGA 705 (for
Airgas cylinder size 200), and needle valve shutoff on delivery side
terminating in a %" Swagelok connector. Like part number 3813-180 or
3813-705 (Matheson Tri-Gas, Montgomeryville, PA, www.matheson-
trigas.com), or equivalent. # Spares = 1.
vii. Disinfectant, for work surfaces: Diluted bleach (1 part household bleach
containing 5.25% sodium hypochlorite + 9 parts water), remade daily, or
equivalent disinfectant.
viii. Standard, Gallium: Like 1,000 mg/L, item # PLGA2-2Y. (SPEX Industries, Inc.,
Edison, NJ, www.spexcsp.com), or equivalent. Used as an internal standard in
diluent. Standards must be traceable to the National Institute for Standards and
Technology and have low trace metal contamination.
ix. Standard, multi-element stock standard: Item number SM-2107-013 (High Purity
Standards, Charleston, SC, http://www.hps.net/). This is a custom mix solution
(see Table 3 in Appendix C for concentrations). This solution is diluted to
prepare the intermediate working standards, which are in turn diluted to prepare
the working calibrators. This solution can be prepared in-house from NIST
traceable single element stock solutions if necessary.
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x. Triton X-100™ surfactant: Like "Baker Analyzed" TritonX-100™ (J.T. Baker
Chemical Co., www.itbaker.com), or equivalent.
6) Preparation of reagents and materials.
a. Intermediate Ga internal standard solution:
i. Purpose: Internal standards solution is prepared to be added to the sample
diluent. During analysis, the internal standard will compensate for instrumental
variations on the analyte signal.
ii. Preparation: To prepare 100 ml_ of 20 pg/mL Ga in 2% (v/v) HNO3 solution:
1. If not previously dedicated to this purpose, acid wash a 100 ml_ container
(PP, PMP, or Teflon™) with dilute nitric acid (e.g. 1% v/v HNO3) and >18
MQ-cm water (at least 3 times each). Verify cleanliness through analysis
of rinsate. Dedicate to purpose, if possible.
2. Partially fill the 100-mL volumetric flask with >18 MQ-cm water.
3. Carefully add 2 ml_ of concentrated HNO3. Mix into solution.
4. Add 0.2 ml_ of 10,000 pg/mL Ga standard. If initial Ga concentration is
different adjust volume proportionally.
5. Fill to mark (100 ml_) and mix thoroughly.
6. Store at ambient temperature and label appropriately. Expiration date is 1
year from preparation.
b. Intermediate Triton X-100 solution
i. Purpose: Use of the intermediate solution reduces the need to frequently
dissolve pure Triton X-100 (frequently an over-night process).
ii. Preparation: To prepare 2 L of 2% Triton X-100™ in 5% (v/v) HNO3 solution:
1. If not previously dedicated to this purpose, acid wash a 2 L PP, PMP, or
Teflon™ container with dilute nitric acid (e.g. 1% v/v) and >18 MQ-cm
water (at least 3 times each). Verify cleanliness through analysis of
rinsate. Dedicate to purpose, if possible.
2. Partially fill the pre-cleaned 2 L bottle with >18 MQ-cm water
(approximately 1-1.5 L).
3. Add 40 ml_ of Triton X-100™ and stir until completely dissolved. Use a
pre-cleaned Teflon™ stir bar and stir plate if necessary.
i. Carefully add 100 ml_ of concentrated HNO3 to the partially filled 2
L bottle.
ii. Fill to 2 L and mix thoroughly.
iii. Store at ambient temperature and label appropriately. Expiration
date is 1 year from preparation.
c. Diluent
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i. Purpose: All samples (blanks, calibrators, QC, or patient samples) are
combined with the diluent during the sample preparation step before analysis.
This is where the internal standards are added which during the analysis will
compensate for instrumental variations on the analyte signal.
ii. Preparation: To prepare 2 L of 10 pg/L Ga in 2% (v/v) HNO3, 5% Ethyl Alcohol,
and 0.01% Triton X-100™:
1. If not previously dedicated to this purpose, acid wash a 2 L container (PP,
PMP, or Teflon™) with dilute nitric acid (e.g. 1% v/v) and >18 MQ-cm water
(at least 3 times each). Verify cleanliness through analysis of rinsate.
Dedicate to purpose, if possible.
2. Partially fill (i.e. 70-80% full) the 2 L container with >18 MQ-cm water.
3. Add 40 ml_ concentrated HNO3 and mix.
4. Add 100 ml_ Ethyl Alcohol and mix.
5. Add 1 ml_ of 20 pg/mL Ga internal standard intermediate solution.
6. Add 10 ml_ of the intermediate 2% Triton X-100™ / 5% (v/v) HNO3 solution
and mix.
7. Make up to 2 L with >18 MQ-cm water.
8. Store at ambient temperature and label appropriately. Expiration date is 1
year from preparation.
d. ICP-DRC-MS rinse solution
i. Purpose: Pump this solution into the sample introduction system between
samples to prevent carry-over of the analytes of interest from one sample
measurement to the next.
ii. Preparation: To prepare 4 L of 0.01% Triton X-100™, 2% (v/v) HNO3, 5% ethyl
alcohol and 0.5% (v/v) HCI:
1. If not previously dedicated to this purpose, acid wash a 4 L container (PP,
PMP, or Teflon™) with dilute nitric acid (e.g. 1% v/v) and >18 MQ-cm water
(at least 3 times each). Verify cleanliness through analysis of rinsate.
Dedicate to purpose, if possible.
2. Partially fill the pre-cleaned 4 L bottle with >18 MQ-cm water
(approximately 2-3 L).
3. Add 80 ml_ of concentrated HNO3 and mix well.
4. Add 200 ml_ Ethyl Alcohol and mix well.
5. Add 20 ml_ of concentrated HCI and mix well.
6. Add 20 ml_ of the 2% Triton X-100™ / 5% (v/v) HNO3 intermediate stock
solution and mix well.
7. Fill to 4 L using >18 MQ-cm water and mix well.
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8. Store at ambient temperature and label appropriately. Expiration date is 1
year from preparation.
e. Standards, calibrators, and QC
i. Multi-element stock calibration standard
1. Purpose: All working intermediate calibrators are prepared by dilution of
this stock standard which contains all 3 elements of interest for this
method, per the concentrations listed in Table 3 of Appendix C.
2. Purchasing from vendors: The multi-element stock standard is typically
purchased as a custom mixture (e.g. part number SM-2107-013 from High
Purity Standards (Charleston, SC)). The vendor must provide
documentation of traceability to the National Institute for Standards and
Technology (NIST). Details of the HPS preparation of the multi-element
stock standard is as follows (per statement on their literature):
3. Storage: Store the solution at ambient temperature. Expiration date is as
defined by vendor or 1 year from date of opening.
ii. Diluent for intermediate working calibration standards
1. Purpose: This diluent is used to dilute stock calibration standards down to
the intermediate working calibration standard concentrations.
2. Preparation: To prepare 1 L of 2% v/v HNO3:
a. If not previously dedicated to this purpose, acid wash a 1 L glass, PP,
PMP, or Teflon™ volumetric flask with dilute nitric acid (e.g. 1% v/v)
and >18 MQ-cm water (at least 3 times each). Verify cleanliness
through analysis of rinsate. Dedicate to purpose, if possible.
b. Partially fill the 1 L volumetric flask with >18 MQ-cm water
(approximately 50% to 75% full).
c. Add 20 ml_ concentrated HNO3.
d. Fill to the mark and mix thoroughly.
e. Store at ambient temperature and label appropriately. Expiration is 1
year from the date of preparation.
iii. Multi-element intermediate working calibration standards
1. Purpose: Use the intermediate working standard solutions 1-5 each day of
analysis to prepare the final working calibrators that will be placed on the
autosampler of the ELAN® ICP-DRC-MS.
2. Preparation: To prepare the volumes and concentrations of intermediate
working standards per Table 4 in Appendix C:
a. If not previously dedicated to this purpose, acid wash PP, PMP, or
Teflon™ volumetric flasks with dilute nitric acid (e.g. 1% v/v) and >18
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MQcm water (at least 3 times each). Verify cleanliness through
analysis of rinsate. Label and dedicate to purpose, if possible.
b. Partially fill the volumetric flasks with the 2% v/v HNO3 diluent
(approximately 50-75% full).
c. Pipette the volumes of the multi-element stock standard listed in Table
4 of Appendix C into each of the labelled volumetric flasks.
d. Dilute each volumetric flask to the mark with the 2% v/v HNO3 diluent
using a pipette for the final drops. Mix each solution thoroughly.
e. Once mixed, transfer to acid-cleaned, labeled, 50-mL containers (PP,
PMP, or Teflon™) for storage.
f. Store at ambient temperature and label appropriately. Expiration is 1
year from the date of preparation. The final concentrations of the 3
elements are listed in Table 4 in Appendix C.
iv. Working multi-element calibrators
1. Purpose: The working multi-element calibrators are dilutions of the
intermediate working standards. Analysis of these calibrators provides
each run with a signal to concentration response curve for each analyte in
the method. The concentration of an analyte in a patient serum sample
dilution is determined by comparing the observed signal from the dilution of
the patient serum sample to the response curve from the working multi-
element calibrators.
2. Preparation: Prepare the volumes and concentrations of the matrix-
matched working standards per Table 7 in Appendix C immediately prior to
analysis.
v. Base serum
1. Purpose: This serum pool material will be mixed with the intermediate
working calibrators just prior to analysis to matrix-match the calibration
curve to the serum matrix of the unknown samples.
2. Collection of serum: A mixture of multiple human serum sources purchased
from Tennessee Blood Services, 807 Poplar Ave., Memphis, TN 38105.
These serum were collected from different anonymous donors are used to
approximate an average serum matrix.
3. Screening serum: Screen serum sources for metal content and choose
sources which reflect the low-normal population range (see Table 2 in
Appendix C for maximum suggested concentrations).
4. Preparation and storage:
a. Once screened, mix the serum collections together in a larger
container (i.e. acid washed polypropylene (PP), polymethylpentene
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(PMP), or Teflon™) and stir for 30+ minutes on a large stir plate (acid
wash large Teflon™ stir bar before use).
b. Dispense into smaller-volume, pre-screened vials for use in the lab.
c. Label appropriately and store frozen (e.g. < -20° C).
vi. Internal quality control materials ("bench" QC)
1. Purpose: Internal (or "bench") quality control (QC) materials are used to
evaluate the accuracy and precision of the analysis process, and to
determine if the analytical system is "in control" (is producing results that
are acceptably accurate and precise). They are included in the beginning
and at the end of each analytical run. These pools will need to be
prepared periodically, as supply indicates, by spiking base serum. Prepare
new pools far enough in advance so that both old and new pools can be
analytes together for a period time (preferably at least 20 runs) before
switching to the new quality control materials.
2. Content: The internal (or "bench") quality control (QC) materials used in
this method are pooled human serum. The serum is spiked, when
necessary, with inorganic, NIST-traceable standards to achieve desired
concentrations. The analyte concentrations in the "low QC" are in the low-
normal concentration range. The analyte concentrations in the "high QC"
are in the high-normal concentration range.
3. Preparation and storage: Quality control materials can be either prepared
by and purchased from an external laboratory or prepared within the CDC
laboratories. Quality control must always be traceable to the National
Institute for Standards and Technology (NIST). The CDC laboratory
currently prepares its own bench QC materials using the following
procedures:
a. Collection of serum: Human serum can be purchased from blood
services companies such as Tennessee Blood Services, 807 Poplar
Ave., Memphis, TN 38105.
b. Screening serum: Screen different bottles for metal content before
mixing together to make 2 separate base serum pools (for preparing
the low and high bench QC materials).
i. Keep serum at < -20C whenever possible to minimize microbial
growth.
ii. Choose base serum with concentrations in the low-normal
population range (see Table 10 in Appendix C) for low QC.
Choose base serum with concentrations below the targeted high-
normal population concentration for high QC.
c. Spiking of serum
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i. Analyze a sample of each serum pool. Record these results for
future recovery calculations.
ii. Use these results to determine target analyte concentrations
possible for the pools
iii. Calculate the volume of single element standards needed to spike
each pool to the desired concentrations.
iv. While stirring the pools on large stir plates, spike each pool with
calculated volumes of single element standards (all spiking
standards used must be traceable to NIST).
v. Continue to stir pools for 30+ minutes after spiking, then reanalyze.
vi. Repeat steps 4 and 5 until all analytes reach target concentrations
keeping track of the total volume of spiking solution added to each
serum pool.
d. Dispensing and storage of serum
i. Container types: Dispense serum into lot screened containers (i.e.
2 ml_ polypropylene cryovials). If possible, prepare tubes of QC
which have only enough volume for one typical run + 1 repeat
analysis. This allows for one vial of QC to be used per day of
analysis, reducing chances of contamination of QC materials due
to multi-day use.
ii. Labels: Place labels on vials after dispensing and capping if the
vials are originally bagged separately from the caps. This
minimizes the chance for contamination during the process.
Include at least the name of QC pool (text and bar code), date of
preparation, and a vial number on the labels.
iii. Dispensing: Dispensing can be accomplished most easily using a
benchtop automatic pipette in continuous cycling dispense mode.
Carry out this process in a clean environment (e.g. a class 100
cleanroom area or hood is preferred to avoid contamination).
1. Allow serum pool to reach ambient temperature before
dispensing (to prevent temperature gradients possibly causing
concentration gradients across the large number of vials being
dispensed and to prevent condensation problems during
labeling of vials).
2. Attach tubing to the syringe of the benchtop automatic pipette
with a length of clean Teflon™ tubing long enough to reach
into the bottom of the carboy while it is sitting on the stir plate.
3. Check cleanliness of benchtop automatic pipette before use
by analyzing 1-2% (v/v) HNO3 which has been flushed through
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the pipette with a portion of the same solution which has not
been through the pipette.
4. Approximately one hour before dispensing begins,
a. With the large stir plate close to the left side of the pipette,
begin stirring the serum pool to be dispensed.
b. Also during this time, flush the pipette syringe(s) with
serum from the pool to be dispensed. Place the ends of
the tubing attached to both the sample and dispensing
syringes into the carboy of serum so that serum won't be
used up during this process. Secure both ends of tubing in
the carboy with Parafilm so they will not come out during
the flushing process.
5. After dispensing the serum into the vials, cap the vials and
label them. Placing labels on vials after capping minimizes the
chance for contamination during the process.
iv. Homogeneity testing: After dispensing, check homogeneity of
analyte concentrations in pool aliquots by analysis of every Nth
sample dispensed (where N ~20 - 50 depending on the pool size).
Sample more heavily from the beginning and the ending portions
of the tubes dispensed (these are the regions where most
homogeneity problems occur). Keep samples pulled for
homogeneity analysis in the sequence that they were dispensed
for the purpose of looking for trends in concentrations. Once
dispensed and homogeneity has been shown to be good
throughout the tubes of a pool, store tubes at < -20°C and pull
tubes out as needed for analysis.
v. Storage: Store serum pools long term at < -20°C. Short term
storage (up to several days) is permitted at refrigerated
temperatures (~2-8°C).
f. Optimization solutions
i. PRC optimization:
1. Purpose: For periodic testing of the DRC cell parameters. Procedure
requires at a minimum a blank (i), an analyte solution (ii), a blank with
interference (iii), and an analyte and interference containing solution (iv).
a. Solutions for testing elimination of 36Ar14N2 plasma interference on
64Zn.
i. Base serum in diluent (1 +29)
ii. Base serum in diluent (1 +29) + 90 pg/dl_ Zn
b. Solutions for testing elimination of 40Ar25Mg interference on 65Cu:
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i. Base serum in diluent (1 +29)
ii. Base serum in diluent (1 +29) + 90 |jg/dL Cu
iii. Base serum in diluent + 3 mg/L Mg
iv. Base serum in diluent + 90 |jg/dL Cu + 3 mg/L Mg
c. Solutions for testing elimination of ^Ar^Ca interference on 78Se:
i. Base serum in diluent (1 +29)
ii. Base serum in diluent (1 +29) + 90 |jg/L Se
iii. Base serum in diluent (1+29) + 100 mg/L Ca
iv. Base serum in diluent (1+29) + 90 |jg/L Se + 100 mg/L Ca
2. Preparation: To prepare these DRC optimization solutions, use the 10 pg/L
Ga, 2% (v/v) HNOs, 5% Ethyl Alcohol, 0.01% Trion X-100™ diluent as
described in section 6 (same as used to prepare serum samples for
analysis). Prepare different volumes by adding proportionally larger or
smaller volumes of solution constituents. Interference concentrations can
be prepared higher as needed by adjusting the volume of this spike. Keep
interference spike volume small (<0.3 mL) using a high concentration stock
solution (i.e. 1000 mg/L). The Ca spike has to be 0.5 mL because a stock
solution at a concentration higher than 10,000 mg/L is not available. In this
case, 0.5 mL of >18 MQ-cm water is added to the non-spike solutions as
well. Analyte concentrations can be made higher if needed for sensitivity
reasons by preparing a higher concentration calibrator.
a. Solutions testing elimination of 36Ar14N2 plasma interference on 64Zn.
i. Base serum in diluent (1 + 29)
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 0 as described
in Table 7 of Appendix C (multiply volumes by 11).
ii. Base serum in diluent (1 +29) + 90 pg/dL Zn
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 3 as described
in Table 7 of Appendix C (multiply volumes by 11).
Store at ambient temperature and label appropriately. Expiration is 8
hours from preparation.
b. Solutions for testing elimination of 40Ar25Mg interference on 65Cu:
i. Base serum in diluent (1 + 29)
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1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 0 as described
in Table 7 of Appendix C (multiply volumes by 11).
ii. Base serum in diluent (1 +29) + 90 pg/dL Cu
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 3 as described
in Table 7 of Appendix C (multiply volumes by 11).
iii. Base serum in diluent + 3 mg/L Mg
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 0 as described
in Table 7 of Appendix C (multiply volumes by 11).
2. Add 0.15 mL of 1000 mg/L Mg standard
iv. Base serum in diluent + 90 pg/dL Cu + 3 mg/L Mg
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 3 as described
in Table 7 of Appendix C (multiply volumes by 11).
2. Add 0.15 mL of 1000 mg/L Mg standard
Store at ambient temperature and label appropriately. Expiration is 1
year from the date of preparation.
c. Solutions for testing elimination of ^Ar^Ca interference on 78Se:
i. Base serum in diluent (1 +29)
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 0 as described
in Table 7 of Appendix C (multiply volumes by 11).
2. Add 0.5 mL of >18 MQ-cm water.
ii. Base serum in diluent (1 +29) + 90 pg/L Se
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 3 as described
in Table 7 of Appendix C (multiply volumes by 11).
2. Add 0.5 mL of >18 MQ-cm water.
iii. Base serum in diluent (1+29) + 100 mg/L Ca
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 0 as described
in Table 7 of Appendix C (multiply volumes by 11).
2. Add 0.5 mL of 10,000 mg/L Ca
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iv. Base serum in diluent (1+29) + 90 |jg/L Se + 100 mg/L Ca
1. In a 50 mL lot screened or acid-washed polypropylene tube,
prepare a 49.5 mL portion of working calibrator 3 as described
in Table 7 of Appendix C (multiply volumes by 11).
2. Add 0.5 mL of 10,000 mg/L Ca
Store at ambient temperature and label appropriately. Expiration is 1
year from the date of preparation.
7) Analytical instrumentation and parameters
(see Section 5 for details on hardware used, including sources)
a. Instrumentation and equipment setup:
i. Configuration for liquid handling
See Figure 1 in Appendix C for an example setup.
1. Tubing for liguid sample uptake:
a. Probe-to-peristaltic pump tubing: Use of a 'peristaltic to Teflon tubing
adapter' is recommended to prevent damage to small i.d. tubing when
making connections.
b. Nebulizer-to-peristaltic pump tubing: It is recommended to use quick
connection fittings on either end of the PFA tubing: a plug which
pushes inside the liquid port of the nebulizer and a 'peristaltic to Teflon
tubing adapter' to prevent damage to small i.d. tubing when making
connections.
2. Spray chamber waste removal
Use of a 'peristaltic to Teflon tubing adapter' is recommended to prevent
damage to small i.d. tubing when making connections.
a. Between spray chamber and peristaltic tubing:
i. Spray chambers with threaded connection: Use vendor-supplied
threaded connector on base of chamber, connecting tubing directly
to peristaltic pump tubing through a PEEK adapter or directly.
ii. Spray chambers without threaded connection: Use of specialized
push-on connectors available from various vendors (like UFT-075
from Glass Expansion, Pocasset, MA) are preferred for safety
reasons to direct connection of PVC tubing (e.g. 1/8" i.d. x %" o.d.).
b. Between peristaltic pump tubing and waste container: Connect 1/8"
i.d. x %" o.d. PVC tubing to the white/black peristaltic pump tubing
using a tubing connector (PerkinElmer item # B3140715). Connect the
free end of the PVC tubing to the lid of the waste jug. The waste jug
must be in a deep secondary containment tray in case of overflow
(large enough to hold 110% of waste container volume).
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3. Rinse solution for autosampler:
a. Rinse solution jug: Leave one of the caps on the top of the rinse jug
loose to allow air venting into the jug as liquid is removed. Otherwise
the jug will collapse on itself as the liquid is removed and a vacuum is
created inside. Use secondary containment tray.
b. Rinse solution uptake to autosampler rinse station: Use tubing of
different lengths and inner diameters between the rinse solution
container and the autosampler rinse station to control uptake rate of
rinse solution. These can be obtained from the autosampler
manufacturer, their distributors, or custom built in the lab. Optimize
these factors along with fill time in the software so that waste of rinse
solution is minimized and rinse station does not go empty.
c. Autosampler rinse station waste removal: Gravity drain of waste to the
waste container is sufficient. Use minimum drain tubing to make this
connection. If this tube is too long, the rinse station will not drain
properly.
ii. Gas delivery and regulation
1. ICP-MS modifications:
a. Plastic tubing between mass flow controllers and dynamic reaction cell
have been replaced with stainless steel. Stainless steel tubing is
preferred between the reaction gas cylinder/regulator and the back of
the ICP-MS instrument.
2. Argon gas: Used for various ICP-MS functions including plasma and
nebulizer.
a. Regulator for argon source (if a dewar): Set delivery pressure of this
regulator at least 10 psi higher than the delivery pressure of the step-
down regulator to allow for pressure drop across tubing that stretches
to the instrument.
b. Step down regulator (if source of argon is a bulk tank): Place this
single stage regulator in the lab so that incoming argon pressure can
be monitored and adjusted. Set delivery pressure to 10 psig above the
delivery pressure of the filter regulator on the ICP-MS.
c. Filter Regulator at ICP-MS: Single stage "argon regulator filter kit"
supplied with the ICP-DRC-MS. Set the delivery pressure depending
on the instrument setup:
i. ELAN with a 0-60psi gauge on the filter regulator: 52±1 psi when
plasma is running (need 0-150 psi regulator if using a PolyPro or
PFA nebulizer made by Elemental Scientific Inc).
ii. ELAN with a 0-150psi gauge on the filter regulator: 90-100 psi
when plasma is running.
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iii. Chiller / heat exchanger: Refrigerated chiller (for ELAN® 6100 DRCP|US
instruments) or heat exchanger (for ELAN® DRC II instruments). For
refrigerated chiller, set temperature control to 18°C.
b. Parameters for instrument and method:
See Tables and Figures in Appendix C for a complete listing of the instrument
and method parameters and software screen shots.
8) The run: quality, execution, evaluation, and reporting
a. Bench QC, reference materials, and calibration verification:
i. Bench "QC": Analysis of bench QC permits assessment of methodological
imprecision, determination of whether the analytical system is 'in control' during
the run, and assessment of time-associated trends. Before QC materials can
be used in the QC process, they must be characterized by at least twenty (20)
analytical runs to determine appropriate QC parameters.
Bench QC pool analyte concentrations in this method span the analyte
concentration range of the calibrators including "low-normal" ('Low QC') and
"high-normal" ('High QC') concentrations.
In each analytical run the analyst will test each of the two bench QC samples
two times, subjecting them to the complete analytical process. Bench QC pool
samples are analyzed first in the run after the calibrators but before any patient
samples are analyzed. This permits making judgments on calibration linearity
and blank levels prior to analysis of patient samples. The second analysis of
the bench QC pools is done after analysis of all patient samples in the run
(typically 20-30 patient samples total when analyzing for all elements in the
method) to ensure analytical performance has not degraded across the time of
the run. If more patient samples are analyzed on the same calibration curve
after the second run of the bench QC, all bench QC must be reanalyzed before
and after the additional samples. For example, the schemes shown in Table 5
in Appendix C are both acceptable ways to analyze multiple consecutive
"runs".
ii. Reference materials: Use standard reference material (SRM, e.g. SRM
1598A) from the National Institute of Standards and Technology (NIST) to
verify method accuracy. Use previously characterized samples from
proficiency testing program or commercially-produced reference materials
when NIST SRMs are unavailable.
iii. Calibration verification: The test system is calibrated as part of each analytical
run with NIST-traceable calibrators. These calibrators, along with the QCs and
blanks, are used to verify that the test system is performing properly.
b. Perform, evaluate, and report a run
i. Starting the equipment for a run
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1. Power on the computer, printer, autosampler, and instrument computer
controller.
2. Peristaltic pump: Set proper tension on peristaltic pump tubing.
3. Software: Start software for the ICP-MS and autosampler control.
4. Daily pre-ignition maintenance checks: Perform and document daily
maintenance checks (e.g., Ar supply pressure, interface components
cleanliness and positioning, interface pump oil condition, vacuum pressure,
etc.).
5. Place probe in adequate volume of rinse solution: Send the autosampler
probe to a rinse solution (e.g. autosampler rinse station).
6. Start the plasma
7. Start the peristaltic pump: Start the pump running slowly, making sure that
the rotational direction is correct for the way the tubing is set up.
8. Warm-up time: Allow warm-up time suggested by the manufacturer for the
ICP-MS (e.g. RF generator) after igniting the plasma. There will be
another warm-up time (or "stability time") for the DRC later in this
procedure.
9. Daily performance check: Perform and document a daily performance
check and any optimizations necessary.
Save new parameters to the "default.tun" and "default.dac" files.
10. Readying the instrument for quick-start analysis: Leave the plasma
running to eliminate the need for an initial instrument warm-up period
and/or a DRC stabilization period as long as appropriate planning is made
for sufficient solution supply and waste collection. Analysis of conditioning
samples (diluted serum matrix) can also be scheduled to occur at roughly a
predetermined time. Accomplish this by setting up multiple sample
analyses with extended rinse times (e.g. one analysis with a 1600s rinse
time will take approximately 30 minutes to complete). Initial samples would
be non-matrix, while final samples would be diluted matrix for conditioning.
If running a DRC-only method during these scheduled analyses, the ICP-
MS will remain in DRC-mode for approximately 45 minutes without
depressurizing the cell. Prepare working dilutions of serum materials close
in time to analysis so that they are not more than 7 hours old when
analyzed (see Appendix B, ruggedness test 5).
11. Software setup for analysis:
a. Workspace (files and folders): Verify and set up the correct files and
data directories for your analysis (See Table 1 in Appendix C for
defaults).
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b. Samples / batch window: Update the software to reflect the current
sample set. Use a bar code scanner to input data whenever possible.
See Table 1 in Appendix C for times and speeds.
1. Serum vs. aqueous method files:
a. The difference: There are two method files for this one
method (see Table 1 in Appendix C). It is necessary to use
both to accomplish each run because the current
PerkinElmer software will not allow for more than one blank
per method file. The ONLY DIFFERENCE between these
two files is on the Sampling tab where one lists the
autosampler positions of the serum blank and serum
calibrators (the "sblk" method file) and the other lists the
autosampler position of the aqueous blank (the "aqblk"
method file).
b. Use: The ONLY TIME when it matters which of these files
is used is when the measurement action includes "Run
blank" or "Run standards". When the measurement action
is only 'run sample', it does not matter whether the "sblk" or
"aqblk" method file is used. Analysts typically follow the
pattern below, however, for the sake of consistency and as
a reminder of which blank must be used for which type of
sample. See Table 6 in Appendix C.
i. The "sblk" method file: Use to analyze the initial serum
blank (blank for the calibration curve), the serum
calibrators, and the serum blank checks at the very
beginning of the run. The serum blank method defines
the autosampler location of the serum blank and the
serum calibrators.
ii. The "aabllc" method file must be used to analyze all QC
materials and patient samples. The aqueous blank
method defines the aqueous blank in autosampler
location.
ii. Preparation of samples for analysis (See Table 7 in Appendix C)
1. Thaw serum samples; allow them to reach ambient temperature.
2. If instrument stability in DRC mode requires it, prepare 50mL+ of a junk
serum sample to be analyzed repeatedly before the beginning of the run
to achieve a stable analyte-to-internal standard ratio. Time to reach
stability is instrument-specific but 1-1.5 hours is typical (~18
measurements of the 3 element serum method can be made in 1 hour).
See Table 6 in Appendix C for example of setup in the Samples/Batch
window.
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NOTE: Selenium is not stable in the diluted sample for more than 7
hours. Diluted serum must be analyzed within 7 hours of
preparation (see ruggedness parameter test 5 in Appendix B for
details)
3. Prepare the following solutions into pre-labeled containers using the
benchtop automatic pipette. See Table 7 of Appendix C for a summary
of sample preparation.
Prepare samples in the cleanest environment available to prevent trace
element contamination and an environment which provides personnel
protection (e.g. Class II, Type A/B3 biological safety cabinet).
a. Aqueous blank: Prepare at least two aqueous blanks. One will be the
actual reagent blank for patient and QC samples and the other will be
a backup ("Aqueous Blank Check") in case the original aqueous blank
is unusable.
b. Calibrators: Prepare the working calibrators (S0-S5). Prepare at least
three separate tubes of SO. One of these SO preparations will be the
zero standard (serum blank) for the calibrators; the other two will be
analyzed after the last calibrator to verify washout.
c. Patient and QC samples: Before taking an aliquot for analysis,
homogenize the sample (e.g. vortex for 3-5 seconds).
After preparation, mix and cover the diluted samples. Place prepared
dilutions on the autosampler of the ICP-MS in the order corresponding to
the sequence setup in the ICP-MS software.
Original serum samples are not compromised by staying at ambient
temperature during the work day. However, store long-term at < -20 °C.
iii. Start the analysis using the ICP-MS software.
iv. Monitor the analysis in real-time as much as possible. If necessary, leave the
run to complete itself unattended as long as appropriate planning is made for
either overnight operation or Auto Stop (see below).
Monitor the analysis for the following:
1. Verify proper operation of the instrument (sample reaching nebulizer in
correct timing, autosampler arm moving properly, etc...).
2. Verify that background signal from instrument and reagents are low.
Helpful checks when diagnosing high background problems include:
a. >18 MQ-cm water to be used in Aq Blank Checks and dilutions.
b. Diluent before and after being flushed through the benchtop automatic
pipette.
If contamination is observed from the pipette, flush the pipette with
>500 ml_ of nitric acid solution (< 5% v/v HNO3) and retest.
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c. Comparison with other instruments.
3. Verify analyte/internal standard ratio stability (esp. DRC measurements)
The net intensity (analyte / internal standard ratio) of the measurements
made while stabilizing the DRC can be evaluated to determine the
readiness of the system to begin analysis. Continual trending in this ratio
indicates that unwanted instrument drift will occur within the run.
4. Verify calibration curves meet R2 requirements (minimum of 0.98, typically
0.99 to 1.000).
5. Verify bench QC results within the acceptable limits.
If an analyte result for the beginning QC material(s) falls outside of the ±
3SD limits, then the following steps are recommended:
a. Evaluate the blank results.
b. Evaluate the reproducibility of the 3 replicates within the
measurements.
c. Evaluate the consistency of the internal standard across the
measurements (especially the calibrators).
d. Evaluate calibration curves. If a particular calibrator is obviously in
error, it can be re-analyzed as a sample (old or new dilution) and
incorporated into the curve through data reprocessing as a calibrator.
As a last resort, a single calibration point per analyte between or
including S2 and S4 can be removed from the curve. Follow-up
repeated problems with calibrators with appropriate corrective actions
(e.g. re-preparation of intermediate working calibration standards or
troubleshooting instrument parameters).
e. Prepare a fresh dilution of the failing QC material (same vial) and
reanalyze it to see if the QC dilution was not properly made.
f. Prepare a fresh dilution of the failing QC material (unused vial) and
analyze it to see if the QC vial had become compromised.
g. Prepare and analyze new working calibrators.
h. Test a different preparation of intermediate working calibration
standards.
If these steps do not result in correction of the out-of-control values for QC
materials, consult the supervisor for other appropriate corrective actions.
6. Verify good precision among replicates of each measurement.
7. Verify consistent measured intensities of the internal standards.
Some sample-to-sample variations are to be expected, however, intensities
drifting continuously in one direction resulting in failing results for ending
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QC indicate the instrument needs additional pre-conditioning before the run
or environmental conditions are changing too much around the instrument.
8. Verify elevated patient results.
Refer to Figure 14 in Appendix C for flowchart.
a. Confirming an elevated concentration: Repeat for confirmation any
sample having a concentration greater than the 1UB threshold (see
Table 9 in Appendix C).
b. Dilution of a sample to within the calibration range: Repeat in duplicate
with extra dilution any sample having a concentration greater than the
highest calibrator to bring the observed result within the concentration
range of the calibrators (see Table 8 in Appendix C).
c. Confirming proper washout after an elevated sample: When monitoring
the analysis in real-time, if a sample concentration is greater than
standard 5 + 10% (see Table 4 in Appendix C), do the following to
verify that the run is still in control for low concentration samples before
proceeding with analysis.
i. Stop run following elevated sample
ii. Verify that the run is still in control for lower concentration samples
before proceeding with analysis. Analyze 2 serum blank checks
followed by a low bench QC washout check. If the low bench QC
wash check is not in control (within ± 3SD limits), repeat these 3
check samples until washout is verified before proceeding with
analysis.
Example:
3006 sblkchk Washl
3006 sblkchk Wash2
LSXXXXX Wash
iii. If the run is not verified in-control for low concentration samples
before the next samples are analyzed, see Section 8.b.viii.2. for
directions.
v. Instrument cleaning between consecutive runs: In between consecutive runs,
aspirate >18 MQ-cm water through the sample introduction system for
approximately 30 minutes at peristaltic pump speed similar to that used in the
analysis. This assists cleaning out the sample introduction system to prevent
clogging.
vi. Overnight operation or using auto stop: Ensure sufficient solution supply and
waste collection during unattended operation. Turn on the AutoStop feature of
the ICP-MS software. Delay the shutdown at least 10 minutes (use peristaltic
pump speed approximately that of the method wash) to rinse the sample
introduction system of serum matrix before turning off the plasma. It will be
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necessary to replace the sample peristaltic pump tubing the next day since it
will have been clamped shut overnight.
vii. Records of results: Run results will be documented after each run in both
electronic and paper form.
1. Electronic records: Transfer data electronically to the laboratory information
system. When keyboard entry must be used, proofread transcribed data
after entry.
a. Export data from the ICP-MS software using "original conditions" or
files and folders used during the analysis. Use descriptive report
filenames (e.g. 2005-0714a_group55.txt). In the ICP-MS software
under "Report Format" (METHOD window, REPORT tab) choose the
"Use Separator" option, and under the "File Write" Section choose
"Append."
b. Move the generated .TXT data file to the appropriate subdirectory on
the network drive where exported data are stored prior to import to the
laboratory information management system.
c. Import the instrument file into the laboratory information system with
appropriate documentation (e.g. instrument ID, analyst, calibrator lot
number, and run or sample specific comments).
2. Paper records: Printed run sheets must be documented with
i. Analyst initials
ii. Instrument ID
iii. Date of analysis and run # for the day
viii. Analyst evaluation of run results:
1. Bench quality control: After completing a run, and importing the results into
the laboratory information system, evaluate the run bench QC according to
laboratory QC rules. The QC limits are based on the average and standard
deviation of the beginning and ending analyses of each of the bench QC
pools, so it will not be possible to know if the run is in control until
statistically reviewed.
a. Quality Control Rules: The SAS program applies the division QC rules
to the data as follows:
i. If both QC run means (low and high bench QC) are within 2Sm
limits and individual results are within 2Si limits, then accept the
run.
ii. If 1 of the 2 QC run means is outside a 2Sm limit - reject run if:
1. Extreme Outlier - Run mean is beyond the characterization
mean +/- 4Sm
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2. 1 3S Rule - Run mean is outside a 3Sm limit
3. 2 2S Rule - Both run means are outside the same 2Sm limit
4. 10 X-bar Rule - Current and previous 9 run means are on
same side of the characterization mean
iii. If one of the 4 QC individual results is outside a 2Si limit - reject
run if:
1. R 4S Rule - Within-run ranges for all pools in the same run
exceed 4Sw (i.e., 95% range limit)
Note: Since runs have multiple results per pool for 2 pools, the R 4S
rule is applied within runs only.
Abbreviations:
Si = Standard deviation of individual results (the limits are not shown
on the chart unless run results are actually single
measurements).
Sm = Standard deviation of the run means (the limits are shown on the
chart).
Sw = Within-run standard deviation (the limits are not shown on the
chart).
b. Implications of QC Failures: If the division SAS program declares the
run out of control" for any analyte, use the following to determine the
implications on usability of the data from the run.
i. If only one analyte of the three fails bench QC, then report results
for the other two which passed bench QC.
ii. If two analytes of the three fail bench QC, then no results are
reportable from the run. Investigate the cause of QC failures and
repeat the run with the appropriate corrective action.
2. Patient results:
a. Concentrations outside of the normal range (refer to Figure 14 in
Appendix C for flowchart on handling elevated concentration samples):
i. Boundaries requiring confirmatory measurement:
1. Results outside of the first (1 LB or 1UB) or second (2LB or
2UB) boundaries.
The concentrations assigned to 2LB, 1LB, 1UB, and 2UB for
an element is determined by study protocol but default
concentrations are in Table 9 in Appendix C.
a. Results lower than the first lower boundary or greater than
the first upper boundary (1 UB): Confirm by repeat analysis
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of a new sample preparation any concentration observed
lower than the 1 LB or greater than the 1UB. Report the first
analytically valid result, as long as the confirmation is within
10% or 3SD of the characterized bench low QC. Continue
repeat analysis until a concentration can be confirmed.
b. Analyst reporting of results outside of the normal range:
Report any patient results confirmed to be less than the
second lower boundary (2LB) as an "unusually low result" or
greater than the second upper boundary (2UB) as an
"elevated result".
2. Results greater than highest calibrator: Samples that exceed
the high calibrator must be prepared with minimum extra
dilution in duplicate to bring the observed result within the
calibration range (< S5). Report the first analytically valid
result (i.e. the first one within the calibration range), as long as
the confirmation is within 10%. Continue repeat analysis until a
concentration can be confirmed.
ii. Concentrations reguiring verification of washout: after a result is
observed that is greater than the highest concentration validated
for washout, do the following:
1. If the run was verified to be in control for lower concentration
samples before subsequent sample analysis was performed,
no further action is required.
2. If the run was not verified to be in control for lower
concentration samples before subsequent sample analysis
was performed, confirm by re-analysis the results for the 2
samples immediately following the elevated sample. Report
the results if they confirm the initial results within ±10% or
±3SD of the low bench QC, whichever is greater.
b. Unacceptable measurement reproducibility: If the range of the three
replicate readings (maximum replicate concentration value - minimum
replicate concentration value) for a single sample analysis is greater
than the range maximum criteria listed in Table 9 of Appendix C and
the range of the three replicate readings is greater than 10% of the
observed concentration, do not use the measurement for reporting.
Repeat the analysis of the sample.
ix. Submitting final work for review: All analyses must undergo quality control and
quality assurance review. After appropriately documenting the run in the
laboratory information system (e.g. sample and run QC, and run and sample
comments), inform the first level reviewer of the completed work and submit
any printed documentation.
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9) Routine equipment maintenance and data backups
Maintenance activities will be documented in the instrument logbook.
a. Equipment maintenance:
Analysts are expected to regularly evaluate the need for, and when necessary,
perform cleaning, replacement, or re-positioning of components in ICP-MS the
sample introduction system, interface, ion optics region, and equipment required
resources (e.g. autosampler, exhaust, compressed gases, and coolant).
Frequency of equipment maintenance will be dependent on instrument
throughput.
b. Parameter optimizations:
Analysts are expected to optimize instrument parameters.
PRC optimizations: DRC conditions (cell gas flow rate and RPq value) can be
verified by analyzing the DRC optimization solutions (see Section 6.f.i) as
needed to ensure proper reduction of potential ICP-MS interferences.
c. Data backup:
Data on the instrument computer will be backed up via two backup routines.
Files used and produced by the ICP-MS in analyzing samples will be backed up
and kept a minimum of two years after analysis.
i. Daily backups to secondary hard drive: Program automatic backups of the
relevant computer files to occur each night onto a secondary hard drive to
prevent loss of data from failure of primary hard drive.
ii. Weekly backup: Backup relevant computer files weekly either to secondary
hard drive which is remote to the laboratory or to removable media which will
be placed remote to the laboratory for retrieval in the case of catastrophic data
loss elsewhere.
10) Reporting thresholds
a. Reportable range:
Serum element concentrations are reportable in the range between the method
LOD and the high calibrator times the maximum permitted extra dilution (see
Table 8 of Appendix C).
Serum multi-element values are reportable in the range between the method
LOD and the highest calibrator (see 'calibrator concentrations' in Table 1 of
Appendix C) times the maximum validated extra dilution (see Table 7 of
Appendix C). Above the highest calibrator, extra dilutions are made of the serum
sample to bring the observed concentration within the calibration range.
b. Reference ranges (normal values):
In this method the 95% reference ranges (see Table 10 in Appendix C) for these
elements in serum fall within the range of the calibrators.
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c. Action levels:
There is no routine notification for levels of every analyte determined with this
method. The protocol for supervisors reporting elevated results to medical
personnel is defined according to the study protocol.
11) Method calculations
a. Method limit of detection (LOP):
The method detection limits for elements in serum specimens are defined as 3
times so, where so is the estimate of the standard deviation at zero analyte
concentration. So is taken as the y-intercept of a linear or 2nd order polynomial
regression of standard deviation versus concentration (4 concentration levels of
the analytes in serum each measured 60 times across at least a 2-month
timeframe). Method LODs are re-evaluated periodically.
b. Method limit of quantitation (LOQ):
The Division of Laboratory Sciences does not currently utilize limits of
quantitation in regards to reporting limits [5],
c. QC limits:
Quality control limits are calculated based on concentration results obtained in at
least 20 separate runs. It is preferable to perform separate analyses on separate
days and using multiple calibrator lot numbers, instruments, and analysts to best
mimic real life variability. The statistical calculations are performed using the
SAS program developed for the Division of Laboratory Sciences).
12) Alternate methods for performing test and storing specimens if test system
fails
If the analytical system fails, setup analysis on other ICP-MS instrument, if available.
If no other instrument is available, store the specimens at < -20 °C until the analytical
system can be restored to functionality.
13) Method performance documentation
Method performance documentation for this method including accuracy, precision,
sensitivity, specificity and stability is provided in Appendix A of this method
documentation. The signatures of the branch chief and director of the Division
of Laboratory Sciences on the first page of this procedure denote that the
method performance is fit for the intended use of the method.
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Appendix A. Method performance documentation
a. Accuracy
i. Copper
Accuracy compared to Reference Material
Mean concentration should be within ±15% of the nominal value except at 3*LOD, where it should be within ± 20%
Method name:
Multi-Elements in Serum by ICP-DRC-MS
Method #:
3006
Matrix:
Serum
Units:
Hg/dL
Reference material:
NISTSRM 1598a lOx,
NISTSRM 1598a 2x,
NISTSRM 1598a
Analyte:
copper
Measured concentration
Reference
material
Replicate
Nominal
value
Day 1
Day 2
Day 3
Day 4
Day 5
Mean
SD CV (%)
Difference from
nominal value (%)
Level 1
1
2
15.8
19
18
17
17
15
13
16
13
12
12
15.13
2.56 16.95
-4.2
Level 2
1
2
79
80
78
75
76
79
78
85
84
71
67
77.24
5.38 6.96
-2.2
Level 3
1
2
158
168
165
161
155
167
167
182
170
157
150
164.28
8.88 5.40
4.0
ii. Selenium
Accuracy compared to Reference Material
Mean concentration should be within ±15% of the nominal value except at 3*LOD, whereitshouldbewithin± 20%
Method name:
Multi-Elements in Serum by ICP-DRC-MS
Method #:
3006
Matrix:
Serum
Units:
Hg/L
Reference material:
NISTSRM 1598a lOx,
NISTSRM 1598a 2x,
NISTSRM 1598a
Analyte:
selenium
Reference
material
Replicate
Nominal
value
Day 1
Day 2
Day 3
Day 4
Day 5
Mean
SD
CV (%)
Difference from
nominal value (%)
Level 1
1
2
13.4
13
13
18
17
10
10
11
10
10
10
12.01
3.06
25.46
-10.4
Level 2
1
2
67.2
89
83
67
65
66
66
65
65
66
66
70.06
8.72
12.44
4.2
Level 3
1
2
134.4
215
189
128
129
132
132
127
127
132
133
144.32
31.09
21.54
7.4
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Appendix A. Method performance documentation
a. Accuracy
i. Copper
Accuracy compared to Reference Material
Mean concentration should be within ±15% of the nominal value except at 3*LOD, where it should be within ± 20%
Method name: Multi-Elements in Serum by ICP-DRC-MS
Method #: 3006
Matrix: Serum
Units: Hg/dL
Reference material: NIST SRM 1598a lOx, NIST SRM 1598a 2x, NIST SRM 1598a
Analyte: copper
Reference
Replicate
material
Measured concentration
Nominal
Day 1 Day 2 Day 3 Day 4 Day 5
value
Mean SD CV (%)
Difference from
nominal value (%)
Level 1
19 17 15 16 12
15.8
18 17 13 13 12
15.13 2.56 16.95
-4.2
Level 2
7g 80 75 79 85 71
78 76 78 84 67
77.24 5.38 6.96
-2.2
Level 3
168 161 167 182 157
158
165 155 167 170 150
164.28 8.88 5.40
4.0
ii. Selenium
Accuracy compared to Reference Material
Mean concentration should be within ±15% of the nominal value except at 3*LOD, whereitshouldbewithin± 20%
Method name: Multi-Elements in Serum by ICP-DRC-MS
Method #: 3006
Matrix: Serum
Units: ng/L
Reference material: NIST SRM 1598a lOx, NIST SRM 1598a 2x, NIST SRM 1598a
Analyte: selenium
Reference
Replicate
material
Nominal
Day 1 Day 2 Day 3 Day 4 Day 5
value
Mean SD CV (%)
Difference from
nominal value (%)
Level 1 1
2
13 18 10 11 10
13.4
13 17 10 10 10
12.01 3.06 25.46
-10.4
Level 2 1
2
g7 89 67 66 65 66
83 65 66 65 66
70.06 8.72 12.44
4.2
Level 3 1
2
„ 215 128 132 127 132
134.4
189 129 132 127 133
144.32 31.09 21.54
7.4
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 44 of 86
iii. Zinc
Accuracy compared to Reference Material
Mean concentration should be within ±15% of the nominal value except at 3*LOD, whereitshouldbewithin± 20%
Method name: Multi-Elements in Serum by ICP-DRC-MS
Method #: 3006
Matrix: Serum
Units: Hg/dL
Reference material: NIST SRM 1598a lOx, NIST SRM 1598a 2x, NIST SRM 1598a
Analyte: zinc
Reference
Replicate
material
Measured concentration
Nominal
Day 1 Day 2 Day 3 Day 4 Day 5
value
Mean SD CV (%)
Difference from
nominal value (%)
Level 1 1
2
gg 15 15 6.4 8.7 11
8.0 13 8.5 6.4 6.5
9.90 3.48 35.14
12.5
Level 2 1
2
44 43 44 39 48 46
41 45 38 48 43
43.50 3.62 8.33
-1.1
Level 3 1
2
gg 93 102 84 105 96
87 90 87 98 94
93.69 6.79 7.24
6.5
-------
b. Precision
i. Copper
Precision
Total relative standard deviation should be < 15% (CV < 15%)
Method name:
Multi-Elements in Serum by ICP-DRC-MS
Method #:
3006
Matrix:
Serum
Units:
Hg/dL
Analyte:
copper
Quality material 1
Run
Result 1
Result 2
Mean
SS 1
SS 2
2*meanA2
1
100
107
103.10
12.4541939
12.4541939
21257.17867
2
92
93
92.31
0.103458722
0.103458723
17043.28763
3
108
107
107.69
0.25170289
0.25170289
23194.0999
4
102
102
101.94
0.046893902
0.046893903
20781.71271
5
101
98
99.74
3.01890625
3.01890625
19895.53676
6
99
94
96.10
6.332520602
6.332520603
18469.01697
7
101
107
104.19
10.91972025
10.91972025
21712.69592
8
106
99
102.76
12.97368361
12.97368361
21119.85176
9
104
101
102.62
1.70380809
1.70380809
21061.27727
10
107
103
104.92
2.765735302
2.765735302
22014.3774
Grand sum
2030.7143
Grand mean
101.535715
Rel Std Dev
Sum squares Mean Sq Error
Std Dev
(%)
Within Run
101.141247
10.1141247
3.180271168
3.13
Between Run
359.0065728
39.8896192
3.858464364
3.80
Total
460.1478199
5.000187192
4.92
Quality material 2
Run
Result 1
Result 2
Mean
SS 1
SS 2
2*meanA2
1
251
271
261.03
92.5838462
92.5838462
136275.0446
2
241
242
241.32
0.621495723
0.621495722
116467.5477
3
239
236
237.54
1.529797923
1.529797923
112852.071
4
278
275
276.63
3.293317563
3.293317563
153052.3526
5
247
240
243.62
10.91575521
10.91575521
118705.5017
6
240
243
241.84
1.825336102
1.825336103
116975.0576
7
236
250
242.97
50.38728256
50.38728256
118064.1768
8
240
244
241.66
4.638208323
4.638208323
116795.0997
9
260
245
252.48
49.60807489
49.60807489
127491.6948
10
241
239
240.21
1.50749284
1.50749284
115396.8841
Grand sum
4958.5906
Grand mean
247.92953
Sum squares Mean Sq Error
Std Dev
Rel Std Dev
Within Run
433.8212147
43.38212147
6.586510568
2.66
Between Run
2694.393548
299.3770609
11.31359668
4.56
Total
3128.214763
13.09120282
5.28
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 46 of 86
ii. Selenium
Precision
Total relative standard deviation should be < 15% (CV < 15%)
Method name:
Multi-Elements in Serum by ICP-DRC-MS
Method #:
3006
Matrix:
Serum
Units:
M-g/L
Analyte:
selenium
Quality material 1
Run
Result 1
Result 2
Mean
SS 1
SS 2
2*meanA2
1
131
132
131.71
0.54745
0.54745
34695.15357
2
125
128
126.51
2.70997
2.70997
32009.25658
3
123
122
122.44
0.48275
0.48275
29982.47052
4
131
131
131.20
0.00853
0.00853
34426.69632
5
129
127
128.36
1.29743
1.29743
32951.06457
6
129
127
127.92
0.35295
0.35295
32729.40657
7
123
123
122.73
0.01943
0.01943
30123.24397
8
126
122
124.24
5.01469
5.01469
30870.98126
9
125
117
120.62
16.35838
16.35838
29096.46304
10
125
122
123.49
3.12883
3.12883
30499.78248
Grand sum
2518.4231
Grand mean
125.921155
Rel Std Dev
Sum squares Mean Sq Error
Std Dev
(%)
Within Run
59.84085507
5.984085507
2.446239053
1.94
Between Run
261.7733426
29.08592696
3.39866455
2.70
Total
321.6141977
4.187482087
3.33
Quality material 2
Run
Result 1
Result 2
Mean
SS 1
SS 2
2*meanA2
1
259
261
259.59
1.06069401
1.06069401
134770.7173
2
258
267
262.12
21.03827556
21.03827556
137409.3328
3
259
255
256.82
4.902460222
4.902460223
131911.7407
4
243
239
241.26
4.700440802
4.700440802
116416.7802
5
282
277
279.48
5.53049289
5.53049289
156214.8988
6
252
251
251.61
0.63059481
0.63059481
126620.1158
7
240
242
241.32
1.252049102
1.252049103
116466.9685
8
251
241
246.08
22.6437981
22.6437981
121108.715
9
241
233
236.90
17.0730108
17.0730108
112245.5416
10
229
226
227.85
2.23293249
2.23293249
103830.1513
Grand sum
5006.0458
Grand mean
250.30229
Sum squares Mean Sq Error
Std Dev
Rel Std Dev
Within Run
162.1294976
16.21294976
4.026530735
1.61
Between Run
3970.23443
441.1371589
14.57607988
5.82
Total
4132.363927
15.12200563
6.04
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 47 of 86
iii. Zinc
Precision
Total relative standard deviation should be < 15% (CV < 15%)
Method name:
Multi-Elements in Serum by ICP-DRC-MS
Method #:
3006
Matrix:
Serum
Units:
Hg/dL
Analyte:
zinc
Quality material 1
Run
Result 1
Result 2
Mean
SS 1
SS 2
2*meanA2
1
67
66
66.26
0.19084
0.19084
8779.54281
2
62
62
61.79
0.03644
0.03644
7636.15650
3
72
72
72.06
0.10775
0.10775
10385.84928
4
69
71
70.06
0.81072
0.81072
9817.78806
5
71
68
69.18
2.10787
2.10787
9570.92849
6
68
61
64.38
10.21346
10.21346
8288.57738
7
69
75
72.34
9.96318
9.96318
10466.28141
8
73
68
70.57
7.23368
7.23368
9959.38886
9
68
68
68.19
0.04933
0.04933
9298.79756
10
72
69
70.47
2.83956
2.83956
9932.80289
Grand sum
1370.5824
Grand mean
68.52912
Rel Std Dev
Sum squares Mean Sq Error
Std Dev
(%)
Within Run
67.10564165
6.710564165
2.590475664
3.78
Between Run
211.3074877
23.47860975
2.895517707
4.23
Total
278.4131294
3.88517528
5.67
Quality material 2
Run
Result 1
Result 2
Mean
SS 1
SS 2
2*meanA2
1
253
247
250.05
9.87907761
9.87907761
125047.7046
2
243
245
243.93
0.892930502
0.892930503
118999.3479
3
238
235
236.55
2.01696804
2.01696804
111914.6436
4
278
279
278.83
0.28643904
0.28643904
155492.3378
5
258
250
253.71
16.02641089
16.02641089
128733.1644
6
245
249
246.64
4.240098722
4.240098723
121661.642
7
233
255
244.08
129.8391881
129.8391881
119148.5307
8
241
257
248.84
62.87934912
62.87934912
123842.94
9
262
245
253.21
73.04693556
73.04693556
128234.4064
10
240
237
238.59
3.514687563
3.514687563
113850.5194
Grand sum
4988.8471
Grand mean
249.442355
Sum squares Mean Sq Error
Std Dev
Rel Std Dev
Within Run
605.2441703
60.52441703
7.779744021
3.12
Between Run
2495.467355
277.2741506
10.41032501
4.17
Total
3100.711526
12.99612572
5.21
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 48 of 86
c. Stability
i. Copper
Stability
The initial measurement can be from the same day for all stability experiments.
Freeze and thaw stability = Assess for a minimum of 3 freeze-thaw cycles; conditions should mimic intended sample handling conditions
Describe condition: Three times frozen at -20°C and then thawed (3 freeze-thaw cycles) to room temperature.
Bench-top stability = Assess short-term stability for length of time needed to handle study samples (typ
cally at room temperature)
Describe condition: Original samples in cryovial stored at room temperature for 1 day prior to preparation and analysis.
Processed sample stability = Assess short-term stability of processed samples, including resident time in autosampler
Describe condition: Processed samples (ready for instrument analysis) stored at room temperature for 1 day prior to analys
s.
Long-term stability = Assess long-term stability that equals or exceeds time between date of first sample collection and date of last sample analysis
Describe condition: Samples from 2 characterized pools stored at -70°C for 3 years.
All stability sample results should be within ±15% of nominal concentration
Method name: Multi-Elements in Serum by ICP-DRC-MS
Method #: 3006
Matrix: Serum
Units: Hg/dL
Analyte: copper
Quality material 1
Initial Three freeze-
Initial
Bench-top
Initial
Processed
Initial
Long-
measurement thaw cycles
measuremen
stability
measuremen
sample
measuremen
term
Replicate 1 96 101
100
100
98
102
96
96
Replicate 2 100 97
99
101
96
99
100
100
Replicate 3 98 98
99
102
97
102
102
98
Mean 97.72366667 98.592
99.50733333
100.9
96.90933333
101.257
99.40943333
97.7
% difference from
0.9
initial measurement
--
1.4
-
4.5
-
-1.7
Quality material 2
Initial Three freeze-
Initial
Bench-top
Initial
Processed
Initial
Long-
measurement thaw cycles
measuremen
stability
measuremen
sample
measuremen
term
Replicate 1 254 244
262
243
245
245
229
254
Replicate 2 258 248
265
245
252
255
243
258
Replicate 3 271 252
250
259
239
251
278
271
Mean 260.9496667 247.9396667
258.9463333
249.1
245.182
250.188
250.3471667
260.9
% difference from
.... "¦ -5.0
initial measurement
--
-3.8
--
2.0
--
4.2
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 49 of 86
ii. Selenium
Stability
The initial measurement can be from the same day for all stability experiments.
Freeze and thaw stability = Assess for a minimum of 3 freeze-thaw cycles; conditions should mimic intended sample handling conditions
Describe condition: Three times frozen at -20°C and then thawed (3 freeze-thaw cycles) to room temperature.
Bench-top stability = Assess short-term stability for length of time needed to handle study samples (typically at room temperature)
Describe condition: Original samples in cryovial stored at room temperature for 1 day prior to preparation and analysis.
Processed sample stability = Assess short-term stability of processed samples, including resident time in autosampler
Describe condition: Processed samples (ready for instrument analysis
) stored at room temperature for 1 day prior to analys
s.
Long-term stability = Assess long-term stability that equals or exceeds time between date of first sample collection and date of last sample analysis
Describe condition: Samples from 2 characterized pools stored at -70°C for 3 years.
All stability sample results should be within ±15% of nominal concentration
Method name: Multi-Elements in Serum by ICP-DRC-MS
Method #: 3006
Matrix: Serum
Units: pig/L
Analyte: selenium
Quality material 1
Initial
Three freeze-
Initial
Bench-top
Initial
Processed
Initial
Long-
measurement
thaw cycles
measuremen
stability
measuremen
sample
measuremen
term
Replicate 1 127
129
128
126
128
130
126
127
Replicate 2 128
124
128
125
127
129
125
128
Replicate 3 126
125
129
126
127
129
125
126
Mean 126.96
125.7446667
128.465
125.7
127.419
129.396
125.4663
127.0
% difference from
initial measurement
-1.0
--
-2.1
-
1.6
--
1.2
Quality material 2
Initial
Three freeze-
Initial
Bench-top
Initial
Processed
Initial
Long-
measurement
thaw cycles
measuremen
stability
measuremen
sample
measuremen
term
Replicate 1 260
247
271
253
259
257
251
260
Replicate 2 266
249
278
254
263
257
241
266
Replicate 3 280
258
266
259
255
260
229
280
Mean 268.5686667
251.046
271.722
255.4
259.2036667
257.9403333
240.4046667
268.6
% difference from
initial measurement
-6.5
--
-6.0
-
-0.5
-
11.7
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 50 of 86
iii. Zinc
Stability
The initial measurement can be from the same day for all stability experiments.
Freeze and thaw stability = Assess for a minimum of 3 freeze-thaw cycles; conditions should mimic intended sample handling conditions
Describe condition: Three times frozen at -20°C and then thawed (3 freeze-thaw cycles) to room temperature.
Bench-top stability = Assess short-term stability for length of time needed to handle study samples (typically at room temperature)
Describe condition: Original samples in cryovial stored at room temperature for 1 day prior to preparation and analysis.
Processed sample stability = Assess short-term stability of processed samples, including resident time in autosampler
Describe condition: Processed samples (ready for instrument analysis
) stored at room temperature for 1 day prior to analys
s.
Long-term stability = Assess long-term stability that equals or exceeds time between date of first sample collection and date of last sample analysis
Describe condition: Samples from 2 characterized pools stored at -70°C for 3 years.
All stability sample results should be within ±15% of nominal concentration
Method name: Multi-Elements in Serum by ICP-DRC-MS
Method #: 3006
Matrix: Serum
Units: pig/dL
Analyte: zinc
Quality material 1
Initial
Three freeze-
Initial
Bench-top
Initial
Processed
Initial
Long-
measurement
thaw cycles
measuremen
stability
measuremen
sample
measuremen
term
Replicate 1 65
68
68
71
66
69
73
65
Replicate 2 68
66
68
72
65
68
68
68
Replicate 3 66
65
67
72
66
69
72
66
Mean 66.389
66.57566667
67.988
71.9
65.76233333
68.527
71.2743
66.4
% difference from
initial measurement
0.3
--
5.7
-
4.2
--
-6.9
Quality material 2
Initial
Three freeze-
Initial
Bench-top
Initial
Processed
Initial
Long-
measurement
thaw cycles
measuremen
stability
measuremen
sample
measuremen
term
Replicate 1 257
242
265
247
247
245
241
257
Replicate 2 262
261
262
249
254
256
262
262
Replicate 3 274
253
271
247
241
252
240
274
Mean 264.2793333
252.086
265.802
247.9
247.354
250.9143333
247.712
264.3
% difference from
initial measurement
-4.6
--
-6.7
-
1.4
-
6.7
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 51 of 86
d. Analytical Sensitivity and Specificity
LOD, specificity and fit for intended use
Method name:
Multi-Elements in Serum by ICP-DRC-MS
Method #:
3006
Matrix:
Serum
Units:
Hg/dL (selenium in |-ig/L)
Analytes
Interferences
Limit of Detection successfully checked in
(LOD) at least 50 human
samples
Accuracy, precision, LOD,
specificity and stability meet
performance specifications for
intended use
copper (SCU)
selenium (SSE)
zinc (SZN)
2.5 Yes
4.5 Yes
2.9 Yes
Yes
Yes
Yes
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 52 of 86
Appendix B. Ruggedness testing results.
a. Ruggedness parameter test #1
Evaluate the impact on analysis results if the set RF power is increased to
1600W (instrument maximum) or decreased to 1150W (by 20%).
i. Test details: Three different PF power settings were tested in separately
prepared, consecutive runs on the instrument without turning off the plasma. At
least 15 minutes stabilization time was allowed between each run after the RF
power was changed. Each run had 20 "Junk serum" samples analyzed between
the beginning and ending QC. All other method parameters were kept per
method.
1. Run #1: Method default with RF power 1450W.
2. Run #2: Decreased RF power by 20% to 1150W.
3. Run #3: Increased RF power to instrument maximum, 1600W.
4. Run #4: Increased RF power to 1525W.
ii. Results: See Ruggedness Table 1.
iii. Conclusion: Results are not compromised by changes in RF power within the
range of 1150Wto 1600W.
Ruggedness Table 1. Impact of changing RF power on observed analyte
concentrations.
QC
pool ID
RF power tested
Zn (|jg/dL)
Cu (|jg/dL)
Se (|jg/L)
LS-03601b
characterized mean
2SD range
50.7
41.9-59.5
64.9
61.9-67.9
75.0
66.7-83.3
1150w (reduced)
52.5
63.1
75.6
1450w (per method)
49.0
62.7
70.1
1525w (increased)
43.3
63.4
75.7
1600w (increased)
54.1
63.9
75.6
HS-03601b
characterized mean
2SD range
175
142-209
203
191 -215
144
130-157
1150w (reduced)
178
197
145
1450w (per method)
168
196
146
1525w (increased)
157
201
145
1600w (increased)
178
199
149
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 53 of 86
Appendix B. Ruggedness testing results (continued).
b. Ruggedness parameter test #2
Evaluate the impact on analysis results if the Cell Gas Flow Rate is increased or
decreased by 20% for the analytical run.
i. Test details: Three different Cell Gas Flow Rates were tested in separately
prepared, consecutive runs on the instrument without turning off the plasma. At
least 15 minutes stabilization time was allowed between each run after the axial
field voltage was changed. "Junk serum" samples (20) were analyzed between
the beginning and ending QC of each run. All other method parameters were
kept per method.
1. Run #1: Method default = 0.5ml_/min.
2. Run #2: Decreased Cell Gas Flow Rate by 20% to 0.4ml_/min.
3. Run #3: Increased Cell Gas Flow Rate by 20% to 0.6ml_/min.
ii. Results: See Ruggedness Table 2.
iii. Conclusion: Results are not compromised by changes in cell gas flow rate within
the range tested (0.40-0.60 mL/min).
Ruggedness Table 2. Impact of changing DRC mode cell gas flow rate on
observed analyte concentrations
QC
pool ID
cell gas flow rate tested
Zn (|jg/dL)
Cu (|jg/dL)
Se (|jg/L)
LS-03601b
characterized mean
2SD range
50.7
41.9-59.5
64.9
61.9-67.9
75.0
66.7-83.3
0.40 ml/min (reduced)
49.5
65.3
80.7
0.50 ml/min (per method)
49.5
67.6
73.8
0.60 ml/min (increased)
47.8
63.4
75.6
HS-03601b
characterized mean
2SD range
175
142-209
203
191 -215
144
130-157
0.40 ml/min (reduced)
167
204
152
0.50 ml/min (per method)
169
205
146
0.60 ml/min (increased)
171
203
147
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 54 of 86
Appendix B. Ruggedness testing results (continued).
c. Ruggedness parameter test #3
Evaluate the impact on analysis results if the RPq is increased or decreased by
20% for the analytical run.
i. Test details: Three different RPq settings were tested in separately prepared,
consecutive runs on the instrument without turning off the plasma. At least 15
minutes stabilization time was allowed between each run after the axial field
voltage was changed. "Junk serum" samples (20) were analyzed between the
beginning and ending QC of each run. All other method parameters were kept
per method.
1. Run #1: Method default DRC RPq: 0.56
2. Run #2: Decreased DRC RPq 20%: 0.70
3. Run #3: Increased DRC RPq 20%: 0.84
ii. Results: See Ruggedness Table 3
iii. Conclusion: Results are not compromised by changes in RPq within the range of
0.56-0.84.
Ruggedness Table 3. Impact of changing RPq value on observed analyte
concentrations.
QC
pool ID
RPq tested
Zn (|jg/dL)
Cu (|jg/dL)
Se (|jg/L)
LS-03601b
characterized mean
2SD range
50.7
41.9-59.5
64.9
61.9-67.9
75.0
66.7-83.3
DRC RPq:0.56
(reduced by 20%)
52.5
63.1
70.8
DRC RPq:0.70
(per method)
49.0
62.7
70.1
DRC RPq:0.84
(increased by 20%)
54.1
63.9
75.9
HS-03601b
characterized mean
2SD range
175
142-209
203
191 -215
144
130-157
DRC RPq:0.56
(reduced by 20%)
178
197
129
DRC RPq:0.70
(per method)
168
196
131
DRC RPq:0.84
(increased by 20%)
178
199
145
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 55 of 86
Appendix B. Ruggedness testing results (continued).
d. Ruggedness parameter test #4
Evaluate the impact on analysis results if the axial field voltage (AFV) is
increased or decreased by 20% for the analytical run.
i. Test details: Three different DRC AFV were tested in separately prepared,
consecutive runs on the instrument without turning off the plasma. At least 15
minutes stabilization time was allowed between each run after the axial field
voltage was changed. "Junk serum" samples (20) were analyzed between the
beginning and ending QC of each run. All other method parameters were kept
per method.
1. Run #1: Method default DRC AFV = 450
2. Decreased DRC AFV to 360
3. Increased DRC AFV to 500
Results: See
ii. Ruggedness Table 4.
iii. Conclusion: Results are not compromised by changes in the axial field voltage
within the range of 360 to 500V.
Ruggedness Table 4. Impact of changing axial field voltage (AFV) on observed
analyte concentrations.
QC
pool ID
axial field
voltage tested
Zn (|jg/dL)
Cu (|jg/dL)
Se (|jg/L)
LS-03601b
characterized mean
2SD range
50.7
41.9-59.5
64.9
61.9-67.9
74.9
66.7-83.3
AFV-360
(reduced)
46.9
61.5
72.8
AFV-360
(per method)
47.2
64.0
75.0
AFV-500
(increased)
48.6
63.5
74.1
HS-03601b
characterized mean
2SD range
175
142-209
203
191 -215
144
130-157
AFV-360
(reduced)
163
195
142
AFV-360
(per method)
170
205
147
AFV-500
(increased)
168
200
146
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 56 of 86
Appendix B. Ruggedness testing results (continued).
e. Ruggedness parameter test #5
Method descriptions and SOP assume preparation and analysis on same day.
Evaluate the impact on analysis results if the analytical run is prepared to
analyze but circumstances do not allow for analysis to occur until 24 or 48 hours
later.
i. Test details (Part 1: 24-hour increments): All runs had 20 "Junk serum" samples
analyzed between the beginning and ending QC of each run, making each a
normal length run. All other method parameters were kept per method.
1. Day 1: Prepare samples for analysis in triplicate (calibrators, blanks, QC
and reference materials in three separate sets of tubes). Set '#1 was
analyzed immediately. Sets #2 and #3 were capped and stored at ambient
temperature.
2. Day 2: Prepare a new run (set #4). Analyze set #4 immediately, then set
#2.
3. Day 3: Prepare a new run (set #5). Analyze set #5 immediately, then set
#3.
ii. Test details (Part 2 within 24 hrs.): Due to the observations in test #1 for
selenium, a shorter time frame was examined in part two of this test.
1. Sample Preparation: Seven preparations of the low bench QC serum
material were made at the beginning of the experiment. Each of these
seven preparations were 4x the normal preparation volume (4 preparations
into each vial).
2. Sample Analysis: Four consecutive runs of the serum method were then
carried out. Each run included blanks, calibrators, and run judge QC
(beginning and ending) prepared immediately prior to the beginning of
each run and seven preparations of the low bench QC prepared
immediately prior to the beginning of each run. The seven preparations of
the low bench QC pool prepared before the first run were measured within
each run alternated with the freshly prepared low bench QC sequentially
throughout the run.
iii. Results: See results in Ruggedness Table 5 and Ruggedness Table 6.
iv. Conclusions:
1. Test part 1: The serum ICP-MS method is rugged for Zn and Cu to delays
in analysis of samples after preparation for up to 48 hours and not rugged
for Se to delay in analysis of samples after preparation for even 24 hours.
The serum ICP-MS method is rugged for Zn and Cu to delays in analysis of
samples after preparation for up to 48 hrs (see part 1).
2. Test part 2: The method is only rugged to delays in analysis for selenium
for up to approximately 7 hours (one 90 patient sample run, or two 40
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 57 of 86
patient sample runs). Suggested maximum amount of time from sample
prep to end of the run is 450 min, which consists of 3 analytical runs.
Ruggedness Table 5. Stability of sample preparations part 1 (24-hour incremen
QC
pool ID
time from
preparation
Zn (|jg/dL)
Cu (|jg/dL)
Se (|jg/L)
LS-03601b
characterized mean
±2SD range
±3SD range
50.7
41.9-59.5
37.5-63.9
64.9
61.9-67.9
60.4-69.4
74.9
66.7-83.3
52.5-87.4
fresh preparation
47.2
65.7
74.7
after 24 hours
51.9
67.1
102
(150, 54.5)
after 48 hours
51.0
66.2
57.1
(123, -8.8)
HS-03602b
characterized mean
±2SD range
±3SD range
175
142-209
126-225
203
191 -215
185-221
144
130-157
124-164
fresh preparation
160
203
143
after 24 hours
167
203
145
after 48 hours
174
207
130
(98.2, 161)
s).
Ruggedness Table 6. Stability of samp
e preparations part 2 (within 24 hours).
QC
pool ID
axial field
voltage tested
Zn (|jg/dL)
Cu (|jg/dL)
Se (|jg/L)
LS-03601b
characterized mean
2SD range
3SD range
50.7
41.9-59.5
37.5-63.9
64.9
61.9-67.9
60.4-69.4
74.9
66.7-83.3
52.5-87.4
Run 1
(up to 139 min elapsed)
41.8
58.3
72.5
Run 2
(up to 303 min elapsed)
43.1
60.0
71.3
Run 3
(up to 427 min elapsed)
51.4
65.9
71.0
Run 4
(up to 576 min elapsed)
43.5
59.1
54.7
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 58 of 86
Appendix B. Ruggedness testing results (continued).
f. Ruggedness parameter test #6
Evaluate the impact on observed concentration if an extra dilution is performed
on the sample relative to the calibration standards.
i. Test details: A large serum sample, spiked to elevated analyte concentrations,
was prepared for analysis each day for 4 days.
1. Day 1: A large serum sample was spiked to elevated concentrations using
single element standards and mixed well. The spiked sample was then
prepared for analysis to dilution levels of 2x, 5x, 10x, and 20x using >18
MQ-cm water as the makeup liquid.
2. Day 2: The spiked sample prepared on Day 1 was prepared for analysis to
dilution levels of 2x, 5x, 10x, and 20x using >18 MQ-cm water as the
makeup liquid.
3. Day 3: The spiked sample prepared on Day 1 was prepared for analysis to
dilution levels of 2x, 5x, 10x, and 20x using >18 MQ-cm water as the
makeup liquid.
4. Day 4: The spiked sample prepared on Day 1 was prepared for analysis to
dilution levels of 2x, 5x, 10x, and 20x using >18 MQ-cm water as the
makeup liquid.
ii. Results: See Ruggedness Table 7, Ruggedness Table 8, and Ruggedness
Table 9.
iii. Conclusion: SCU results are not unacceptably affected by the matrix difference
in the dilution with >18 MQ-cm water when performing a 2x, 5x or 10x dilution.
However, the average observation of the 20x dilution is affected more than is
acceptable (>10% bias with noticeable impact on reproducibility).
SSE results are not unacceptably affected by the matrix difference in the dilution
with >18 MQ-cm water when performing a 2x or 5x dilution. However, the
average observation of the 10x and 20x dilutions are affected more than is
acceptable (>10% bias with noticeable impact on reproducibility).
SZN results are not unacceptably affected by the matrix difference in the dilution
with >18 MQ-cm water when performing a 2x, 5x or 10x dilution. However, the
average observation of the 20x dilution is affected more than is acceptable
>10% bias with noticeable impact on reproducibility).
In summary, an extra dilution up to 10x with >18 MQ-cm water was successful
for SCU and SZN with less than a 10% impact on the observed concentration.
However only up to a 5x extra dilution with >18 MQ-cm water was acceptable for
SSE.
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DLS Method Code: DLS: 3006.8-03 Page 59 of 86
Appendix B. Ruggedness testing results (continued).
Ruggedness Table 7. Impact of extra dilutions on observed concentrations of
serum copper (SCU) in |jg/dL.
Dilution level
4/20/12
b
5/8/12
b
5/9/12
b
6/6/12
b
SCU
Average
SCU
STDEV
SCU
Normalized
Average and
Relative
STDEV
No Extra
353
348
347
350
350
3
1.00 ±0.01
2x dilution
363
355
396
354
367
20
1.05 ±0.05
5x dilution
414
342
343
366
366
34
1.05 ±0.09
10x dilution
378
345
342
347
353
17
1.01 ±0.05
20x dilution
334
313
269
337
313
31
0.90 ±0.10
Ruggedness Table 8. Impact of extra dilutions on observed concentrations of
serum selenium (SSE) in pg/L.
Dilution level
4/20/12
b
5/8/12
b
5/9/12
b
6/6/12
b
SSE
Average
SSE
STDEV
SSE
Normalized
Average and
Relative
STDEV
No Extra
367
340
347
343
349
12
1.00 ±0.03
2x dilution
361
343
387
331
355
24
1.02 ±0.07
5x dilution
392
326
337
316
343
34
0.98 ±0.10
10x dilution
347
316
340
262
316
38
0.91 ±0.12
20x dilution
283
272
268
191
253
42
0.72 ±0.17
Ruggedness Table 9. Impact of extra dilutions on observed concentrations of
Dilution level
4/20/12
b
5/8/12
b
5/9/12
b
6/6/12
b
SZN
Average
SZN
STDEV
SZN
Normalized
Average and
Relative
STDEV
No Extra
343
335
334
336
337
4
1.00 ±0.01
2x dilution
348
340
382
338
352
20
1.05 ±0.06
5x dilution
390
326
330
351
349
29
1.04 ±0.08
10x dilution
344
320
329
340
333
11
0.99 ±0.03
20x dilution
293
283
260
340
294
34
0.87 ±0.12
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 60 of 86
Appendix C. Tables and figures.
Table 1. Instrument and method parameters.
Instrument: PerkinElmer ELAN DRCP|US or DRC II ICP-MS
ESI SC4 autosampler
Optimization window parameters
RF power
1.45 KW
plasma gas flow (Ar)
15 L/min
auxiliary gas flow (Ar)
1.2 L/min
nebulizer gas flow (Ar)
0.80 - 1.0 L/min (optimized as needed for sensitivity)
ion lens voltage(s)
AutoLens (optimized as needed for sensitivity)
QRO, CRO, CPV,
AFV,Discriminator Threshold
Optimized per instrument by service engineer, or
advanced user.
Parameters of x-y alignment, nebulizer gas flow, AutoLens voltages, mass calibration,
and detector voltages are optimized regularly. Optimization file name = default.dac.
Configurations window parameters
cell gas changes pause
times
pressurize delay (From Standard to DRC mode) = 30
exhaust delay (From DRC to Standard mode) = 30
flow delay (Gas changes while in DRC mode) = 25
channel delay (Gas channel change in DRC mode) = 25
File names and directories
method file names
Serum multi panel_DLS3006.8_sblk.mth
Serum multi panel_ DLS3006.8_aqblk.mth
dataset
Create a new dataset subfolder each day. Name as
"2006-0718" for all work done on July 18, 2006
sample file
Create for each day's work
report file name
See Figure 7 of Appendix C.
For sample results printouts
cdc_quant comprehensive.rop
For calibration curve information
CDC_Quant Comprehensive (calib curve info).rop
tuning
Default.tun
optimization
Default.dac
calibration
N/A
polyatomic
elan.ply
report options template
(transferring results to the
database)
CDC_Database Output.rop
Report Format Options: select only "Use Separator"
File Write Option: Append
Report File name: include date, instrument, and group
being analyzed in file name (i.e. 20060724a DRCC HM-
0364.txt)
Method parameters
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 61 of 86
Method parameters: timing
page (see Figure 2 in Appendix C)
sweeps/reading
90
readings/replicate
1
replicates
3
enable qc checking
on
isotopes monitored
and internal standard
associations
(exact mass)
use 71 Ga as an internal standard
64Zn (63.9291), 65Cu (64.9278), 71Ga (70.9247), 78Se
(77.9173)
dwell times
30 ms for 64Zn, 65Cu, 71 Ga (70.9247), 78Se (77.9173)
scan mode
Peak Hopping for all isotopes (1 MCA channel)
drc channel a gas
flow rate
Ammonia (5-7 psig delivery pressure)
0.5 L/min *
(*Optimized per instrument)
RPa
0 for all isotopes
RPq
0.7 for all isotopes
Method Parameters: processing page (see Figure 3 in Appendix C)
detector mode
pulse (see Section 6.f.ii)
process spectral peak
N/A
autolens
On
isotope ratio mode
Off
enable short settling time
Off
blank subtraction
after internal standard
measurement units
Cps
process signal profile
N/A
Method Parameters: equations page (see Figure 4 in Appendix C)
equations
On 64Zn, use "-0.035297 * Ni60"
On 78Se, use "-0.030461 * Kr83"
Method Parameters: calibration page (see Figure 5 in Appendix C)
calibration type
external std.
curve type
simple linear
sample units
pg/L
calibration standard
concentrations
Zn (pg/dL): 3, 9, 30, 90, 300
Cu (pg/dl_): 3, 9, 30, 90, 300
Se (ug/L): 3, 9, 30, 90, 300
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 62 of 86
Method Parameters: sampling page (see Figure 6 in Appendix C)
"peristaltic pump under
computer control"
On
sample flush
~40s at typically -10.8 rpm (optimize time so that solution
reaches nebulizer before Read Delay begins)
read delay
45s at typically -8.1 rpm (optimize time so that signal is
stable before analysis begins)
wash
60s at typically -10.8 rpm (optimize time as needed for
effective washout of unusually elevated samples)
extended wash
(via ICP-MS software
QC checking)
For sample concentrations greater than these, setup the
ICP-MS software's 'QC checking' feature to "Wash for X
and continue." See Figure 8 in Appendix C.
Extended Rinse Extended
Analyte Trigger Cone.* Rinse Time
Cu >330 pg/dL 120 s
Se >330 pg/L 120 s
Zn >330 pg/dL 120 s
autosampler locations of
blanks and standards
For calibration curve (points to serum blank)
Serum multi panel_DLS3006.8_sblk.mth
Serum Blank and Calibration Stds 1 - 5 in autosampler
positions 101 - 106.
For QC and patient sample analysis (points to aqueous
blank)
Serum multi panel_DLS3006.8_aqblk.mth
Aqueous Blank in autosampler position 109.
See figures 9 through 13 in Appendix C for other default
autosampler settings.
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 63 of 86
Appendix C. Tables and figures (continued).
Table 2. Suggested maximum analyte concentrations for base serum.
Analyte
Concentration (ijg/L)
Zn
800 (80 |jg/dL)
Cu
1100 (110 |jg/dL)
Se
130
Table 3. Stock calibration standard concentrations.
Analyte
stock standard concentrations (mg/L)
High Purity Standards
Item # SM-2107-013 (2% HNOs)
Cu
300
Zn
300
Se
30
Table 4. Preparation of multi-element intermediate working calibration standards.
Standard #
Units
1
2
3
4
5
Vol of flask
(mL)
500
200
100
100
100
Vol spike of
int. stock
std. (mL)
0.050
0.060
0.10
0.30
1.0
Concentrations
Zn
Mg/L
UP/dL*
30
3
90
9
300
30
900
90
3,000
300
Cu
Mg/L
|jg/dL*
30
3
90
9
300
30
900
90
3,000
300
Se
Mg/L
3
9
30
900
300
* Use |jg/dL units for Zn and Cu in the ELAN software and for reporting.
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 64 of 86
Appendix C. Tables and figures (continued).
Table 5. Acceptable ways to perform two consecutive analytical runs, bracketing
with bench quality control samples.
Setup 1*
Setup 2 (typical)*
Run #1
Run #1
calibration standards
calibration standards
low bench QC
low bench QC
high bench QC
high bench QC
patient samples
patient samples
low bench QC
low bench QC
high bench QC
high bench QC
Run #2
Run #2
low bench QC
calibration standards
high bench QC
low bench QC
patient samples
high bench QC
low bench QC
patient samples
high bench QC
low bench QC
high bench QC
* Use >18 MQ cm_water
* Use >18 MQ-cm water
to rinse the system
to rinse the system
for ~30 min.
for ~30 min.
between the two runs.
between the two runs.
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 65 of 86
Appendix C. Tables and figures (continued).
Table 6. A typical SAMPLE/BATCH window.
AS
Location*
Sample ID
Measurements Action
Method
5
DRCstabilityl
Run sample
. . . sblk.mth
5
DRCstability2
Run sample
. . . sblk.mth
5
DRCstability3
Run sample
. . . sblk.mth
5
DRCstability4
Run sample
. . . sblk.mth
Continue DRC stability samples . . .
5
DRCstability9
Run sample
. . . sblk.mth
5
DRCstabilityl 0
Run sample
. . . sblk.mth
100
Sblkchkl
Run blank, standards, and sample **
. . . sblk.mth
101
Sblkchk2
Run sample
. . . sblk.mth
127
Aq Blk Check
Run blank and sample ¥
. . ,_aqblk.mth
138
L Bench QC
Run sample
. . . aqblk.mth
134
H Bench QC
Run sample
. . . aqblk.mth
146
Sample 1
Run sample
. . ,_aqblk.mth
147
Sample 2
Run sample
. . . aqblk.mth
148
Sample 3
Run sample
. . ,_aqblk.mth
139
L Bench QC
Run sample
. . ,_aqblk.mth
135
H Bench QC
Run sample
. . ,_aqblk.mth
* The exact autosampler positions of QCs and patient samples do not have to be those
shown above.
** When executing this row, the ELAN will first analyze the serum blank at AS position
101, then standards 1 -5 at autosampler positions 102-106, then the "sblkchkl" sample
at A/S position 100. The sampling information about AS positions 101-106 are stored
in the "sblk" method file.
¥ When executing this row, the ELAN will first analyze the aqueous blank at AS
position 109, then the "Aq Blk Check" at AS position 20. The sampling information
about AS positions 109 is stored in the "aqblk" method file.
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 66 of 86
Appendix C. Tables and figures (continued).
Table 7. Preparation of samples, working calibrators, and QC materials for
analysis.
Dilution ID
Water
(ML)
Base
Serum
(ML)
AQ
Intermediate
Working
Calibration
Standard (|jL)
Patient
or QC
Serum
sample
(ML)
Diluent *
(ML)
Total
volume
(ML)
Working Calibrators
(S0-S5)
And SBIkchk (SO)
-
150x1
150x1
-
4,200
(2,100x2)
4,500
AQ Blank
300
(150x2)
-
-
-
4,200
(2,100x2)
4,500
Patient Serum or
Serum-Based QC
150x1
-
-
150x1
4,200
(2,100x2)
4,500
Patient Serum
2x Extra Dilution H
225
(225 x 1)
-
-
75x1
4,200
(1,400x3)
4,500
Patient Serum
3x Extra Dilution H
250
(250x 1)
-
-
50 x 1
4,200
(2,100x2)
4,500
Patient Serum
5x Extra Dilution H
540
(150x3, 90x 1)
60 x 1
8,400
(1,680x5)
9,000
Patient Serum
10x Extra Dilution H
570
(150x3, 120x 1)
-
-
30 x 1
8,400
(1,680x5)
9,000
If a different total volume is prepared, adjust the volumes for each component proportionally.
These directions are written with the expectation of a 5,000 |jL syringe on the left side and a 250 pi-
syringe on the right side of the benchtop automatic pipettor.
* By splitting the dispense step of diluent into two or more portions, liquids pulled up into the right pipette
tip are flushed out more completely. For example, when preparing a working serum blank (SO) above, do
the preparation in 2 steps: in step 1, dispense 150 |jL intermediate working SO + 2100 |jL diluent; in step
2, dispense 150 |jL base serum + 2100 |jL diluent.
H Extra dilution is performed on serum samples whose concentration is greater than the concentration of
the highest working calibrator listed in Table 8 of Appendix C.
Any extra dilution within these limits can be prepared as long as the 14:15 ratio of diluent to total dilution
volume is maintained. Use of the lowest extra dilution level is preferred to minimize differences between
the calibrators and the samples (i.e. 2x dilution is preferred over 10x if 2x is sufficient to dilute analyte into
the documented linearity range).
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DLS Method Code: DLS: 3006.8-03
Page 67 of 86
Appendix C. Tables and figures (continued).
Analyte
(units)
Limit of
Detection
(LOD)*
High
Calibrator
Maximum
Extra
Dilution**
Reportable
Range Upper
Boundary
Zn (pg/dl_)
2.9
300
10
3,000
Cu (pg/dL)
2.5
300
10
3,000
Se (ug/L)
4.5
300
5
1,500
*Re-evaluated periodically (2+ years) or at significant method changes. LODs shown
were calculated 1/26/2011.
**See ruggedness test 6 in Appendix B for supporting validation data.
Table 9. Boundary concentrations and replicate range maximums for serum.
Analyte
(units)
Lo\a
Bound
ler
aries
Upper
Boundaries
Range
Maximum
("Rep Delta Limit")f
Highest
Concentration
Validated for
Washout
2LB*
1LB*
1UB*
2UB*
Zn (Mg/dL)
35
35
120
240
17 for values <170
10% for values >170
330
Cu (|jg/dL)
50
50
300
600
20 for values < 200
10% for values > 200
330
Se (pg/L)
45
45
165
330
20 for values < 200
10% for values > 200
330
* The concentrations assigned to these boundaries is determined by study protocol but
default concentrations are listed in this table.
t Range maximum is the range of the three replicate readings for a single sample
analysis. This value is also called "Rep Delta Limit" in the LIMS.
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DLS Method Code: DLS: 3006.8-03 Page 68 of 86
Appendix C. Tables and figures (continued).
Table 10. Reference ranges for concentrations of zinc, copper, and selenium in
serum [6] . . .
analyte
(units)
survey
years
geometric
mean
50th
75th
95th
N
Zn
(ljg/dL)
11-12
81.9
(80.9-82.9)
81.8
(80.8-82.9)
91.5
(89.8 -93.1)
109
(105-112)
2329
13-14
80.4
(78.2-82.6)
80.7
(78.4-82.9)
90.5
(88.0-93.1)
109
(104-113)
2519
Cu
(ljg/dL)
11-12
114
(111 - 116)
112
(109-114)
130
(127- 134)
169
(161-183)
2329
13-14
115
(112-118)
114
(110-117)
132
(129-135)
171
(165-180)
2520
Se
(|jg/L)
11-12
127
(125- 130)
127
(124-130)
139
(136- 142)
161
(156-164)
2329
13-14
128
(126-130)
127
(126-130)
139
(137-142)
159
(156-161)
2519
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 69 of 86
Appendix C. Tables and figures (continued).
Figure 1. Example configuration of tubing and devices for liquid handling.
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-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 70 of 86
Appendix C. Tables and figures (continued).
Figure 2. ELAN ICP-DRC-MS method screen shots (timing page).
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 71 of 86
Appendix C. Tables and figures (continued).
Figure 3. ELAN ICP-DRC-MS method screen shots (processing page).
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 72 of 86
Appendix C. Tables and figures (continued).
Figure 4. ELAN ICP-DRC-MS method screen shots (equation page).
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-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 73 of 86
Appendix C. Tables and figures (continued).
Figure 5. ELAN ICP-DRC-MS method screen shots (calibration page).
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-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 74 of 86
Appendix C. Tables and figures (continued).
Figure 6. ELAN ICP-DRC-MS method screen shots (sampling page).
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-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 75 of 86
Appendix C. Tables and figures (continued).
Figure 7. ELAN ICP-DRC-MS method screen shots (report page).
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-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 76 of 86
Appendix C. Tables and figures (continued).
Figure 8. ELAN ICP-MS method screen shots (QC/Sample page).
£71 Rpnnrt WntFR
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 77 of 86
Appendix C. Tables and figures (continued).
Figure 9. ESI SC4 autosampler screen shots used (main page).
Additional flush times and "Max Rinse Time" are default, but can be optimized for best
reduction of elemental carry-over between samples. Tray types can be changed to
allow for different volumes of diluted sample digests. Do not enable 'FAST control'.
Rinse and additional flush times for eliminating carry-over from one sample to the next
while using the minimum amount of rinse solution.
A rinse time of -1 causes the rinse station to be skipped.
A rinse time of 0 causes the probe to only dip into the station, but spends no time there.
Additional flush times can be optimized to keep the rinse station full while not using too
much rinse solution. The inner diameter size of the tubing providing the rinse solution to
the rinse station determines how quickly the station will fill. Various sizes are available
for purchase or can be made in the laboratory.
E?| ESI SC Autosampler
File Calibrate Manual Configure Diagnosis Communication FAST About Language
|~| Enable FAST Control
Rinse Settings (sec)
Additional
Rinse
FAST Method File: FAST LRT 1mL.M
Rinse Time
Flush Time
Count Down
Rinse 1: -1
I I
Rinse 2: 110
|10 I
I \
0 "Max Rinse Time" Enabled
Select Tray
Configuration File: default.sc Instrument: Perkin Elmer ELAN Autosampler Model:
SC-4DX SC COM Port: COM9 Instrument COM Port: COM7
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-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 78 of 86
Appendix C. Tables and figures (continued).
Figure 10. ESI SC4 autosampler screen shots used (configuration page).
"High Speed" option is to only be used for 'High Speed' models of the SC4 (look for
"HS" in serial number). Speeds and accel/decel values can be optimized per analyst
preference and to minimize droplet splatter off of probe.
|i| ConfjgureAutosampler
Horizontal
Start Speed I''
Max Speed
Accel/Decel r
E0®
H High Speed (HS)
Rotational
Start Speed
150
0-5
1-5
1-5
0-5
Configuration File
Configuration File Name default, sc
[ Open File
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Autosampler Model
Autosampler Model
Save File
Cancel
SC-4
Max Speed IE I 1*
1 [3 I 1-5
Accel/Decel
0 Enable RAF [3
Vertical
Start Speed
Max Speed J ^
Accel/Decel F ] F
Rail Height 16 inches
Instrument/Autosampler Emulation
0-5
I nstrument Type Perkin E Imer E LAN
1-5
1-5
Autosampler Type I AS S3
Dilutor Model
None
M High Speed (HS)
n Enable Z Homing
Figure 11. ESI SC4 autosampler screen shots used (communication page).
Communication ports will differ depending on available ports on instrument control
computer.
1*1 Co nfigu reComm u nicatio n
SC Autosampler Communication Port:
Instrument Communication Port:
Instrument Communication
® GPIB or Physical COM Port
O Virtual COM Port
COM3
COM 7
AutoConfigure
OK
Cancel
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 79 of 86
Appendix C. Tables and figures (continued).
Figure 12. ESI SC4 autosampler screen shots (5x12 rack setup window).
Settings are approximate. To be sure the loop is filled, setup the probe to go down
close to the bottom of the cup, but not touch. Optimize retraction speed for least droplet
splatter.
I»l Rack Setup
Select Array
LR21 (3x7)
LR24 (3x8)
LR40 (4x10)
LR60 (5x121
LR90 (6x15)
MR 21 (3x7)
MR40 (4x10)
MR60 (5x12)
MR 90 (6x15)
Micro 24
Micro 48
Micro 96
MT24G
Probe Settings
Down Height(mm)
141
R enaction S peed(1 -5) £
1500
Save
Cancel
0
3 Time"
Figure 13. ESI SC4 autosampler screen shots (50mL tube rack setup window).
Settings are approximate. To be sure the loop is filled, setup the probe to go down
close to the bottom of the cup, but not touch. Optimize retraction speed for least droplet
splatter.
litialee
II Rack Setup
Select Array
: stio
ST10CP
ST12
ST7
ST9
ST10
+ STEX5
ST1QCP
* ST-EX5
ST12
~ STEX5
ST7
+ STEX5
ST9
+ STEX5
Probe Sellings
Down Height (mm)
Redaction Speed(1-5)
132
2
Save
Cancel
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03
Page 80 of 86
Appendix C. Tables and figures (continued).
Figure 14. Flow chart for handling an elevated result.
Result > 1UB
no
no
no
no
no
repeat elevated result for
confirmation by dilution in
duplicate, and report the first
analytically valid result as >2UB
Report the first analytically
valid result.
Repeat elevated result for
confirmation, and report the
first analytically valid result.
Repeat elevated result for
confirmation, and report the
first analytically valid result
as >2UB.
Repeat elevated result for
confirmation by dilution in
duplicate, and report the first
analytically valid result as >2UB.
Repeat elevated result for confirmation
by dilution in duplicate, and report the
first analytically valid result as >2UB.
Confirm by re-analysis the results for the
2 samples immediately following the
elevated sample. Report first analytically
valid result when it is confirmed within
±10% or ±3SD of the low bench QC,
whichever is larger.
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 81 of 86
Appendix D. Help sheets
Reagent Preparation (page 1 of 2)
NOTE:
mg/L = ppm
|jg/L = ppb
|jg/mL = ppm
Rinse solution
(0.01% Triton X-100. 5% ethyl alcohol. 2% (v/v) HNQ3. 0.5% (v/v) HCI)
1. Partially fill the pre-cleaned 4 L bottle with >18 MQ-cm water (approximately 2-3 L).
2. Add 80 mL of concentrated HNO3 and mix well.
3. Add 200 mL ethyl alcohol and mix well.
4. Add 20 mL of concentrated HCI and mix well.
5. Add 20 mL of the 2% Triton X-100 and mix well.
6. Fill to 4 L using >18 MQ-cm water and mix well.
Sample diluent
(10 uq/L Ga. 0.01% Triton X-100. 5% ethyl alcohol. 2% (v/v) HNQ3)
1. Partially fill (i.e. 70-80% full) the 2 L container with >18 MQ-cm water.
2. Add 40 mL concentrated HNO3 and mix.
3. Add 100 mL ethyl alcohol and mix.
4. Add 1 mL of 20 pg/mL Ga internal standard intermediate solution.
5. Add 10 mL of the intermediate 2% Triton X-100 solution and mix.
6. Fill to 2 L with >18 MQ-cm water and mix well.
5% (v/v) HNOs
1. Partially fill a 2 L bottle with >18 MQ-cm water.
2. Add 100 mL of concentrated HNO3.
3. Fill to 2 L using >18 MQ-cm water
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 82 of 86
Appendix D. Help sheets (continued).
Reagent Preparation (page 2 of 2)
2% Triton X-100 in 5% (v/v) HNOs
1. Partially fill a 2 L bottle with >18 MQ-cm water.
2. Add 40 mL of Triton X-100.
3. Add 100 mL of concentrated HNO3.
4. Fill to 2 L using >18 MQ-cm water.
5. Allow to dissolve overnight (or add a Teflon magnetic stirring bar and stir on
stirrer until dissolved).
6. Mix well by gently inverting several times.
20 uq/ml Ga internal standard solution
1. Partially fill the 100-mL volumetric flask with >18 MQ-cm water.
2. Carefully add 2 mL of concentrated HNO3. Mix into solution.
3. Add 0.2 mL of 10 |jg/mL Ga standard. If initial Ga concentration is different, adjust
volume proportionally.
4. Fill to mark (100 mL) and mix thoroughly.
Daily solution (1 uq/L) in 2% (v/v) HNO3
1. Partially fill a 1 L volumetric flask with >18 MQ-cm water.
2. Add 1 mL of High Purity Standard SM-2107-018 (or current lot #)
3. Add 20 mL of concentrated HNO3.
4. Fill to 1 L using >18 MQ-cm water.
5. Mix well by gently inverting several times.
PRC Stability Solution (Junk Serum)
1. Add 33 mL of diluent into a plastic bottle
2. Add 1.2 mL of >18 MQ-cm water
3. Add 1.2 mL of junk serum
4. Repeat until you've reached your desired volume.
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 83 of 86
Appendix D. Help sheets (continued).
Dav-to-Dav Operations (page 1 of 2)
Readying ICP-MS and materials
1. Remove "Junk Serum", QC materials and patient samples from the -70C freezer
and place into a biological safety cabinet (BSC) to warm up to ambient
temperature.
2. Check the peristaltic pump for proper tension on the tubing
3. Perform daily maintenance checks
a. Ar supply pressure, interface components etc.
4. Start the plasma
5. Place autosampler probe into freshly poured >18 MQ-cm water
a. Allow for warm-up time (=30 minutes)
Optimization of the ICP-MS
1. Perform daily performance checks
2. Record the daily into the Daily Logbook
3. Prepare materials for DRC stability time
Preparing and analyzing the curve
1. Prepare the calibrators while the DRC stability is running,
2. Evaluate the calibration curve
a. The minimum acceptable R2 value for each curve is 0.98.
b. Check that the blank is not over-subtracting from the standards (i.e. each
successive standard has a net intensity greater than the previous
standard). Ensure that net intensity for all standards is positive.
Preparing and monitoring the run
1. Preparing the Run
a. Thoroughly wash the benchtop automatic pipette probe in-between
samples
b. Ensure the prepared samples are homogenized (e.g. vortex for 3-5
seconds, or invert 5-10 times) before placing them in the autosampler.
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 84 of 86
-------
Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 85 of 86
Appendix D. Help sheets (continued).
1. Dav-to-Dav Operations (page 2 of 2)
2. Monitoring the Run
a. Ensure proper operation of the instrument (sample reaching nebulizer in
correct timing, autosampler arm moving properly, etc...).
b. Ensure DRC stability (analyte / internal standard ratio stability) before
starting the run.
c. Verify that bench QC results are within the acceptable limits.
i. If an analyte result for the beginning QC material(s) falls outside of
the ± 3SD limits, then follow the steps listed on page 37.
ii. If these steps do not result in correction of the out-of-control values
for QC materials, consult the supervisor for other appropriate
corrective actions.
d. Verify good precision among replicates
e. Verify consistent measured intensities of the internal standards.
f. Confirm elevated patient results.
i. Repeat for confirmation any sample having a concentration greater
than the 1UB.
ii. Repeat with extra dilution (in duplicate) any sample having a
concentration greater than the highest calibration standard.
3. After analysis,
a. flush the ICP-MS sample introduction system with >18 MQ-cm water
b. turn off the plasma
c. flush the benchtop automatic pipette
i. 10% Ethyl Alcohol
ii. >18 MQ-cm water
d. Leave the benchtop automatic pipette syringes with >18 MQ-cm water in
the lines and turn off the power
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Serum Multi-Element ICP-DRC-MS
DLS Method Code: DLS: 3006.8-03 Page 86 of 86
References
1. Thomas, R., Practical guide to ICP-MS: a tutorial for beginners. Third ed. 2013,
New York, New York: Marcel Dekker. 336.
2. Tanner, S.D., Baranov, Vladimir I, Theory, Design, and Operation of a Dynamic
Reaction Cell for ICP-MS. Atomic Spectroscopy, 1999. 20(2): p. 45-52.
3. Tanner, S.D., V.I. Baranov, and D.R. Bandura, Reaction cells and collision cells
for ICP-MS: a tutorial review. Spectrochimica Acta Part B-Atomic Spectroscopy,
2002. 57(9): p. 1361-1452.
4. PerkinElmer SCIEX Instruments, ELAN DRCII Hardware Guide. 2001, Canada.
5. Division of Laboratory Sciences, Division of Laboratory Sciences Policies and
Procedures Manual. 2017, version 6.0, Centers for Disease Control and
Prevention: Atlanta, GA.
6. Centers for Disease Control and Prevention. Fourth Report on Human Exposure
to Environmental Chemicals, Updated Tables, (Jan 2017). Atlanta, GA: U.S.
Department of Health and Human Services, Centers for Disease Control and
Prevention.
-------
Appendix G
Video Activity Data
829
-------
Table G-l. The Micro-activities (Events/Hour) of Child Athletes Playing Soccer, Field Hockey, and
Football from Publicly-available Videotapes (Phase 1)
Child
Micro-activity
Statistic
Soccer
(n = 10)a
Field Hockey
(n = 10)
Football
(n = 10)
Total
(n = 30)
Hand-to-mouth
Mean
14
15
58
29
SD
9.9
13
75
47
Minimum
0.0
0.0
0.0
0.0
25th
8.0
4.0
9.0
6.0
50th
16
15
30
18
75th
22
26
69
28
Maximum
28
32
250
250
Object-to-mouth
Mean
0.0
3.6
17
7.0
SD
0.0
5.1
14
11
Minimum
0.0
0.0
0.0
0.0
25th
0.0
0.0
7.5
0.0
50th
0.0
0.0
15
0.0
75th
0.0
7.0
29
12
Maximum
0.0
12
36
36
Hand-to-turf
Mean
12
5.8
83
33
SD
26
7.5
51
48
Minimum
0.0
0.0
6.0
0.0
25th
0.0
0.0
57
0.0
50th
2.0
3.0
75
8.0
75th
8.0
10
110
63
Maximum
84
20
190
190
Body-to-turf
Mean
6.4
2.8
52
21
SD
12
5.0
25
28
Minimum
0.0
0.0
12
0.0
25th
1.0
0.0
44
0.0
50th
4.0
0.0
48
4.0
75th
4.0
4.0
68
42
Maximum
40
16
90
90
a Number of athletes
830
-------
Table G-2. The Micro-activities (Events/Hour) of Adult Athletes Playing Soccer, Field Hockey, and
Football from Publicly-available Videotapes (Phase 1)
Adult
Micro-activity
Statistic
Soccer
(n = 10)a
Field Hockey
(n = 10)
Football
(n = 10)
Total
(n = 30)
Hand-to-mouth
Mean
4.2
11
74
30
SD
6.5
14
99
65
Minimum
0.0
0.0
36
0.0
25th
0.0
0.0
15
0.0
50th
0.0
6.0
39
7.0
75th
5.5
17
99
30
Maximum
16
0.0
320
320
Object-to-mouth
Mean
4.0
5.2
25
10
SD
1.3
9.1
33
22
Minimum
0.0
0.0
0.0
0.0
25th
0.0
0.0
0.0
0.0
50th
0.0
0.0
6.0
0.0
75th
0.0
7.0
47
7.0
Maximum
4.0
28.
90
90
Hand-to-turf
Mean
14
2.4
110
42
SD
17
6.3
150
99
Minimum
0.0
0.0
18
0.0
25th
0.0
0.0
26
0.0
50th
8.0
0.0
60
12
75th
22
0.0
92
35
Maximum
48
20
530
530
Body-to-turf
Mean
11
1.2
49
21
SD
11
3.8
54
37
Minimum
0.0
0.0
6.0
0.0
25th
2.0
0.0
24
0.0
50th
8.0
0.0
36
8.0
75th
16
0.0
47
24
Maximum
32
12
190
190
a Number of athletes
831
-------
Table G-3. Guide for Activity Levels of Athletes3
Activity Level
Activity
Resting
Kneeling
Resting
Sitting
Resting
Standing
Low
Catching/kicking/throwing (stationary)
Low
Shuffling
Low
Stretching
Low
Walking
High
Jogging
High
Jumping
High
Jumping jacks
High
Knee lifting
High
Lunging
High
Planks/push-ups/pull ups
High
Running
High
Scissors/grapevines/crossovers
High
Sit-ups
High
Skipping
High
Sprinting
High
Squatting
High
Tackling
High
Tire-drills
a Adapted from CDC activity levels (https://www.cdc.gov/nccdphp/dnpa/phYsical/pdf/PA Intensity table 2 l.pdf)
832
-------
Table G-4. The Micro-activities (Events/Hour) of Child Athletes Playing Soccer and Football on Videotape
(Phase 2)
Children
Statistic
Soccer (n = 9)a
Football (n = 5)
Total (n = 14)
Hand-to-mouth
Mean
19
10
16
SD
13
5.2
12
Minimum
6.0
2.0
2.0
25th
9.0
8.0
8.3
50th
17
12
13
75th
19
b
18
Maximum
44
15
44
Object-to-mouth
Mean
3.8
22
10
SD
3.6
17
13
Minimum
0.0
2.0
0.0
25th
1.0
11
1.4
50th
1.6
18
5.5
75th
6.0
--
11
Maximum
10
43
43
Hand-to-turf
Mean
16
21
18
SD
28
10
23
Minimum
0.0
6.0
0.0
25th
0.0
15
1.0
50th
1.0
25
9.4
75th
11
--
27
Maximum
81
31
81
Body-to-turf
Mean
3.6
6.8
4.7
SD
5.7
2.6
4.9
Minimum
0.0
3.0
0.0
25th
0.0
6.0
1.0
50th
1.0
7.0
3.0
75th
3.0
--
7.8
Maximum
16
10
16
a Number of athletes
b The 75th percentile was not reported when the sample size was less than 9 athletes
833
-------
Table G-5. The Micro-activities (Events/Hour) of Adult Athletes Playing Soccer on
Videotape (Phase 2)a
Adults
Statistic
Soccer (n = 3)b
Hand-to-mouth
Mean
7.3
SD
4.0
Minimum
3.0
Maximum
11
Object-to-mouth
Mean
10
SD
13
Minimum
1.0
Maximum
25
Hand-to-turf
Mean
26
SD
28
Minimum
4.0
Maximum
57
Body-to-turf
Mean
2.0
SD
3.5
Minimum
0.0
Maximum
6.0
834
-------
Appendix H
Feasibility Assessment for Silicone
Wristband Passive Samplers at Synthetic
Turf Fields
835
-------
Final Report
^ln^<
Vspjet^
for
Feasibility Assessment for Silicone Wristband
Passive Samplers at Synthetic Turf Fields
Solicitation RFQ-SAB-17-00056
In conjunction with
US EPA
Project Officer - Jose Zambrana PhD
February 20, 2018
Prepared by
Peter Hoffman - Assistant Director
FOOD SAFETY & ENVIRONMENTAL STEWARDSHIP
LABORATORY
ENVIRONMENTAL AND MOLECULAR TOXICOLOGY
DEPT
1007 AGRICULTURAL AND LIFE SCIENCES BUILDING
OREGON STATE UNIVERSITY
CORVALLIS, OR 97331-7301
Contact: Dr. Kim A. Anderson, Director
Phone: 541-737-8501, Fax: 541-737-0497
Email: kim.anderson@oregonstate.edu
-------
Table of Contents
Deliverables checklist- From Statement of Work 2
Section 1 - Executive Summary 3
Section 2 - Sampling 4
2a - Site one (indoor) 4
2b - Site two (outdoor) 5
2c - Site pictures 6
Section 3 - Deployment, Recovery and Processing 7
3a - Deployment 7
3b - Recovery. 7
3c - Processing and extraction 7
Section 4 -Analytical Determinations 8
Section 5 - Results 9
Section 5a - PAHs 10
Section 5b - OPAHs 11
Section 5c - Multiple Analyte Screen with DRS 12
Section 5d - VOCs 13
1) Appendix 1: PAHs by GC-MS-MS
2) Appendix 2: OPAHs by GC-MS
3) Appendix 3: Multiple Analyte Screen by GC-MS and deconvolution software (DRS)
4) Appendix 4: Volatile Organic Compounds (VOCs) by thermal desorption
Abbreviations:
PAHs - Polycyclic aromatic hydrocarbons
OPAHs - Oxygenated polycyclic aromatic hydrocarbons
VOCs - Volatile organic compounds
DRS - Deconvolution Reporting Software
CV - Calibration verification
IB - Instrument blank
MC - Microchamber blank
GT- Glass tube blank
PD - Post-deployment blank
LOD - Limit of Detection
1
-------
Deliverables checklist- From Statement of Work
1) Brief description of the sample collection procedures and parameters.
a. Wristband deployment information
/'. Sample ID numbers - table one
Collection dates and times - table one
Hi. Sampling locations - table one, figure one and two
iv. Sampling height sections - 2a and2b
v. Sampling duration - table one
vi. Other relevant information for interpreting results - sections 2a and2b
b. Facility information associated and linkable to the samples
/'. Facility type (outdoor or indoor) sections 2a and2b
Facility uses - general sections 2a and2b
iii. Facility uses - during sampler deployment sections 2a and2b
iv. Infill type sections 2a and2b
v. Field installation date sections 2a and2b
vi. Most recent date of infill additions (if available) sections 2a and2b
2) Brief description of laboratory method used for analysis of wristbands.
a. Extraction methods and materials - section 3c
b. Analytical system and materials (manufacturer and model/product numbers) - section 4
c. Analytical conditions - section 4 and previously supplied SOPs
3) Brief descriptions of the methods used for data analysis/chemical identification in wristband
analysis.
a. Software (including version), procedures, and databases used for
identification/confirmation previously supplied SOPs
b. Chemicals/standards included in target database previously supplied SOPs
c. Method used to provide concentration estimates previously supplied SOPs
4) List of all identified chemicals in sampler extracts and for relevant sampling methods, the
amounts intensity (e.g., peak abundance) or concentration estimates for each compound
identified. - In appendices one through four
5) Relevant quality assurance/quality control data (e.g., accuracy, precision, uncertainty) to
support compound identification and concentration estimates. - Summarized sections 5a -5d
A. Electronic data file with measurement results
An electronic file version of the sample measurement results (sample ID, chemical names,
intensities and/or estimated concentrations) in a readily usable format (e.g. Excel). - Excel versions
of appendices attached
-------
Section 1 - Executive Summary
In October of 2017, the Food Safety and Environmental Stewardship (FSES) program at Oregon State
University (OSU) was contracted by US EPA to evaluate the application of FSES silicone wristband
sampling technologies in a pilot project examining potential exposures related to the use of crumb-
rubber infilled synthetic turf athletic fields. Two sampling sites were identified, one indoor and one
outdoor (described below). Conditioned wristbands installed in FSES standard air cages were deployed
for seven days at each site, approximately one meter above or directly adjacent to the surface of the
synthetic turf, at locations indicated on the associated maps. Additional samplers were deployed at
sampling sites away from the synthetic turf surface. Using duplicate wristband samplers at each site
allowed one to be used for liquid extraction and one for thermal desorption. Additionally, two samplers
were held in their transport bags for the duration of the sampling campaign. These are designated as
trip blanks one and two and their results reported with the field-deployed samplers. Date of deployment
was November 10th through 17th, 2017.
After recovery, one set of field samples and trip blanks were liquid extracted and analyzed for polycyclic
aromatic hydrocarbons (PAHs) and their oxidized derivatives (OPAHs) as well as a broad analyte
presence/absence screen for 1528 chemicals. The replicate set was thermally desorbed and analyzed for
volatile organic compounds (VOCs). Appropriate quality assurance samples were included in every
analytical batch. This report will provide summary statistics of the analytical findings and summaries of
the quality control/quality assurance data produced in support of these results. Four appendices
summarizing the complete analytical findings are appended to this report. Sampling sites are identified
in table one below and fully described in sections 2a and 2b:
Sample name
Site description
deployment
time
retrieval
time
site 1
NW corner of indoor practice facility
7:15AM
8:04AM
site 1 dup
NW corner of indoor practice facility
7:15AM
8:08AM
site 2
SE corner of indoor practice facility
7:25AM
8:18AM
site 3
Sampler mounted on fence in atrium of indoor facility
7:35AM
8:31AM
site 4
Northern perimeter of outdoor field
7:35AM
8:55AM
site 5
Northern perimeter of outdoor field
7:55AM
8:58AM
site 6
Western perimeter of outdoor field
8:30AM
8:45AM
site 7
Sampler mounted to lamp post ~ 25M due West of turf field
8:40AM
8:50AM
trip blank 1
N/A
N/A
N/A
trip blank 2
N/A
N/A
N/A
Table 1. Sampler identification
3
-------
Section 2 - Sampling
2a - Indoor site
The indoor sampling site is an indoor athletic practice facility with a wall-to-wall synthetic turf field
approximately 125M long and 62M wide (see figure one). The synthetic turf in this facility is fifteen
months old. Crumb rubber is stored on site and added to the field on a continual as-needed basis. This
field is very well maintained and heavily used by a rotation of different teams who utilize the indoor
facility. Two collocated samplers were deployed in the NW corner (site 1) of the facility. Because of the
difficulty of attaching air cages without disrupting ongoing activities, these samplers were collocated
within a single cage. These samplers are identified as site 1 and site 1 dup (duplicate). A sampler was
also placed at the SE corner (site 2) of the facility. These wristbands were designated site 2. In both site
1 and 2 samplers were directly above the turf bed. Two additional samplers were deployed at sample
site 3, an adjacent atrium with a concrete floor, separated from the turf field by a 3' door and a
secondary partial wall. These samplers are designated site 3. Site 3 was approximately 12 meters from
the turf. In normal use, the door is expected to be opened whenever teams are practicing, which is the
majority of the day. Mean temperature during deployment was 14.6°C ± 1.6°C, with a range from 11.4°C
to 22.7 °C. Figure 1 drawing is not to scale.
62M
Sample site 1
N
Indoor turf
field
125M
Sample site 3 -
Concrete floored
atrium
Figure 1. Indoor sampling site map.
4
-------
2b - Outdoor site
The outdoor site has a synthetic turf field approximately 115M long and 100M wide (see Figure two).
The synthetic turf in this facility is approximately five years old. Crumb rubber is available to the
caretakers and added to the field on an as-needed basis. This field is moderately maintained and heavily
used by a rotation of different activities ranging from organized classes to recreational organizations. In
discussions with facility staff, fresh crumb rubber is added approximately every six months to a year.
Collocated air cages were attached to the perimeter fence on the Northern edge of the field. These
samples are designated as site 4 and site 5. A single air cage was attached to the western perimeter
fence and these samples are designated as site 6. These cages are directly adjacent to the turf and 1
meter above the ground. Because these samplers are adjacent to the field, their theoretical sampling
perimeter will include non-turfed ground. Sample site 7 was on a lamppost adjacent to a concrete
walkway and natural grass area, separated from the turf field by approximately 18 meters. Typical
fall/winter wind patterns are from the SW to the NE,
but vary widely dependent on weather (see table 2).
There was rain recorded on six of the seven days of
deployment, averaging 0.94 cm per day. Mean
temperature during deployment was 9.7°C ± 3.2°C,
with a range from 3.1°C to 22.7 °C. By contrast,
summer surface temperatures on this field have
been measured as high as 65° C. Adjacent roadways
are paved and will see significant traffic during
working hours. Drawing is not to scale. Table 2. Outdoor site weather parameters
wind max
max gust
Date
Rain (cm)
Wind (kph)
(kph)
(kph)
11/10/2017
1.39
14.4 SSE
22.4
NA
11/11/2017
0
14.4 SSE
24
NA
11/12/2017
0.53
8 SSE
28.8
NA
11/13/2017
1.45
20.8 S
35.2
54.4
11/14/2017
0.05
16.0 S
36.8
46.4
11/15/2017
2.97
12.8 S
25.6
NA
11/16/2017
2.41
14.4 S
22.4
NA
11/17/2017
0.43
6.4 SSW
25.6
NA
115M
Sampling
perimeter
(t)
V J Sample site 6
Sample site 7-
lamppost
Prevailing
wind
n
Sampling^ Sample site 4 and 5
perimeter
Outdoor turf
field
N
100M
Adjacent roadways
Figure 2. Outdoor sampling site map.
5
-------
2c - Site pictures
Site 6
Site 7
Outdoor site
Sites 4 & 5
6
-------
Section 3 - Deployment; Recovery and Processing
3a - Deployment
Air cages were temporarily mounted to facility walls or fences using available support structures. These
cages are designed to allow unrestricted air flow and have been used in multiple successful
environmental sampling campaigns. Conditioned wristbands were transported to the site within
individual PTFE (Teflon) bags. Once sampling cages were installed, conditioned wristbands were
removed from their bags and affixed within the cages using zip ties. Deployment times are provided in
Table 1.
3b - Recovery
After a seven-day deployment, FSES air cages were carefully opened and each wristband removed and
placed in a pre-labeled, air-tight PTFE bag for storage and transport to the FSES laboratory. Air cages
were removed from support structures. Samplers were transported to the FSES laboratory at Oregon
State University where they were logged in and stored as appropriate, described further in SOP 2003.03
Sample Inspection upon Receipt.
3c - Processing and extraction
All samplers were post-deployment cleaned as per SOP 110.00 Cleaning Field Deployed Silicone Passive
Sampling Devices. Samples destined for PAH, OPAH and DRS analysis were extracted as per SOP 419.00
Extraction of Organic Compounds from Silicone Passive Sampling Devices. Wristbands for VOC analysis
were thermally desorbed as per SOP 422.0 Determination of Volatile Organic Compounds (VOCs) using
thermal desorption purge and trap interfaced with El GC/MS.
7
-------
Section 4 - Analytical Determinations
Aliquots from each ethyl-acetate extract were injected on triple-quadrapole (PAHs; Agilent 7890/7000C
GC/MS/MS) or single quadrapole (OPAHs and DRS; Agilent 6890/5975 GC/MS) gas chromatograph mass
spectrometers as per SOP 418.00 Determination of Parent and Alkyl Substituted PAHs by GC-MS/MS,
SOP 414.00 Determination of Oxygenated Poiycyciic Aromatic Hydrocarbons (OPAHs) using GC/MS or
SOP 423.00 Multiple Analyte Screen by GC-MS and deconvolution software as appropriate.
Aliquots from the thermal tubes were analyzed by SOP 422.00 Determination of Volatile Organic
Compounds (VOCs) using thermal desorption purge and trap interfaced with El GC/MS (Agilent
6890/5975 GC/MS). Each analytical run was individually quantified and all peak values manually
confirmed. Additional quality control samples were run with each analytical batch. The results of these
quality control analyses will be presented with each analytical method summary below. Additional
method parameters including oven profiles, flow rates and instrument specifics are provided within the
previously supplied SOPs (approved 12/4/17).
Analytical effort associated with this project generated over 1,100 quantified chemical data points and
over 15,000 chemical presence/absence determinations. Additionally, over 2,100 quality control data
points were rigorously quantified and reviewed.
All field samples were analyzed on all methods with QC that met applicable DQOs defined in each SOP.
8
-------
Section 5 - Results
Four appendices are associated with this document. They are provided in PDF and Excel formats. The
appendices correspond to individual client reports for:
1) PAHs by GC-MS-MS
2) OPAHsbyGC-MS
3) Multiple Analyte Screen by GC-MS and deconvolution software (DRS)
4) Volatile Organic Compounds (VOCs) by thermal desorption
Continuing calibration (CV) quality control samples were analyzed within each analytical batch as
defined in our SOPs. All CVs meet the data quality objectives outlined in each of our SOPs unless
otherwise indicated. FSES generated instrument blanks (IB), field blanks (FB) and lab-process blanks (LB)
meet DQOs defined in our SOP. Background subtraction using values derived from LBs are designated
with a "B" flag in the client report. Method-specific summations are provided by tabulating the QC
performed for each method and designated Quality Control Summary.
Reported concentration units are ng/g wristband for all methods except DRS, which is reported as
presence/absence.
As further detailed in our Quality Assurance Program Plan, all samples and quality control samples
were reviewed by the Senior Chemist and reviewed and approved by the Program Director.
9
-------
Section 5a - PAHs
Quality Control Summary -
In addition to the two trip blanks reportable as part of this study, seventeen additional quality control/
quality assurance samples were run along with the field wristband samplers, representing 170% QC.
Quality assurance samples included four CVs, seven IBs, and trip, cleaning, construction, and multiple
reagent blanks. All CVs showed greater than 80 % of their analytes within 20 % of true values, passing
DQOs.
ZPAHs from indoor samples (mean 80 ± 16.5 ng/g). ZPAHs from outdoor samples (mean 31.7 ± 1.7 ng/g).
Trip blank wristbands one and two show no PAHs above LOD.
The complete data report for PAHs is attached as Appendix 1.
Location
163 PAHs
ng/g
wristband
Number of
detections
S ite 1
71.8
15
S ite 1 - d u p
60.9
14
S ite 2
105
17
S ite 3
81.9
17
S ite 4
28.9
14
S ite 5
33.9
14
S ite 6
33.4
14
S ite 7
31.9
13
T rip b Ian k 1
0
0
T rip b Ian k 2
0
0
Table 3. PAH Summary stats
10
-------
Section 5b - OPAHs
Quality Control Summary -
In addition to the two trip blanks reportable as part of this study, seventeen additional quality control/
quality assurance samples were run along with the field wristband samplers, representing 170% QC.
Quality assurance samples included five CVs, seven IBs, and trip, cleaning, construction, and multiple
reagent blanks. All CVs showed greater than 85 % of their analytes within 50 % of true values, passing
DQOs.
The complete data report for OPAHs is attached as appendix 2.
11
-------
Section 5c - Multiple Analyte Screen with DRS
Quality Control Summary -
Fourteen quality control/ quality assurance samples were run in addition to the ten wristband samplers,
representing 140% QC. Quality assurance samples included five CVs, five IBs, and trip, cleaning,
construction, and reagent blanks. All CVs passed DQOs. The reagent blank showed a positive detection
of bis(2-ethyhexyl)phthalate. All additional QC samples showed no analytes above the limits of
detection.
Table 4 indicates the chemicals detected in this study. Note "J" and "*" superscript flags denote
compounds near the limit of detection or shared isomers respectively.
Appendix 4 describes these results in fuii and includes a brief description of the chemical classes
represented by these detections.
* Indicates a compound that shares an isomer, see table 3 for more information,
i indicates a compound that was observed near the limit of detection.
Sample Name | Number Compounds Found
Trip blank 1 | A171396
Dicyclohexyl phthalate
Trip blank 2 | A171397
naphthalene
Site 1 | A170976
2.6-dimethylnaphthalenei*
acenaphthenei
Benzothiazole
Bis(2-ethylhexyl )phthalate
Butylated hydroxyanisole
Dibenzofuran
fluorene
naphthalene)
Site 1 - dup | A170978
1,5-dimethylnaphthalene*
1 -methylnaphthalene*
Benzothiazole
Butylated hydroxyanisole
Dicyclohexyl phthalate"
Phthalimide
Site 2 | A170980
1.6-dimethylnaphthalene*
1 -methylnaphthalene*
Benzothiazole
Bis(2-ethylhexyl)phthalate
Butylated hydroxyanisole
fluorene
naphthalene
Phthalimide
Site 3 | A170982
1 -methylnaphthalene*
2-ethylnaphthalenei*
Benzothiazole
Bis(2-ethylhexyl )phthalate
d-Limonene
Dibenzofuran
Triethyl phosphate
Site 4 | A170984
Benzothiazole
Bis(2-ethylhexy I )phthalate
naphthalene)
Site 5 | A170986
1 -methylnaphthalene)*
Benzothiazole
Bis(2-ethylhexyl)phthalate
Di-n-butyl phthalate
Site 6 | A170988
1 -methylnaphthalene)*
Bis(2-ethylhexyl )phthalate)
Site 7 | A170990
1 -methylnaphthalene'*
Bis(2-ethylhexyl)phthalate
naphthalene'
Table 4. DRS detections
Compund Alternative Isomers
1,5-
dimethylnaphthalene
2-Ethylnaphthalene,2,6-dimethylnaphthalene, 1.6-dimethylnaphthalene. 1,4-
dimethylnaphthalene,1,2-dimethylnaphthalene,1.8-dimethylnaphthalene
1,6-
dimethylnaphthalene
2-Ethylnaphthalene,2,6-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1.2-
dimethylnaphthalene, 1.5-dimethylnaphthalene
1 -methylnaphthalene
2-methylnaphthalene
2,6-
dimethylnaphthalene
2-Ethylnaphthalene, 1.6-dimethylnaphthalene, 1,4-dimethylnaphthalene. 1.2-
dimethylnaphthalene. 1.5-dimethylnaphthalene
2-ethylnaphthalene
2,6-dimethylnaphthalene, 1.6-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,2-
dimethylnaphthalene, 1.5-dimethylnaphthalene
Table 5. DRS isomers
12
-------
Section 5d - VOCs
Quality Control Summary -
Twenty-one quality control/ quality assurance samples were run in addition to the ten wristband
samplers, representing 210% QC. Quality assurance samples included three CVs, fourteen GT, one
on PD and two cleaning blanks. MC levels were assigned as background. All CVs passed DQOs. All
additional QC samples showed no analytes above the limits of detection.
Sample
Name
129 VOCs ng/g
wristband
Number of
detections
Site 1
87.29
6
Site 1 - dup
23.19
3
Site 2
68.78
6
Site 3
7.14
4
Site 4
2.13
2
Site 5
38.51
7
Site 6
89.68
9
Site 7
19.99
8
Trip blank 1
0.34
1
Trip blank 2
14.86
3
Table 5. VOC Summary stats
13
-------
Oregon State
University
Food Safety and Environmental Stewardship Program
1007 Agricultural and Life Sciences Building
Corvallis, OR 97331
Phone: (541)737-1766
Fax: (541) 737-0497
Email: fseslab@oregonstate.edu
Web: fses.oregonstate.edu
Certificate of Analysis
-------
Project Name: EPA turf (wristbands) - Appendix 1
Food Safety and Environmental Stewardship Program ^
J? . ^
COA Report '#
Project Number: F17-20
Methodology:
SOP 418.00: Determination of Parent and Alkyl Substituted PAHs by Gas Chromatography-Tandem Mass
Spectrometry
Unit Conversions:
ppb = parts per billion
ppm = parts per million
ppt = parts per trillion
ng/g = ppb
ng/L = ppt
ng/mL = ppb
ng/jjL = ppm
ng/g(Wristband) = ppb
pg/|jL = ppb
|jg/ml_ = ppm
Abbreviations:
J flag: Indicates lower precision in quantitation due to values near limits of detection or matrix effects.
B flag: The sample was background corrected.
< 123.45 U: Detection limit, indicates value was below limit of detection.
COA Notes:
Concentrations reported in ng/g wristband
1 -1
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
"%pjer^
Client Sample Name:
Site 1
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170976
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
4.83
benzo[c]fluorene, 205-12-9
0.435
1,4-dimethylnaphthalene, 571 -58-4
1.04 JB
benzo[e]pyrene, 192-97-2
<0.171 U
1,5-dimethylnaphthalene, 571-61-9
2.23
benzo[ghi]perylene, 191-24-2
< 0.0821 U
1,8-dimethylnaphthalene, 569-41-5
< 0.200 U
benzo[j]fluoranthene, 205-82-3
< 0.135 U
1-methylnaphthalene, 90-12-0
6.59 B
benzo[k]fluoranthene, 207-08-9
< 0.128 U
1-methylphenanthrene, 832-69-9
< 0.256 U
chrysene, 218-01-9
< 0.121 U
1-methylpyrene, 2381-21-7
< 0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
<0.128 U
2,6-diethylnaphthalene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
<0.114 U
2,6-dimethylnaphthalene, 581-42-0
<0.215 U
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethylnaphthalene, 939-27-5
4.71 B
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methylanthracene, 613-12-7
1.26
dibenzo[a,h]pyrene, 189-64-0
< 0.126 U
2-methylnaphthalene, 91-57-6
10.3 B
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methylphenanthrene, 2531-84-2
2.17
dibenzo[a,l]pyrene, 191-30-0
< 0.116 U
3,6-dimethyiphenanthrene, 1576-67-6
< 0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methylchrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
2.21
6-methylchrysene, 1705-85-7
< 0.215 U
fluoranthene, 206-44-0
1.97
7,12-dimethylbenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
16.4
9,10-dimethylanthracene, 781 -43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
< 0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
7.51
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
<0.403 U
benzo[a]chrysene, 213-46-7
< 0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84
-6
< 0.403 U
phenanthrene, 85-01-8
15.6
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
<0.101 U
benzo[b]fluoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
<0.203 U
benzo[b]fluorene, 243-17-4
1.06 J
triphenylene, 217-59-4
< 0.0990 U
benzo[b]perylene, 197-70-6
< 0.403 U
1 -2
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 1 - dup
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170978
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
4.35
benzo[c]fluorene, 205-12-9
0.447
1,4-dimethylnaphthalene, 571 -58-4
0.944 JB
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
1.91
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
7.42 B
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methylpyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthalene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethyinaphthaiene, 581-42-0
<0.215 U
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethyinaphthaiene, 939-27-5
4.44 B
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methylanthracene, 613-12-7
<0.114 U
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methyinaphthaiene, 91-57-6
11.8 B
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methylphenanthrene, 2531-84-2
1.57
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethyiphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methylchrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
1.81
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
1.81
7,12-dimethyibenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
13.1
9,10-dimethylanthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methyianthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
7.29
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
11.0
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
<0.101 U
benzo[b]fluoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
< 0.203 U
benzo[b]fiuorene, 243-17-4
1.04 J
triphenylene, 217-59-4
< 0.0990 U
benzo[b]perylene, 197-70-6
< 0.403 U
1 -3
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 2
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170980
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
4.88
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
1.09 JB
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
2.26
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
7.15 B
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methylpyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthalene, 59919-41 -4
1.62
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethyinaphthaiene, 581-42-0
14.3 B
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethylnaphthalene, 939-27-5
4.78 B
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
1.84
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methyinaphthaiene, 91-57-6
11.6 B
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methylphenanthrene, 2531-84-2
2.92
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethyiphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methylchrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
2.73
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
2.70
7,12-dimethylbenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
19.0
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methyianthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
9.11
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
22.0
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
1.91
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
2.00
benzo[b]fiuorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]perylene, 197-70-6
< 0.403 U
1 -4
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 3
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170982
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
3.91
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
0.638 JB
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
1.71
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
5.65 B
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methylpyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthalene, 59919-41 -4
1.21
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethyinaphthaiene, 581-42-0
10.2 B
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethylnaphthalene, 939-27-5
3.72 B
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
1.01
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methylnaphthalene, 91-57-6
9.06 B
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
1.42
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethyiphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methylchrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
1.95
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
2.66
7,12-dimethylbenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
16.1
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
7.54
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthyiene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fiuorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
16.2
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
1.10
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
1.52
benzo[b]fluorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 - 5
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 4
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170984
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
2.00
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
< 0.300 U
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
0.534 J
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
< 0.0676 U
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methyipyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthaiene, 59919-41 -4
0.942 J
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethylnaphthalene, 581-42-0
1.04 JB
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethyinaphthaiene, 939-27-5
0.409 JB
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
1.41
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methylnaphthalene, 91-57-6
<0.169 U
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
< 0.0942 U
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethylphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methyichrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
< 0.0580 U
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
2.49
7,12-dimethyibenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
3.48
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
< 0.258 U
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
6.86
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
1.50
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
3.62
benzo[b]fluorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 - 6
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 5
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170986
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
2.13
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
< 0.300 U
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
0.580 J
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
< 0.0676 U
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methylpyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthalene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethylnaphthalene, 581-42-0
1.23 B
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethyinaphthaiene, 939-27-5
0.462 JB
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
1.66
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methylnaphthalene, 91-57-6
<0.169 U
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
1.42
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethylphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methyichrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
< 0.0580 U
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
2.58
7,12-dimethyibenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
4.18
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
< 0.258 U
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
8.79
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
1.65
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
4.23
benzo[b]fluorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 - 7
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 6
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170988
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
2.04
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
< 0.300 U
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
0.633 J
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
0.169 JB
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methylpyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthalene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethyinaphthaiene, 581-42-0
1.45 B
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethylnaphthalene, 939-27-5
0.540 JB
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
1.57
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methylnaphthalene, 91-57-6
<0.169 U
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
1.31
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethyiphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methylchrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
< 0.0580 U
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
2.44
7,12-dimethylbenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
4.83
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
1.42
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthyiene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fiuorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
7.56
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
1.66
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
3.94
benzo[b]fluorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 - 8
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 7
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A170990
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
2.20
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
< 0.300 U
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
0.698 J
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
0.942 B
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methyipyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthaiene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethylnaphthalene, 581-42-0
1.84 B
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethyinaphthaiene, 939-27-5
0.702 JB
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
1.40
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methylnaphthalene, 91-57-6
1.35 B
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
1.29
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethylphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methyichrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
< 0.0580 U
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
2.33
7,12-dimethyibenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
3.82
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
2.06
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
7.12
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
<0.101 U
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
3.70
benzo[b]fluorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 - 9
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Trip blank 1
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A171396
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
<0.227 U
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
< 0.300 U
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
<0.287 U
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
< 0.0676 U
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methylpyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethyianthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthaiene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethylnaphthalene, 581-42-0
<0.215 U
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethyinaphthaiene, 939-27-5
< 0.234 U
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methylanthracene, 613-12-7
<0.114 U
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methyinaphthaiene, 91-57-6
<0.169 U
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
< 0.0942 U
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethylphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methyichrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
< 0.0580 U
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
< 0.130 U
7,12-dimethyibenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
< 0.191 U
9,10-dimethylanthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methyianthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
< 0.258 U
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
<0.111 U
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
<0.101 U
benzo[b]fluoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
< 0.203 U
benzo[b]fiuorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 - 10
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Trip blank 2
Test Method:
Parent and Alkyi Substituted PAHs by GC-MS/MS
FSES Sample ID:
A171397
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-dimethylnaphthalene, 573-98-8
<0.227 U
benzo[c]fluorene, 205-12-9
< 0.0725 U
1,4-dimethylnaphthalene, 571 -58-4
< 0.300 U
benzo[e]pyrene, 192-97-2
< 0.171 U
1,5-dimethylnaphthalene, 571-61 -9
<0.287 U
benzo[ghi]perylene, 191-24-2
<0.0821 U
1,8-dimethylnaphthalene, 569-41 -5
<0.200 U
benzo[j]fluoranthene, 205-82-3
<0.135 U
1-methylnaphthalene, 90-12-0
< 0.0676 U
benzo[k]fluoranthene, 207-08-9
<0.128 U
1-methylphenanthrene, 832-69-9
<0.256 U
chrysene, 218-01-9
<0.121 U
1-methyipyrene, 2381-21-7
<0.0918 U
coronene, 191-07-1
<0.169 U
2,3-dimethylanthracene, 613-06-9
<0.0821 U
cyclopenta[cd]pyrene, 27208-37-3
< 0.128 U
2,6-diethylnaphthaiene, 59919-41 -4
<0.196 U
dibenzo[a,e]fluoranthene, 5385-75-1
< 0.114 U
2,6-dimethylnaphthalene, 581-42-0
<0.215 U
dibenzo[a,e]pyrene, 192-65-4
< 1.56 U
2-ethyinaphthaiene, 939-27-5
< 0.234 U
dibenzo[a,h]anthracene, 53-70-3
< 0.246 U
2-methyianthracene, 613-12-7
<0.114 U
dibenzo[a,h]pyrene, 189-64-0
<0.126 U
2-methylnaphthalene, 91-57-6
<0.169 U
dibenzo[a,i]pyrene, 189-55-9
< 0.343 U
2-methyiphenanthrene, 2531-84-2
< 0.0942 U
dibenzo[a,l]pyrene, 191-30-0
<0.116 U
3,6-dimethylphenanthrene, 1576-67-6
<0.101 U
dibenzo[e,l]pyrene, 192-51-8
< 0.403 U
5-methyichrysene, 3697-24-3
< 0.403 U
dibenzothiophene, 132-65-0
< 0.0580 U
6-methylchrysene, 1705-85-7
<0.215 U
fluoranthene, 206-44-0
< 0.130 U
7,12-dimethyibenz[a]anthracene, 57-97-6
< 0.227 U
fluorene, 86-73-7
< 0.191 U
9,10-dimethyianthracene, 781-43-1
< 0.205 U
indeno[1,2,3-cd]pyrene, 193-39-5
< 0.0628 U
9-methylanthracene, 779-02-2
<0.210 U
naphthalene, 91-20-3
<0.251 U
acenaphthene, 83-32-9
< 0.258 U
naphtho[1,2-b]fluoranthene, 111189-32-3
< 0.403 U
acenaphthylene, 208-96-8
< 0.563 U
naphtho[2,3-a]pyrene, 196-42-9
< 0.403 U
anthanthrene, 191-26-4
< 0.0797 U
naphtho[2,3-e]pyrene, 193-09-9
< 0.403 U
anthracene, 120-12-7
< 0.254 U
naphtho[2,3-j]fluoranthene, 205-83-4
< 0.403 U
benz[a]anthracene, 56-55-3
<0.181 U
naphtho[2,3-k]fluoranthene, 207-18-1
< 0.403 U
benzo[a]chrysene, 213-46-7
<0.179 U
perylene, 77392-71-3
< 0.242 U
benzo[a]fluorene, 238-84-6
<0.403 U
phenanthrene, 85-01-8
<0.111 U
benzo[a]pyrene, 50-32-8
<0.285 U
pyrene, 129-00-0
<0.101 U
benzo[b]fiuoranthene, 205-99-2
< 0.0894 U
retene, 483-65-8
< 0.203 U
benzo[b]fluorene, 243-17-4
< 0.403 U
triphenylene, 217-59-4
< 0.0990 U
benzo[b]peryiene, 197-70-6
< 0.403 U
1 -11
-------
Oregon State
University
Food Safety and Environmental Stewardship Program
1007 Agricultural and Life Sciences Building
Corvallis, OR 97331
Phone: (541) 737-1766
Fax: (541) 737-0497
Email: fseslab@oregonstate.edu
Web: fses.oregonstate.edu
Certificate of Analysis
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Client Report For:
EPA - Jose L. Zambrana, Jr., PhD
National Exposure Research Laboratory
US EPA Office of Research and Development
zambrana.jose@epa.gov
Project Name:
Project Number:
Report Date:
EPA turf (wristbands) - Appendix 2
F17-20
February 23 2018
QC Review
Date
FSES Director Approval: Kim A. Anderson
Date
-------
Project Name: EPA turf (wristbands)
Food Safety and Environmental Stewardship Program ^
J? . ^
COA Report '#
Project Number: F17-20
Methodology:
SOP 414.00: Determination of Oxygenated Polycyclic Aromatic Hydrocarbons by Gas Chromatography-Mass
Spectrometry
Unit Conversions:
ppb = parts per billion
ppm = parts per million
ppt = parts per trillion
ng/g = ppb
ng/L = ppt
ng/mL = ppb
ng/jjL = ppm
ng/g(Wristband) = ppb
pg/|jL = ppb
|jg/ml_ = ppm
Abbreviations:
J flag: Indicates lower precision in quantitation due to values near limits of detection or matrix effects.
B flag: The sample was background corrected.
< 123.45 U: Detection limit, indicates value was below limit of detection.
COA Notes:
Concentrations are reported in ng/g wristband
2-1
-------
Project Name: EPA turf (wristbands) - Appendix 2
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 1
A170976
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
<0.411 U
2-Ethylanthraquinone, 84-51-5
<0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
< 0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
< 0.362 U
Perinaphthenone, 548-39-0
<0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-2
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 1 - dup
A170978
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-3
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 2
A170980
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-4
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 3
A170982
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-5
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 4
A170984
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyciopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-6
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 5
A170986
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
2.13
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-7
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 6
A170988
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
6.86
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
0.838 J
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-8
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Site 7
A170990
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyciopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fiuorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-9
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Trip blank 1
A171396
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
< 0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fluorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-10
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
Ento
''/i.'pjcr1
Client Sample Name:
FSES Sample ID:
Trip blank 2
A171397
Test Method: OPAHs by GC-MS
Matrix: Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2-Naphthoquinone, 524-42-5
<604 U
Acenaphthenequinone, 82-86-0
< 2.66 U
1,4-Anthraquinone, 635-12-1
< 1.35 U
Benz[a]anthracene-7,12-dione, 2498-66-0
< 0.205 U
1,4-Benzoquinone, 106-51-4
<0.118 U
Benzanthrone, 82-05-3
<0.188 U
1,4-Naphthoquinone, 130-15-4
<0.109 U
Benzo(c)phenanthrene(1,4)quinone, 109699-80-1
<0.411 U
2-Ethylanthraquinone, 84-51-5
< 0.085 U
Benzo(cd)pyrenone,
< 0.266 U
4H-cyclopenta[def]phenanthren-4-one, 5737-13-3
<0.051 U
Benzofluorenone, 76723-60-9
<0.109 U
5,12-Naphthacene-quinone, 1090-13-7
<0.314 U
Chromone, 491-38-3
<0.215 U
9,10-Anthraquinone, 84-65-1
<0.362 U
Perinaphthenone, 548-39-0
< 0.215 U
9,10-Phenanthrenequinone, 84-11-7
< 60.4 U
Phenanthrene-1,4-dione, 569-15-3
< 0.208 U
9-Fluorenone, 486-25-9
< 0.048 U
Pyrene-4,5-dione, 6217-22-7
<604 U
Aceanthracenequinone,
<604 U
Xanthone, 90-47-1
< 0.092 U
2-11
-------
Oregon State
University
Food Safety and Environmental Stewardship Program
1007 Agricultural and Life Sciences Building
Corvallis, OR 97331
Phone: (541) 737-1766
Fax: (541) 737-0497
Email: fseslab@oregonstate.edu
Web: fses.oregonstate.edu
Certificate of Analysis
<2^
<0
T3
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Vspje^'
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CD
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<-+
Qj
Client Report For: EPA - Jose L. Zambrana, Jr., PhD
National Exposure Research Laboratory
US EPA Office of Research and Development
zambrana.jose@epa.gov
Project Name:
Project Number:
Report Date:
EPA turf (wristbands) - Appendix 3
F17-20
February 23 2018
QC Review
Date
FSES Director Approval: Kim A. Anderson
Date
-------
Project#: F17-20: EPA turf
(wristbands)
^ * * *¦&
ti/sp
Table 1: Sample detections
* Indicates a compound that shares an isomer, see table 3 for more information,
i indicates a compound that was observed near the limit of detection.
Sample Name | Number Compounds Found
COA Report - Appendix 3
University
Trip blank 1 | A171396
Dicyclohexyl phthalate
Trip blank 2 | A171397
naphthalene
Site 1 | A170976
2,6-dimethylnaphthalenei*
acenaphthenei
Benzothiazole
Bis(2-ethylhexyl)phthalate
Butylated hydroxyanisole
Dibenzofuran
fluorene
naphthalenei
Site 1 - dup | A170978
1,5-dimethylnaphthalene*
1 -methylnaphthalene*
Benzothiazole
Butylated hydroxyanisole
Dicyclohexyl phthalatei
Phthalimide
Site 2 | A170980
1,6-dimethylnaphthalene*
1-methylnaphthalene*
Benzothiazole
Bis(2-ethylhexyl)phthalate
Butylated hydroxyanisole
fluorene
naphthalene
Phthalimide
Site 3 | A170982
1-methylnaphthalene*
2-ethylnaphthalenei*
Benzothiazole
Bis(2-ethylhexyl)phthalate
d-Limonene
Dibenzofuran
Triethyl phosphate
Site 4 | A170984
Benzothiazole
Bis(2-ethylhexyl)phthalate
naphthalenei
Site 5 | A170986
1-methylnaphthalenei*
Benzothiazole
Bis(2-ethylhexyl)phthalate
Di-n-butyl phthalate
Site 6 | A170988
1-methylnaphthalenei*
Bis(2-ethylhexyl)phthalatei
Site 7 | A170990
1-methylnaphthalenei*
Bis(2-ethylhexyl)phthalate
naphthalenei
3-1
-------
COA Report
Oregon State
University
Table 2: Compound Isomers
Compund Alternative Isomers
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjef-
1,5-
dimethylnaphthalene
2-Ethylnaphthalene,2,6-dimethylnaphthalene,1,6-dimethylnaphthalene,1,4-
dimethylnaphthalene,1,2-dimethylnaphthalene,1,8-dimethylnaphthalene
1,6-
dimethylnaphthalene
2-Ethylnaphthalene,2,6-dimethylnaphthalene,1,4-dimethylnaphthalene,1,2-
dimethylnaphthalene,1,5-dimethylnaphthalene
1 -methylnaphthalene
2-methylnaphthalene
2,6-
dimethylnaphthalene
2-Ethylnaphthalene,1,6-dimethylnaphthalene,1,4-dimethylnaphthalene,1,2-
dimethylnaphthalene,1,5-dimethylnaphthalene
2-ethylnaphthalene
2,6-dimethylnaphthalene,1,6-dimethylnaphthalene,1,4-dimethylnaphthalene,1,2-
dimethylnaphthalene,1,5-dimethylnaphthalene
3-2
-------
COA Report
Table 3: Compound classification summary
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjef-
Classification
Number of
samples
with
detections
Compounds
Dioxins and Furans
2
Dibenzofuran
Endocrine Disruptors
10
Bis(2-ethylhexyl)phthala, Butylated hydroxyanisole, Di-n-butyl phthalate, Dicyclohexyl
phthalate, fluorene, naphthalene
Flame Retardant
1
Triethyl phosphate
Industrial
9
1-methylnaphthalene, Benzothiazole, Bis(2-ethylhexyl)phthala, Di-n-butyl phthalate,
Dicyclohexyl phthalate, Phthalimide, Triethyl phosphate
OPAH
0
N/A
PAH
9
1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 1-methylnaphthalene, 2,6-
dimethylnaphthalene, 2-ethylnaphthalene, acenaphthene, fluorene, naphthalene
PBB
0
N/A
PBDE
0
N/A
PCB
0
N/A
Personal Care
5
Butylated hydroxyanisole, d-Limonene, Di-n-butyl phthalate
Pesticides
8
Bis(2-ethylhexyl)phthala, Di-n-butyl phthalate, Phthalimide, Triethyl phosphate
Pharmacological
3
Butylated hydroxyanisole
Un categorized
0
N/A
3-3
-------
COA Report
Appendix A: All compounds and their classifications
Project#: F17-20: EPA turf
(wristbands)
.&En^
Oregon State
University
•'Vspje*
* Data taken from World Health Organization (WHO) International Agency for Research on Cancer (IARC) Agents Classified by
the IARC Monographs, Volumes 1-118, last updated 3/1/2017
Groups are indicated by the Group and year classified, e.g. 2B(1999), for more info visit
http://fses.oregonstate.edu/who-iarc
• Group 1: Carcinogenic to humans
• Group 2A: Probably carcinogenic to humans
• Group 2B: Probably carcinogenic to humans
• Group 3: Not classifiable as to its carcinogenicity to humans
• Group 4: Probably not carcinogenic to humans
** Data taken from the United States Environmental Protection Agency (EPA) Integrated Risk Information System (IRIS),
last updated on 5/1/2017,
for more info visit http://fses.oregonstate.edu/epa-iris
*** Data taken from State of California Environmental Protection Agency (Cal/EPA) Chemicals Known to the State to Cause
Cancer or Reproductive Toxicity, last updated 3/1/2017,
for more info visit http://fses.oregonstate.edu/cal-epa
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS** |Cal/EPA***
(2,3-Dibromopropyl) (2,4,6-
tribromophenyl) ether
35109-60-5
Flame Retardant
-
1,2,3,4,6,7,8,9-Octachlorodibenzo-p-
dioxin
3268-87-9
Dioxins/Furans
-
1,2,3,4,6,7,8,9-
Octachlorodibenzofuran
39001-02-0
Dioxins/Furans
-
1,2,3,4,6,7,8-Heptachlorodibenzo-p-
dioxin
35822-46-9
Dioxins/Furans
-
1,2,3,4,6,7,8-
Heptachlorodibenzofuran
38998-75-3
Dioxins/Furans
-
1,2,3,4,6,7,9-Heptachlorodibenzo-p-
dioxin
58200-70-7
Dioxins/Furans
-
1,2,3,4,6,7-Hexachlorodibenzo-p-
dioxin
58200-66-1
Dioxins/Furans
-
1,2,3,4,7,8-Hexachlorodibenzo-p-
dioxin
39227-28-6
Dioxins/Furans
-
1,2,3,4,7,8-Hexachlorodibenzofuran
55684-94-1
Dioxins/Furans
-
1,2,3,4,7-Pentachlorodibenzo-p-
dioxin
39227-61 -7
Dioxins/Furans
-
1,2,3,4-Tetrachlorodibenzo-p-dioxin
30746-58-8
Dioxins/Furans
-
1,2,3,4-Tetrachlorodibenzofuran
24478-72-6
Dioxins/Furans
-
1,2,3,6,7,8-Hexachlorodibenzo-p-
dioxin
57653-85-7
Dioxins/Furans
Carcinoaenicitv
Assessment: Yes
(Last revised: 03-
31-1987)
1,2,3,7,8,9-Hexachlorodibenzo-p-
dioxin
19408-74-3
Dioxins/Furans
-
1,2,3,7,8-Pentachlorodibenzo-p-
dioxin
40321-76-4
Dioxins/Furans
-
1,2,3,7,8-Pentachlorodibenzofuran
57117-41 -6
Dioxins/Furans,
-
1,2,3,8,9-Pentachlorodibenzo-p-
dioxin
71925-18-3
Dioxins/Furans
-
1,2,3-Trichlorodibenzo-p-dioxin
54536-17-3
Dioxins/Furans
-
1,2,4,6,7,9/1,2,4,6,8,9-
Hexachlorodibenzo-p-dioxin
Dioxins/Furans
-
1,2,4,6,8/1,2,4,7,9-
Pentachlorodibenzo-p-dioxin
71998-76-0
Dioxins/Furans
-
3-4
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
1,2,4,7,8-Pentachlorodibenzo-p-
dioxin
58802-08-7
Dioxins/Furans
-
-
-
1,2,4-Trichlorobenzene
120-82-1
Insecticide, Industrial
-
Oral RfD
Assessment: Yes
-
(Last revised: 05-
01-1992V
Carcinoaenicitv
Assessment: Yes
(Last revised: 06-
01-19891
1,2,4-Trichlorodibenzo-p-dioxin
39227-58-2
Dioxins/Furans
-
-
-
1,2,5,6,9,10-
Hexabromocyclododecane
3194-55-6
Flame Retardant,
-
-
-
1,2,6,7-Tetrachlorodibenzo-p-dioxin
41903-57-5
Dioxins/Furans
-
-
-
1,2,6,8-Tetrachlorodibenzo-p-dioxin
67323-56-2
Dioxins/Furans
-
-
-
1,2,7,8-Tetrachlorodibenzo-p-dioxin
34816-53-0
Dioxins/Furans
-
-
-
1,2,8,9-Tetrachlorodibenzo-p-dioxin
116889-69-1
Dioxins/Furans
-
-
-
1,2-Bis(2,4,6-tribromophenoxy)
ethane
37853-59-1
Flame Retardant
-
-
-
1,2-Dibromo-3-chloropropane
96-12-8
Fungicide, Insecticide,
2B(1999)
Inhalation RfC
Assessment: Yes
cancer (1 -Jul-87)
male (27-Feb-87)
(Last revised: 10-
01-19911.
1,2-Dibromo-4-(1,2-dibromoethyl)
cyclohexane
3322-93-8
Flame Retardant,
-
-
-
1,2-Dichlorodibenzo-p-dioxin
54536-18-4
Dioxins/Furans
-
-
-
1,2-dimethylnaphthalene
573-98-8
PAH
-
-
-
1,3,5-Tribromobenzene
626-39-1
Flame Retardant, Industrial
-
-
-
1,3,6,8-Tetrachlorodibenzo-p-dioxin
33423-92-6
Dioxins/Furans
-
-
-
1,3,6,8-Tetrachlorodibenzofuran
30402-14-3
Dioxins/Furans
-
-
-
1,3,7,8-Tetrachlorodibenzo-p-dioxin
50585-46-1
Dioxins/Furans,
-
-
-
1,3,7,9-Tetrachlorodibenzo-p-dioxin
116889-70-4
Dioxins/Furans
-
-
-
1,3-Dichlorobenzene
541-73-1
Insecticide, Industrial,
3(1999)
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
01-19901
1,3-Dichlorodibenzo-p-dioxin
50585-39-2
Dioxins/Furans
-
-
-
1,3-Dinitropyrene
75321-20-9
PAH
2B(2013)
-
cancer (2-Nov-12)
1,4-Anthraquinone
635-12-1
OPAH
-
-
-
1,4-Dichlorodibenzo-p-dioxin
54536-19-5
Dioxins/Furans
-
-
-
1,4-dimethylnaphthalene
571-58-4
PAH
-
-
-
1,4-Dioxino(2,3,b,5,6,b')dipyridine
262-16-8
Dioxins/Furans
-
-
-
1,4-Naphthoquinone
130-15-4
OPAH
-
-
-
1,5-dimethylnaphthalene
571-61-9
PAH
|-
1,6-Benzo(a)pyrene-quinone
3067-13-8
OPAH
|- ~
1,6-Dichlorodibenzo-p-dioxin
38178-38-0
Dioxins/Furans
|- ~
1,6-dimethylnaphthalene
575-43-9
PAH
-
1,6-Dinitropyrene
42397-64-8
PAH
2B(2013)
-
cancer (1 -Oct-90)
1,7,8-Trichlorodibenzo-p-dioxin
82306-65-8
Dioxins/Furans
|- ^
1,8-dimethylnaphthalene
569-41 -5
PAH
|-
1,8-Dinitropyrene
42397-65-9
PAH
2B(2013)
-
cancer (1 -Oct-90)
1 -Chlorodibenzo-p-dioxin
39227-53-7
Dioxins/Furans
|- ^
1 -Hydroxynaphthalene
90-15-3
PAH, Industrial,
|- ~
1 -methylnaphthalene
90-12-0
PAH, Industrial
-
3-5
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
1 -methylphenanthrene
832-69-9
PAH
3(2010)
-
-
1-methylpyrene
2381-21-7
PAH,
-
-
-
1-Naphthylamine
134-32-7
Industrial
3(1987)
-
cancer (1 -Oct-89)
1-Nitronaphthalene
86-57-7
PAH, Industrial
3(1989)
-
-
1-Nitropyrene
5522-43-0
PAH
2A(2014)
-
cancer (1 -Oct-90)
17a-Ethynylestradiol
57-63-6
Pharmacological
-
-
cancer (1-Jan-88)
2'-Hydroxy-2,4,4'-tribromodiphenyl
ether
N/A
Flame Retardant, PBDE
-
-
-
2'-Hydroxy-4-monobromodiphenyl
ether
N/A
Flame Retardant, PBDE
-
-
-
2'-Methoxy-2,4,4'-tribromodiphenyl
ether
N/A
Flame Retardant, PBDE
-
-
-
2,3,4,5-Tertrachloronitrobenzene
879-39-0
Fungicide, Industrial
-
-
-
2,3,4,5-Tetrachlorophenol
4901-51-3
General Pesticide,
-
-
-
2,3,4,6-Tetrachlorophenol
58-90-2
Fungicide, Industrial, Pulp/Paper,
Oral RfD
Assessment: Yes
(Last revised: 03-
01-1988V
2,3,4,7,8-PeCDF
57117-31-4
Dioxins/Furans,
1(2012)
-
-
2,3,4-Tribromophenol
138507-65-0
Flame Retardant,
-
-
-
2,3,4-Trichlorophenyl-4-nitrophenyl
ether
142022-61-5
Industrial, Halo Ethers
-
-
-
2,3,5,6-Tetrachloro-p-terphenyl
61576-99-6
Flame Retardant, Industrial
-
-
-
2,3,5,6-Tetrachlorophenol
935-95-5
General Pesticide,
-
-
-
2,3,5-Trichlorophenol
933-78-8
Industrial,
-
-
-
2,3,5-Trichlorophenyl-4-nitrophenyl
ether
142022-59-1
Industrial, Halo Ethers
-
-
-
2,3,5-Trimethacarb
2655-15-4
Insecticide
-
-
-
2,3,5-trimethylphenol
697-82-5
Personal Care, Industrial,
-
-
-
2,3,6-Trichloroanisole
50375-10-5
General Pesticide
-
-
-
2,3,6-Trichlorophenyl-4-nitrophenyl
ether
142022-58-0
Industrial, Halo Ethers
-
-
-
2,3,6-trimethylphenol
2416-94-6
Industrial,
-
-
-
2,3,7,8-TCDD
1746-01-6
Industrial,
1(2012)
Oral RfD
Assessment: Yes
(Last revised: 02-
17-2012).
Carcinoaenicitv
Assessment:
Messaae (Last
revised: 02-17-
2012)
cancer (1-Jan-88)
developmental (1-
Apr-91)
2,3,7,8-Tetrabromodibenzo-p-dioxin
50585-41 -6
Dioxins/Furans,
-
-
-
2,3,7,8-Tetrachlorodibenzofuran
51207-31 -9
Industrial,
-
-
-
2,3,7-Trichlorodibenzo-p-dioxin
33857-28-2
Dioxins/Furans
-
-
-
2,3-Dibromoanisole
95970-22-2
Industrial
-
-
-
2,3-Dibromophenol
57383-80-9
Flame Retardant,
-
-
-
2,3-Dichlorodibenzo-p-dioxin
29446-15-9
Dioxins/Furans
-
-
-
2,3-Dichlorophenyl-4-nitrophenyl
ether
82239-20-1
Industrial, Halo Ethers
-
-
-
2,3-dimethylaniline
87-59-2
Industrial,
-
-
-
2,3-dimethylanthracene
613-06-9
PAH
-
-
-
2,3-xylenol
526-75-0
Industrial,
-
-
-
2,4'-DDD
53-19-0
Insecticide, Pharmacological,
-
-
-
2,4'-DDE
3424-82-6
Insecticide,
-
-
-
3-6
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
2,4'-DDT
789-02-6
Insecticide,
"
'
developmental,
female, male (15-
May-98)
2,4'-Dichlorobenzophenone (2,4'-
Dicofol decomposition product)
85-29-0
General Pesticide
-
-
-
2,4,5-T methyl ester
1928-37-6
Herbicide,
-
-
-
2,4,5-Tribromoanisole
N/A
Industrial
-
-
-
2,4,5-Trichloro-p-terphenyl
999008-03-6
Flame Retardant, Industrial
-
-
-
2,4,5-Trichloroaniline
636-30-6
General Pesticide,
-
-
-
2,4,5-Trichlorophenol
95-95-4
Fungicide, Herbicide, Industrial,
Pulp/Paper,
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871,
Inhalation RfC
Assessment:
Messaae (Last
revised: 07-01-
19911.
2,4,5-Trichlorophenyl-4-nitrophenyl
ether
22532-68-9
Industrial, Halo Ethers
-
-
-
2,4,5-Trimethylaniline
137-17-7
Industrial,
3(1987)
-
-
2,4,6-tri-tert-butylphenol
732-26-3
Industrial,
-
-
-
2,4,6-Tribromoanisole
607-99-8
Industrial
-
-
-
2,4,6-Tribromophenol
118-79-6
Flame Retardant,
-
-
-
2,4,6-Tribromophenyl allyl ether
3278-89-5
Flame Retardant
-
-
-
2,4,6-trichloroaniline
634-93-5
General Pesticide, Industrial,
-
-
-
2,4,6-Trichloroanisole
87-40-1
General Pesticide
-
-
-
2,4,6-Trichlorophenol
88-06-2
Fungicide, Herbicide, Industrial,
Pulp/Paper,
2
Inhalation RfC
Assessment:
Messaae (Last
revised: 07-01-
19911.
Carcinoaenicitv
Assessment: Yes
(Last revised: 06-
01-19901
cancer (1-Jan-88)
2,4,6-triiodophenol
609-23-4
Industrial,
-
-
-
2,4,6-trimethylphenol
527-60-6
Industrial,
-
-
-
2,4,8-Trichlorodibenzofuran
54589-71 -8
Dioxins/Furans
-
-
-
2,4-bis(alpha,alpha-dimethylbenzyl)
phenol
2772-45-4
Industrial,
-
-
-
2,4-D methyl ester
1928-38-7
General Pesticide
-
-
-
2,4-D sec-butyl ester
94-79-1
Herbicide
-
-
-
2,4-DB methyl ester
18625-12-2
General Pesticide
-
-
-
2,4-di-tert-amylphenol
120-95-6
Industrial,
-
-
-
2,4-di-tert-butylphenol
96-76-4
Industrial,
-
-
-
2,4-Dibromoanisole
21702-84-1
Industrial
-
-
-
2,4-Dibromophenol
615-58-7
Flame Retardant,
-
-
-
2,4-Dibromophenyl-4-nitrophenyl
ether
2671 -93-4
Industrial, Halo Ethers
-
-
-
2,4-dichloro-3,5-dimethylphenol
133-53-9
Industrial,
-
-
-
2,4-dichloroaniline
554-00-7
Industrial,
-
-
-
2,4-Dichlorophenol
120-83-2
Fungicide, Herbicide, Industrial,
Pulp/Paper,
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
3-7
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
2,4-Dichlorophenyl
benzenesulfonate
97-16-5
General Pesticide
-
-
-
2,4-Dimethylaniline
95-68-1
Industrial,
3(1987)
-
-
2,4-Dimethylphenol
105-67-9
Pharmacological, Industrial,
Oral RfD
Assessment: Yes
(Last revised: 11-
01-1990V
2,4-dinitroaniline
97-02-9
Industrial,
-
-
-
2,5-Dibromoanisole
95970-08-4
Industrial
-
-
-
2,5-Dibromophenol
28165-52-8
Flame Retardant,
-
-
-
2,5-dichloroaniline
95-82-9
Industrial,
-
-
-
2,5-dichlorophenol
583-78-8
Industrial,
-
-
-
2,5-Dichlorophenyl-4-nitrophenyl
ether
391-48-7
Industrial, Halo Ethers
-
-
-
2,5-dimethylaniline
95-78-3
Industrial,
3(1987)
-
-
2,5-dimethylphenol
95-87-4
Industrial,
-
-
-
2,6-di-tert-butyl-4-
dimethylaminomethylphenol
88-27-7
Industrial,
-
-
-
2,6-Di-tert-butyl-4-ethylphenol
4130-42-1
Industrial,
-
-
-
2,6-Di-tert-butylphenol
128-39-2
Industrial,
-
-
-
2,6-dibromo-4-nitroaniline
827-94-1
Industrial,
-
-
-
2,6-Dibromoanisole
38603-09-7
Industrial
-
-
-
2,6-Dibromophenol
608-33-3
Flame Retardant,
-
-
-
2,6-Dichlorobenzamide
2008-58-4
Herbicide
-
-
-
2,6-Dichlorobenzonitrile
1194-65-6
Herbicide
-
-
-
2,6-Dichlorophenol
87-65-0
Industrial, Pulp/Paper,
-
-
-
2,6-Dichlorophenyl-4-nitrophenyl
ether
2093-28-9
Industrial, Halo Ethers
-
-
-
2,6-Dichlorosyringaldehyde
76330-06-8
Industrial, Pulp/Paper
-
-
-
2,6-diethylaniline
579-66-8
Industrial,
-
-
-
2,6-diethylnaphthalene
59919-41 -4
PAH
-
-
-
2,6-diisopro pylaniline
24544-04-5
Industrial,
-
-
-
2,6-dimethoxyphenol
91-10-1
Industrial,
-
-
-
2,6-Dimethylaniline
87-62-7
Industrial,
2B(1993)
-
cancer (1 -Jan-91)
2,6-dimethylnaphthalene
581-42-0
PAH
2,6-dimethylphenol
576-26-1
Industrial,
Oral RfD
Assessment: Yes
CLast revised: 09-
07-1988V
2,6-ditertbutyl-4-methoxyphenol
489-01-0
Industrial,
-
-
-
2,7-Dichlorodibenzo-p-dioxin
33857-26-0
Dioxins/Furans
-
-
-
2,8-Dichlorodibenzo-p-dioxin
38964-22-6
Dioxins/Furans,
-
-
-
2,8-Dichlorodibenzofuran
5409-83-6
Dioxins/Furans,
-
-
-
2-(1 -methylbutyl)phenol
87-26-3
Industrial,
-
-
-
2-(1 -naphthyl)acetamide
86-86-2
General Pesticide, PAH
-
-
-
2-(2-Butoxyethoxy)ethyl thiocyanate
112-56-1
Insecticide
-
-
-
2-(3-Chlorophenoxy)propionamide
5825-87-6
General Pesticide
-
-
-
2-(4-chlorophenyl)benzothiazole
6265-91-4
Industrial
-
-
-
2-(morpholinothio)benzothiazole
102-77-2
Industrial
-
-
-
2-(Octylthio)ethanol
3547-33-9
Insecticide
-
-
-
2-Amino-4-chlorophenol
95-85-2
Industrial,
-
-
-
2-amino-p-cresol
95-84-1
Industrial,
-
-
-
3-8
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
2-aminophenol
95-55-6
Industrial,
-
-
-
2-benzothiazolyl sulfide
4074-77-5
Industrial
-
-
-
2-bromo-4,6-dinitroaniline
1817-73-8
Industrial,
-
-
-
2-Bromoanisole
578-57-4
Industrial
-
-
-
2-bromophenol
95-56-7
Industrial,
-
-
-
2-chloro-4,6-dinitroaniline
3531 -19-9
Industrial,
-
-
-
2-chloro-4-nitroaniline
121-87-9
Industrial,
-
-
-
2-chloroaniline
95-51-2
Industrial,
-
-
-
2-Chlorodibenzo-p-dioxin
39227-54-8
Dioxins/Furans
-
-
-
2-chlorodibenzofuran
51230-49-0
Dioxins/Furans,
-
-
-
2-Chlorophenol
95-57-8
General Pesticide, Industrial,
Oral RfD
Assessment: Yes
(Last revised: 08-
22-1988V
2-Chlorophenyl-4-nitrophenyl ether
2303-23-3
Industrial, Halo Ethers
-
-
-
2-Chlorosyringaldehyde
76341-69-0
Industrial, Pulp/Paper
-
-
-
2-ethoxyphenol
94-71-3
Industrial,
-
-
-
2-Ethyl-1,3-hexanediol
94-96-2
Insecticide
-
-
-
2-ethyl-6-methylaniline
24549-06-2
Industrial,
-
-
-
2-ethylaniline
578-54-1
Industrial,
-
-
-
2-ethylnaphthalene
939-27-5
PAH
I"
2-ethylphenol
90-00-6
Industrial,
-
-
-
2-Hydroxyestradiol
362-05-0
Pharmacological
-
-
-
2-isopropylaniline
643-28-7
Industrial,
-
-
-
2-isopropylphenol
88-69-7
Industrial,
-
-
-
2-Mercaptobenzothiazole
149-30-4
Industrial
2
-
-
2-methoxy-4-methylphenol
93-51-6
Natural,
-
-
-
2-methyl-9,10-anthraquinone
84-54-8
OPAH
-
-
-
2-methylanthracene
613-12-7
PAH
-
-
-
2-methylnaphthalene
91-57-6
PAH, Industrial
-
Oral RfD
Assessment: Yes
-
(Last revised: 12-
22-2003).
Inhalation RfC
Assessment:
Discussion (Last
revised: 12-22-
2003).
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
22-2003)
2-methylphenanthrene
2531 -84-2
PAH
-
-
-
2-Methylphenol
95-48-7
Industrial,
Oral RfD
Assessment: Yes
(Last revised: 09-
07-1988V
Inhalation RfC
Assessment:
Messaae (Last
revised: 04-01-
1992V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
01-19901
2-Naphthylamine
91-59-8
PAH, Industrial
1(2012)
-
cancer (27-
Feb-87)
3-9
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
2-nitro-p-cresol
119-33-5
industrial,
-
-
-
2-Nitroaniline
88-74-4
Industrial,
-
-
-
2-Nitroanthracene
3586-69-4
PAH
-
-
-
2-Nitrobiphenyl
86-00-0
Fungicide
-
-
-
2-Nitrofluorene
607-57-8
PAH, Industrial
2B(2013)
-
cancer (1 -Oct-90)
2-Nitronaphthalene
581-89-5
PAH, Industrial
3(1989)
-
-
2-Nitrophenol
88-75-5
Industrial,
-
-
-
2-Nitropyrene
789-07-1
PAH
3(1989)
-
-
2-Phenoxypropionic acid
940-31-8
Pharmacological
-
-
-
2-propylphenol
644-35-9
Industrial,
-
-
-
2-sec-butylphenol
89-72-5
Industrial,
-
-
-
3,3'-Dimethoxy benzidine
119-90-4
Industrial
2B(1987)
-
cancer (1-Jan-88)
3,4,5-trichlorophenol
609-19-8
Industrial,
-
-
-
3,4,5-Trichlorophenyl-4-nitrophenyl
ether
Industrial, Halo Ethers
-
-
-
3,4,5-Trimethacarb
2686-99-9
Insecticide
-
-
-
3,4,6-Trichloroguaiacol
60712-44-9
Industrial, Pulp/Paper
-
-
-
3,4-Dichloroaniline
95-76-1
General Pesticide, Pharmacological,
Industrial,
-
-
-
3,4-Dichlorocatechol
3978-67-4
Industrial, Pulp/Paper
-
-
-
3,4-Dichloroguaiacol
77102-94-4
Industrial, Pulp/Paper
-
-
-
3,4-Dichlorophenyl-4-nitrophenyl
ether
22532-80-5
Industrial, Halo Ethers
-
-
-
3,4-dimethylaniline
95-64-7
Industrial,
-
-
-
3,4-dimethylphenol
95-65-8
Industrial,
Oral RfD
Assessment: Yes
(Last revised: 09-
07-1988V
3,5-Dibromoanisole
74137-36-3
Industrial
-
-
-
3,5-Dibromophenol
626-41 -5
Flame Retardant,
-
-
-
3,5-Dichloroaniline
626-43-7
General Pesticide, Pharmacological,
Industrial,
-
-
-
3,5-Dichlorophenyl-4-nitrophenyl
ether
21105-77-1
Industrial, Halo Ethers
-
-
-
3,5-dimethylaniline
108-69-0
Industrial,
-
-
-
3,5-dimethylphenol
108-68-9
Industrial,
-
-
-
3,6-dimethylphenanthrene
1576-67-6
PAH
-
-
-
3-(dimethylamino)phenol
99-07-0
Industrial,
-
-
-
3-Aminophenol
591-27-5
Personal Care, Industrial,
-
-
-
3-Bromoanisole
2398-37-0
Industrial
-
-
-
3-Bromophenol
591-20-8
Flame Retardant,
-
-
-
3-Bromostyrene
2039-86-3
Flame Retardant
-
-
-
3-Chloro-4-fluoroaniline
367-21-5
Industrial,
-
-
-
3-Chloro-4-methoxyaniline
5345-54-0
General Pesticide,
-
-
-
3-Chloroaniline
108-42-9
Industrial,
-
-
-
3-chlorophenol
108-43-0
Pharmacological, Industrial, Pulp/Paper,
-
-
-
3-Chlorophenyl-4-nitrophenyl ether
2303-23-3
Industrial, Halo Ethers
-
-
-
3-ethylphenol
620-17-7
Industrial,
-
-
-
3-hydroxybiphenyl
580-51-8
Industrial,
-
-
-
3-Hydroxycarbofuran
16655-82-6
Industrial
-
-
-
3-lndolylacetonitrile
771-51-7
General Pesticide
-
-
-
3-10
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
3-Methoxy-2,2',4,4',6-
pentabromodiphenyl ether
N/A
Flame Retardant, PBDE
-
-
-
3-methoxyphenol
150-19-6
Pharmacological, Industrial, Natural,
-
-
-
3-Nitroaniline
99-09-2
Industrial,
-
-
-
3-Nitrobenzanthrone
17117-34-9
PAH
2B(2014)
-
-
3-Nitrobiphenyl
2113-58-8
Industrial
-
-
-
3-nitrodibenzofuran
5410-97-9
Dioxins/Furans
-
-
-
3-Nitrofluoranthene
892-21-7
PAH
3(1987)
-
-
3-Nitrophenanthrene
17024-19-0
PAH
-
-
-
3-nitrophenol
554-84-7
Industrial,
-
-
-
3-tert-butylphenol
585-34-2
Industrial,
-
-
-
3-Trifluormethylaniline
98-16-8
Herbicide, Industrial,
-
-
-
4,4'-DDD
72-54-8
Insecticide,
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
cancer (1-Jan-89)
4,4'-DDE
72-55-9
Insecticide,
Carcinoaenicitv
Assessment: Yes
developmental,
male (30-Mar-10)
cancer (1-Jan-89)
(Last revised: 08-
22-19881
4,4'-DDT
50-29-3
Insecticide,
2
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
cancer (1 -Oct-87)
developmental,
female, male (15-
May-98)
4,4'-Dichlorobenzophenone
90-98-2
General Pesticide
-
-
-
4,4'-Methylenedianiline
101-77-9
Industrial,
2B(1987)
-
cancer (1-Jan-88)
4,4'-Oxydianiline
101-80-4
Industrial,
2B(1987)
-
cancer (1-Jan-88)
4,5-Dichloroguaiacol
2460-49-3
Industrial, Pulp/Paper
-
-
-
4,6-Dichloroguaiacol
16766-31-7
Industrial, Pulp/Paper
-
-
-
4,6-Dinitro-o-cresol (DNOC)
534-52-1
Fungicide, Herbicide, Insecticide, Industrial,
-
-
-
4-(2-benzothiazolyldithio)morpholine
95-32-9
Industrial
-
-
-
4-alpha-cumylphenol
599-64-4
Industrial,
-
-
-
4-amino-2,6-dichlorophenol
5930-28-9
Industrial,
-
-
-
4-Aminobiphenyl
92-67-1
Industrial
1(2012)
-
cancer (27-
Feb-87)
4-aminophenol
123-30-8
Industrial,
-
-
-
4-benzylphenol
101-53-1
Industrial,
-
-
-
4-Bromoaniline
106-40-1
Herbicide, Industrial,
-
-
-
4-Bromoanisole
104-92-7
Industrial
-
-
-
4-Bromophenol
106-41-2
Flame Retardant,
-
-
-
4-Bromostyrene
2039-82-9
Flame Retardant
-
-
-
4-butylphenol
1638-22-8
Industrial,
-
-
-
4-Chloro-2-methylaniline
95-69-2
General Pesticide, Industrial,
2A(2010)
-
cancer (1-Jan-90)
4-chloro-2-methylphenol
1570-64-5
Industrial,
-
-
-
4-chloro-2-nitroaniline
89-63-4
Industrial,
-
-
-
4-chloro-3,5-dimethylphenol
88-04-0
Industrial,
-
-
-
4-Chloro-3-methylphenol
59-50-7
Fungicide, Industrial,
-
-
-
4-Chloroaniline
106-47-8
Herbicide, Industrial,
2B(1993)
Oral RfD
Assessment: Yes
cancer (1 -Oct-94)
(Last revised: 08-
22-1988V
3-11
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
4-Chlorocatechol
2138-22-9
Industrial, Pulp/Paper
-
-
-
4-Chlorodibenzofuran
74992-96-4
Dioxins/Furans,
-
-
-
4-Chloroguaiacol
16766-30-6
Industrial, Pulp/Paper
-
-
-
4-Chlorophenol
106-48-9
Industrial, Pulp/Paper,
-
-
-
4-Chlorophenyl isocyanate
104-12-1
Herbicide, Industrial
-
-
-
4-Chlorophenyl phenyl ether
7005-72-3
Industrial, Halo Ethers
-
-
-
4-Chlorophenyl-4-nitrophenyl ether
1836-74-4
Industrial, Halo Ethers
-
-
-
4-ethoxyphenol
622-62-8
Industrial,
-
-
-
4-ethylphenol
123-07-9
Personal Care, Industrial,
-
-
-
4-hydroxy-3-chlorobiphenyl
92-04-6
Industrial,
-
-
-
4-hydroxybiphenyl
92-69-3
Industrial,
-
-
-
4-lsopropylaniline
99-88-7
Industrial,
-
-
-
4-isopropylphenol
99-89-8
Personal Care, Industrial,
-
-
-
4-methoxyphenol
150-76-5
Pharmacological, Industrial,
-
-
-
4-Methylphenol
106-44-5
Industrial,
Oral RfD
Assessment:
Withdrawn (Last
revised: 08-01-
19911, Inhalation
RfC Assessment:
Messaae CLast
revised: 04-01-
19921,
Carcinoaenicitv
Assessment: Yes
CLast revised: 09-
01-19901
4-n-octylphenol
1806-26-4
Industrial,
-
-
-
4-Nitroaniline
100-01-6
Industrial,
-
-
-
4-Nitrobiphenyl
92-93-3
Industrial
3(1987)
-
cancer (1 -Apr-88)
4-Nitrophenol
100-02-7
Fungicide, Industrial,
Inhalation RfC
Assessment:
Messaae CLast
revised: 10-01-
19911.
4-Nitrophenyl phenyl ether
620-88-2
Industrial, Halo Ethers
-
-
-
4-Nonylphenol
104-40-5
Fungicide, Industrial,
-
-
-
4-tert-butylphenol
98-54-4
Industrial,
-
-
-
4H-cyclopenta[def]phenanthren-4-
one
5737-13-3
OPAH, Industrial
-
-
-
5,12-Naphthacene-quinone
1090-13-7
OPAH
-
-
-
5,6-Dichlorovanillin
18268-69-4
Industrial, Pulp/Paper
-
-
-
5,7-Dihydroxy-4'-methoxyisoflavone
491-80-5
Pharmacological,
-
-
-
5-Chlorovanillin
19463-48-0
Industrial, Pulp/Paper
-
-
-
5-methylchrysene
3697-24-3
PAH,
2B(2010)
-
cancer (1 -Apr-88)
5-Nitroacenaphthene
602-87-9
PAH
2B(1987)
-
cancer (1 -Apr-88)
6-chloro-m-cresol
615-74-7
Industrial,
-
-
-
6-Chlorovanillin
18268-76-3
Industrial, Pulp/Paper
-
-
-
6-methylchrysene
1705-85-7
PAH
3(2010)
-
-
6-Nitrobenzo(a)pyrene
63041-90-7
PAH
3(1989)
-
-
6-Nitrochrysene
7496-02-8
PAH
2A(2014)
-
cancer (1 -Oct-90)
7,12-dimethylbenz[a]anthracene
57-97-6
PAH,
-
-
cancer (1-Jan-90)
7-Nitrobenz(a)anthracene
20268-51 -3
PAH
3(1989)
-
-
9,10-Anthraquinone
84-65-1
OPAH, Industrial
2B(2013)
-
cancer (28-
Sep-07)
3-12
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
9,10-dimethylanthracene
781-43-1
PAH
I" I"
9,10-Phenanthrenequinone
84-11 -7
Fungicide, OPAH, Industrial
L
9-Fluorenone
486-25-9
OPAH, Industrial
L
9-methylanthracene
779-02-2
PAH
L
9-Nitroanthracene
602-60-8
PAH
3(1987)
9-Nitrophenanthrene
954-46-1
PAH
L
a-lonone
127-41-3
Personal Care, Natural
r r
acenaphthene
83-32-9
PAH
3(2010)
Oral RfD
Assessment: Yes
(Last revised: 11-
01-1990V
Acenaphthenequinone
82-86-0
OPAH
-
-
-
acenaphthylene
208-96-8
PAH
Carcinoaenicitv
Assessment: Yes
(Last revised: 01-
01-19911
Acephate
30560-19-1
Insecticide,
-
-
-
Acequinocyl
57960-19-7
General Pesticide, OPAH
-
-
-
acetamiprid
135410-20-7
Insecticide
-
-
-
Acetochlor
34256-82-1
Herbicide, Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1993V
cancer (1-Jan-89)
Acifluorfen methyl ester
50594-67-7
Herbicide,
-
-
-
Aclonifen
74070-46-5
Herbicide
-
-
-
Acrinathrin
101007-06-1
Insecticide
-
-
-
Alachlor
15972-60-8
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1993V
cancer (1-Jan-89)
Aldrin
309-00-2
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
30-19871
cancer (1 -Jul-88)
Allidochlor
93-71-0
Herbicide
-
-
-
alpha, alpha-Dibromo-m-xylene
626-15-3
Flame Retardant, Industrial
-
-
-
alpha-BHC
319-84-6
Insecticide, Pharmacological,
Carcinoaenicitv
Assessment: Yes
(Last revised: 03-
31-19871
alpha-Chlordane
5103-71-9
Insecticide,
-
-
-
Ametryne
834-12-8
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 09-
30-19871.
Amidithion
919-76-6
Insecticide
-
-
-
Aminocarb
2032-59-9
Insecticide
-
-
-
Amitraz
33089-61 -1
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 08-
22-19881.
developmental
(30-Mar-99)
Amitraz metabolite
[Methanimidamide, N-(2,4-
dimethylphenyl)-N'-methyl-]
33089-74-6
Insecticide
amyl cinnamal
122-40-7
Personal Care
-
-
-
3-13
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
amylcinnamyl alcohol
101-85-9
Personal Care
-
-
-
Ancymidol
12771-68-5
General Pesticide
-
-
-
Anilazine
101-05-3
Fungicide
-
-
-
Aniline
62-53-3
Industrial,
3(1987)
Inhalation RfC
Assessment: Yes
(Last revised: 11-
01-1990V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
cancer (1-Jan-90)
Anilofos
64249-01 -0
Herbicide,
-
-
-
Anisyl alcohol
105-13-5
Personal Care, Natural
-
-
-
anthanthrene
191-26-4
PAH
3(2010)
-
-
anthracene
120-12-7
PAH,
3(2010)
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1990V
Carcinoaenicitv
Assessment: Yes
(Last revised: 01-
01-19911
Aramite
140-57-8
General Pesticide
2B(1987)
Carcinoaenicitv
Assessment: Yes
cancer (1 -Jul-87)
(Last revised: 06-
01-19911
Aramite II
999009-03-9
General Pesticide
-
-
-
Atraton
1610-17-9
Herbicide
-
-
-
Atrazine
1912-24-9
Herbicide, Pharmacological,
3(1999)
Oral RfD
Assessment: Yes
(Last revised: 10-
01-19931.
developmental,
female (15-Jul-16)
Atrazine-desethyl
6190-65-4
Herbicide,
-
-
developmental,
female (15-Jul-16)
Azaconazole
60207-31 -0
Fungicide
-
-
-
Azamethiphos
35575-96-3
Insecticide
-
-
-
Azibenzolar-S-methyl
135158-54-2
Fungicide
-
-
-
Azinphos-ethyl
2642-71-9
Insecticide
-
-
-
Azinphos-methyl
86-50-0
Insecticide, Pharmacological,
-
-
-
Aziprotryn metabolite [2-Amino-4-
isopropylamino-6-methylthio-1,3,5-
triazine]
4147-57-3
Pesticide Product
Aziprotryne
4658-28-0
Herbicide
-
-
-
Azobenzene
103-33-3
Fungicide, Insecticide, Industrial
3(1987)
Carcinoaenicitv
Assessment: Yes
cancer (1-Jan-90)
(Last revised: 09-
07-19881
Azoxybenzene
495-48-7
Insecticide, Industrial
-
-
-
Azoxystrobin
131860-33-8
Fungicide
-
-
-
b-citronellol
106-22-9
Personal Care, Natural
-
-
-
b-Estradiol
50-28-2
Pharmacological
-
-
cancer (1-Jan-88)
b-lonone
79-77-6
Personal Care, Natural
-
-
-
Barban
101-27-9
Herbicide
-
-
-
Beflubutamid
113614-08-7
Herbicide
-
-
-
Benalaxyl
71626-11-4
Fungicide
-
-
-
Benazolin-ethyl
25059-80-7
Herbicide
-
-
-
Bendiocarb
22781-23-3
Insecticide,
-
-
-
3-14
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Benfluralin
1861-40-1
Herbicide
-
-
-
Benfuracarb
82560-54-1
Insecticide
-
-
-
Benfuresate
68505-69-1
Herbicide
-
-
-
Benodanil
15310-01-7
Fungicide
-
-
-
Benoxacor
98730-04-2
Herbicide
-
-
-
Bentazone
25057-89-0
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 03-
02-1998V
Inhalation RfC
Assessment:
Messaae (Last
revised: 03-02-
19981.
Carcinoaenicitv
Assessment: Yes
(Last revised: 03-
02-19981
Bentazone methyl derivative
61592-45-8
Herbicide
-
-
-
Benthiocarb
28249-77-6
Herbicide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 09-
30-19871.
Benz(a)anthracene-7,12-dione
2498-66-0
OPAH
-
-
-
benz[a]anthracene
56-55-3
PAH,
2B(2010)
Inhalation RfC
Assessment: No
(Last revised: 09-
01-19941.
Carcinoaenicitv
Assessment: Yes
(Last revised: 03-
01-19941
cancer (1 -Jul-87)
benz[j]and[e]aceanthrylene
202-33-5 and
199-54-2
PAH
2B(2010)
-
-
Benzanthrone
82-05-3
OPAH, Industrial,
-
-
-
Benzenesuifonamide
98-10-2
Pharmacological
-
-
-
Benzidine
92-87-5
Industrial
1(2012)
Oral RfD
Assessment: Yes
(Last revised: 01-
01-19891.
Inhalation RfC
Assessment:
Messaae (Last
revised: 07-01-
19911.
Carcinoaenicitv
Assessment: Yes
cancer (27-
Feb-87)
(Last revised: 03-
31-19871
Benzo(a)fluoren-11 -one
479-79-8
OPAH
-
-
-
Benzo(a)pyrene-7,8-dione
65199-11-3
OPAH
-
-
-
Benzo(c)phenanthrene(1,4)quinone
109699-80-1
OPAH
-
-
-
benzo[a]chrysene
213-46-7
PAH,
3(2010)
-
-
benzo[a]fiuorene
238-84-6
PAH
3(2010)
-
-
3-15
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
benzo[a]pyrene
50-32-8
PAH,
1(2012)
Oral RfD
Assessment: Yes
cancer (1 -Jul-87)
(Last revised: 01-
19-20171.
Inhalation RfC
Assessment: Yes
(Last revised: 01-
19-20171.
Carcinoaenicitv
Assessment: Yes
(Last revised: 01-
19-2017)
benzo[b]fluoranthene
205-99-2
PAH,
2B(2010)
Carcinoaenicitv
Assessment: Yes
cancer (1-Jul-87)
(Last revised: 03-
01-19941
benzo[b]fluorene
243-17-4
PAH,
3(2010)
-
-
benzo[b]perylene
197-70-6
PAH
-
-
-
benzo[c]fluorene
205-12-9
PAH
3(2010)
-
-
benzo[e]pyrene
192-97-2
PAH,
3(2010)
-
-
benzo[ghi]perylene
191-24-2
PAH
3(2010)
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
01-19901
benzo[j]fluoranthene
205-82-3
PAH,
2B(2010)
-
cancer (1-Jul-87)
benzo[k]fluoranthene
207-08-9
PAH,
2B(2010)
Carcinoaenicitv
Assessment: Yes
(Last revised: 03-
01-19941
cancer (1-Jul-87)
Benzophenone
119-61-9
Personal Care, Industrial,
2B(2013)
-
cancer (22-Jun-12)
Benzothiazole
95-16-9
Industrial
-
-
-
benzotriazole
95-14-7
Industrial
-
-
-
Benzoximate metabolite
55440-55-6
General Pesticide
-
-
-
Benzoylprop ethyl
22212-55-1
Herbicide
-
-
-
Benzyl alcohol
100-51-6
Pharmacological, Personal Care, Industrial,
Natural
-
-
-
Benzyl benzoate
120-51-4
Insecticide
-
-
-
Benzyl cinnamate
103-41-3
Personal Care, Natural
-
-
-
benzyl salicylate
118-58-1
Personal Care, Natural
-
-
-
beta-BHC
319-85-7
Insecticide,
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
30-19871
BHC epsilon isomer
6108-10-7
Insecticide
-
Carcinoaenicitv
Assessment: Yes
-
(Last revised: 03-
31-19871
Bifenazate metabolite (5-Phenyl-o-
anisidine )
39811-17-1
General Pesticide
-
-
-
Bifenox
42576-02-3
Herbicide,
-
-
-
Bifenthrin
82657-04-3
Insecticide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 08-
22-19881,
Bifenthrin
82657-04-3
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 08-
22-19881.
3-16
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Bifenthrin
82657-04-3
Insecticide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 08-
22-1988V
Binapacryl
485-31-4
Fungicide
-
-
-
Bioallethrin
584-79-2
Insecticide
-
-
-
Bioallethrin S-cyclopentenyl isomer
28434-00-6
Insecticide
-
-
-
Bioresmethrin
28434-01 -7
Insecticide
-
-
-
Biphenyl
92-52-4
Fungicide, Industrial,
-
Oral RfD
Assessment: Yes
-
(Last revised: 08-
27-20131,
Inhalation RfC
Assessment:
Discussion (Last
revised: 08-27-
20131.
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
27-20131
Bis(2,3,3,3-tetrachloropropyl) ether
127-90-2
Insecticide
-
-
-
Bis(2-butoxyethyl) phthalate
117-83-9
Industrial
-
-
-
Bis(2-ethylhexyl)phthalate
117-81-7
Insecticide, Industrial,
2B(2013)
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
cancer (1-Jan-88)
developmental,
male (24-Oct-03)
Bisphenol A
80-05-7
Industrial,
Oral RfD
Assessment: Yes
(Last revised: 09-
26-19881.
female (11-
May-15)
bisphenol B
77-40-7
Industrial,
-
-
-
bisphenol E
2081 -08-5
Industrial,
-
-
-
bisphenol Z
843-55-0
Industrial,
-
-
-
bisphenol AF
1478-61-1
Industrial,
-
-
-
Bitertanol I
55179-31-2
Fungicide,
-
-
-
Bitertanol II
999027-03-1
Fungicide
-
-
-
Boscalid (Nicobifen)
188425-85-6
Fungicide
-
-
-
Bromacil
314-40-9
Herbicide,
-
-
-
Bromfenvinphos-(E)
58580-14-6
Insecticide
-
-
-
Bromfenvinphos-(Z)
58580-13-5
Insecticide
-
-
-
Bromobutide
74712-19-9
Herbicide
-
-
-
Bromocyclen
1715-40-8
Insecticide
-
-
-
Bromophos
2104-96-3
Insecticide,
-
-
-
Bromophos-ethyl
4824-78-6
Insecticide,
-
-
-
Bromopropylate
18181-80-1
General Pesticide,
-
-
-
Bromoxynil
1689-84-5
Herbicide,
-
-
developmental (1-
Oct-90)
Bromoxynil octanoic acid ester
1689-99-2
Herbicide
-
-
developmental
(18-May-99)
Bromuconazole I
116255-48-2
Fungicide
-
-
-
Bromuconazole II
999010-03-6
Fungicide
-
-
-
Bufencarb
8065-36-9
Insecticide
-
-
-
Bupirimate
41483-43-6
Fungicide,
-
-
-
3-17
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Buprofezin
69327-76-0
Insecticide
-
-
-
Butachlor
23184-66-9
Herbicide,
-
-
-
Butafenacil
134605-64-4
Herbicide
-
-
-
Butamifos
36335-67-8
Herbicide,
-
-
-
Butoxycarboxim
34681-23-7
Insecticide
-
-
-
Butralin
33629-47-9
Herbicide
-
-
-
Butyl benzyl phthalate
85-68-7
Industrial,
3(1999)
Oral RfD
Assessment: Yes
developmental (2-
Dec-05)
(Last revised: 09-
01-19891,
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
Butylate
2008-41-5
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 10-
01-19941.
Butylated hydroxyanisole
25013-16-5
Pharmacological, Personal Care,
2B(1987)
-
cancer (1-Jan-90)
butylated hydroxytoluene
128-37-0
Industrial,
3(1987)
-
-
Cadusafos
95465-99-9
Insecticide
-
-
-
Cafenstrole
125306-83-4
Herbicide
-
-
-
Caffeine
58-08-2
Pharmacological,
3(1991)
-
-
Captafol
2425-06-1
Fungicide
2A(1991)
Oral RfD
Assessment: Yes
(Last revised: 09-
30-19871.
cancer (1 -Oct-88)
Captan
133-06-2
Fungicide,
3(1987)
Oral RfD
Assessment: Yes
(Last revised: 03-
01-19891.
cancer (1-Jan-90)
Carbaryl
63-25-2
Insecticide, PAH,
3(1987)
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
Inhalation RfC
Assessment:
Messaae (Last
revised: 11-01-
19911.
cancer (5-Feb-10)
developmental,
female, male (7-
Aug-09)
Carbazole
86-74-8
Industrial
2B(2013)
-
cancer (1 -May-96)
Carbetamide
16118-49-3
Herbicide
-
-
-
Carbofuran
1563-66-2
Insecticide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 09-
30-19871.
Carbofuran-3-keto
16709-30-1
General Pesticide
-
-
-
Carbofuran-7-phenol
1563-38-8
Pesticide Product,
-
-
-
Carbophenothion
786-19-6
Insecticide
-
-
-
Carbosulfan
55285-14-8
Insecticide
-
Oral RfD
Assessment: Yes
-
(Last revised: 01-
31-19871.
Carboxin
5234-68-4
Fungicide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
Carfentrazone-ethyl
128639-02-1
Herbicide
-
-
-
Carpropamid
104030-54-8
Fungicide
-
-
-
Carvone
99-49-0
Fungicide, Personal Care
-
-
-
3-18
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Cashmeran
33704-61 -9
Personal Care,
-
-
-
Cekafix
121227-99-4
Fungicide, Insecticide
-
-
-
Celestolide
13171-00-1
PAH, Personal Care,
-
-
-
Chinomethionat
2439-01-2
Fungicide
cancer (20-
Aug-99)
developmental (6-
Nov-98)
Chloramben methyl ester
7286-84-2
Herbicide
-
-
-
Chloranocryl
2164-09-2
Herbicide
-
-
-
Chlorbenside
103-17-3
General Pesticide
-
-
-
Chlorbenside sulfone
7082-99-7
General Pesticide
-
-
-
Chlorbicyclen
2550-75-6
Insecticide
-
-
-
Chlorbromuron
13360-45-7
Herbicide
-
-
-
Chlorbufam
1967-16-4
Herbicide
-
-
-
Chlordene, trans-
3734-48-3
Insecticide, Industrial
-
-
-
Chlordimeform
6164-98-3
Insecticide,
3(1987)
-
cancer (1-Jan-89)
Chlorethoxyfos
54593-83-8
Insecticide
-
-
-
Chlorfenapyr
122453-73-0
Insecticide
-
-
-
Chlorfenethol
80-06-8
General Pesticide
-
-
-
Chlorfenprop-methyl
14437-17-3
Herbicide
-
-
-
Chlorfenson
80-33-1
Fungicide, Insecticide
-
-
-
Chlorfenvinphos
470-90-6
Insecticide,
-
-
-
Chlorfenvinphos, cis-
18708-87-7
Insecticide
-
-
-
Chlorfenvinphos, trans-
18708-86-6
Insecticide
-
-
-
Chlorflurecol-methyl ester
2536-31-4
Herbicide, PAH
-
-
-
Chlormefos
24934-91 -6
Insecticide
-
-
-
Chlornitrofen
1836-77-7
Herbicide,
-
-
-
Chlorobenzilate
510-15-6
General Pesticide,
3(1987)
Oral RfD
Assessment: Yes
cancer (1-Jan-90)
(Last revised: 12-
01-1989V
Chloroneb
2675-77-6
Fungicide
-
-
-
Chloropropylate
5836-10-2
General Pesticide,
-
-
-
Chlorothalonil
1897-45-6
General Pesticide, Fungicide, Insecticide,
2B(1999)
Oral RfD
Assessment: Yes
(Last revised: 03-
01-1988V
cancer (1-Jan-89)
Chlorotoluron
15545-48-9
Herbicide
-
-
-
Chlorpropham
101-21-3
Herbicide,
3(1987)
-
-
Chlorpyrifos
2921 -88-2
Insecticide, Pharmacological,
Oral RfD
Assessment: No
(Last revised: 03-
01-1988V
Chlorpyrifos Methyl
5598-13-0
Insecticide,
-
-
-
Chlorthiamid
1918-13-4
Herbicide
-
-
-
Chlorthion
500-28-7
Insecticide
-
-
-
Chlorthiophos
60238-56-4
Insecticide
-
-
-
Chlorthiophos sulfone
999053-03-1
General Pesticide
-
-
-
Chlorthiophos sulfoxide
29185-21-5
Pesticide Product
-
-
-
Chlozolinate
84332-86-5
Fungicide
-
-
-
chrysene
218-01-9
PAH,
2B(2010)
Carcinoaenicitv
Assessment: Yes
cancer (1-Jan-90)
(Last revised: 12-
01-19901
3-19
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Cinerin 1
25402-06-6
Insecticide
-
-
-
Cinerin II
121-20-0
Insecticide
-
-
-
Cinidon-ethyl
142891-20-1
Herbicide
-
-
-
cinnamal
104-55-2
Fungicide, Personal Care, Industrial,
Natural
-
-
-
cinnamyl alcohol
104-54-1
Personal Care, Natural
-
-
-
cis-Nonachlor
5103-73-1
Insecticide,
-
-
-
Citral A
5392-40-5
Personal Care, Natural
-
-
-
Citral B
5392-40-5
Personal Care, Natural
-
-
-
Clodinafop-propargyl
105512-06-9
Herbicide
-
-
-
Clomazone
81777-89-1
Herbicide
-
-
-
Cloquintocet-mexyl
99607-70-2
Herbicide
-
-
-
coronene
191-07-1
PAH
3(1987)
-
-
Coumaphos
56-72-4
Insecticide
-
-
-
Coumarin
91-64-5
Personal Care, Natural
3(2000)
-
-
Crimidine
535-89-7
Rodenticide
-
-
-
Crotoxyphos
7700-17-6
Insecticide
-
-
-
Crufomate
299-86-5
Insecticide
-
-
-
Cyanazine
21725-46-2
Herbicide,
Oral RfD
Assessment:
developmental (1-
Apr-90)
Withdrawn (Last
revised: 07-01-
19921.
Cyanofenphos
13067-93-1
Insecticide,
-
-
-
Cyanophos
2636-26-2
Insecticide,
-
-
-
Cyclafuramid
34849-42-8
Fungicide
-
-
-
Cycloate
1134-23-2
Herbicide
-
-
developmental
(19-Mar-99)
cyclopenta[cd]pyrene
27208-37-3
PAH,
2A(2010)
-
cancer (29-Apr-11)
Cyclopentadecanone
502-72-7
Personal Care
-
-
-
Cycluron
2163-69-1
Herbicide
-
-
-
Cyflufenamid
180409-60-3
Fungicide
-
-
-
Cyfluthrin 1
68359-37-5
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 03-
01-19881,
Cyfluthrin II
999028-03-4
Insecticide
-
-
-
Cyfluthrin III
999029-03-7
Insecticide
-
-
-
Cyfluthrin IV
999030-03-4
Insecticide
-
-
-
Cyhalofop-butyl
122008-85-9
Herbicide
-
-
-
Cyhalothrin (Gamma)
76703-62-3
Insecticide
-
-
-
Cyhalothrin 1 (lambda)
68085-85-8
Fungicide, Insecticide,
-
-
-
Cymiazole
61676-87-7
General Pesticide
-
-
-
Cymoxanil
57966-95-7
Fungicide
-
-
-
Cypermethrin-1
52315-07-8
Insecticide,
-
-
-
Cypermethrin-2
52315-07-8
Insecticide,
-
-
-
Cypermethrin-3
52315-07-8
Insecticide,
-
-
-
Cypermethrin-4
52315-07-8
Insecticide,
-
-
-
Cyphenothrin cis-
39515-40-7
Insecticide
-
-
-
Cyphenothrin trans-
999011-03-9
Insecticide
-
-
-
Cyprazine
22936-86-3
Herbicide
-
-
-
3-20
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
| EPA IRIS"
Cal/EPA***
Cyproconazole
113096-99-4
Insecticide
|- |-
Cyprodinil
121552-61-2
Fungicide,
|- |-
Cyprofuram
69581-33-5
Fungicide
|- |-
Cyromazine
66215-27-8
Insecticide
|- |-
d-(cis-trans)-Phenothrin-l
26002-80-2
Insecticide,
|- |-
d-(cis-trans)-Phenothrin-ll
999034-03-6
Insecticide
|- |-
d-Limonene
5989-27-5
Personal Care, Natural
3(1999)
Inhalation RfC
Assessment:
Discussion (Last
revised: 12-01-
19931.
Dacthal
1861-32-1
Herbicide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 08-
01-1994V
Dazomet
533-74-4
Fungicide, Herbicide, Insecticide, Industrial
|-
-
DDMU [1-Chloro-2,2-bis(4'-
chlorophenyl)ethylene]
1022-22-6
General Pesticide
-
-
delta-BHC
319-86-8
Insecticide,
-
Carcinoaenicitv
Assessment: Yes
-
(Last revised: 03-
31-19871
Deltamethrin
52918-63-5
Insecticide,
3(1991)
-
Demephion
8065-62-1
General Pesticide
|-
-
Demeton-s
126-75-0
Insecticide
|-
-
Demeton-S-methyl
919-86-8
Insecticide
|-
-
Demeton-S-methylsulfon
17040-19-6
Insecticide
|-
-
Desbromo-bromobutide
999055-03-7
Herbicide
|-
-
Desmedipham
13684-56-5
Herbicide
|-
-
Desmetryn
1014-69-3
Herbicide
|-
-
Di-n-butyl phthalate
84-74-2
Insecticide, Personal Care, Industrial,
-
Oral RfD
Assessment: Yes
developmental,
female, male (2-
(Last revised: 01-
31-19871.
Inhalation RfC
Assessment:
Messaae (Last
revised: 10-01-
19901.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
Dec-05)
Di-n-hexyl phthalate
84-75-3
Industrial,
-
female, male (2-
Dec-05)
Di-n-nonyl phthalate
84-76-4
Industrial
|-
-
Di-n-octyl phthalate
117-84-0
Industrial,
|-
-
Di-n-propyl phthalate
131-16-8
Pharmacological, Industrial,
|-
-
Dialifos
10311-84-9
Insecticide
|-
-
Diallate I
2303-16-4
Herbicide
3(1987)
-
Diallate II
999035-03-9
Herbicide
|-
-
Diamyl phthalate
131-18-0
Industrial,
|-
-
Diazinon
333-41 -5
Insecticide, Pharmacological,
2
-
Diazinon-oxon
962-58-3
General Pesticide
|-
-
Dibenzo-p-dioxin
262-12-4
Dioxins/Furans
3(1997)
-
dibenzo[a,e]fluoranthene
5385-75-1
PAH,
3(2010)
-
dibenzo[a,e]pyrene
192-65-4
PAH,
3(2010)
cancer (1-Jan-88)
3-21
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
dibenzo[a,h]anthracene
53-70-3
PAH,
2A(2010)
Carcinoaenicitv
Assessment: Yes
cancer (1-Jan-88)
(Last revised: 12-
01-19901
dibenzo[a,h]pyrene
189-64-0
PAH,
2B(2010)
-
cancer (1-Jan-88)
dibenzo[a,i]pyrene
189-55-9
PAH,
2B(2010)
-
cancer (1-Jan-88)
dibenzo[a,l]pyrene
191-30-0
PAH,
2A(2010)
-
cancer (1-Jan-88)
dibenzo[e,l]pyrene
192-51-8
PAH
3(2010)
-
-
Dibenzofuran
132-64-9
Dioxins/Furans
-
Carcinoaenicitv
Assessment: Yes
-
(Last revised: 10-
01-19901
dibenzothiophene
132-65-0
PAH, Pharmacological, Personal Care,
Industrial,
3(2013)
-
-
Dicamba
1918-00-9
Herbicide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 08-
22-19881.
Dicamba methyl ester
6597-78-0
Pharmacological
-
-
-
Dicapthon
2463-84-5
Insecticide
-
-
-
Dichlofenthion
97-17-6
Insecticide,
-
-
-
Dichlofluanid
1085-98-9
Fungicide
-
-
-
Dichlofluanid metabolite (DMSA)
4710-17-2
Pharmacological
-
-
-
Dichlone
117-80-6
Fungicide, Herbicide, OPAH,
-
-
-
Dichloran
99-30-9
Fungicide, Industrial
-
-
-
Dichlormid
37764-25-3
Herbicide, Insecticide
-
-
-
Dichlorophen
97-23-4
Fungicide, Pharmacological,
-
-
developmental
(27-Apr-99)
Dichlorprop
120-36-5
Herbicide,
-
-
-
Dichlorprop methyl ester
57153-17-0
General Pesticide
-
-
-
Dichlorvos
62-73-7
Insecticide,
2B(1991)
Oral RfD
Assessment: Yes
(Last revised: 11-
01-19931.
Inhalation RfC
Assessment: Yes
(Last revised: 06-
01-19941.
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19891
cancer (1-Jan-89)
Diclobutrazol
75736-33-3
Fungicide,
-
-
-
Diclocymet 1
139920-32-4
Fungicide
-
-
-
Diclocymet II
999059-03-9
Fungicide
-
-
-
Diclofop methyl
51338-27-3
Herbicide,
developmental (5-
Mar-99)
cancer (6-Apr-10)
Dicrotophos
141-66-2
Insecticide
-
-
-
Dicyclohexyl phthalate
84-61-7
Industrial,
-
-
-
Dicyclopentadiene
77-73-6
PAH, Industrial
-
-
-
Dieldrin
60-57-1
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 09-
07-19881.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
cancer (1 -Jul-88)
3-22
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Diethatyl ethyl
38727-55-8
Herbicide
-
-
-
Diethofencarb
87130-20-9
Fungicide,
-
-
-
Diethyl dithiobis(thionoformate)
(EXD)
502-55-6
Herbicide
-
-
-
Diethyl phthalate
84-66-2
Insecticide, Industrial,
Oral RfD
Assessment: Yes
(Last revised: 09-
30-1987V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
Diethylene glycol
111-46-6
Industrial
-
-
-
Diethylstilbestrol
56-53-1
Pharmacological
1(2012)
cancer (27-
Feb-87)
developmental (1-
Jul-87)
Difenoconazol 1
119446-68-3
Fungicide,
-
-
-
Difenoconazol II
999036-03-2
Fungicide
-
-
-
Difenoxuron
14214-32-5
Herbicide
-
-
-
Diflufenican
83164-33-4
Herbicide
-
-
-
Diisobutyl phthalate
84-69-5
Industrial,
-
-
-
Dimefox
115-26-4
Insecticide
-
-
-
Dimepiperate
61432-55-1
Herbicide
-
-
-
Dimethachlor
50563-36-5
Herbicide
-
-
-
Dimethametryn
22936-75-0
Herbicide
-
-
-
Dimethenamid
87674-68-8
Herbicide
-
-
-
Dimethipin
55290-64-7
General Pesticide
-
-
-
Dimethoate
60-51-5
Insecticide, Pharmacological,
-
-
-
Dimethomorph-(E)
110488-70-5
Fungicide,
-
-
-
Dimethomorph-(Z)
999012-03-2
Fungicide
-
-
-
Dimethyl phthalate
131-11-3
Insecticide, Industrial
Inhalation RfC
Assessment:
Messaae (Last
revised: 09-01-
19901.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
Dimethylvinphos(E)
71363-52-5
Insecticide
-
-
-
Dimethylvinphos(Z)
67628-93-7
Insecticide
-
-
-
Dimetilan
644-64-4
Insecticide
-
-
-
Dimoxystrobin
149961-52-4
Fungicide
-
-
-
Diniconazole
83657-24-3
Fungicide
-
-
-
Dinitramine
29091-05-2
Herbicide
-
-
-
Dinobuton
973-21-7
Fungicide
-
-
-
Dinocap
39300-45-3
Fungicide,
-
-
developmental (1-
Apr-90)
Dinocap II
999037-03-5
Fungicide
-
-
-
Dinocap III
999038-03-8
Fungicide
-
-
-
Dinocap IV
999039-03-1
Fungicide
-
-
-
3-23
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Dinoseb
88-85-7
Fungicide, Herbicide, Insecticide,
Oral RfD
Assessment: Yes
developmental,
male (1-Jan-89)
(Last revised: 01-
31-1987V
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
01-19891
Dinoseb acetate
2813-95-8
Herbicide
-
-
-
Dinoseb methyl ether
6099-79-2
General Pesticide
-
-
-
Dinoterb
1420-07-1
Herbicide
-
-
-
Dinoterb acetate
3204-27-1
Herbicide, Insecticide
-
-
-
Diofenolan 1
63837-33-2
Insecticide
-
-
-
Diofenolan II
999013-03-5
Insecticide
-
-
-
Dioxabenzofos
3811-49-2
Insecticide
-
-
-
Dioxacarb
6988-21-2
Insecticide
-
-
-
Dioxathion
78-34-2
Insecticide
-
-
-
Diphacinone
82-66-6
Rodenticide, PAH
-
-
-
Diphenamid
957-51-7
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 09-
30-1987V
Diphenyl phthalate
84-62-8
General Pesticide, Industrial,
-
-
-
Diphenylamine
122-39-4
Fungicide
-
-
-
Dipropetryn
4147-51-7
Herbicide
-
-
-
Dipropyl isocinchomeronate
136-45-8
Insecticide
-
-
cancer (1 -May-96)
Disulfoton
298-04-4
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Disulfoton sulfone
2497-06-5
Insecticide
-
-
-
Ditalimfos
5131 -24-8
Fungicide
-
-
-
Dithiopyr
97886-45-8
Herbicide
-
-
-
Diuron
330-54-1
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 08-
22-1988V
cancer(31-
May-02)
Diuron Metabolite [3,4-
Dichlorophenyl isocyanate]
102-36-3
Industrial
-
-
-
Dodemorph 1
1593-77-7
Fungicide,
-
-
-
Dodemorph II
999040-03-8
Fungicide
-
-
-
Drazoxolon
5707-69-7
Fungicide
-
-
-
drometrizole
2440-22-4
Industrial
-
-
-
Edifenphos
17109-49-8
Fungicide
-
-
-
Empenthrin 1
54406-48-3
Insecticide
-
-
-
Empenthrin II
999014-03-8
Insecticide
-
-
-
Empenthrin III
999015-03-1
Insecticide
-
-
-
Empenthrin IV
999016-03-4
Insecticide
-
-
-
Empenthrin V
999017-03-7
Insecticide
-
-
-
Endosulfan ether
3369-52-6
General Pesticide
-
-
-
Endosulfan 1
959-98-8
Insecticide,
-
-
-
Endosulfan II
33213-65-9
Insecticide,
-
-
-
Endosulfan lactone
3868-61-9
General Pesticide
-
-
-
Endosulfan sulfate
1031-07-8
Insecticide,
-
-
-
3-24
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Endrin
72-20-8
Fungicide, Insecticide, Rodenticide,
3(1987)
Oral RfD
Assessment: Yes
developmental
(15-May-98)
(Last revised: 09-
07-1988V
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19891
Endrin aldehyde
7421 -93-4
Fungicide, Insecticide, Rodenticide
-
-
-
Endrin ketone
53494-70-5
General Pesticide
-
-
-
EPN
2104-64-5
Insecticide, Pharmacological,
Oral RfD
Assessment: Yes
(Last revised: 09-
30-1987V
Epoxiconazole
106325-08-0
General Pesticide,
-
-
cancer (15-Apr-11)
EPTC
759-94-4
Herbicide,
-
-
developmental
(27-Apr-99)
Erbon
136-25-4
Herbicide
-
-
-
Esfenvalerate
66230-04-4
Insecticide,
-
-
-
Esprocarb
85785-20-2
Herbicide
-
-
-
Etaconazole
60207-93-4
Fungicide
-
-
-
Ethalfluralin
55283-68-6
Herbicide
-
-
-
Ethidimuron
30043-49-3
Herbicide
-
-
-
Ethiofencarb
29973-13-5
Insecticide
-
-
-
Ethiolate
2941 -55-1
Herbicide
-
-
-
Ethion
563-12-2
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1989V
Ethofenprox
80844-07-1
Insecticide,
-
-
-
Ethofumesate
26225-79-6
Herbicide
-
-
-
Ethofumesate, 2-Keto
26244-33-7
General Pesticide
-
-
-
Ethoprophos
13194-48-4
Insecticide
-
-
cancer (27-
Feb-01)
Ethoxyfen-ethyl
131086-42-5
Herbicide
-
-
-
Ethoxyquin
91-53-2
Fungicide,
-
-
-
Ethylene brassylate
105-95-3
Personal Care
-
-
-
Ethylenethiourea
96-45-7
Fungicide, Industrial,
3(2001)
Oral RfD
Assessment: Yes
cancer (1-Jan-88)
developmental (1-
Jan-93)
(Last revised: 05-
01-1991V
Etoxazole
153233-91-1
General Pesticide
-
-
-
Etridiazole, deschloro- (5-ethoxy-3-
dichloromethyl-1,2,4-thiadiazole)
999001 -03-5
Pesticide Product
-
-
-
Etrimfos
38260-54-7
Insecticide
-
-
-
Eugenol
97-53-0
Insecticide, Pharmacological, Personal
Care, Industrial
3(1987)
-
-
Exaltolide [15-Pentadecanolide]
106-02-5
Personal Care
-
-
-
Famoxadon
131807-57-3
Fungicide
-
-
-
Famphur
52-85-7
Fungicide, Insecticide
-
-
-
Farnesol I
4602-84-0
Personal Care, Natural
-
-
-
Farnesol II
4602-84-0
Personal Care, Natural
-
-
-
Farnesol III
4602-84-0
Personal Care, Natural
-
-
-
Farnesol IV
4602-84-0
Personal Care, Natural
-
-
-
Fenamidone
161326-34-7
Fungicide
-
-
-
3-25
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Fenamiphos
22224-92-6
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 09-
30-1987V
Fenamiphos sulfoxide
31972-43-7
General Pesticide
-
-
-
Fenamiphos-sulfone
31972-44-8
General Pesticide
-
-
-
Fenarimol
60168-88-9
Fungicide, Industrial,
-
-
-
Fenazaflor
14255-88-0
Insecticide
-
-
-
Fenazaflor metabolite
4228-88-0
Insecticide
-
-
-
Fenazaquin
120928-09-8
General Pesticide
-
-
-
Fenbuconazole
119611-00-6
Fungicide
-
-
-
Fenchlorazole-ethyl
103112-35-2
Herbicide
-
-
-
Fenchlorphos
299-84-3
Insecticide,
-
-
-
Fenchlorphos-oxon
3983-45-7
Pesticide Product
-
-
-
Fenclorim
3740-92-9
Herbicide
-
-
-
Fenfuram
24691-80-3
Fungicide
-
-
-
Fenhexamid
126833-17-8
Fungicide,
-
-
-
Fenitrothion
122-14-5
Insecticide,
-
-
-
Fenitrothion-oxon
2255-17-6
Insecticide
-
-
-
Fenobucarb
3766-81-2
Insecticide
-
-
-
Fenoprop
93-72-1
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 09-
07-1988V
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
Fenoprop methyl ester
4841 -20-7
Herbicide
-
-
-
Fenothiocarb
62850-32-2
General Pesticide
-
-
-
Fenoxanil
115852-48-7
Fungicide
-
-
-
Fenoxaprop-ethyl
66441-23-4
Herbicide
-
-
developmental
(26-Mar-99)
Fenoxycarb
79127-80-3
Insecticide,
-
-
cancer (2-Jun-00)
Fenpiclonil
74738-17-3
Fungicide
-
-
-
Fenpropathrin
64257-84-7
Insecticide
-
-
-
Fenpropidin
67306-00-7
Fungicide
-
-
-
Fenson
80-38-6
General Pesticide
-
-
-
Fensulfothion
115-90-2
Insecticide
-
-
-
Fensulfothion-oxon
6552-21-2
Insecticide
-
-
-
Fensulfothion-oxon -sulfone
6132-17-8
Insecticide
-
-
-
fensulfothion-sulfone
14255-72-2
Insecticide
-
-
-
Fenthion
55-38-9
Insecticide,
-
-
-
Fenthion sulfoxide
3761-41-9
Insecticide
-
-
-
Fenthion-sulfone
3761 -42-0
Insecticide
-
-
-
Fenuron
101-42-8
Herbicide
-
-
-
Fenvalerate
51630-58-1
Insecticide,
3(1991)
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Fenvalerate II
999041 -03-1
Insecticide
-
-
-
Fepropimorph
67564-91 -4
Fungicide
-
-
-
Fipronil
120068-37-3
Insecticide, Pharmacological,
-
-
-
3-26
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS" |Cal/EPA***
Fipronil, Desulfinyl-
205650-65-3
General Pesticide
-
|- ~
Fipronil-sulfide
120067-83-6
Insecticide
-
|- ~
Fipronil-sulfone
120068-36-2
Insecticide
-
|- ~
Flamprop-isopropyl
52756-22-6
Herbicide
-
|- ~
Flamprop-methyl
52756-25-9
Herbicide
-
|- ~
Fluacrypyrim
229977-93-9
General Pesticide
-
|- ~
Fluazifop-p-butyl
79241-46-6
Herbicide
-
|- ~
Fluazinam
79622-59-6
Fungicide
-
|- ~
Fluazolate
174514-07-9
Herbicide
-
|- ~
Flubenzimine
37893-02-0
Fungicide
-
|- ~
Fluchloralin
33245-39-5
Herbicide
-
|- ~
Flucythrinate 1
70124-77-5
Insecticide,
-
|- ~
Flucythrinate II
999042-03-4
Insecticide
-
|- ~
Fludioxonil
131341 -86-1
Fungicide,
-
|- ~
Flufenacet
142459-58-3
Herbicide,
-
|- ~
Flumetralin
62924-70-3
Herbicide
-
|- ~
Flumiclorac-pentyl
87546-18-7
Herbicide
-
|- ~
Flumioxazin
103361-09-7
Herbicide
-
|- ~
Fluometuron
2164-17-2
Herbicide
3(1987)
Oral RfD
Assessment: Yes
(Last revised: 09-
30-1987V
fluoranthene
206-44-0
PAH, Pharmacological,
3(2010)
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1990V
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
01-19901
fluorene
86-73-7
PAH,
3(2010)
Oral RfD
Assessment: Yes
(Last revised: 11-
01-1990V
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
01-19901
Fluorodifen
15457-05-3
Herbicide
-
|- ~
Fluoroglycofen-ethyl
77501-90-7
Herbicide
-
|- ~
Fluoroimide
41205-21 -4
Fungicide
-
|- ~
Fluotrimazole
31251-03-3
Fungicide
-
|- ~
Fluoxastrobin cis-
361377-29-9
Fungicide, Herbicide
-
|- ~
Fluquinconazole
136426-54-5
Fungicide
-
|- ~
Flurenol-butyl ester
2314-09-2
Herbicide
-
|- ~
Flurenol-methylester
1216-44-0
General Pesticide
-
|- ~
Fluridone
59756-60-4
Herbicide
-
Oral RfD
Assessment: Yes
(Last revised: 08-
22-19881,
Flurochloridone 1
61213-25-0
Herbicide
-
|- ~
Flurochloridone II
999043-03-7
Herbicide
-
|- ~
Flurochloridone, deschloro-
999003-03-1
Pesticide Product
-
|- ~
Fluroxypyr-1-methylheptyl ester
81406-37-3
Herbicide
-
|- ~
Flurprimidol
56425-91 -3
General Pesticide
-
|-
3-27
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Flurtamone
96525-23-4
Herbicide
-
-
-
Flusilazole
85509-19-9
Fungicide,
-
-
-
Fluthiacet-methyl
117337-19-6
Herbicide
-
-
-
Flutolanil
66332-96-5
Fungicide,
-
-
-
Flutriafol
76674-21 -0
Fungicide,
-
-
-
Fluvalinate-tau-l
102851-06-9
Insecticide
-
-
-
Fluvalinate-tau-ll
999044-03-0
Insecticide
-
-
-
Folpet
133-07-3
Fungicide
-
-
cancer (1-Jan-89)
Fonofos
944-22-9
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Formothion
2540-82-1
Insecticide
-
-
-
Fosthiazate 1
98886-44-3
Insecticide
-
-
-
Fosthiazate II
999018-03-0
Insecticide
-
-
-
Fuberidazole
3878-19-1
Fungicide
-
-
-
Furalaxyl
57646-30-7
Fungicide
-
-
-
Furathiocarb
65907-30-4
Insecticide
-
-
-
Furilazole
121776-33-8
Herbicide
-
-
cancer (22-
Mar-11)
Furmecyclox
60568-05-0
Fungicide
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
cancer (1-Jan-90)
Galaxolide
1222-05-5
Personal Care, Industrial,
-
-
-
gamma-Chlordane
5103-74-2
Insecticide,
-
-
-
Geraniol
106-24-1
Personal Care, Natural
-
-
-
guaiacol
90-05-1
Industrial, Natural,
-
-
-
Halfenprox
111872-58-3
Insecticide
-
-
-
Haloxyfop-methyl
69806-40-2
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 05-
01-1990V
Heptachlor
76-44-8
Fungicide, Insecticide,
2B(2001)
Oral RfD
Assessment: Yes
(Last revised: 09-
30-1987V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
30-19871
cancer (1 -Jul-88)
developmental
(20-Aug-99)
Heptachlor epoxide
1024-57-3
Insecticide,
Oral RfD
Assessment: Yes
cancer (1-Jul-88)
(Last revised: 09-
30-1987V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
30-19871
Heptachlor epoxide isomer A
28044-83-9
General Pesticide
-
-
-
Heptenophos
23560-59-0
Insecticide
-
-
-
Hexabromobenzene
87-82-1
Flame Retardant
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
3-28
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Hexachlorobenzene
118-74-1
Fungicide, Industrial,
2B(2001)
Oral RfD
Assessment: Yes
cancer (1 -Oct-87)
developmental (1-
Jan-89)
(Last revised: 09-
26-1988V
Inhalation RfC
Assessment:
Messaae (Last
revised: 03-01-
19911.
Carcinoaenicitv
Assessment: Yes
(Last revised: 03-
01-19911
Hexachlorophene
70-30-4
Fungicide, Pharmacological,
3(1987)
Oral RfD
Assessment: Yes
(Last revised: 08-
22-19881.
Hexaconazole
79983-71 -4
Fungicide,
-
-
-
Hexazinone
51235-04-2
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 09-
30-19871.
Hexestrol
84-16-2
Pharmacological
-
-
-
Hydroprene
41096-46-2
Insecticide,
-
-
-
hydroxy-citronellal
107-75-5
Personal Care
-
-
-
Imazalil
35554-44-0
Fungicide, Industrial,
-
-
cancer (20-
May-11)
Imazamethabenz-methyl 1
81405-85-8
Herbicide
-
-
-
Imazamethabenz-methyl II
999019-03-3
Herbicide
-
-
-
Imibenconazole
86598-92-7
Fungicide
-
-
-
Imibenconazole-desbenzyl
199338-48-2
Pesticide Product
-
-
-
Imidan
732-11 -6
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
indeno[1,2,3-cd]pyrene
193-39-5
PAH,
2B(2010)
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
01-19901
cancer (1-Jan-88)
indole
120-72-9
Personal Care, Industrial,
-
-
-
Indoxacarb and Dioxacarb
decomposition product [Phenol, 2-
(1,3-dioxolan-2-yl)-]
999058-03-6
Insecticide,
loxynil
1689-83-4
Herbicide,
-
-
-
loxynil octanoate
3861 -47-0
Herbicide
-
-
-
Ipconazole
125225-28-7
Fungicide
-
-
-
Iprobenfos
26087-47-8
Fungicide
-
-
-
Iprodione
36734-19-7
Fungicide,
Oral RfD
Assessment: Yes
(Last revised: 06-
30-19881.
cancer (1 -May-96)
Iprovalicarb I
140923-25-7
Fungicide
-
-
cancer (1 -Jun-07)
Iprovalicarb II
999020-03-0
Fungicide
-
-
-
Irgarol
28159-98-0
General Pesticide
-
-
-
Isazophos
42509-80-8
Fungicide, Insecticide
-
-
-
Isobenzan
297-78-9
Insecticide
-
-
-
Isobornyl thiocyanoacetate
115-31-1
Insecticide
-
-
-
Isocarbamide
30979-48-7
Herbicide
-
-
-
Isocarbophos
24353-61 -5
Insecticide
-
-
-
3-29
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Isodrin
465-73-6
Insecticide
-
-
-
isoeugenol
97-54-1
Personal Care, Natural
-
-
-
Isofenphos
25311-71-1
Insecticide,
-
-
-
Isofenphos-oxon
31120-85-1
General Pesticide
-
-
-
Isomethiozin
57052-04-7
Herbicide
-
-
-
Isoprocarb
2631 -40-5
Insecticide
-
-
-
Isopropalin
33820-53-0
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871,
Isoprothiolane
50512-35-1
Fungicide, Insecticide,
-
-
-
Isoproturon
34123-59-6
Herbicide,
-
-
-
Isoxaben
82558-50-7
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 09-
26-1988V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
01-19911
Isoxadifen-ethyl
163520-33-0
Herbicide
-
-
-
Isoxaflutole
141112-29-0
Herbicide
-
-
cancer (22-
Dec-00)
Isoxathion
18854-01-8
Insecticide,
-
-
-
Jasmolin 1
4466-14-2
Insecticide
-
-
-
Jasmolin II
1172-63-0
Insecticide
-
-
-
Jodfenphos
18181-70-9
Insecticide
-
-
-
Kepone
143-50-0
Fungicide, Insecticide,
2B(1987)
Oral RfD
Assessment: Yes
cancer (1-Jan-88)
developmental (1-
Jan-89)
(Last revised: 09-
22-20091.
Inhalation RfC
Assessment:
Discussion (Last
revised: 09-22-
20091.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
22-20091
Kinoprene
42588-37-4
Insecticide,
-
-
-
Kresoxim-methyl
143390-89-0
Fungicide
-
-
cancer (3-Feb-12)
Lactofen
77501-63-4
Herbicide
-
-
cancer (1-Jan-89)
Lenacil
2164-08-1
Herbicide
-
-
-
Leptophos
21609-90-5
Insecticide,
-
-
-
Leptophos oxon
25006-32-0
Insecticide
-
-
-
lilial
80-54-6
Personal Care,
-
-
-
Linalool
78-70-6
Insecticide, Personal Care
-
-
-
Lindane
58-89-9
Fungicide, Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
Linuron
330-55-2
Herbicide,
-
-
developmental
(19-Mar-99)
lyral
31906-04-4
Personal Care
-
-
-
3-30
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
m-Cresol
108-39-4
Industrial
Oral RfD
Assessment: Yes
(Last revised: 08-
22-1988V
Inhalation RfC
Assessment:
Messaae (Last
revised: 04-01-
19921.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
01-19901
m-toluidine
108-44-1
Industrial,
-
-
-
Malathion
121-75-5
Insecticide, Pharmacological,
2
Oral RfD
Assessment: Yes
cancer (20-
May-16)
(Last revised: 09-
30-19871,
Malathion-o-analog
1634-78-2
Insecticide,
-
-
-
MCPA methyl ester
2436-73-9
General Pesticide
-
-
-
MCPA-butoxyethyl ester
19480-43-4
Herbicide
-
-
-
MCPB methyl ester
57153-18-1
Herbicide
-
-
-
Mecarbam
2595-54-2
Insecticide
-
-
-
Mecoprop methyl ester
23844-56-6
General Pesticide
-
-
-
Mefenacet
73250-68-7
Herbicide,
-
-
-
Mefenpyr-diethyl
135590-91-9
Herbicide
-
-
-
Mefluidide
53780-34-0
Herbicide
-
-
-
Menazon
78-57-9
Insecticide
-
-
-
Mepanipyrim
110235-47-7
Fungicide
-
-
cancer (1 -Jul-08)
Mephosfolan
950-10-7
Insecticide
-
-
-
Mepronil
55814-41 -0
Fungicide
-
-
-
Merphos
150-50-5
General Pesticide
Oral RfD
Assessment: Yes
(Last revised: 09-
07-19881.
Inhalation RfC
Assessment:
Messaae (Last
revised: 11-01-
19921.
Metalaxyl
57837-19-1
Fungicide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
Metamitron
41394-05-2
Herbicide
-
-
-
Metazachlor
67129-08-2
Herbicide
-
-
-
Metconazole I
125116-23-6
Fungicide
-
-
-
Metconazole II
999021 -03-3
Fungicide
-
-
-
Methabenzthiazuron [decomposition
product]
16954-69-1
Herbicide
-
-
-
Methacrifos
62610-77-9
Insecticide
-
-
-
Methamidophos
10265-92-6
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 09-
30-19871.
Methfuroxam
28730-17-8
Fungicide
-
-
-
Methidathion
950-37-8
Insecticide
-
-
-
Methiocarb
2032-65-7
Insecticide,
-
-
-
Methiocarb Sulfone
2179-25-1
General Pesticide
-
-
-
3-31
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Methiocarb sulfoxide
2635-10-1
General Pesticide
-
-
-
Methomyl
16752-77-5
Insecticide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 01-
31-19871,
Methoprene 1
40596-69-8
Insecticide,
-
-
-
Methoprene II
999045-03-3
Insecticide
-
-
-
Methoprotryne
841-06-5
Herbicide
-
-
-
Methoxychlor
72-43-5
Insecticide, Pharmacological,
3(1987)
Oral RfD
Assessment: Yes
-
(Last revised: 09-
01-19901,
Inhalation RfC
Assessment:
Discussion (Last
revised: 12-01-
19931.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
07-19881
Methoxychlor olefin
2132-70-9
General Pesticide
-
-
-
Methyl (2-naphthoxy)acetate
1929-87-9
Herbicide
-
-
-
METHYL 2-OCTYNOATE
111-12-6
Personal Care
-
-
-
Methyl paraoxon
950-35-6
Insecticide,
-
-
-
Methyl-1-naphthalene acetate
2876-78-0
General Pesticide
-
-
-
Methyldymron
42609-73-4
Herbicide
-
-
-
Methyleugenol
93-15-2
Personal Care, Natural
2B(2013)
-
cancer (16-
Nov-01)
Metobromuron
3060-89-7
Herbicide
-
-
-
Metolachlor
51218-45-2
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 10-
01-19901.
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
Metolcarb
1129-41-5
Insecticide
-
-
-
Metominostrobin (E)
133408-50-1
Fungicide
-
-
-
Metominostrobin (Z)
999022-03-6
Fungicide
-
-
-
Metrafenone
220899-03-6
Fungicide
-
-
-
Metribuzin
21087-64-9
Herbicide,
-
Oral RfD
Assessment: Yes
-
(Last revised: 01-
31-19871.
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
01-19931
Mevinphos
7786-34-7
Insecticide,
-
-
-
Mi rex
2385-85-5
Insecticide,
2B(1987)
Oral RfD
Assessment: Yes
cancer (1-Jan-88)
(Last revised: 10-
01-19921.
Molinate
2212-67-1
Herbicide,
-
Oral RfD
Assessment: Yes
developmental,
female, male (11-
(Last revised: 09-
26-19881.
Dec-09)
Monalide
7287-36-7
Herbicide
-
-
-
Monocrotophos
6923-22-4
Insecticide,
-
-
-
3-32
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Monolinuron
1746-81-2
Herbicide
-
-
-
Musk amberette
83-66-9
Personal Care
3(1996)
-
-
Musk Ketone
81-14-1
Personal Care,
-
-
-
Musk Moskene
116-66-5
Personal Care
-
-
-
Musk Tibetene (Moschustibeten)
145-39-1
Personal Care
-
-
-
Musk xylene
81-15-2
Personal Care,
3(1996)
-
-
Myclobutanil
88671-89-0
Fungicide,
Oral RfD
Assessment: Yes
developmental,
male (16-Apr-99)
(Last revised: 09-
26-19881,
n,n-diethyl-3-aminophenol
91-68-9
Industrial,
-
-
-
N,N-Diethyl-m-toluamide
134-62-3
Insecticide
-
-
-
N-1 -Naphthylacetamide
575-36-0
PAH
-
-
-
N-Cyclohexyl-2-
benzothiazolylsulfenamide
95-33-0
Industrial
-
-
-
N-Methyl-N-1-naphthyl acetamide
5903-13-9
Insecticide, PAH
-
-
-
n-phenyl-1 -naphthylamine
90-30-2
Industrial
-
-
-
n-phenyl-2-naphthylamine
135-88-6
Industrial
3(1987)
-
-
Naled
300-76-5
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 03-
31-19871,
naphthalene
91-20-3
PAH,
2B(2002)
Oral RfD
Assessment: Yes
(Last revised: 09-
17-19981.
Inhalation RfC
Assessment: Yes
(Last revised: 09-
17-19981.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
17-19981
cancer (19-
Apr-02)
Naphthalic anhydride
81-84-5
Herbicide, PAH, Industrial
-
-
-
Naphthanthrone
3074-00-8
OPAH
-
-
-
naphtho[1,2-b]fluoranthene
111189-32-3
PAH
3(2010)
-
-
naphtho[2,3-a]pyrene
196-42-9
PAH,
-
-
-
naphtho[2,3-e]pyrene
193-09-9
PAH
3(2010)
-
-
naphtho[2,3-j]fluoranthene
205-83-4
PAH
-
-
-
naphtho[2,3-k]fluoranthene
207-18-1
PAH
-
-
-
Naproanilide
52570-16-8
Herbicide, PAH
-
-
-
Napropamide
15299-99-7
Herbicide, PAH
-
-
-
Nickel dibutyldithiocarbamate
13927-77-0
Personal Care, Industrial
-
-
-
Nicotine
54-11 -5
Insecticide, Pharmacological,
-
-
developmental (1-
Apr-90)
Nitralin
4726-14-1
Herbicide
-
-
-
Nitrapyrin
1929-82-4
Fungicide, Insecticide
Oral RfD
Assessment:
Withdrawn (Last
revised: 07-01-
19921.
developmental
(30-Mar-99)
cancer (5-Oct-05)
Nitrofen
1836-75-5
Herbicide,
2B(1987)
-
cancer (1-Jan-88)
Nitrothal-isopropyl
10552-74-6
Fungicide
-
-
-
Norflurazon
27314-13-2
Herbicide
-
-
-
Norflurazon, Desmethyl-
23576-24-1
Herbicide
-
-
-
3-33
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Nuarimol
63284-71 -9
Fungicide,
-
-
-
o-Dichlorobenzene
95-50-1
Herbicide, Insecticide, Industrial,
3(1999)
Oral RfD
Assessment: Yes
(Last revised: 08-
01-19891,
Carcinoaenicitv
Assessment: Yes
(Last revised: 11-
01-19901
o-Phenylphenol
90-43-7
Fungicide, Insecticide, Industrial,
3(1999)
-
cancer (4-Aug-00)
o-Toluidine
95-53-4
Industrial,
1(2012)
-
cancer (1-Jan-88)
Octachlorostyrene
29082-74-4
Industrial,
-
-
-
Octamethyl pyrophosphoramide
152-16-9
Insecticide
-
-
-
Ofurace
58810-48-3
Fungicide
-
-
-
Omethoate
1113-02-6
Insecticide
-
-
-
Orbencarb
34622-58-7
Herbicide
-
-
-
ortho-Aminoazotoluene
97-56-3
Industrial
2B(1987)
-
cancer (1 -Jul-87)
Oryzalin
19044-88-3
Herbicide,
-
-
cancer (12-
Sep-08)
Oxabetrinil
74782-23-3
Herbicide
-
-
-
Oxadiazon
19666-30-9
Herbicide,
Oral RfD
Assessment: Yes
cancer (1 -Jul-91)
developmental
(15-May-98)
(Last revised: 09-
30-19871.
Oxadixyl
77732-09-3
Fungicide
-
-
-
Oxamyl
23135-22-0
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 03-
31-19871.
Oxycarboxin
5259-88-1
Fungicide
-
-
-
Oxychlordane
27304-13-8
Insecticide
-
-
-
Oxydemeton-methyl
301-12-2
Insecticide
-
-
female, male (6-
Nov-98)
Oxyfluorfen
42874-03-3
Herbicide,
-
-
-
p,p'-DDM [bis(4-chlorophenyl)
methane]
101-76-8
Industrial
-
-
-
p,p'-Dibromobenzophenone
3988-03-2
General Pesticide
-
-
-
p,p'-Dicofol
115-32-2
Insecticide,
3(1987)
Carcinoaenicitv
Assessment:
Withdrawn (Last
revised: 04-01-
19921
p-Dichlorobenzene
106-46-7
Fungicide, Insecticide, Industrial
2B(1999)
Inhalation RfC
Assessment: Yes
cancer (1-Jan-89)
(Last revised: 01-
01-19941.
p-Nitrotoluene
99-99-0
Industrial
3(1996)
-
-
p-toluidine
106-49-0
Industrial,
-
-
-
Paclobutrazol
76738-62-0
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 03-
31-19871.
Paclobutrazol
76738-62-0
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 03-
31-19871.
3-34
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Paraoxon
311-45-5
Insecticide, Pharmacological,
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19921
Parathion-ethyl
56-38-2
Insecticide,
2
Oral RfD
Assessment: No
(Last revised: 08-
22-1988V
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19931
cancer (20-
May-16)
Parathion-methyl
298-00-0
Fungicide, Insecticide,
3(1987)
Oral RfD
Assessment: Yes
(Last revised: 03-
31-19871.
PBB 1
2052-07-5
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 10
59080-32-9
Flame Retardant, PBB
2A(2016)
'
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 101
67888-96-4
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 15
92-86-4
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 169 Hexabrombiphenyl
60044-26-0
Flame Retardant, PBB,
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 18
59080-34-1
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 2
2113-57-7
Flame Retardant, PBB
2A(2016)
"
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 26
59080-35-2
Flame Retardant, PBB
2A(2016)
'
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 29
115245-07-3
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 3
92-66-0
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 30
59080-33-0
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 31
59080-36-3
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 4
13029-09-9
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 49
60044-24-8
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 52
59080-37-4
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 53
60044-25-9
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
3-35
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
PBB 7
53592-10-2
Flame Retardant, PBB
2A(2016)
'
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB77
77102-82-0
Flame Retardant, PBB,
2A(2016)
'
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 80
16400-50-3
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB 9
57422-77-2
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-101
67888-96-4
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-103
59080-39-6
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-114
96551-70-1
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-137
81381-52-4
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-141
120991-47-1
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-153
59080-40-9
Flame Retardant, PBB,
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-155
59261-08-4
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-156
77607-09-1
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-159
120991-48-2
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-169
60044-26-0
Flame Retardant, PBB,
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-180
67733-52-2
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-189
88700-06-5
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBB-200
119264-60-7
Flame Retardant, PBB
2A(2016)
cancer (1-Jan-88)
developmental (1-
Oct-94)
PBDE 103
446254-67-7
Flame Retardant, PBDE
-
-
-
PBDE 108
446254-71-3
Flame Retardant, PBDE
-
-
-
PBDE 115
446254-78-0
Flame Retardant, PBDE
-
-
-
PBDE 127
N/A
Flame Retardant, PBDE
-
-
-
PBDE 128
N/A
Flame Retardant, PBDE
-
-
-
PBDE 142
N/A
Flame Retardant, PBDE
-
-
-
PBDE 144
N/A
Flame Retardant, PBDE
-
-
-
PBDE 160
N/A
Flame Retardant, PBDE
-
-
-
PBDE 185
N/A
Flame Retardant, PBDE
-
-
-
3-36
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
PBDE 19
147217-73-0
Flame Retardant, PBDE,
-
-
-
PBDE 201
N/A
Flame Retardant, PBDE
-
-
-
PBDE 21
337513-67-4
Flame Retardant, PBDE
-
-
-
PBDE 26
337513-75-4
Flame Retardant, PBDE
-
-
-
PBDE 27
337513-53-8
Flame Retardant, PBDE
-
-
-
PBDE 31
65075-08-3
Flame Retardant, PBDE
-
-
-
PBDE 4
51452-87-0
Flame Retardant, PBDE
-
-
-
PBDE 50
446254-23-5
Flame Retardant, PBDE
-
-
-
PBDE 51
189084-57-9
Flame Retardant, PBDE,
-
-
-
PBDE 6
147217-72-9
Flame Retardant, PBDE
-
-
-
PBDE 62
446254-33-7
Flame Retardant, PBDE
-
-
-
PBDE 69
327185-09-1
Flame Retardant, PBDE
-
-
-
PBDE 88
446254-55-3
Flame Retardant, PBDE
-
-
-
PBDE 89
N/A
Flame Retardant, PBDE
-
-
-
PBDE 9
337513-66-3
Flame Retardant, PBDE
-
-
-
PBDE 1
7025-06-1
Flame Retardant, PBDE
-
-
-
PBDE 10
51930-04-2
Flame Retardant, PBDE
-
-
-
PBDE 100
189084-64-8
Flame Retardant, PBDE,
-
-
-
PBDE 11
6903-63-5
Flame Retardant, PBDE
-
-
-
PBDE 116
189084-65-9
Flame Retardant, PBDE
-
-
-
PBDE 118
446254-80-4
Flame Retardant, PBDE
-
-
-
PBDE 119
189084-66-0
Flame Retardant, PBDE,
-
-
-
PBDE 12
189084-59-1
Flame Retardant, PBDE
-
-
-
PBDE 13
83694-71 -7
Flame Retardant, PBDE
-
-
-
PBDE 138
182677-30-1
Flame Retardant, PBDE
-
-
-
PBDE 15
2050-47-7
Flame Retardant, PBDE
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
01-19901
PBDE 153
68631-49-2
Flame Retardant, PBDE,
Oral RfD
Assessment: Yes
CLast revised: 06-
30-20081,
Inhalation RfC
Assessment:
Discussion CLast
revised: 06-30-
20081.
Carcinoaenicitv
Assessment: Yes
CLast revised: 06-
30-20081
PBDE 154
207122-15-4
Flame Retardant, PBDE
-
-
-
PBDE 155
35854-94-5
Flame Retardant, PBDE,
-
-
-
PBDE 166
189084-58-0
Flame Retardant, PBDE,
-
-
-
PBDE 17
147217-75-2
Flame Retardant, PBDE
-
-
-
PBDE 2
6876-00-2
Flame Retardant, PBDE
-
-
-
PBDE25
147217-77-4
Flame Retardant, PBDE
-
-
-
PBDE28
41318-75-6
Flame Retardant, PBDE,
-
-
-
PBDE 3
101-55-3
Flame Retardant, PBDE
Carcinoaenicitv
Assessment: Yes
CLast revised: 08-
01-19901
PBDE30
155999-95-4
Flame Retardant, PBDE,
-
-
-
3-37
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
PBDE32
189084-60-4
Flame Retardant, PBDE,
-
-
-
PBDE33
147217-78-5
Flame Retardant, PBDE
-
-
-
PBDE35
147217-80-9
Flame Retardant, PBDE
-
-
-
PBDE37
147217-81-0
Flame Retardant, PBDE
-
-
-
PBDE47
5436-43-1
Flame Retardant, PBDE,
Oral RfD
Assessment: Yes
(Last revised: 06-
30-20081.
Inhalation RfC
Assessment:
Discussion (Last
revised: 06-30-
20081.
Carcinoaenicitv
Assessment: Yes
(Last revised: 06-
30-20081
PBDE49
243982-82-3
Flame Retardant, PBDE,
-
-
-
PBDE66
189084-61-5
Flame Retardant, PBDE
-
-
-
PBDE7
171977-44-9
Flame Retardant, PBDE
-
-
-
PBDE71
189084-62-6
Flame Retardant, PBDE,
-
-
-
PBDE75
189084-63-7
Flame Retardant, PBDE,
-
-
-
PBDE77
93703-48-1
Flame Retardant, PBDE
-
-
-
PBDE8
147217-71-8
Flame Retardant, PBDE
-
-
-
PBDE85
182346-21-0
Flame Retardant, PBDE,
-
-
-
PBDE99
60348-60-9
Flame Retardant, PBDE,
Oral RfD
Assessment: Yes
(Last revised: 06-
30-20081.
Inhalation RfC
Assessment:
Discussion (Last
revised: 06-30-
20081.
Carcinoaenicitv
Assessment: Yes
(Last revised: 06-
30-20081
PCB 1
2051 -60-7
PCB,
1(2012)
Oral RfD
Assessment:
cancer (1 -Oct-89)
developmental (1-
Jan-91)
Messaae (Last
revised: 06-01-
19941.
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19961
PCB 10
33146-45-1
PCB,
1(2012)
Oral RfD
Assessment:
cancer (1 -Oct-89)
developmental (1-
Jan-91)
Messaae (Last
revised: 06-01-
19941.
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19961
PCB 101
37680-73-2
PCB
1(2012)
Oral RfD
Assessment:
cancer (1 -Oct-89)
developmental (1-
Jan-91)
Messaae (Last
revised: 06-01-
19941.
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19961
3-38
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 102
68194-06-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 103
60145-21-3
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 104
56558-16-8
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 105
32598-14-4
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 106
70424-69-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 107
70424-68-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 108
70362-41-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-39
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 109
74472-35-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 11
2050-67-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 110
38380-03-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 111
39635-32-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 112
74472-36-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 113
68194-10-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 114
74472-37-0
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-40
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 115
74472-38-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 116
18259-05-7
PCB,
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 117
68194-11-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 118
31508-00-6
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 119
56558-17-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 12
2974-92-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 120
68194-12-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-41
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 121
56558-18-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 122
76842-07-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 123
65510-44-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 124
70424-70-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 125
74472-39-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 126
57465-28-8
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 127
39635-33-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-42
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 128
38380-07-3
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 129
55215-18-4
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 13
2974-90-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 130
52663-66-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 131
61798-70-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 132
38380-05-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 133
35694-04-3
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-43
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 134
52704-70-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 135
52744-13-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 136
38411-22-2
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 137
35694-06-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 138
35065-28-2
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 139
56030-56-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 14
34883-41-5
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-44
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 140
59291-64-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 141
52712-04-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 142
41411-61-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 143
68194-15-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 144
68194-14-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 145
74472-40-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 146
51908-16-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-45
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 147
68194-13-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 148
74472-41-6
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 149
38380-04-0
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 15
2050-68-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 150
68194-08-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 151
52663-63-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 152
68194-09-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-46
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 153
35065-27-1
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 154
60145-22-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 155
33979-03-2
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 156
38380-08-4
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 157
69782-90-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 158
74472-42-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 159
39635-35-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-47
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 16
38444-78-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 160
41411-62-5
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 161
74472-43-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 162
39635-34-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 163
74472-44-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 164
74472-45-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 165
74472-46-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-48
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 166
41411-63-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 167
52663-72-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 168
59291-65-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 169
32774-16-6
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 17
37680-66-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 170
35065-30-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 171
52663-71-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-49
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 172
52663-74-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 173
68194-16-1
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 174
38411-25-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 175
40186-70-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 176
52663-65-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 177
52663-70-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 178
52663-67-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-50
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 179
52663-64-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 18
37680-65-2
PCB,
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 180
35065-29-3
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 181
74472-47-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 182
60145-23-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 183
52663-69-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 184
74472-48-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-51
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 185
52712-05-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 186
74472-49-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 187
52663-68-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 188
74487-85-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 189
39635-31-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 19
38444-73-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 190
41411-64-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-52
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 191
74472-50-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 192
74472-51-8
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 193
69782-91-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 194
35694-08-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 195
52663-78-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 196
42740-50-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 197
33091-17-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-53
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 198
68194-17-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 199
52663-75-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 2
2051-61-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 20
38444-84-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 200
52663-73-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 201
40186-71-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 202
2136-99-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-54
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB203
52663-76-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 204
74472-52-9
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 205
74472-53-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 206
40186-72-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 207
52663-79-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 208
52663-77-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 21
55702-46-0
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-55
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 22
38444-85-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB23
55720-44-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 24
55702-45-9
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 25
55712-37-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 26
38444-81-4
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 27
38444-76-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 28
7012-37-5
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-56
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 29
15862-07-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 3
2051-62-9
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 30
35693-92-6
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 31
16606-02-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 32
38444-77-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 33
38444-86-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 34
37680-68-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-57
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 35
37680-69-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 36
38444-87-0
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 37
38444-90-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 38
53555-66-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 39
38444-88-1
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 4
13029-08-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 40
38444-93-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-58
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB41
52663-59-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB42
36559-22-5
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 43
70362-46-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB44
41464-39-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 45
70362-45-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 46
41464-47-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 47
2437-79-8
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-59
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB48
70362-47-9
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB49
41464-40-8
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 5
16605-91-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 50
62796-65-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 51
68194-04-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 52
35693-99-3
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 53
41464-41-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-60
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 54
15968-05-5
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 55
74338-24-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 56
41464-43-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 57
70424-67-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 58
41464-49-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 59
74472-33-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 6
25569-80-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-61
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB60
33025-41-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB61
33284-53-6
PCB,
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 62
54230-22-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 63
74472-34-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 64
52663-58-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 65
33284-54-7
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 66
32598-10-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-62
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 67
73575-53-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB68
73575-52-7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 69
60233-24-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 7
33284-50-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 70
32598-11-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 71
41464-46-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 72
41464-42-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-63
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 73
74338-23-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 74
32690-93-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 75
32598-12-2
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 76
70362-48-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 77
32598-13-3
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 78
70362-49-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 79
41464-48-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-64
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 8
34883-43-7
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB80
33284-52-5
PCB
1(2012)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 81
70362-50-4
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 82
52663-62-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 83
60145-20-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 84
52663-60-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 85
65510-45-4
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-65
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 86
55312-69-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB87
38380-02-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 88
55215-17-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 89
73575-57-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 9
34883-39-1
PCB,
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 90
68194-07-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 91
68194-05-8
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-66
-------
COA Report
University
Project#: F17-20: EPA turf
(wristbands)
&. Enuv,
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS**
Cal/EPA***
PCB 92
52663-61-3
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 93
73575-56-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 94
73575-55-0
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 95
38379-99-6
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 96
73575-54-9
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 97
41464-51-1
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
PCB 98
60233-25-2
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
1994).
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-1996)
cancer (1-Oct-89)
developmental (1-
Jan-91)
3-67
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
PCB99
38380-01 -7
PCB
1(2012)
Oral RfD
Assessment:
Messaae (Last
revised: 06-01-
19941.
Carcinoaenicitv
Assessment: Yes
cancer (1 -Oct-89)
developmental (1-
Jan-91)
(Last revised: 10-
01-19961
Pebulate
1114-71-2
Herbicide
-
-
-
Penconazole
66246-88-6
Fungicide,
-
-
-
Pendimethalin
40487-42-1
Herbicide,
-
-
-
Pentabromoethylbenzene
85-22-3
Flame Retardant
-
-
-
Pentabromotoluene
87-83-2
Flame Retardant
-
-
-
Pentachloroaniline
527-20-8
Fungicide,
-
-
-
Pentachloroanisole
1825-21-4
General Pesticide
-
-
-
Pentachlorobenzene
608-93-5
Fungicide, Insecticide, Industrial,
Oral RfD
Assessment: Yes
(Last revised: 01-
31-19871.
Carcinoaenicitv
Assessment: Yes
(Last revised: 11-
01-19921
Pentachloronitrobenzene
82-68-8
Fungicide,
3(1987)
Oral RfD
Assessment: Yes
(Last revised: 09-
30-19871.
Pentachlorophenol
87-86-5
Fungicide, Herbicide, Insecticide, Industrial,
Pulp/Paper,
Oral RfD
Assessment: Yes
cancer (1-Jan-90)
(Last revised: 09-
30-20101.
Inhalation RfC
Assessment:
Discussion (Last
revised: 09-30-
20101.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
30-20101
Pentanochlor
2307-68-8
Herbicide
-
-
-
Permethrin
52645-53-1
Insecticide,
3(1991)
Oral RfD
Assessment: Yes
(Last revised: 03-
31-19871.
Permethrin II
999046-03-6
Insecticide
-
-
-
Perthane
72-56-0
Insecticide
-
-
-
Phantolide
15323-35-0
PAH, Personal Care,
-
-
-
phenanthrene
85-01-8
PAH,
3(2010)
Carcinoaenicitv
Assessment: Yes
(Last revised: 12-
01-19901
Phenanthrene-1,4-dione
569-15-3
OPAH
-
-
-
Phenkapton
2275-14-1
Insecticide
-
-
-
3-68
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Phenol
108-95-2
Pharmacological,
3(1999)
Oral RfD
Assessment: Yes
(Last revised: 09-
30-20021.
Inhalation RfC
Assessment:
Discussion (Last
revised: 09-30-
20021.
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
30-20021
Phenothiazine
92-84-2
Fungicide, Insecticide, Pharmacological,
Industrial
-
-
-
Phenothrin 1
51186-88-0
Insecticide
-
-
-
Phenothrin II
26046-85-5
Insecticide
-
-
-
Phenoxyacetic acid
122-59-8
Pesticide Product
-
-
-
Phenthoate
2597-03-7
Insecticide,
-
-
-
P ho rate
298-02-2
Insecticide
-
-
-
P ho rate sulfone
2588-04-7
Insecticide
-
-
-
Phorate sulfoxide
2588-05-8
General Pesticide
-
-
-
Phorate-oxon
2600-69-3
General Pesticide
-
-
-
Phosalone
2310-17-0
Insecticide,
Oral RfD
Assessment:
Withdrawn (Last
revised: 12-01-
19881.
Phosfolan
947-02-4
Insecticide
-
-
-
Phosphamidon
13171-21-6
Insecticide
-
-
-
Phthalide
27355-22-2
Fungicide
-
-
-
Phthalimide 85-41-6 Fungicide, Industrial
Picloram methyl ester
14143-55-6
Herbicide
-
-
-
Picolinafen
137641 -05-5
Herbicide
-
-
-
Picoxystrobin
117428-22-5
Fungicide
-
-
-
Pindone
83-26-1
Insecticide, Rodenticide
-
-
-
Piperalin
3478-94-2
Fungicide
-
-
-
Piperonyl butoxide
51-03-6
Insecticide,
3(1987)
-
-
Piperophos
24151-93-7
Herbicide,
-
-
-
Pirimicarb
23103-98-2
Insecticide,
-
-
cancer (1 -Jul-08)
Pirimiphos-ethyl
23505-41 -1
Insecticide
-
-
-
Pirimiphos-methyl
29232-93-7
Insecticide,
-
-
-
Plifenat
21757-82-4
Insecticide
-
-
-
Potasan
299-45-6
Insecticide
-
-
-
Prallethrin, cis-
23031-36-9
Insecticide
-
-
-
Prallethrin, trans-
999023-03-9
Insecticide
-
-
-
Pretilachlor
51218-49-6
Herbicide,
-
-
-
Probenazole
27605-76-1
Fungicide
-
-
-
Prochloraz
67747-09-5
Fungicide, Industrial,
Oral RfD
Assessment: Yes
(Last revised: 01-
01-19891.
Carcinoaenicitv
Assessment: Yes
(Last revised: 10-
01-19891
Procymidone
32809-16-8
Fungicide,
-
-
cancer (1 -Oct-94)
3-69
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Prodiamine
29091-21-2
Herbicide,
-
-
-
Profenofos
41198-08-7
Insecticide,
-
-
-
Profenofos metabolite (4-Bromo-2-
chlorophenol)
3964-56-5
General Pesticide,
-
-
-
Profluralin
26399-36-0
Herbicide
-
-
-
Prohydrojasmon 1
158474-72-7
Herbicide
-
-
-
Prohydrojasmon II
999060-03-6
Herbicide
-
-
-
Promecarb
2631 -37-0
Insecticide
-
-
-
Promecarb artifact [5-isopropyl-3-
methylphenol]
3228-03-3
Insecticide,
-
-
-
Prometon
1610-18-0
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-1987V
Prometryn
7287-19-6
Herbicide,
-
-
-
Propachlor
1918-16-7
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-1987V
cancer (27-
Feb-01)
Propamocarb
24579-73-5
Fungicide,
-
-
-
Propanil
709-98-8
Herbicide,
Oral RfD
Assessment: Yes
CLast revised: 03-
01-1988V
Propaphos
7292-16-2
Insecticide
-
-
-
Propargite
2312-35-8
General Pesticide
cancer (1 -Oct-94)
developmental
(15-Jun-99)
Propargite metabolite [Cyclohexanol,
2-(4-tert-butylphenoxy)]
999004-03-4
Insecticide
-
-
-
Propazine
139-40-2
Herbicide,
Oral RfD
Assessment: Yes
CLast revised: 08-
28-1987V
developmental,
female (15-Jul-16)
propenyl guaethol
94-86-0
Personal Care,
-
-
-
Propetamphos
31218-83-4
Insecticide
-
-
-
Propham
122-42-9
Herbicide
3(1987)
Oral RfD
Assessment: Yes
CLast revised: 09-
30-1987V
Propiconazole-ll
999048-03-2
Fungicide
-
-
-
Propisochlor
86763-47-5
Herbicide
-
-
-
Propoxur
114-26-1
Insecticide,
Oral RfD
Assessment: Yes
CLast revised: 07-
01-1992V
cancer (11-
Aug-06)
Propyzamide
23950-58-5
Herbicide,
Oral RfD
Assessment: Yes
CLast revised: 01-
31-1987V
cancer (1 -May-96)
Prosulfocarb
52888-80-9
Herbicide
-
-
-
Prothioconazole-desthio
999007-03-3
General Pesticide
-
-
-
Prothiofos
34643-46-4
Insecticide,
-
-
-
Prothoate
2275-18-5
Insecticide
-
-
-
Pyracarbolid
24691-76-7
Fungicide
-
-
-
Pyraclofos
89784-60-1
Insecticide
-
-
-
Pyraflufen-ethyl
129630-19-9
Herbicide
-
-
-
3-70
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Pyrazon
1698-60-8
Herbicide
-
-
-
Pyrazophos
13457-18-6
Fungicide, Insecticide
-
-
-
Pyrazoxyfen
71561-11-0
Herbicide,
-
-
-
pyrene
129-00-0
PAH, Industrial,
3(2010)
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1990V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
01-19901
Pyrethrin I
121-21-1
Insecticide
-
-
-
Pyrethrin II
121-29-9
Insecticide
-
-
-
Pyr
buticarb
88678-67-5
Herbicide
-
-
-
Pyr
da ben
96489-71 -3
Insecticide
-
-
-
Pyr
daphenthion
119-12-0
Insecticide
-
-
-
Pyr
date
55512-33-9
Herbicide,
-
-
-
Pyr
dinitril
1086-02-8
Fungicide
-
-
-
Pyr
fenox I
88283-41 -4
Fungicide,
-
-
-
Pyr
fenox II
999049-03-5
Fungicide
-
-
-
Pyr
ftalid
135186-78-6
Herbicide
-
-
-
Pyr
methanil
53112-28-0
Fungicide,
-
-
-
Pyr
midifen
105779-78-0
Insecticide
-
-
-
Pyr
minobac-methyl (E)
136191-64-5
Herbicide
-
-
-
Pyr
minobac-methyl (Z)
999024-03-2
Herbicide
-
-
-
Pyr
proxyfen
95737-68-1
Insecticide,
-
-
-
Pyroquilon
57369-32-1
Fungicide
-
-
-
Quinalphos
13593-03-8
Insecticide,
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Quinoclamine
2797-51-5
Fungicide, Herbicide, OPAH
-
-
-
Quinoline
91-22-5
Industrial,
Oral RfD
Assessment:
Discussion (Last
revised: 09-27-
2001V Inhalation
RfC Assessment:
Discussion (Last
revised: 09-27-
2001V
Carcinoaenicitv
Assessment: Yes
(Last revised: 09-
27-20011
Quinoxyfen
124495-18-7
Fungicide,
-
-
-
Quintozene metabolite
(pentachlorophenyl methyl sulfide)
1825-19-0
Fungicide
-
-
-
Quizalofop-ethyl
76578-14-8
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 09-
26-19881.
Carcinoaenicitv
Assessment: Yes
(Last revised: 06-
01-19911
male (24-Dec-99)
Rabenzazole
40341-04-6
Fungicide
-
-
-
3-71
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Resmethrin
10453-86-8
Insecticide,
Oral RfD
Assessment: Yes
cancer (1 -Jul-08)
developmental (6-
Nov-98)
(Last revised: 09-
26-1988V
Resmethrine II
999025-03-5
Insecticide
-
-
-
retene
483-65-8
PAH,
-
-
-
Rotenone
83-79-4
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 09-
07-1988V
S,S,S-Tributylphosphorotrithioate
78-48-8
Herbicide,
-
-
cancer (25-
Feb-11)
Sebuthylazine
7286-69-3
Herbicide
-
-
-
Sebuthylazine-desethyl
37019-18-4
General Pesticide
-
-
-
Secbumeton
26259-45-0
Herbicide
-
-
-
Silafluofen
105024-66-6
Insecticide
-
-
-
Silthiopham
175217-20-6
Fungicide
-
-
-
Simazine
122-34-9
Herbicide,
3(1999)
Oral RfD
Assessment: Yes
(Last revised: 09-
01-1993V
developmental,
female (15-Jul-16)
Simeconazole
149508-90-7
Fungicide
-
-
-
Simetryn
1014-70-6
Herbicide
-
-
-
Spirodiclofen
148477-71-8
Insecticide
-
-
cancer (8-Oct-10)
Spiromesifen
283594-90-1
Insecticide
-
-
-
Spiroxamine 1
118134-30-8
Fungicide, PAH
-
-
-
Spiroxamine II
999026-03-8
Fungicide
-
-
-
Spiroxamine metabolite (4-tert-
butylcyclohexanone)
98-53-3
Pesticide Product
-
-
-
Sudan 1
842-07-9
PAH, Industrial
3(1987)
-
cancer (15-
May-98)
Sudan II
3118-97-6
PAH, Industrial
3(1987)
-
-
Sudan Red
1229-55-6
Industrial
-
-
-
Sulfallate
95-06-7
Herbicide
2B(1987)
-
cancer (1-Jan-88)
Sulfanilamide
63-74-1
Pharmacological
-
-
-
Sulfentrazone
122836-35-5
Herbicide
-
-
-
Sulfotep
3689-24-5
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 09-
07-1988V
Sulfur (S8)
10544-50-0
Fungicide, Natural
-
-
-
Sulprofos
35400-43-2
Insecticide
-
-
-
Swep
1918-18-9
Fungicide, Herbicide
-
-
-
Tamoxifen
10540-29-1
Pharmacological
1(2012)
-
cancer (1-Sep-96)
TCEP
115-96-8
Flame Retardant
3(1999)
-
cancer (1 -Apr-92)
TCMTB
21564-17-0
Fungicide, Industrial
-
-
-
TCPP
26248-87-3
Flame Retardant, Industrial, Pulp/Paper
-
-
-
Tebuconazole
107534-96-3
Fungicide,
-
-
-
Tebufenpyrad
119168-77-3
Insecticide
-
-
-
Tebupirimifos
96182-53-5
Insecticide
-
-
-
Tebutam
35256-85-0
Herbicide
-
-
-
Tebuthiuron
34014-18-1
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 08-
22-1988V
3-72
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Tecnazene
117-18-0
Fungicide
-
-
-
Tefluthrin, cis-
79538-32-2
Insecticide
-
-
-
Temephos
3383-96-8
Insecticide
-
-
-
Terbacil
5902-51-2
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 01-
31-1987V
developmental
(18-May-99)
Terbucarb
1918-11-2
Herbicide
-
-
-
Terbufos
13071-79-9
Insecticide,
-
-
-
Terbufos-oxon-sulfone
999005-03-7
General Pesticide
-
-
-
Terbufos-sulfone
56070-16-7
General Pesticide
-
-
-
Terbumeton
33693-04-8
Herbicide
-
-
-
Terbuthylazine
5915-41-3
Herbicide
-
-
-
Terbuthylazine-desethyl
30125-63-4
General Pesticide
-
-
-
Terbutryn
886-50-0
Herbicide,
Oral RfD
Assessment: Yes
(Last revised: 09-
26-1988V
Terrazole
2593-15-9
Fungicide,
-
-
cancer (1 -Oct-94)
Tetrabromo-o-chlorotoluene
39569-21 -6
Flame Retardant
-
-
-
Tetrabromophthalate diol
20566-35-2
Flame Retardant
-
-
-
Tetrachloroguaiacol
2539-17-5
Industrial, Pulp/Paper
-
-
-
Tetrachlorvinphos
961-11-5
Insecticide
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Tetraconazole
112281 -77-3
Fungicide
-
-
-
Tetradifon
116-29-0
General Pesticide
-
-
-
Tetraethyl pyrophosphate
107-49-3
Insecticide, Pharmacological
-
-
-
Tetrahydrophthalimide, cis-1,2,3,6-
27813-21 -4
Fungicide
-
-
-
Tetramethrin I
7696-12-0
Insecticide,
-
-
-
Tetramethrin II
999050-03-2
Insecticide
-
-
-
Tetrapropyl thiodiphosphate
3244-90-4
Insecticide
-
-
-
Tetrasul
2227-13-6
General Pesticide
-
-
-
Thenylchlor
96491-05-3
Herbicide,
-
-
-
Theobromine
83-67-0
Pharmacological
3(1991)
-
-
Thiabendazole
148-79-8
Fungicide, Pharmacological
-
-
-
Thiazopyr
117718-60-2
Herbicide,
-
-
-
Thifluzamide
130000-40-7
Fungicide
-
-
-
Thiofanox
39196-18-4
Insecticide
-
-
-
Thiometon
640-15-3
Insecticide
-
-
-
Thionazin
297-97-2
Insecticide
-
-
-
Thymol
89-83-8
Pharmacological
-
-
-
Tilt
60207-90-1
Fungicide,
-
-
-
Tiocarbazil I
36756-79-3
Herbicide
-
-
-
Tiocarbazil II
999051 -03-5
Herbicide
-
-
-
Tolclofos-methyl
57018-04-9
Fungicide,
-
-
-
Tolfenpyrad
129558-76-5
Insecticide
-
-
-
Tolylfluanid
731-27-1
Fungicide,
-
-
-
Tolylfluanid metabolite (DMST)
66840-71 -9
General Pesticide
-
-
-
Tolyltriazole [1 H-Benzotriazole, 4-
methyl-]
29878-31 -7
Industrial
-
-
-
3-73
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Tolyltriazole [1 H-Benzotriazole, 5-
methyl-]
136-85-6
Industrial
-
-
-
Tonalide
1506-02-1
Personal Care,
-
-
-
Toxaphene Parlar 26
142534-71-2
Insecticide
2B(2001)
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
cancer (1-Jan-88)
Toxaphene Parlar 50
66860-80-8
Insecticide
2B(2001)
Carcinoaenicitv
Assessment: Yes
cancer (1-Jan-88)
CLast revised: 08-
22-19881
Toxaphene Parlar 62
154159-06-5
Insecticide
2B(2001)
Carcinoaenicitv
Assessment: Yes
CLast revised: 08-
22-19881
cancer (1-Jan-88)
TPP
115-86-6
Flame Retardant, Industrial,
-
-
-
trans-Nonachlor
39765-80-5
General Pesticide,
-
-
-
Transfluthrin
118712-89-3
Insecticide
-
-
-
Traseolide
68140-48-7
Personal Care,
-
-
-
Tri-p-tolyl phosphate
78-32-0
Industrial
-
-
-
Triadimefon
43121-43-3
Fungicide,
developmental,
female, male (30-
Mar-99)
Tr
adimenol
55219-65-3
Fungicide,
-
-
-
Tr
a Mate
2303-17-5
Herbicide
-
-
-
Tr
amiphos
1031-47-6
Fungicide, Insecticide
-
-
-
Tr
apenthenol
76608-88-3
General Pesticide
-
-
-
Tr
azamate
112143-82-5
Insecticide
-
-
-
Tr
azophos
24017-47-8
Insecticide
-
-
-
Tr
bromoneopentyl alcohol
1522-92-5
Flame Retardant
-
-
-
Tr
butyl phosphate
126-73-8
Flame Retardant, Industrial,
-
-
-
Tr
chlamide
70193-21-4
Fungicide
-
-
-
Tr
chlorfon
52-68-6
Insecticide,
3(1987)
-
-
Tr
chloronate
327-98-0
Insecticide
-
-
-
Tr
chlorosyringol
2539-26-6
Industrial, Pulp/Paper
-
-
-
Tr
clopyr methyl ester
60825-26-5
Pesticide Product
-
-
-
Tr
closan
3380-34-5
Pharmacological, Personal Care, Industrial,
-
-
-
Tr
closan-methyl
4640-01-1
General Pesticide
-
-
-
Tr
cresylphosphate, meta-
563-04-2
Flame Retardant, Industrial
-
-
-
Tr
cresylphosphate, ortho-
78-30-8
Flame Retardant, Industrial
-
-
-
Tr
cyclazole
41814-78-2
Fungicide,
-
-
-
Tr
demorph , 4-tridecyl-
24602-86-6
Fungicide
-
-
-
Tr
diphane
58138-08-2
Herbicide
-
Oral RfD
Assessment: Yes
-
CLast revised: 01-
31-1987V
Trietazine
1912-26-1
Herbicide
-
-
-
Triethyl phosphate
78-40-0
Insecticide, Flame Retardant, Industrial
-
-
Trifenmorph
1420-06-0
General Pesticide
-
-
Trifloxystrobin
141517-21-7
Fungicide
-
-
Triflumizole
68694-11-1
Fungicide,
-
-
3-74
-------
COA Report
Oregon State
University
Project#: F17-20: EPA turf
(wristbands)
.fcEni®.
'Is pjeM-
Compound
CAS#
Classification
Risk
WHO IARC *
EPA IRIS"
Cal/EPA***
Trifluralin
1582-09-8
Herbicide,
3(1991)
Oral RfD
Assessment: Yes
(Last revised: 07-
01-1989V
Carcinoaenicitv
Assessment: Yes
(Last revised: 08-
22-19881
triphenylene
217-59-4
PAH
3(2010)
-
-
Tris(2-butoxyethyl) phosphate
78-51-3
Industrial,
-
-
-
Tris(2-ethylhexyl) phosphate
78-42-2
Flame Retardant, Industrial,
-
-
-
Triticonazole
131983-72-7
Fungicide
-
-
-
T rydopyrbutoxyethy 1
64470-88-8
Herbicide
-
-
-
Tycor (SMY 1500)
64529-56-2
Herbicide,
-
-
-
Uniconizole-P
83657-17-4
Fungicide
-
-
-
Vamidothion
2275-23-2
Fungicide, Insecticide
-
-
-
Vernolate
1929-77-7
Herbicide
Oral RfD
Assessment: Yes
(Last revised: 03-
31-1987V
Vinclozolin
50471-44-8
Fungicide,
developmental
(15-May-98)
cancer (20-
Aug-99)
XMC (3,4-Dimethylphenyl N-
methylcarbamate)
2425-10-7
Insecticide
-
-
-
XMC (3,5-Dimethylphenyl N-
methylcarbamate)
2655-14-3
Insecticide
-
-
-
Zinc diethyldithiocarbamate
14324-55-1
Personal Care, Industrial
-
-
-
Zoxamide
156052-68-5
Fungicide
-
-
-
Zoxamide decomposition product
999006-03-0
Fungicide
-
-
-
3-75
-------
Oregon State
University
Food Safety and Environmental Stewardship Program
1007 Agricultural and Life Sciences Building
Corvallis, OR 97331
Phone: (541) 737-1766
Fax: (541) 737-0497
Email: fseslab@oregonstate.edu
Web: fses.oregonstate.edu
Certificate of Analysis
&
,tr
T3
O
O
\X
&. Eni/y
V/,
^li-
re
3
t—h
Qj
Client Report For:
EPA - Jose L. Zambrana, Jr., PhD
National Exposure Research Laboratory
US EPA Office of Research and Development
zambrana.jose@epa.gov
Project Name:
Project Number:
Report Date:
EPA turf (wristbands) - Appendix 4
F17-20
February 23 2018
QC Review
Date
FSES Director Approval: Kim A. Anderson
Date
-------
Project Name: EPA turf (wristbands) - Appendix 4
Food Safety and Environmental Stewardship Program ^
J? . ^
COA Report '#
Project Number: F17-20
Methodology:
SOP 422.00 Determination of Volatile Organic Compounds (VOCs) using thermal desorption
purge and trap interfaced with El GC/MSs
Unit Conversions:
ppb = parts per billion
ppm = parts per million
ppt = parts per trillion
ng/g = ppb
ng/L = ppt
ng/mL = ppb
ng/jjL = ppm
ng/g(Wristband) = ppb
pg/|jL = ppb
|jg/ml_ = ppm
Abbreviations:
J flag: Indicates lower precision in quantitation due to values near limits of detection or matrix effects.
B flag: The sample was background corrected.
< 123.45 U: Detection limit, indicates value was below limit of detection.
COA Notes:
Concentrations in ng/g wristband
4-1
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 1
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170977
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
8.36 B
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
1.92 B
2,6-dimethylnaphthalene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
< 0.24 U
2-methylnaphthalene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
2.39 B
Bromobenzene, 108-86-1
1.41
tert-Butylbenzene, 98-06-6
< 0.24 U
Chlorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
63.9 B
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethylbenzene, 100-41-4
2.51 B
4-2
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 1 - dup
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170979
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
13.5 B
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
8.62 B
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethyinaphthaiene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
< 0.24 U
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chiorotoiuene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
1.07
tert-Butylbenzene, 98-06-6
< 0.24 U
Chlorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
< 2.42 U
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethylbenzene, 100-41-4
< 0.24 U
4-3
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 2
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170981
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
1.33
n-Decane, 124-18-5
9.53 B
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
1.32 B
n-Octane, 111-65-9
< 0.24 U
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethyinaphthaiene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
2.57 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
3.43
tert-Butylbenzene, 98-06-6
< 0.24 U
Chiorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
50.6 B
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
< 0.24 U
4-4
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 3
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170983
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
5.56 B
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
0.43 B
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethyinaphthaiene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
0.32 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
0.83
tert-Butylbenzene, 98-06-6
< 0.24 U
Chiorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
< 2.42 U
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
< 0.24 U
4-5
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 4
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170985
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
< 0.24 U
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethyinaphthaiene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
0.54 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
1.59
tert-Butylbenzene, 98-06-6
< 0.24 U
Chiorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
< 2.42 U
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
< 0.24 U
4-6
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 5
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170987
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
0.79
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
6.03 B
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
0.32 B
n-Octane, 111-65-9
1.91 B
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethylnaphthalene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoiuene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
2.42 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
3.94
tert-Butylbenzene, 98-06-6
< 0.24 U
Chlorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
23.1 B
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
< 0.24 U
4-7
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 6
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170989
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
0.30 B
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
4.83 B
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
0.59 B
2,6-dimethyinaphthaiene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
0.58 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
0.90 B
Bromobenzene, 108-86-1
1.22
tert-Butylbenzene, 98-06-6
< 0.24 U
Chiorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
76.9 B
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
1.47 B
4-8
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Site 7
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A170991
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
2.43 B
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
9.83 B
1,3-Dichlorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthalene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
0.90 B
2,6-dimethyinaphthaiene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoluene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
0.34 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
0.78 B
Bromobenzene, 108-86-1
1.25
tert-Butylbenzene, 98-06-6
< 0.24 U
Chiorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
< 2.42 U
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
0.99 B
4-9
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Trip blank 1
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A171394
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
< 0.24 U
1,3-Dichiorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthaiene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethylnaphthalene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoiuene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
0.34 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
< 0.24 U
tert-Butylbenzene, 98-06-6
< 0.24 U
Chlorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
< 2.42 U
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
< 0.24 U
4-10
-------
,j||pj Project Name: EPA turf (wristbands)
Project Number: F17-20
Food Safety and Environmental Stewardship Program
COA Report
& Eni,ir
Client Sample Name:
Trip blank 2
Test Method:
SOP 422.00 Determination of Volatile Organic Compo
FSES Sample ID:
A171395
Matrix:
Passive Sampling Device - Air
Chemical Name
Concentration
(ng/g)
Chemical Name
Concentration
(ng/g)
1,2,3-Trichlorobenzene, 87-61-6
< 2.42 U
n-Butylbenzene, 104-51-8
< 0.24 U
1,2,3-Trimethylbenzene, 526-73-8
< 0.24 U
n-Decane, 124-18-5
< 0.24 U
1,2,4-Trichlorobenzene, 120-82-1
< 2.42 U
n-Heptane, 142-82-5
< 0.24 U
1,2,4-Trimethylbenzene, 95-63-6
< 0.24 U
n-Nonane, 111-84-2
< 0.24 U
1,3,5-Trimethylbenzene, 108-67-8
< 0.24 U
n-Octane, 111-65-9
< 0.24 U
1,3-Dichiorobenzene, 541-73-1
< 0.24 U
n-Propylbenzene, 103-65-1
< 0.24 U
1,3-dimethylnaphthalene, 575-41-7
< 0.24 U
o-Dichlorobenzene, 95-50-1
< 0.24 U
1-methylnaphthaiene, 90-12-0
< 0.24 U
o-Xylene, 95-47-6
< 0.24 U
2,6-dimethylnaphthalene, 581-42-0
< 0.24 U
p-Dichlorobenzene, 106-46-7
< 0.24 U
2-Chlorotoiuene, 95-49-8
< 0.24 U
p-lsopropyltoluene, 99-87-6
0.94 B
2-methylnaphthaiene, 91-57-6
< 0.24 U
sec-Butylbenzene, 135-98-8
< 0.24 U
4-Chlorotoluene, 106-43-4
< 0.24 U
Styrene, 100-42-5
< 0.24 U
Bromobenzene, 108-86-1
0.72
tert-Butylbenzene, 98-06-6
< 0.24 U
Chlorobenzene, 108-90-7
< 0.24 U
Toluene, 108-88-3
13.2 B
Cumene, 98-82-8
< 0.24 U
Tributyl phosphate, 126-73-8
< 2.42 U
Ethyibenzene, 100-41-4
< 0.24 U
4-11
-------
SEPA
United States
Environmental Protection
Agency
Office of Research and Development (8101R)
Washington, DC 20460
Official Business
Penalty for Private Use
$300
PRESORTED STANDARD
POSTAGE & FEES PAID
EPA
PERMIT NO. G-35
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